Making and breaking covalent bonds across the magnetic transition in the giant magnetocaloric material Gd5(Si2Ge2)

A temperature-dependent, single crystal x-ray diffraction study of the giant magnetocaloric material, Gd5(Si2Ge2), across its Curie temperature (276 K) reveals that the simultaneous orthorhombic to monoclinic transition occurs by a shear mechanism in which the (Si, Ge)-(Si,Ge) dimers that are richer in Ge increase their distances by 0.859(3) A and lead to twinning. The structural transition changes the electronic structure, and provides an atomic-level model for the change in magnetic behavior with temperature in the Gd5(SixGe1-x)(4).     

Role of Ge in bridging ferromagnetism in the giant magnetocaloric Gd5(Ge1-xSix)4 alloys

X-ray magnetic circular dichroism (XMCD) measurements and density functional theory (DFT) are used to study the electronic conduction states in Gd5(Ge(1-x)Si(x))4 materials through the first-order bond-breaking magnetostructural transition responsible for their giant magnetocaloric effect. Spin-dependent hybridization between Ge 4p and Gd 5d conduction states, which XMCD senses through the induced magnetic polarization in Ge ions, enables long-range Ruderman-Kittel-Kasuya-Yosida ferromagnetic interactions between Gd 4f moments in adjacent Gd slabs connected by Ge(Si) bonds. These interactions are strong below but weaken above the Ge(Si) bond-breaking transition that destroys 3D ferromagnetic order.     

Field and temperature induced magnetic transition in Gd5Sn4: a giant magnetocaloric material

Gd5Sn4 exhibits a giant magnetocaloric effect comparable to that reported in the Gd5(Si,Ge)(4) system. The giant magnetocaloric effect is associated with a first-order change that occurs at approximately 82 K in zero field, and can be reversed by the application of an external field of a few Tesla. 119Sn M?ssbauer spectroscopy shows that this material is magnetically inhomogeneous over a wide range of temperatures and fields.     

Phase transitions and magnetocaloric effects in intermetallic compounds MnFeX（X=P,As,Si,Ge）

Since the discovery of giant magnetocaloric effect in MnFeP1-x As x compounds,much valuable work has been performed to develop and improve Fe2P-type transition-metal-based magnetic refrigerants.In this article,the recent progress of our studies on fundamental aspects of theoretical considerations and experimental techniques,effects of atomic substitution on the magnetism and magnetocalorics of Fe2P-type intermetallic compounds MnFeX(X=P,As,Ge,Si) is reviewed.Substituting Si(or Ge) for As leads to an As-free new magnetic material MnFeP1-xSi(Ge)x.These new materials show large magnetocaloric effects resembling MnFe(P,As) near room temperature.Some new physical phenomena,such as huge thermal hysteresis and ’virgin’ effect,were found in new materials.On the basis of Landau theory,a theoretical model was developed for studying the mechanism of phase transition in these materials.Our studies reveal that MnFe(P,Si) compound is a very promising material for room-temperature magnetic refrigeration and thermo-magnetic power generation.     

Microstructural changes in Fe-doped Gd5Si2Ge2

Gd₅Si₂Ge₂-based alloys can exhibit a giant magnetocaloric effect (GMCE); this gives them the potential for use in cooling technologies. It has also been reported that a small addition of iron reduces the hysteresis losses in Gd₅Si₂Ge₂-based alloys, thus increasing the net refrigerating capacity. In this investigation, we have been the first to look at the effect on the microstructure and magnetic properties of Gd₅Si₂Ge₂ resulting from a wide range of substitutions of Si by Fe. The macrostructures of the arc-melted buttons revealed some very unusual surface morphologies, and the analytical results revealed a gradual substitution of the Gd₅(Si,Ge,Fe)₄-type phase by a Gd₅(Si,Ge,Fe)₃-type phase and the presence of three grain-boundary phases, two of which contain substantial amounts of iron. The magnetic measurements indicated that larger amounts of iron reduced the hysteresis losses, but at the same time reduced the Curie temperatures to below lower values that would make the material useful in practice.     

