Effects of Transition Metal (TM = V,Cr, Mn,Fe, Co,and Ni) Elements on Magnetic Mechanism of LiZnP with Decoupled Charge and Spin Doping

The electronic structure and magnetism of a series of 111-type diluted magnetic semiconductors Li(Zn,TM)P (TM = V, Cr, Mn, Fe, Co, and Ni) are investigated on the basis of density functional theory. Our results indicate that V-, Cr-, Mn-, and Fe-doped LiZnP are magnetic while Co- and Ni-doped LiZnP systems show no magnetisms. But all TM-doped LiZnP systems prefer antiferromagnetic behavior by magnetic coupling calculations. In contrast, V/Li- and Cr/Li-codoped LiZnP prefer ferromagnetic ordering, and Mn/Li-, Fe/Li- and Co/Li-codoped LiZnP display antiferromagnetic spin ordering. Hence, Li dopant is very vital for the ferromagnetic formation of Li(Zn,TM)P materials. It is revealed that the magnetic moments come mainly from the TM 3d orbitals. The ferromagnetic coupling between the TM atoms is explained by through-bond spin polarization. Our work demonstrates that the magnetic properties of Li(Zn,TM)P can be mediated by doping different TM atoms. These results may provide theoretical guidance for further experimental research on DMS.     

钙钛矿型复合氧化物催化剂中过渡金属离子的状态及其间的相互作用

讨论了Ｂ位二元复下钛矿型复合氧化物ＬａＭｙＭ＇１－ｙＯ３（Ｍ，Ｍ＇＝Ｍｎ，Ｆｅ，Ｃｏ；ｙ＝０．０￣１．０）中过渡金属离子的状态及其间的相互作用。在Ｍｎ－Ｃｏ复合体系中，富锰区（ｙ〉０．５）Ｍｎ＾３＋－Ｏ＾２－－Ｍｎ＾４＋的铁磁超交换作用对样品的磁性起决定作用。富钴区（ｙ〉０．５）Ｃｏ＾２＋和Ｃｏ＾ＩＩＩ离子的存在及其浓度是影响磁性和电导性的主要因素。ｙ＝０．５时样品的结构决定了样品的强铁磁性质。在     

The Effect of d-orbital Electrons of Transition Metals on the Electronic and Magnetic Properties of GaN:TM (TM: Cr, Mn, Fe, Co)

Based on the density functional theory and using the plane wave pseudopotential method, we study the effect of number of d-orbital electrons on the electronic and magnetic properties of GaN:TM (TM: Cr, Mn, Fe, Co). We consider the TM impurity in the samples studied to be 6.25%. Self- and non-self-consistent calculations are performed to calculate the density of states (DOSs) of the samples. Our results show that doping magnetic ions on the host semiconductor can induce spin polarization in the band gap of the doped sample. Cr and Mn doping leads to the ferromagnetic phase, while Fe and Co doping leads to the anti-ferromagnetic phase. In other words, as the number of d-orbital electrons increase, a transition from ferromagnetic to antiferromagnetic phase is observed. Besides, the gap between the valence band and the non-bonding states of the d-orbitals is reduced, and a reverse behavior is observed for the gap between the conduction band and the antibonding states of the d-orbitals. In addition, the magnetic moment of each transition metal is calculated.     

