In-plane optical anisotropy of two-dimensional VOCl single crystal with weak interlayer interaction

Transition-metal oxyhalides $MOX$ ($M = {\rm Fe}$, Cr, V; $O ={\rm oxygen}$, $X= {\rm F}$, Cl, Br, I), an emerging type of two-dimensional (2D) van der Waals materials, have been both theoretically and experimentally demonstrated to possess unique electronic and magnetic properties. However, the intrinsic in-plane anisotropic properties of 2D VOCl still lacks in-depth research, especially optical anisotropy. Herein, a systematic Raman spectroscopic study is performed on VOCl single-crystal with different incident laser polarization at various temperatures. The polarized-dependent Raman scattering spectra reveal that the ${{ A}}_{{\rm g}}$ mode of VOCl show a 2-lobed shape in parallel polarization configuration while a 4-lobed shape in vertical configuration. In addition, the temperature-dependent and thickness-dependent Raman scattering spectra confirm a relatively weak van der Waals interaction between each layers among VOCl single crystal. These findings might provide better understanding on the in-plane anisotropic phenomenon in VOCl layers, thus will accelate further application of 2D single crystals for nanoscale angle-dependent optoelectronics.     

Controlled vapor growth of 2D magnetic Cr_2Se_3 and its magnetic proximity effect in heterostructures

Two-dimensional(2 D) magnetic materials have aroused tremendous interest due to the 2 D confinement of magnetism and potential applications in spintronic and valleytronic devices. However, most of the currently 2 D magnetic materials are achieved by the exfoliation from their bulks, of which the thickness and domain size are difficult to control, limiting the practical device applications. Here, we demonstrate the realization of thickness-tunable rhombohedral Cr_2Se_3 nanosheets on different substrates via the chemical vapor deposition route. The magnetic transition temperature at about 75 K is observed. Furthermore, van der Waals heterostructures consisting of Cr_2Se_3 nanosheets and monolayer WS_2 are constructed.We observe the magnetic proximity effect in the heterostructures, which manifests the manipulation of the valley polarization in monolayer WS_2. Our work contributes to the vapor growth and applications of 2 D magnetic materials.     

Mössbauer-effect studies of multilayers and interfaces

The usefulness of Mössbauer spectroscopy for the investigation of magnetic multilayer systems is described. By applying ⁵⁷Fe Mössbauer spectroscopy, the behavior of ultrathin magnetic layers, such as FCC-like Fe films on Cu(0 0 1), is studied. Position-specified (depth-selective) information is available by preparing samples in which monatomic ⁵⁷Fe probe layers are placed at specific vertical positions, e.g. at interfaces or at the surface. As demonstrated for epitaxial chemically ordered Fe₅₀Pt₅₀ alloy films and polycrystalline nanostructured Tb/Fe multilayers, the Fe-spin structure can be determined directly, and a site-selective Fe-specific magnetic hysteresis loop can be traced in very-high-coercivity materials. For the studies of non-magnetic layers, on the other hand, hyperfine field observations by ¹⁹⁷Au and ¹¹⁹Sn probes are worthwhile. Spin polarizations in Au layers penetrating from neighboring ferromagnetic 3D layers are estimated ¹⁹⁷Au from Mössbauer spectra and are also studied by inserted ¹¹⁹Sn probes in Au/3D multilayers. In the Sn spectra for Cr/Sn multilayers, it was found that remarkably large spin polarization is penetrating into Sn layers from a contacting Cr layer, which suggests that Cr atoms in the surface layer have a ferromagnetic alignment.     

