Application of M?ssbauer spectroscopy in magnetism

An overview is provided on our recent work that applies ⁵⁷Fe M?ssbauer spectroscopy to specific problems in nanomagnetism. ⁵⁷Fe conversion electron M?ssbauer spectroscopy (CEMS) in conjunction with the ⁵⁷Fe probe layer technique as well as ⁵⁷Fe nuclear resonant scattering (NRS) were employed for the study of various nanoscale layered systems: (i) metastable fct-Fe; a strongly enhanced hyperfine magnetic field B_hf of ～39?T at 25?K was observed in ultrahigh vacuum (UHV) on uncoated three-monolayers thick epitaxial face-centered tetragonal (fct) ⁵⁷Fe(110) ultrathin films grown by molecular-beam epitaxy (MBE) on vicinal Pd(110) substrates; this indicates the presence of enhanced Fe local moments, μ_Fe, as predicted theoretically; (ii) Fe spin structure; by applying magnetic fields, the Fe spin structure during magnetization reversal in layered (Sm–Co)/Fe exchange spring magnets and in exchange-biased Fe/MnF₂ bilayers was proven to be non-collinear and depth-dependent; (iii) ferromagnet/semiconductor interfaces for electrical spin injection; CEMS was used as a diagnostic tool for the investigation of magnetism at the buried interface of Fe electrical contacts on the clean surface of GaAs(001) and GaAs(001)-based spin light-emitting diodes (spin LED) with in-plane or out-of-plane Fe spin orientation; the measured rather large average hyperfine field of ～27?T at 295?K and the distribution of hyperfine magnetic fields, P(B_hf), provide evidence for the absence of magnetically “dead” layers and the existence of relatively large Fe moments (μ_Fe ～ 1.8?μ_B) at the ferromagnet/semiconductor interface. - Finally, a short outlook is given for potential applications of M?ssbauer spectroscopy on topical subjects of nanomagnetism/spintronics.     

Magnetic properties of NpM4Al8−x (M=Cr,Fe, Cu) intermetallics: Mössbauer effect and neutron diffraction studies

Mössbauer effect and neutron diffraction studies on the tetragonal NpM₄Al_8?x (M=Cr, Fe, Cu) of the 14/mmm space group are reported. In NpFe₄Al_8?x, both the Np and Fe sites order magnetically at close temperatures: the Np order ferromagnetically at 115(15) K (μ(Np)) ～ 0.6 μ_B and the Fe moments order antiferromagnetically at 130(10) K (μ(Fe) = 1.05(15) μ_B) with a ++?? sequence. In NpCr₄Al_8?x, the Np order magnetically around 50K. From the susceptibility data we conclude possible antiferromagnetic order of both Np and Cr sites. NpCu₄Al_8?x does not order magnetically down to at least 2 K. The magnetic hyperfine splitting observed below 45 K is explained by slow paramagnetic relaxation. The Np isomer shifts and also its magnetic behavior point to a trivalent ion (⁵I₄ Hund's rule ground state). The observed relaxation and magnetic phenomena are discussed in terms of crystalline electric field effects. In contrast to the isostructural rare-earth RM₄Al₈ compounds with practically independent order of R and M magnetic sublattices, we show that Np and M sublattices in NpM₄Al₈ are strongly coupled. This is caused by hybridization of both Np and M atoms with Al.     

Electronic structure and magnetism of a Pd monolayer on Fe(100)

Spin-polarized self-consistent localized-orbital (SCLO) calculations have been performed for a five-plane slab simulating Pd/Fe(100). Pd monolayers were placed in registry with both faces of a three-plane Fe(100) slab. We chose a PdFe bond length equal to the sum of metallic radii, 2.62 Å, and an FeFe bond length equal to the bulk value, 2.49 A. The computed energy bands for the Pd/Fe₃/Pd slab resemble those calculated for a five-plane Fe(100) slab, except for a positive work-function shift of 0.5 eV. The Pd monolayer has a magnetic moment of 0.37μ_B/atom. The magnetic moment of an adjacent iron atom is 2.74μ_B, slightly smaller than the value 2.89μ_B at the surface of Fe₅, but still significantly larger than the central-plane value 2.37μ_B. The d bands of the two metals are strongly hybridized, but very little charge transfer takes place across the interface. Compared with the isolated Pd(100) monolayer, or the clean Fe(100) slab, the surface density of states of Pd/Fe(100) is rather weak near the Fermi level, suggesting a reduced chemical reactivity for this surface.     