Effect of Si/Ge ratio on resistivity and thermopower in Gd5SixGe4−x magnetocaloric compounds

The effect of Si/Ge ratio on resistivity and thermopower behavior has been investigated in the magnetocaloric ferromagnetic Gd₅Si_xGe_4−x compounds with x=1.7-2.3. Microstructural studies reveal the presence of Gd₅(Si,Ge)₄-matrix phase (5:4-type) along with traces of secondary phases (5:5 or 5:3-type). The x=1.7 and 2.0 samples display the presence of a first order structural transition from orthorhombic to monoclinic phase followed by a magnetic transition of the monoclinic phase. The alloys with x=2.2 and 2.3 display only magnetic transitions of the orthorhombic phase. A low temperature feature apparent in the AC susceptibility and resistivity data below 100 K reflects an antiferromagnetic transition of secondary phase(s) present in these compounds. The resistivity behavior study correlates with microstructural studies. A large change in thermopower of −8 μV/K was obtained at the magneto-structural transition for the x=2 compound.     

Observation of a Griffiths-like phase in the magnetocaloric compound Tb5Si2Ge2

The onset of a Griffiths-like phase has been observed in Tb5Si2Ge2 (TC=110 K) by means of magnetic susceptibility and small-angle neutron scattering experiments. We show the growth of a ferromagnetic cluster system characterized by an inverse susceptibility exponent lower than unity at TC相似文献   

不同周期结构硅锗超晶格导热性能研究

构造了均匀、梯度、随机3种不同周期分布的硅/锗(Si/Ge)超晶格结构.采用非平衡分子动力学(NEMD)方法模拟了硅/锗超晶格在3种不同周期分布下的热导率,并研究了样本总长度和温度对热导率的影响.模拟结果表明:梯度和随机周期Si/Ge超晶格的热导率明显低于均匀周期结构超晶格;在不同的周期结构下,声子分别以波动和粒子性质输运为主;均匀周期超晶格热导率具有显著的尺寸效应和温度效应,而梯度、随机周期Si/Ge超晶格的热导率对样本总长度和温度的依赖性较小.     

Crystal structures,phase relationships,and magnetic phase transitions of R_5M_4 compounds (R = rare earths,M = Si,Ge)

Our recent studies of the crystal structures, phase transitions, and magnetic properties of intermetallic compounds R5M4 (R = rare earths; M = Si, Ge) are reviewed briefly. First, crystal structures, phase relationships, and magnetic properties of several 5:4 compounds, including Nd5Si4xGex , Pr5Si4xGex, Gd5xLaxGe4,La5Si4, and Gd5Sn4 , are presented. In particular, the canted spin structures as well as the magnetic phase transitions in Pr5Si2Ge2 and Pr 5 Ge 4 investigated by neutron powder diffractions and small-angle neutron scattering are reviewed. Second, the crystal structures and magnetic properties of the most studied compounds Gd5(Si,Ge)4 are summarized. The focus is on the parent compound Gd5Ge4 , which is an amazing material exhibiting magnetic anisotropy, angular dependent spin-flop transition, metastable magnetic response, Griffiths-like phase, thermal effect under pulsed fields, antiferromagnetic and ferromagnetic resonances, pronounced effects of impurities, and high-field induced magnetic transitions.     

Structural, magnetic, magnetocaloric and magnetotransport properties in Ge doped Ni-Mn-Sb Heusler alloys

The effect of Ge substitution on the magnetic, magnetocaloric and transport properties of Ni₄₅Co₅Mn₃₈Sb_12−xGe_x (x=0-3) has been investigated. The decrease in the exchange interaction brought by Ge substitution can be seen from the reduction in the magnetization of austenite phase and the increase in the martensitic transition temperature. The magnetocaloric effect and the magnetoresistance values are found to be quite sensitive to small changes in Sb/Ge ratio. Taking into account various properties, the present series seems to be a promising multifunctional system.     

Ferromagnetic Mn-doped Si0.3Ge0.7 nanodots self-assembled on Si(100)

Densely packed epitaxial Mn-doped Si(0.3)Ge(0.7) nanodots self-assembled on Si(100) have been obtained. Their structural properties were studied using reflection high-energy electron diffraction, energy dispersive x-ray diffraction, atomic force microscopy, extended x-ray absorption fine structure measurements and high-resolution transmission electron microscopy. Mn(5)Ge(1)Si(2) crystallites embedded in Si(0.3)Ge(0.7) were found. They exhibit a ferromagnetic behaviour with a Curie temperature of about 225?K.     