M位与A位双固溶MAX相的磁学性能研究

三元层状化合物MAX相兼具金属与陶瓷优良的力学性质, 通常被认为是一类高安全结构材料。有研究显示, 通过熔盐法可以将副族元素插入到MAX相A位层间, 获得具有铁磁性能的V₂(Sn, A)C (A =Fe、Co、Ni和Mn)材料。因而, 如何构建新的MAX相结构并对实现其磁性调控备受关注。本研究通过MAX相M位和A位双固溶的方式设计了四种新型MAX相(V, Nb)₂(Sn, A)C (A =Fe、Co、Ni和Mn)。XRD、SEM、EDS结合TEM分析证实了上述新相的合成。超导量子磁强计(Superconducting quantum interference device magnetometer, SQUID)测试磁学性能发现, M位固溶后的MAX相的居里温度与其四方率(c/a)、元素组成有关。(V, Nb)₂(Sn, Fe)C、(V, Nb)₂(Sn, Ni)C、(V, Nb)₂(Sn, Mn)C相较于M位固溶Nb元素之前的V₂(Sn, A)C相, 其矫顽力H_c和剩余磁化强度M_r减小, 饱和磁化强度M_s增大。而V₂(Sn, Co)C在M位固溶Nb元素之后磁性变化均与前述MAX相相反。通过以上结果, 揭示了M/A位双固溶对MAX相磁性的影响规律, 为调控MAX相磁性提供了新的思路。     

Interactions between transition metals and defective carbon nanotubes

Interactions between 3d transition-metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) and (5,5) carbon nanotube (CNT) with a vacancy defect are quantitatively characterized using first-principles calculations. The binding energies between CNT and transition metals are found to be significantly enhanced when vacancy defects are introduced into the CNT. For the defective CNTs doped with Sc, Cr and Zn atoms, the structures of defective CNTs are found to be intact. The doping of Ti, Mn, Cu, Fe, Ni and Co alternates the structures of defective CNTs. Among all 3d transition metals, only the ferromagnetic metal atoms Fe, Co and Ni form bonds with carbon atoms of CNT, suggesting the important role of magnetic exchange interaction in the p–d hybridisation between carbons and transition-metal atoms. The results also indicate that the 3d transition-metal atoms acting as substitutional defects can substantially modify the electronic structure of CNT. It is suggested that these stable CNT-metal systems could become promising engineering materials in many fields such as CNT devices for various spintronics applications and CNT metal–matrix composites.     

(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B:A novel high-entropy monoboride with good electromagnetic interference shielding performance in K-band

A novel equimolar high-entropy(HE)transition metal monoboride,(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B,was designed and prepared in powder and bulk form by high temperature elemental reac-tion method and spark plasma sintering(SPS)method,respectively.XRD analysis shows that HE(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B possesses orthorhombic structure with Pnma space group.Through Rietveld refinement,the lattice parameters of HE(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B are a=5.6675,b=2.9714,c=4.2209 and the theoretical density is 6.95 g/cm3.The Vickers hardness and electrical conductivity of HE(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B bulk with relative density of 90％is 12.3±0.5 GPa and 0.49±0.04×106 S/m,respectively.Due to high electrical conductivity,HE(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B bulk with 3.0 mm thickness displays superior EMI shielding performance in 18.0-26.5 GHz(K-band),and the average values of SET,SER,and SEA are 23.3 dB,13.9 dB,and 9.4 dB,respectively.The EMI shielding mechanism of HE(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B mainly results from reflection.     

Physical properties of the quarternary chalcogenides Cu2IBIICIVX4 (BII = Zn,Mn, Fe,Co; CIV = Si,Ge, Sn; X = S,Se)

X-ray, electrical and magnetic measurements have been made on several quarternary chalcogenides of the type Cu₂^IB^IIC^IVX₄ with B^II = Zn, Mn, Fe, Co; C^IV = Si, Ge, Sn; X = S, Se. The structures of these compounds result from a superstructure of zincblende or wurtzite. The resistivities have been found to be extrinsic. The magnetic measurements show that the susceptibilities of the compounds containing zinc are independent of temperature, whereas those of the transition metal compounds obey the Curie Weiss law above 77 K. The sulfur compounds have a negative Weiss constant whereas the selenide compounds show a positive Weiss constant.     