Metal adsorption on monolayer blue phosphorene: A first principles study

We investigated the electronic structure, adsorption energies, magnetic properties, dipole moment and work function of metal adatoms (Mg, Cr, Mo, Pd, Pt, and Au) adsorption on a blue phosphorene monolayer. For Mg, Pt and Au metals, the most stable state was found in hollow site while for Cr, Mo and Pd metals we found an adsorption in valley site. We suggest that the Pd and Pt atoms prefer 2D growth mode while the Mg, Cr, Mo and Au atoms prefer 3D island growth mode on monolayer phosphorene. The electronic band structures and magnetic properties were dependent on the doping site and dopant materials. For instance, the semiconducting features were preserved in Mg, Pd, Pt, and Au doped systems. However, the Cr and Mo doped systems displayed half-metallic band structures. The total magnetic moment of 4.05, 2.0 and $0.77{\text{μ}}_B/\text{impurity}$ atom were obtained in Cr, Mo and Au doped systems whereas the Mg, Pd and Pt doped systems remained nonmagnetic. We also investigated the magnetic interaction between two transition metal impurities. We observed ferromagnetic coupling between two transition metal impurities in Cr and Mo doped systems while the Au doped system displayed almost degenerated magnetic state. For Mg, Cr, and Mo adsorptions, we found relatively large values of dipole moments compared to those in the Pd, Pt and Au adsorptions. This resulted in a significant suppression of the work function in Mg, Cr and Mo adsorptions. Overall, adsorption can tune the physical and magnetic properties of phosphorene monolayer.     

First observation of nonreciprocal X-Ray gyrotropy

We report the first observation of a nonreciprocal x-ray linear dichroism caused by the time-reversal odd, real part zeta of the complex gyrotropy tensor zeta(*) which is dominated by electric dipole-electric quadrupole E1E2 interference terms. A nonreciprocal transverse anisotropy was observed in the low temperature insulating phase of a Cr doped V2O3 Mott crystal when a single antiferromagnetic domain was grown by magnetoelectric annealing along the hexagonal c axis. This new element (edge) specific spectroscopy could nicely complement x-ray magnetic circular dichroism which is silent for antiferromagnetic materials.     

范德瓦尔斯磁性材料CrOCl变磁性相变的磁力显微镜研究

近年来,二维范德瓦尔斯磁性材料因为在自旋电子学的应用前景而吸引了广泛的关注.CrOCl是一种范德瓦尔斯磁性材料,理论预言其单层具有高达160 K的居里温度,因此吸引了广泛的关注。为了更好的理解这一材料的磁性,我们利用磁力显微镜研究了CrOCl变磁性相变中磁畴结构随磁场的变化。实验发现,在2K下CrOCl样品表面出现随磁场变化的方格条纹,给出了变磁性相比中反铁磁相和铁磁相竞争的图样,并通过二维快速傅里叶变换证实了CrOCl磁性的各向异性。我们的结果为后续研究CrOCl薄层的磁性提供了参考依据。     

Multifractal analysis of the electronic states in the Fibonacci superlattice under weak electric fields

We report the effect of substitution of Cr by V and Mn in the spin- \frac12\frac{1}{2} 1 2 dimer compound Sr₃Cr₂O₈. In the pentavalent Cr site, V ion has zero effective moment, while Mn remains in the spin-1 state. For both V and Mn substitutions, the gap in the spin excitation spectra remains almost unchanged in the dilute doping regime. The low temperature Curie tail, expected to be originated from free or quasi-free magnetic ions, is found to be larger in case of V doped samples. However, inter-dimer interaction is found to be stronger in the Mn doped samples. The underlying magnetic behaviour of these doped samples is presumably related to the effect of broken dimers due to random substitutions.     

Electronic and magnetic properties of V- and Cr-doped zinc-blende AlN

The electronic and magnetic properties of the zinc-blende aluminum nitride doped with V and Cr are studied using the density functional theory (DFT), namely the KKR-CPA-PBE method. Pure AlN is found to be a wide band gap semiconductor, and doping V and Cr single impurities generate ferromagnetic half-metallic behavior. Moreover, the values of the formation energy reveal that these compounds are stable systems for all dopant concentrations. A self-consistent energy minimization scheme determines the ferromagnetic state as the stable magnetic state for V- and Cr-doping AlN. A double exchange mechanism is identified as the mechanism responsible for magnetism in our systems. When increasing doping impurities, the total magnetic moments increase linearly and the Curie temperature T_C, calculated using the mean-field approximation, shows a significant change. The present findings reveal Cr- and V-doped zinc-blende AlN as potential candidates for high Curie temperature ferromagnetic materials.     