Anodic oxidation during electrostatic bonding

During electrostatic bonding, anodic oxidation of the anode material, for instance silicon, is thought to be the essential step in the bonding mechanism, leading to the formation of a permanent, strong and vacuum-tight bond. Despite the perceived importance of this step in the bonding mechanism of this well-established bonding technique, there is little experimental evidence for anodic oxidation during electrostatic bonding. One reason is that a thin (approximately 10–20?nm) amorphous anodic oxide layer is difficult to detect adjacent to an amorphous cation-depleted glass. Here, silicon–Pyrex and aluminium–Pyrex electrostatic bonds are made and the anodic oxidation process is studied directly using transmission electron microscopy. The consumption of silicon is demonstrated by the movement of the crystalline–amorphous interface compared with a marker under the original silicon–Pyrex interface. The formation of an anodic silica layer can also be demonstrated using electron-energy-loss spectrometry. An amorphous reaction layer 5–20?nm thick is formed during the bonding cycle. For aluminium anode materials bonded at 450°C a nanocrystalline γ-Al₂O₃ reaction layer is formed, which can be readily detected by transmission electron microscopy. At a bonding temperature of 350°C, no such crystalline reaction layer can be detected between Pyrex and aluminium.     

超薄Fe(4?)膜磁特性极化中子反射研究

Ultrathin Fe film 200  V/4  Fe/900  V/MgO（100） has been prepared by molecular beam epitaxy （MBE）. The structure parameters, such as the surface and interface roughness and the thickness of each layer, were obtained by X-ray and neutron reflectivity mea 关键词： 超薄Fe膜 磁特性 极化中子反射 分子束外延     

TiB2-reinforced B4C composites produced by reaction sintering at high-pressure and high temperature

ABSTRACT

Obtaining both high hardness and toughness is a challenge in B₄C-nano-adhesive composites. Solving the inhomogeneous distribution of nano-adhesives in B₄C and forming the chemical bonding at grain boundary is an effective method. Here, we reported that the uniform distribution of titanium diboride (TiB₂)-reinforced B₄C composites synthesized by high-pressure and high temperature (HPHT). It is found that HPHT sintering can effectively inhibit the grain growth and increase the relative density. Moreover, HPHT sintering can cross high reaction energy barrier and effectively promote the formation of chemical bonding at grain boundary between B₄C and TiB₂. The optimal hardness and toughness value reach 30.0?±?0.9?GPa and 7.87?MPa·m^1/2, respectively. The improvement of hardness and toughness in the final products are ascribed to the strengthening of nanoTiB₂ connection of B₄C boundary and intergranular fracture mechanism. This work suggests a new way to achieve the uniform distribution of nanoTiB₂ in B₄C and form the chemical bonding at grain boundary, which is of great significance to the further development of TiB₂-reinforced B₄C composites with excellent mechanical properties.     

The structures and electronic properties of ferrous nitride–fulminic acid clusters

The structures and electronic properties of ferrous nitride–fulminic acid (FeN–HCNO) clusters are investigated by using PW91 functional. The results reveal that the Fe atom of an FeN molecule prefers to be absorbed on the N–O of an HCNO molecule and it shows the highest kinetic stability. The Fe–N–C–N ring structure has the highest kinetic stability, while the FeN–HCNO chain configuration shows the highest kinetic activity. The N–Fe–ONCH chain structure displays the maximum dipole magnitude (DM) value (8.246 Debye). The Fe atom of the FeN molecule adsorbed on the C atom of the HCNO molecule has the minimum DM value (0.641 Debye). The linear FeN–HCNO configuration displays the largest total spin (2.945?μ_B/atom). The hybridization of sp orbital of the FeN–HCNO clusters is very important.     

Die magnetische Struktur und das magnetische Verhalten von ErFe2: Eine Neutronenbeugungsuntersuchung

The magnetic structure of ErFe₂ has been determined from neutron diffraction measurements on a powderd sample in the temperature region between 4.2°K and 700°K. ErFe₂ exhibits ferrimagnetic ordering below 600°K with the Er- and Fe-ions being antiparallel oriented. The separate sublattice magnetisations of the Er- and Fe-sublattices have been determined. The saturation moments at 4.2°K have been found to beμ(Fe)=1.97μ _B andμ(Er)=8.47μ _B. The coupling between the two sublattices is by an antiparallel spin-spin interaction of the Er and Fe ions. The temperature dependence of the sublattice magnetization of the Er-ions is explained by a separation into two parts: an induced magnetization at high temperatures and a spontaneous magnetization at lower temperatures.     