Iron doped hexagonal ErMnO3: structural, magnetic, and dielectric properties

The single phase ErFe(x)Mn1-xO3 (0 < or = x < or = 0.15) compounds were synthesized by the solid-state reaction method. The doping effects on the crystal structural, magnetic, thermal, and dielectric properties were systematically investigated. The XRD patterns show all samples crystallize in the hexagonal structure with P6(3)cm space group. The lattice parameters a and c first decrease with doping, which is followed by a subsequent increase at higher doping levels. Although both the Fe3+ and Mn3+ ions remain stable in high spin trivalent states in all samples, the magnetization is weakened with increasing Fe contents. The heat capacity data shows the antiferromagnetic transition slightly shifts from 77 K for ErMnO3 to 80 K for ErFe015Mn0.85O3, which can not be observed in the magnetic susceptibility data. The real part of complex impedance of these samples rises as the doping level increases, indicating the enhancement of insulativity of doped samples.     

On the formation of M2+ -Sb3+ -alkoxide precursors and sol-gel processing of M-Sb oxides with M = Cr,Mn, Fe,Co, Ni,Cu and Zn

Binary alkoxide complexes of compositions close to MSb(OEt)₅, with M = Mn, Fe, Co and Ni, have been prepared and characterized by their i.r. and u.v.-VIS spectra, while Cr, Cu and Zn do not form similar ethoxide complexes with Sb(OEt)₃. The Mn and Fe complexes must be prepared in inert atmosphere as they are very easily oxidized. The Fe complex is metastable and decomposes within a few hours. The Co complex can only be prepared in the presence of acetonitrile. X-ray amorphous gels were formed upon hydrolysis of solutions containing M to Sb species in the ratio 12 for M = Mn, Fe, Co and Ni. The gels consisted of agglomerated particles of sizes from 75 to 300 nm. The decomposition of the gels in air and in nitrogen has been monitored by means of thermogravimetric measurements. Samples of heated gels were quenched from various temperatures in the region 50–950°C, and the formed oxides were characterized by their X-ray powder patterns and by their infrared spectra. At 950 °C MSb₂O₆ was formed in air, while in nitrogen MSb₂O₄ (M = Mn, Co and Ni) was formed at intermediate temperatures. At higher temperatures the latter compound decomposed and Sb₂O₃ sublimated.     

Possible weak ferromagnetism in pure and M (Mn, Cu, Co, Fe and Tb) doped NiGa2O4 nanoparticles

We report on the structural and magnetic properties of nanoparticles of NiGa2O4 and 5 at.% M doped (M = Mn2+, Cu2+, Co2+, Fe3+ and Tb3+) at Ga site of NiGa2O4, synthesized by gel-combustion method. The particle size, as investigated by X-ray diffraction and transmission electron microscopy, could be fine tuned by a controlled annealing process. Weak ferromagnetism becomes significant, when the particles are in the nano regime (5-7 nm). The magnetization becomes insignificant at larger particle size ( 150 nm). Cu2+ and Tb3+ doped NiGa2O4 nanoparticles showed relatively large room temperature ferromagnetism compared to other doped (Fe, Mn and Co) and undoped NiGa2O4 samples. The weak ferromagnetism observed in the nanoparticles of NiGa2O4, which is antiferromagnetic in the bulk, is due to the surface disordered states with uncompensated spins.     

Interface effects in spin-dependent tunneling

In the past few years the phenomenon of spin-dependent tunneling (SDT) in magnetic tunnel junctions (MTJs) has aroused enormous interest and has developed into a vigorous field of research. The large tunneling magnetoresistance (TMR) observed in MTJs garnered much attention due to possible application in random access memories and magnetic field sensors. This led to a number of fundamental questions regarding the phenomenon of SDT. One such question is the role of interfaces in MTJs and their effect on the spin polarization of the tunneling current and TMR. In this paper we consider different models which suggest that the spin polarization is primarily determined by the electronic and atomic structure of the ferromagnet/insulator interfaces rather than by their bulk properties. First, we consider a simple tight-binding model which demonstrates that the existence of interface states and their contribution to the tunneling current depend on the degree of hybridization between the orbitals on metal and insulator atoms. The decisive role of the interfaces is further supported by studies of spin-dependent tunneling within realistic first-principles models of Co/vacuum/Al, Co/Al₂O₃/Co, Fe/MgO/Fe, and Co/SrTiO₃/Co MTJs. We find that variations in the atomic potentials and bonding strength near the interfaces have a profound effect resulting in the formation of interface resonant states, which dramatically affect the spin polarization and TMR. The strong sensitivity of the tunneling spin polarization and TMR to the interface atomic and electronic structure dramatically expands the possibilities for engineering optimal MTJ properties for device applications.     

