过渡金属(Fe,Co,Ni,Zn)掺杂金红石TiO2的电子结构和光学性质

采用基于密度泛函理论的第一性原理方法对未掺杂以及不同浓度过渡金属Fe,Co,Ni,Zn掺杂金红石TiO₂的超晶胞体系进行了几何优化,并讨论了其晶格常数,电子能带结构和光学性质.研究结果表明:掺杂前后的晶格参数与实验值偏差在3.6%以下;适量的过渡金属掺杂不但影响体系能带结构,拓宽光吸收范围,而且扮演着俘获电子的重要角色,有利于光生电子-空穴对的有效分离以及增强光吸收能力;Fe,Co,Ni,Zn最佳理论掺杂体系分别为Ti_0.75Fe_0.25O₂,Ti_0.75Co_0.25O₂,Ti_0.75Ni_0.25O₂,Ti_0.83Zn_0.17O₂;Fe,Co,Ni3d态分裂为t_2g和e_g态,分别贡献于价带高能级和导带低能级部分,促进了电子-空穴对的生成,从而可提高TiO₂的光催化性能;Zn3d态电子成对填满轨道,不易被激发,故光催化活性无明显提高.     

过渡金属掺杂GaN的电子结构和光学性质理论研究

采用基于密度泛函理论的第一性原理平面波赝势法计算不同过渡金属（V, Cr, Mn, Fe, Co, Ni）掺杂GaN的电子结构及光学性质,分析掺杂对电子结构及光学性质的影响.结果表明,过渡金属掺杂在GaN的禁带中引入杂质能带,除掺Fe体系外其它掺杂体系都表现为半金属性.除掺Fe和Ni体系在低能区没有出现光吸收外,其它体系均在低能区杂质能级处出现光吸收.     

Modulation of magnetic properties of bilayer SnSe with transition-metals doping in the interlayer

We investigate the spin-polarized electronic and magnetic properties of bilayer SnSe with transition-metal (TM) atoms doped in the interlayer by using a first-principles method. It shows that Ni dopant cannot induce the magnetism in the doped SnSe sheet, while the ground state of V, Cr, Mn, Fe and Co doped systems are magnetic and the magnetic moment mainly originates from 3d TM atom. Two types of factors, which reduce the magnetic moment of TM atoms doped in bilayer SnSe, are identified as spin-up channel of the 3d orbital loses electrons to SnSe sheet and spin-down channel of the 3d orbital gains electrons from 4s orbital. The spin polarization is found to be 100% at Fermi level for the Mn and Co atoms doped system, while the Ni-doped system is still a semiconductor with a gap of 0.26 eV. These results are potentially useful for development of spintronic devices.     

TM掺杂的Ⅲ-Ⅴ族稀磁半导体电磁性质的第一原理计算

使用基于自旋局域密度泛函理论的第一性原理方法对3d过渡金属(TM=V，Cr，Mn，Fe，Co和Ni)掺杂的Ⅲ-Ⅴ族半导体(GaAs和GaP)的电磁性质进行了计算.结果发现：用V，Cr和Mn掺杂时体系将出现铁磁状态，而Fe掺杂时将出现反铁磁状态，Co和Ni掺杂时，其磁性则不稳定.其中，Cr掺杂的GaAs和GaP将可能是具有较高居里温度的稀磁半导体(DMS).在这些DMS系统中，V离子的磁矩大于理论期待值，Fe，Co和Ni离子的磁矩小于理论期待值，Cr和Mn离子的磁矩与期待值的差距取决于晶体的对称性以及磁性离子的能带分布.此外，使用Si和Mn共同对Ⅲ-Ⅴ族半导体进行掺杂，将有利于DMS表现为铁磁状态，并可以使体系的T_C进一步提高. 关键词： 稀磁半导体 过渡金属 掺杂 共掺杂     