CaAl2X2(X=C,Si,Ge)的稳定性、电子结构和力学性质研究

由于AB2X2类型的材料在储能、催化、超导、发光等领域都有着潜在应用价值,因此得到了广泛关注。本文通过第一原理方法计算分析了CaAl2X2(X=C,Si,Ge)的材料声子谱、电子结构、力学性质和硬度,其主要结果为：材料晶格常数的计算结果和实验值都与理论结构符合的很好;CaAl2C2和CaAl2Si2材料的声子谱没有出现虚频,表明这两种材料在热力学及动力学上是稳定的;计算的材料的能带结构表明,CaAl2Si2和 CaAl2Ge2具有金属特性, CaAl2C2具有较小带隙的间接半导体材料。这类材料的金属特性,热稳定性及力学各项异性特征对于其作为二次电池活性电极有着重要影响,因此本文的研究结果可为相关领域的研究提供较好的理论依据及参考。     

Theoretical study on stability,mechanical properties and thermodynamic parameters of the orthorhombic-A2N2O (A=C,Si and Ge)

The structural stability, mechanical properties and thermodynamic parameters such as Debye temperature, minimum thermal conductivities of orthorhombic-A₂N₂O (A=C, Si and Ge) are calculated by first principles calculations based on density functional theory. The calculated lattice parameters, elastic constants of Si₂N₂O and Ge₂N₂O using PBEsol function are consisted with the experimental data and other calculated values. The full set elastic constants of the orthorhombic-A₂N₂O (A=C, Si and Ge) are calculated by stress–strain method. The mechanical moduli (bulk modulus, shear modulus and Young's modulus) are evaluated by the Voigt–Reuss–Hill approach. The orthorhombic-C₂N₂O exhibits larger mechanical moduli than the other two structures. The hardness of orthorhombic-A₂N₂O (A=C, Si and Ge) is evaluated according to the intrinsic hardness calculation theory of covalent crystal relying on Mulliken overlap population. The results indicate that the orthorhombic-C₂N₂O is a super hard material. Furthermore, the mechanical anisotropy, Debye temperature and minimum thermal conductivity of the orthorhombic-A₂N₂O (A=C, Si and Ge) have been estimated by empirical methods. The orthorhombic-Ge₂N₂O shows the lowest thermal conductivity, which may have useful applications as gas turbine engines and diesel engines.     

Effect of composition modulation on the structural and optical properties of Si/Ge bilayers

We report structural as well as optical studies on Si/Ge bilayer structures having different individual layer thicknesses. The Raman spectrum of [Ge (5 nm)/Si (5 nm)] bilayer structure shows amorphous nature, while the [Si (5 nm)/Ge (5 nm)] bilayer structure shows a mixed nanocrystalline/amorphous behaviour of the layers. As the thickness of the individual layers increases to 10 nm, the introduction of large number of Si atoms at the interface results in reduction of Ge crystallization as well as higher intensity of interfacial SiGe alloy formation. This may be regarded as a consequence of the island growth induced surface roughening in the later case (i.e. in [Si (10 nm)/Ge (10 nm)] bilayer) as also revealed by corresponding atomic force microscopy (AFM) images. These results are also supported by Photoluminescence (PL) spectra recorded using two different photon energies of 300 and 488 nm along with the optical absorption measurements giving higher values of band gap as compared to their corresponding bulks, revealing the effect of quantum confinement in the deposited layers.     

Magnetocaloric and barocaloric effects in a Gd5Si2Ge2 compound

The first-order phase transition in Gd5Si2Ge2 is sensitive to both magnetic field and pressure.It may indicate that the influences of the magnetic field and the pressure on the phase transition are virtually equivalent.Moreover,theoretical analyses reveal that the total entropy change is almost definite at a certain Curie temperature no matter whether the applied external field is a magnetic field or a pressure.The entropy change curve can be broadened dramatically under pressure,and the refrigerant capacity is improved from 284.7 J/kg to 447.0 J/kg.     