Magnetic Properties of SrO Doped with 3d Transition Metals

Based on the density functional theory and using the Korringa–Kohn–Rostoker coherent potential approximation (KKR-CPA) method, we study the (Sr, TM)O doped systems where TM = V, Cr, Mn, Fe, Co, and Ni atoms. In particular, we start first by relaxing the parameters of the corresponding structures. Then we discuss its electronic structures, magnetic stabilities, and half-metal properties using 3d transition metals. Among others, it has been shown that doping with Cr, Mn, Fe, and Co, the ferromagnetic phase can be stabilized using a double exchange mechanism. Moreover, we find that the half-metallic properties of these compounds are formed due to a large exchange splitting and the delocalized properties of the majority spin e _g state and the minority spin t _eg states.     

过渡金属掺杂金红石相TiO2能带结构的第一性原理计算

本文采用第一性原理能带计算方法和超晶胞模型计算金红石相TiO2掺杂过渡金属元素的电子结构.计算结果表明,Zn掺杂对TiO2的带隙宽度影响不明显,V、Cr、Mn、Fe、Co、Ni、Cu的掺杂都有可能使TiO2吸收带出现红移现象或产生在可见光区的吸收,其中杂质原子的t2g态起了重要作用.     

Monoclinic perovskite family of Ca3 (XTa2)O9 (X = Ca,Cd, Mn,Fe, Zn,Co, Mg,Ni) caused by 1:2 ordering of X and Ta ions

Perovskite-type compounds of Ca₃(XTa₂)O₉ for X = Cd, Mn, Zn, Co, Mg and Ni were newly synthesized and their lattice deformations were investigated by a powder X-ray diffraction method. The compounds had a monoclinic perovskite structure of Ca₃(CaTa₂)O₉-type. The elongations and shrinks along the body-diagonal of the perovskitecell caused by the 1:2 ordering of X and Ta ions in Ca₃(XTa₂)O₉ were discussed relative to the orthorhombic perovskite-type compounds of CaBO₃-type (B = U, Zr, Hf, Sn, Mo, Ti, V, Cr, Mn).     

Structural and Magnetic Properties of Transition Metal-Adsorbed MoS<Subscript>2</Subscript> Monolayer

The electronic and magnetic properties of transition metal (TM) atoms (TM = Co, Cu, Mn Fe, and Ni) adsorbed on a MoS₂ monolayer are investigated by density functional theory (DFT). Magnetism appears in the case of Co, Mn, and Fe. Among the three magnetic cases, the Co-adsorbed system has the most stable structure. Therefore, we further study the interaction in the two-Co-adsorbed system. Our results show that the interaction between the two Co atoms is always ferromagnetic (FM) and the p–d hybridization mechanism results in such ferromagnetic states. However, the FM interaction is obviously suppressed by increasing the Co–Co distance, which could be well explained by the Zener–Ruderman–Kittel–Kasuya–Yosida (RKKY) theory. Moreover, similar magnetic behavior is observed in the two-Mn-adsorbed system and a longrange FM state is shown. Such interesting phenomena suggest promising applications of TM-adsorbed MoS₂ monolayer in the future.     