3d过渡金属在NiAl中的占位及对键合性质的影响

通过赝势平面波方法系统地研究了3d过渡金属元素在B2-NiAl中的占位以及对键合性质的影响.通过形成能得出Sc,Ti,V 和Zn元素优先取代NiAl中的Al位,而Cr,Mn,Fe,Co和Cu优先取代Ni位.通过分析晶格常数变化量、电荷聚居数、交叠聚居数以及价电荷密度分布, 讨论了晶格畸变和键合性质的变化.结果表明: 取代Al的Sc,Ti,V和Zn元素掺杂使NiAl中晶格发生畸变,这对NiAl键合性质的变化起着重要作用,这些掺杂元素与第一近邻Ni原子产生强烈的排斥作用,形成反键,同时它们之间发生较大的电荷转 关键词： NiAl金属间化合物 3d过渡金属 第一性原理 键合性质     

A first-principles theoretical simulation on the electronic structures and optical absorption properties for O vacancy and Ni impurity in TiO2 photocatalysts

The band structures and optical absorption spectra of O vacancy and Ni ion doped anatase TiO₂ were successfully calculated and simulated by a plane wave pseudopotential method based on density functional theory (DFT). From the calculated results, a phenomenon of “impurity compensation” was found: the lower formation energy for O vacancy than Ni impurity indicated that introducing the intrinsic defect of O vacancy into Ni ion doped TiO₂ sample was very possible; the positive binding energy for the combination of O vacancy and Ni impurity indicated that two defects were apt to bind to each other; While Ni impurity produced the donor levels in the forbidden band of TiO₂, Ni impurity with O vacancy produced the acceptor levels upon which the excitation led to the photogenerated electrons with high energy and transferability. The combination of absorption spectra for O vacancy and Ni impurity with O vacancy models could reproduce the experimental measurement very well.     

3d过渡金属掺杂锐钛矿相TiO2的第一性原理研究

采用基于密度泛函理论的平面波超软赝势方法研究了纯锐钛矿相TiO₂及掺杂3d过渡金属TiO₂的几何、电子结构及光学性质. 计算结果表明掺杂能级的形成主要是掺杂过渡金属3d轨道的贡献，掺杂能级在禁带中的位置是决定TiO₂吸收带边能否出现红移的重要因素. Cr，Mn，Fe，Ni，Co，Cu掺杂使TiO₂的吸收带边产生红移，并在可见光区有一定的吸收系数； Sc，Zn掺杂使TiO₂的吸收带边产生蓝移，但在可见光区有较大的吸收系数；掺V不但使TiO₂的吸收带边产生红移，增强了在紫外光区的光吸收，而且在可见光区有非常大的吸收系数.     

A comparison between shake-up and UV charge-transfer transitions

The He(II) spectra of the unsubstituted metallocenes {M(η-C₅H₅)₂}, M  V, Cr, Mn, Fe, Co, Ni and Ru, and of {Mn(η-C₅H₄Me)₂} are reported; both He(I) and He(II) spectra of some decamethylmetallocenes {M(η-C₅Me₅)₂}, where M  Mg, V, Cr, Mn, Fe, Co and Ni, are also given. Intensity changes between the He(I) and He(II) spectra are shown to provide a reliable guide to band assignment. A ligand field treatment of the decamethylmanganocene cation, including limited configuration interaction, gives values for Δ₂, B and C; these values are also in good agreement with the photoelectron spectra of {M(η-C₅Me₅)₂} where M  V, Cr and Fe. Overlap between the ligand and metal “d” band structures prevents complete assignment in the cases of Co and Ni.     

Investigation of impurity phase formation for (ZnO)1−x(TMO)x bulk samples formed by ball milling

Structural, compositional, optical and magnetic properties have been studied for polycrystalline (ZnO)_0.90(TMO)_0.10 bulk samples, where TM (transition metal ions) = Mn, Fe, and Co. The quantitative Rietveld analysis showed relatively higher percentage of impurity (spinel and oxide) phases of about 33.76, 52.38 and 55.61% for Mn, Fe and Co doped ZnO samples, respectively. The de-convolution of XPS spectra indicated the presence of different phases. The appearance of shaking satellites in XPS spectra confirmed the presence of different valence states of dopant ions. The red shift in energy band gap, estimated from reflectance UV-vis spectroscopy, was observed for all TM doped bulk samples. For Mn doping, paramagnetic behavior was obtained while for Co and Fe, weak ferromagnetic behavior was observed at room temperature.     