Successive inverse and normal magnetocaloric effects in the Mn-vacancy compound Mn_(0.95)Co_(0.75)Cu_(0.25)Ge

Ferromagnetic-structural transformation has been studied widely in MnCoGe-based materials. However, the magnetostructural transition(MST) from antiferromagnetic(AFM) orthorhombic phase to ferromagnetic(FM) hexagonal phase, which may lead to a large inverse magnetocaloric effect(MCE), has rarely been reported. Here, the introduction of Mn vacancy lowers the structural transition temperature while retains the AFM state in the orthorhombic phase, thus successfully realizing the AFM-FM MST in Mn_(0.95)Co_(0.75)Cu_(0.25)Ge. Moreover, successive inverse and normal MCEs are observed around the first-order AFM-FM MST and the second-order FM-paramagnetic(PM) transition, respectively. A thermostat is proposed based on this special feature, which could release heat above the critical temperature while absorb heat below the critical temperature by simply applying the same magnetization/demagnetization cycles. This thermostat can be very useful in many applications where a constant temperature is required, such as cryostats and incubators.     

First-principle investigation on the thermodynamics of X_2N_2O(X = C,Si, Ge) compounds

The structures under different pressures, elastic properties, electronic structures and lattice vibrations of the X_2N_2O(X = C, Si, Ge) compounds are investigated by using the first-principle method. Based on the phonon density of state,the thermodynamic properties of the present compounds are studied under different pressures and at different temperatures. The structural parameters including the bond lengths and bond angles are in agreement with available experimental measurements and theoretical calculations. We employ the elastic theory to calculate the nine independent elastic constants(C_(ij)) and the derived elastic moduli(B, G, E, v). Results indicate that these X_2N_2O(X = C, Si, Ge) compounds are mechanically stable and show the brittle behaviors. The electronic properties of the present compounds are analyzed by using the band structure and density of states. The phonon dispersion calculations imply that the present compounds are dynamically stable. Based on the quasi-harmonic approximation, the calculations of the specific heat indicate that the temperature in a range of 0 K–1500 K and pressure in a range of 0 GPa–40 GPa have a large effect on the thermal quantities of Ge_2N_2O,compared with on those of the C_2N_2O and Si_2N_2O compounds.     

XPS study of annealing induced effects on surface and interface electronic properties of Si/Ge nanostructures

The present study is focused on the influence of vacuum thermal treatment on surface/interface electronic properties of Si/Ge multilayer structures (MLS) characterized using X-ray photoelectron spectroscopy (XPS) technique. Desired [Si(5 nm)/Ge(5 nm)]_×10 MLS were prepared using electron beam evaporation technique under ultra high vacuum (UHV) conditions. The core-level XPS spectra of as-deposited as well as multilayer samples annealed at different temperatures such as 100 °C, 150 °C and 200 °C for 1 h show substantial reduction in Ge 2p peak integrated intensity, whereas peak intensity of Si 2p remains almost constant. The complete interdiffusion took place after annealing the sample at 200 °C for 5 h as confirmed from depth profiling of annealed MLS. The asymmetric behaviour in intensity patterns of Si and Ge with annealing was attributed to faster interdiffusion of Si into Ge layer. However, another set of experiments on these MLS annealed at 500 °C suggests that interdiffusion can also be studied by annealing the system at higher temperature for relatively shorter time duration.     

Magnetic entropy change of Ce6Ni2Si3-type and large refrigerant capacity GdCoSiGe compound＊

Magnetic entropy change （△SM） and refrigerant capacity （RC） of Ce6Ni2Si3-type Gd6Co1.67Si2.5Geo.5 compounds have been investigated. The Gd6Col.67Si2.5Geo.5 undergoes a reversible second-order phase transition at the Curie temperature Tc = 296 K. The high saturation magnetization leads to a large ASM and the maximal value of △SM is found to be 5.9 J/kg. K around TC for a field change of 0-5 T. A broad distribution of the △SM peak is observed and the full width at half maximum of the △SM peak is about 101 K under a magnetic field of 5 T. The large RC is found around TC and its value is 424 J/kg.     

Multiple metamagnetic transitions in the magnetic refrigerant La(Fe,Si)13Hx

The effect of hydrostatic pressure on thermally and field-induced first-order magnetic phase transitions is studied in the La(Fe,Si)_(13)-type compounds. A peculiar series of consecutive field-induced transitions is realized using a distinct combination of hydrostatic pressure and negative pressure created by the interstitial insertion of hydrogen. The pressure-induced discontinuous magnetization jumps result in an enhanced cooling power, thus opening up the possibility to exploit in full the magnetocaloric potential of this compound class.