Suppression of incommensurate spin-density waves in thin epitaxial Cr(110) layers of a V/Cr multilayer

We observed a complete suppression of the incommensurate spin-density wave in thin Cr layers of a V/Cr multilayer in a temperature range from 550 K down to 2 K. The (110)-oriented V/Cr multilayer consisting of 30 nm thick Cr layers and 5 nm thick V layers was investigated by neutron and X-ray diffraction (XRD). From the XRD experiments we were able to determine that the epitaxial strain of the Cr layers in the V/Cr multilayer is about 90% larger than in earlier studied Fe/Cr(110) multilayers. That leads to a completely different magnetic phase diagram as revealed by neutron diffraction experiments. The existence of the commensurate antiferromagnetic structure in the Cr layers can be observed in the whole temperature range without a phase transition to an incommensurate spin-density wave at lower temperatures. In order to elucidate the proximity effects further we also performed experiments in an external magnetic field. Up to a field of 4 T we found no change in the magnetic structure of the Cr films whereas in earlier experiments on Fe/Cr(110) multilayers we could observe a strong perpendicular pinning of the Cr polarization to the Fe magnetization.Received: 28 August 2003, Published online: 8 December 2003PACS: 75.30.Fv spin-density waves - 75.70.-i magnetic properties of thin films, surfaces, and interfaces - 61.12.-q Neutron diffraction and scattering     

Magnetodielectric CuCr0.5V0.5O2: an example of a magnetic and dielectric multiglass

The complex dielectric susceptibility and spin glass properties of polycrystalline CuCr(0.5)V(0.5)O(2) delafossite have been investigated. Electron diffraction, high resolution electron microscopy and electron energy loss spectroscopy show that the Cr(3+) and V (3+) magnetic cations are randomly distributed on the triangular network of CdI(2)-type layers. In contrast to CuCrO(2), CuCr(0.5)V(0.5)O(2) exhibits two distinctive (magnetic and electric) glassy states evidenced by memory effects in electric and magnetic susceptibilities. A large magnetodielectric coupling is observed at low temperature.     

Magnetic properties in transition-metal-doped gold clusters: M@Au6 (M = Ti, V, Cr)

The electronic structure and magnetic properties in a series of transition-metal-doped Au clusters, MAu6- (M = Ti, V, Cr), are investigated experimentally using photoelectron spectroscopy (PES) and density functional calculations. PES features due to the impurity atoms and the host are clearly observed. It is found that all the MAu6- and MAu6 clusters possess a planar structure, in which the transition metal atom is located in the center of an Au6 ring and carries large magnetic moments (2, 3, and 4 muB for MAu6, M = Ti, V, and Cr, respectively).     

Computational study on the half-metallicity in transition metal–oxide-incorporated 2D g-C3N4 nanosheets

In this study, based on the first-principles calculations, we systematically investigated the electronic and magnetic properties of the transition metal–oxide-incorporated 2D g-C₃N₄ nanosheet (labeled C₃N₄– TM–O, TM= Sc–Mn). The results suggest that the TM–O binds to g-C₃N₄ nanosheets strongly for all systems. We found that the 2D C₃N₄–TM–O framework is ferromagnetic for TM= Sc, Ti, V, Cr, while it is antiferromagnetic for TM= Mn. All the ferromagnetic systems exhibit the half-metallic property. Furthermore, Monte Carlo simulations based on the Heisenberg model suggest that the Curie temperatures (T_c) of the C₃N₄–TM–O (TM= Sc, Ti, V, Cr) framework are 169 K, 68 K, 203 K, and 190 K, respectively. Based on Bader charge analysis, we found that the origin of the half-metallicity at Fermi energy can be partially attributed to the transfer of electrons from TM atoms to the g-C₃N₄ nanosheet. In addition, we found that not only electrons but also holes can induce half-metallicity for 2D g-C₃N₄ nanosheets, which may help to understand the origin of half-metallicity for graphitic carbon nitride.     

Alloying and magnetic disordering effects on phase stability of Co2 YGa (Y=Cr,V, and Ni) alloys: A first-principles study