Nanoscratch-induced deformation behaviour in B4C particle reinforced ultrafine grained Al alloy composites: a novel diagnostic approach

We report on the novel application of nanoscratch characterization to provide insight into the plasticity mechanisms responsible for the behaviour of composites. Accordingly, we conduct deformation characterization with nanoscratch testing (DCNT) to study the deformation behaviour of two B₄C reinforced ultrafine grained Al alloy tri-modal composites with average B₄C particle sizes of ~1–6?μm and ~500?nm, respectively. To highlight the type of mechanistic information revealed in a DCNT study of composites, we concentrate on the influence of B₄C particle size on deformation mechanisms.     

Mössbauer spectroscopical investigation of the exchange biased Fe/MnF2 interface

Two different Fe/MnF₂ samples have been prepared by e-beam evaporation on MgO(001) substrates. The Fe layer in the samples includes a 10 Å thick ⁵⁷Fe probe layer either at the Fe/MnF₂ interface (interface sample) or 35 Å away from the interface (center sample). The samples are characterized by X-ray diffraction, conversion electron Mössbauer spectroscopy (CEMS) and SQUID magnetometry. ⁵⁷Fe CEMS has been employed to study the depth dependent hyperfine interactions in Fe/MnF₂ as a function of temperature between 18 K to 300 K. The hyperfine field B _hf has been obtained for the interfacial and off-interfacial ⁵⁷Fe layers. At the interface, besides B _hf of bcc-Fe, the presence of a component with a distribution P(B _hf ) is observed. The latter is assigned to interfacial ⁵⁷Fe atoms, indicating some (～15%, equivalent to ～1 Fe atomic layer) intermixing at the Fe/MnF₂ interface and a decrease of the average hf > by 21%. The influence of the interface disappears as the ⁵⁷Fe probe layer is placed away from the interface. The temperature dependence of the average hf > of the interface has been measured. The Fe spins, at remanence, are found to lie in the film plane.     

Magnetic clusters in Fe3−x V x Al alloys with DO3 type structure forx≤1.1

Polycrystalline Fe_3?x V _x Al alloys with the DO₃ type structure were investigated by magnetostatic and Mössbauer methods. In alloys with 0.2<x<0.5 the ferro- and superpara-magnetic phases coexist. For alloys withx≥0.5 these investigations showed that in spite of the lack of magnetic order, they are characterized by strong nonlinear variations of the magnetization in a magnetic field over a wide temperature range. This indicates the presence of magnetic clusters of Fe atoms with very large magnetic moments. Analysis of the magnetization isotherms indicates that in these alloys a distribution of magnetic moments of clusters (μ_c) from 10 μ_B to 10⁴ μ_B exists.     

Temperature evolution of frustrated spin states in the system with competing exchange interactions. Fe0.65Ni0.35)1−x Mnx (x=0, 0.024, 0.034)

The influence of temperature on the distribution function P(B _hf) of the magnetic hyperfine fields for ⁵⁷Fe in (Fe_0.65Ni_0.35)_1?x Mn_x alloys (x=0, 0.024, 0.034) are investigated by Mössbauer spectroscopy. The Mössbauer absorption spectra are measured in the temperature interval 5–300 K; in the interval 5–80 K the measurements are performed in a magnetic field of 0.2 T. Anomalies are found in the temperature curves of the intensity of the principal maximum of the functions P(B _hf)[B _hf=30–38 T] and the total (integrated) intensities of the low-field components [B _hf=(4–13) T]. The detected anomalies in the behavior of the total intensities are interpreted as resulting from a change in the balance of competing exchange interactions due to the thermal annihilation of antiferromagnetic Fe-Fe exchange interaction. The emergence of strong satellite lines in the interval B _hf=20–29 T in Mn-doped alloys is attributed to reorientation of the spins of Fe atoms under the influence of strong antiferromagnetic Mn-Fe exchange interaction.     

The influence of SiCp oxidized on the interface layer and thermal conductivity of SiCp/Al composites

In this work, oxidation of silicon carbide particles (SiCp) at elevated temperature and its influence on the interface layer and thermal conductivity of SiCp/ZL101 composites prepared using pressure infiltration process were investigated respectively. It is found that initial temperature for the oxidation of SiCp is about 850?°C, and that the oxidation increment of SiCp and the thickness of SiO₂ layer increase with the increase in pre-oxidation temperature and time, when the oxidized temperature exceeds 1100?°C, or the duration time exceeds 2?h at 1100?°C, a small amount of ablation will take place on the SiCp, as well as the oxidized layer has some loss. The formation of SiO₂ layer can provide certain interface reactions with interface layers (3.1–6.36?μm), and the higher the thickness of SiO₂ layer, the thicker the interface layer in SiCp/Al composites. However, the thickness of SiO₂ layer is more than 5.9?μm, which is not benefit for the formation of interface layer. With the increase in the thickness of interface layer, thermal conductivity declines, but is not linear.     