Effect of 3d doping on the electronic structure of BaFe2As2

The electronic structure of BaFe(2)As(2) doped with Co, Ni and Cu has been studied by a variety of experimental and theoretical methods, but a clear picture of the dopant 3d states has not yet emerged. Herein we provide experimental evidence of the distribution of Co, Ni and Cu 3d states in the valence band. We conclude that the Co and Ni 3d states provide additional free carriers to the Fermi level, while the Cu 3d states are found at the bottom of the valence band in a localized 3d(10) shell. These findings help shed light on why superconductivity can occur in BaFe(2)As(2) doped with Co and Ni but not Cu.     

Low-temperature heat capacity upon the transition from paramagnetic to ferromagnetic Heusler alloys Fe<Subscript>2</Subscript> <Emphasis Type="Italic">Me</Emphasis>Al (<Emphasis Type="Italic">Me</Emphasis> = Ti,V, Cr,Mn, Fe,Co, Ni)

The heat capacity of band magnets Fe₂MeAl (Me = Ti, V, Cr, Mn, Fe, Co, Ni) ordered in crystal structure L2₁ has been measured in the range 2 K ≤ T ≤ 50 K. The dependences of the Debye temperature Θ_D, the Sommerfeld coefficient γ, and the temperature-independent contribution to heat capacity C₀ on the number of valence electrons z in the alloys have been determined.     

First-principles calculations of the monoclinic transition-metal doped NaMnO2 cathode material

ABSTRACT

Using spin-polarised generalised gradient approximation (GGA?+?U), I successfully investigate the electronic properties of the monoclinic NaMnO₂ doped with Cr, Fe and V atom to enhance the electrochemical performance. The expansion of volumes is induced by the dopants. The lowest conduction band and highest valence band are mostly from d orbital of Mn atom and transition-metal dopants which are responsible for the electronic conductivity. Na(Mn, Fe)O₂ is a semiconductor with the reduced band gap. Cr and V doping in NaMnO₂ compound reveal the half-metallic performance. The enhancement of the insertion potentials is induced by transition-metal dopants. The electronic conductivity of NaMnO₂ cathode material is improved by Cr-doping scheme. Finally, this research presents the new horizons for the expenditure of transition-metal doping for designing and improving the NaMnO₂ cathode materials in Na-ion rechargeable batteries.     

Survey of intermediate band material candidates

A systematic ab initio study, using the local spin density approximation, of the electronic properties of Ga_xP_yM compounds, where M is a transition metal substituting Ga or P atoms in a GaP host semiconductor lattice is presented. This study is oriented towards the early identification of intermediate band materials of recent interest as new photovoltaic materials to exceed the efficiency of single gap and even tandems of two solar cells. M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn have been explored as transition metals and Sc, V, Cr, and Fe in Ga₃₂P₃₁M and Cr in Ga₃₁P₃₂M have exhibited the desired intermediate band.     

Mg12O12纳米线掺杂3过渡金属元素的第一性原理计算研究

基于密度泛函第一性原理计算,系统研究了Mg12O12笼状团簇组装一维纳米线及其掺杂3d族元素体系的几何结构与电子结构。结果表明：Mg12O12团簇组装一维纳米线为非磁性半导体,带隙值为3.16 eV;掺杂Sc和V后,体系由半导体转变为金属;掺杂Ti、Cr、Mn、Fe、Co、Ni、Cu后体系仍然保持半导体特性、但带隙值明显减小,而掺杂Zn时带隙值变化不大;掺杂V、Cr、Mn、Fe、Co、Ni、Cu后纳米线具有磁性。     

Combined Optical/MCD/ODMR investigations of photochromism in doubly-doped Bi 12 GeO 20

Electron paramagnetic resonance is detected optically via the change of magnetic circular dichroism under microwaves at 35 v GHz. The technique is applied to Bi 12 GeO 20 samples co-doped with vanadium and a second transition metal (Cr, Mn, Co, Cu). The optical and magnetic properties of several paramagnetic defects (V Ge 4+ and Cr Ge 4+ ) are directly correlated. The basic photochromic processes occuring in samples doped with V, Mn, and Mn+V are explained. The V Ge 4+/5+ level is positioned roughly 2.2 v eV above the valence band.     