The alloying and magnetic disordering effects on site occupation, elastic property, and phase stability of Co$_{2}Y$Ga ($Y={\rm Cr}$, V, and Ni) shape memory alloys are systematically investigated using the first-principles exact muffin-tin orbitals method. It is shown that with the increasing magnetic disordering degree $y$, their tetragonal shear elastic constant $C'$ (i.e., $(C_{11}-C_{12})/2$) of the $L2_{1}$ phase decreases whereas the elastic anisotropy $A$ increases, and upon tetragonal distortions the cubic phase gets more and more unstable. Co$_{2}$CrGa and Co$_{2}$VGa alloys with $y\geq0.2$ thus can show the martensitic transformation (MT) from $L2_{1}$ to $D0_{22}$ as well as Co$_{2}$NiGa. In off-stoichiometric alloys, the site preference is controlled by both the alloying and magnetic effects. At the ferromagnetism state, the excessive Ga atoms always tend to take the $Y$ sublattices, whereas the excessive Co atom favor the $Y$ sites when $Y={\rm Cr}$, and the excessive $Y$ atoms prefer the Co sites when $Y={\rm Ni}$. The Ga-deficient $Y={\rm V}$ alloys can also occur the MT at the ferromagnetism state by means of Co or V doping, and the MT temperature $T_{\rm M}$ should increase with their addition. In the corresponding ferromagnetism $Y={\rm Cr}$ alloys, nevertheless, with Co or Cr substituting for Ga, the reentrant MT (RMT) from $D0_{22}$ to $L2_{1}$ is promoted and then $T_{\rm M}$ for the RMT should decrease. The alloying effect on the MT of these alloys is finally well explained by means of the Jahn-Teller effect at the paramagnetic state. At the ferromagnetism state, it may originate from the competition between the austenite and martensite about their strength of the covalent banding between Co and Ga as well as $Y$ and Ga.     

Experimental evidence supported by simulations of a very high H2 diffusion in metal organic framework materials

Quasielastic neutron scattering measurements are combined with molecular dynamics simulations to extract the self-diffusion coefficient of hydrogen in the metal organic frameworks MIL-47(V) and MIL-53(Cr). We find that the diffusivity of hydrogen at low loading is about 2 orders of magnitude higher than in zeolites. Such a high mobility has never been experimentally observed before in any nanoporous materials, although it was predicted in carbon nanotubes. Either 1D or 3D diffusion mechanisms are elucidated depending on the chemical features of the MIL framework.     

Electronic and magnetic properties of new quaternary oxybismuthides LaOMBi (where M = V, Cr, …, Ni, Cu) from first principles

For prediction of new parent phases for Fe-containing superconducting materials by means of the FPLAPW-GGA method the structural, electronic and magnetic properties of series of quaternary oxybismuthides LaOMBi (where M = V, Cr, …, Ni, Cu) are investigated for the first time. Our preliminary conclusion is that LaONiBi may be a suitable phase for search of new superconducting materials.     

一种在室温下具有强磁介电耦合的钙钛矿型金属有机框架介电材料

磁电耦合材料在下一代存储器件中具有巨大的潜在应用, 其中钙钛矿型多铁性金属有机框架材料因其易于实现对磁性和电性的调控而受到广泛关注. 在这项工作中, 我们将Cr2+ 引入到[NH4 ][Mn(HCOO)3 ]晶体框架中. 当Cr2+ 掺杂比例为2.38%时, 铁电有序温度从零掺杂的231 K 上升到270 K, 在外加5 T 磁场作用下, 其铁电有序温度从零场的270 K 提高到296 K, 磁介电系数达到154%, 金属有机框架表现出明显的磁介电效应. 这个结果表明, 引入Cr2+ 离子作为晶体结构的构建块, 是合成具有较高磁介电耦合效应材料的一种可行性方法.     

非晶态合金FeTmB的磁矩和居里温度

本文系统地报道单辊液淬方法制备FeTmB(Tm=Ti,V,Cr,Mn,Zr,Nb,Mo,Ta,W)非晶态合金的磁性,讨论了3d,4d,5d元素的加入对非晶态FeB合金的磁矩和居里温度的影响。实验结果表明在非晶态FeTmB合金系中Fe原子磁矩都在2.0μ_B左右。Tm原子在非晶态Fe基合金中比在相应的晶态合金中显示更强的局域特性。Tm原子的磁矩与元素的外层电子数有关,IVB(Ti),VB(V),VIB(Cr),VIIB(Mn)族原子的磁矩分别约为4,5,4,3μ_B,Tm的磁矩与铁原子磁矩反平行耦合。合金磁矩随Tm含量的变化率dμ/dx与混合模型的计算值相符合。用虚拟束缚态讨论,得到IVB(Ti),VB(V)族元素的虚拟束缚态在费密面以上,VIB(Cr),VIIB(Mn)族元素的虚拟束缚态与费密面交迭。 关键词：     

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.     

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