Spin Carrier Exchange Interactions in (Ga,Mn)N and (Zn,Co)O Wide Band Gap Diluted Magnetic Semiconductor Epilayers

(Ga,Mn)N and (Zn,Co)O wide band gap diluted magnetic semiconductor epilayers have been investigated by magneto-optical spectroscopy. In both cases, absorption bands observed below the energy gap allow us to study the nature of the valence and spin state of the incorporated magnetic element. Exchange interactions between magnetic ions and carriers can be observed by analyzing the magnetic circular dichroism in transmission or the exciton Zeeman splitting in reflection for (Zn,Co)O. A first estimation of the exchange integrals can be given for both materials.     

Photoluminescence decay kinetics of doped ZnS nanophosphors

Doped nanophosphor samples of ZnS:Mn, ZnS:Mn, Co and ZnS:Mn, Fe were prepared using a chemical precipitation method. Photoluminescence (PL) spectra were obtained and lifetime studies of the nanophosphors were carried out at room temperature. To the best of our knowledge, there are very few reports on the photoluminescence investigations of Co-doped or Fe-doped ZnS:Mn nanoparticles in the literature. Furthermore, there is no report on luminescence lifetime shortening of ZnS:Mn nanoparticles doped with Co or Fe impurity. Experimental results showed that there is considerable change in the photoluminescence spectra of ZnS:Mn nanoparticles doped with X (X = Co, Fe). The PL spectra of the ZnS:Mn, Co nanoparticle sample show three peaks at 410, 432 and 594?nm, while in the case of the ZnS:Mn, Fe nanoparticle sample the peaks are considerably different. The lifetimes are found to be in microsecond time domain for 594?nm emission, while nanosecond order lifetimes are obtained for 432 and 411?nm emission in ZnS:Mn, X nanophosphor samples. These lifetimes suggest a new additional decay channel of the carrier in the host material.     

First-Principles Study of Structural,Electronic, Magnetic and Half-Metallic Properties of the Heusler Alloys Ti<Subscript>2</Subscript>ZAl (Z = Co,Fe, Mn)

Using the first-principles calculations based on density functional theory within the generalized gradient approximation (GGA), we investigate the structural, electronic and magnetic properties of the Ti₂ZAl (Z = Co, Fe, Mn) alloys with the CuHg₂Ti-type structure. The optimized equilibrium lattice constants were found to be 6.08 Å for Ti₂CoAl, 6.07 Å for Ti₂FeAl and 6.16 Å for Ti₂MnAl. The Ti₂ZAl (Z = Co, Fe, Mn) alloys are found to be half-metallic ferromagnets. The total magnetic moment of Ti₂ZAl (Z = Co, Fe, Mn) is 2, 1 and 0 µ _B, respectively, which is in agreement with the Slater–Pauling rule M _tot=Z _tot- 18. The Ti₂ZAl (Z = Co, Fe, Mn) have a band gap of 0.64745, 0.57795 and 0.39327 eV, respectively.     

Electronic Structure of New Superconducting Perovskite MgCNi3

The electronic structures of new superconducting perovskite MgCNi3 and related compounds MgCNi2T (T=Co, Fe, and Cu) have been studied using MS-Xa method. In MgCNi3, the main peak of density of states is located below the Fermi level and dominated by Ni d. From the results of total energy calculations, it was found that the number of Ni valence electron decreases faster for the Fe-doped case than that for the Co-doped case. The valence state of Ni changes from +1.43 in MgCNi2Co to +3.02 in MgCNi2Fe. It was confirmed that Co and Fe dopants in MgCNi3 behave as a source of d-band holes and the suppression of superconductivity occurs faster for the Fe-doped case than that for the Co-doped case. In order to explain the fact that Co and Fe dopants in MgCNi3 behave as a source of d-band holes rather than magnetic scattering centers that quench superconductivity, we have also investigated the effects of electron (Cu) doping on the superconductivity and found that both electron (Cu) doping and hole (Co, Fe) dopin