Magnetic properties of intercalation compounds MxTiS2 (M = 3d transition metal)

Magnetization measurements have been made on 3d transition-metal intercalation compounds of M_xTiS₂ (M = V, Cr, Mn, Fe, Co and Ni; 0 ⩽ x ⩽ 1) at 4.2, 77 and 300 K in static fields up to 20 kOe and in pulsed fields up to 160 kOe. The ac magnetic susceptibility measurements in dc fields have also been made for Fe_xTiS₂. We have identified various types of magnetic phases in M_xTiS₂, such as paramagnetic, spin-glass, cluster-glass or mictomagnetic, and ferromagnetic ones, depending on the kind of guest 3d metals and their concentrations. Magnetic properties of these materials can be understood in terms of an itinerant or band picture rather than a localized or rigid band model.     

Structural and magnetic properties of Ti12M clusters (M=Sc to Zn)

The geometries, electronic, and magnetic properties of the 3d atom doped icosahedron (ICO) Ti₁₂M (M=Sc to Zn), where a dopant atom replaces either the centra l(Ti₁₂M^c) or surface (Ti₁₂M^s) Ti atom in ICO Ti₁₃ cluster, have been systematically investigated by using the density functional theory. The structures of all the optimized Ti₁₂M^c and Ti₁₂M^s clusters are distorted ICO. Sc, Ni, Cu, and Zn atoms prefer to displace surface Ti atom, V, Cr, Mn, and Fe atoms prefer to displace central Ti atom. The position of impurity atom depends on the strength of the interaction between the central atom and the surface atoms. As compared to the pure Ti₁₃ cluster, Ti₁₂M^c and Ti₁₂M^s (M=V, Fe, Co, and Ni) clusters are more stable, Ti₁₂M^c and Ti₁₂M^s (M=Sc, Cr, Mn, Cu, and Zn) are less stable. Both Ti₁₂Ni^s and Ti₁₂Ni^c are magic clusters, which originate from their electronic as well as geometric closed shells. Because the exchange interaction prevails over the crystal field in Ti₁₂M clusters, the valence electrons fill molecular orbitals in terms of Hund’s rule of maximum spin.     

Electronic structures,magnetic properties and band alignments of 3d transition metal atoms doped monolayer MoS2

Utilizing first-principles calculations, the electronic structures, magnetic properties and band alignments of monolayer MoS₂ doped by 3d transition metal atoms have been investigated. It is found that in V, Cr, Mn, Fe-doped monolayers, the nearest neighboring S atoms (S_NN) are antiferromagnetically polarized with the doped atoms. While in Co, Ni, Cu, Zn-doped systems, the S_NN are ferromagnetically coupled with the doped atoms. Moreover, the nearest neighboring Mo atoms also demonstrate spin polarization. Compared with pristine monolayer MoS₂, little change is found for the band edges' positions in the doped systems. The Fermi level is located in the spin-polarized impurity bands, implying a half-metallic state. These results provide fundamental insights for doped monolayer MoS₂ applying in spintronic, optoelectronic and electronic devices.     

Antiferromagnetism of the α-Mn system

The variation of the Néel temperature (T_N) of antiferromagnetic alloys of Mn with 3-d elements has been studied by electrical resistivity measurements. Binary Mn-rich alloys Fe, Co, Ni, Ti, Rh, Os, Ir, and Ru were investigated. The results show a strong and systematic dependence on the number of d-electrons of the impurity element. Elements with more d electrons than Mn raise T_N, while those with fewer d electrons depress T_N. The change of T_N per atomic percent impurity also exhibits a striking, non-monotonic dependence on the impurity used. The dependence shows inversion symmetry with impurities around Mn.To further elucidate the properties of the Mn-rich antiferromagnetic system, a study was made of ternary Mn-rich alloys in the MnFeCr, MnCoNi, and MnVTi systems. The results from the MnFeCr system are consistent with the rigid-band model, the average number of d-electrons per atom being of primary importance determiningh the antiferromagnetism in this system.Our goal in these studies has been to provide a firm experimental data baseupon which future theoretical work can be built. A more detailed understanding of the very intriguing α-Mn magnetic system now awaits further theoretical investigation.