Magnetic ordering of Fe atoms in icosahedral Al70−x BxPd30−y Fey quasicrystals

Novel icosahedral quasicrystals, in which Fe atoms possess a magnetic moment, have been found in Al_70?x B_xPd_30?y Fe_y compounds with 5<x<10 and 10<y<20. The compounds have ferromagnetic properties, and their Curie temperature ranges between 280 and 340 K, the saturation magnetization σ _s(5 K)≈7.5 emu/g. It follows from Mössbauer spectra that only a fraction of Fe atoms (12 to 15%) are magnetically ordered at 4.2 K, and the mean saturation field 〈H _hf〉=96 kOe. The isomer shift values confirm that the atomic volume of magnetic Fe sites is larger than that of nonmagnetic Fe sites. The magnetic properties of these quasicrystals can be interpreted in terms of large magnetic clusters with a size of 185 to 290 Å. This size correspond to about 4×10⁴ “unit cells,” hence the magnetic state can be described in terms of bulk parameters. The localized magnetic moment of Fe atoms is tentatively ascribed to bonding between Fe and B, similarly to that in the amorphous Fe_～50B_～50 alloy.     

Mössbauer study of the invar Fe–Ni and Fe–Ni–C alloys in magnetic field

F.C.C. Fe–30.3%Ni and Fe–30.5%Ni–1.5%C (wt.%) alloys were studied by means of Mössbauer spectroscopy in external magnetic field B _ext?=?2.5, 5, 7 T parallel to the gamma-beam. It is shown that distribution of effective magnetic field in the alloys is broad and that carbon expands the range of B _eff. The external magnetic field increases B _eff in the Fe–Ni alloy and decreases it more evidently in the Fe–Ni–C alloy. Antiferromagnetic spin coupling along the ferromagnetic component is proposed to explain data.     

Influence of hydrogen absorption on magnetic properties of Zr(Fe1−xVx)2 ternaries

Measurements of magnetization, susceptibility and Mössbauer effect were made on Zr(Fe_1?xV_x)₂ ternaries and their hydrides. Absorbed hydrogen leads to a large increase (20–30%) in volume without a change in the crystal structure. Ferromagnetism in the Fe-rich region is enhanced by hydrogen absorption, whereas hydrogenation leads to suppression of superconductivity in the V-rich range. The Fe moments in the Zr(Fe_1?xV_x)₂ hydrides are remarkably larger than those in the corresponding host compounds. The Fe moment in the β-ZrFe₂ hydride extrapolated reaches to 2.9μ_B, which exceeds the saturation value in bcc Fe. The hyperfine fields of ⁵⁷Fe in both Zr(Fe_0.8V_0.2)₂ and the hydride distribute widely, indicating that the Fe moments are very sensitive to the local environment arround the Fe atoms. Arguments are presented that it is possible to interprete the Fe moment increase by hydrogenation in terms of a decrease in occupancy of the 3d-band state due to electron transfers from Fe to hydrogen and/or vanadium.     

YFe2B2电子结构的第一性原理计算

基于密度泛函理论,从头计算了具有ThCr₂Si₂型四方晶系的稀土金属化合物Yfe₂B₂体相的物理特性.能量计算结果表明Yfe₂B₂体相处于顺磁金属态;而能带结构、态密度、布居数以及差分电荷　分布的计算结果表明Y原子的5s,5p电子具有很强的局域性;Fe原子的3d电子和B的1s,2s和2p电子强烈耦合,使得最近邻Fe原子与B原子形成了Fe—B共价键;最近邻的两个Fe原子之间由于 关键词： 稀土金属化合物 第一性原理计算 能带结构 态密度     

Graphite–boron composite heater in a Kawai-type apparatus: the inhibitory effect of boron oxide and countermeasures

We have investigated the performance of a graphite–boron composite (GBC) with 3?wt % boron as a precursor for a boron-doped diamond heater in a Kawai-type apparatus at 15?GPa. We first tested a machinable cylinder of GBC sintered at 1000°C in Ar/H₂ gas (99:1 molar ratio). Boron oxide (B₂O₃) formed during sintering frequently hindered the GBC heater from stable operation at temperatures higher than 1400°C by producing melt throughout the heater together with oxide and/or silicates. We then rinsed the GBC heater in hydrochloric acid to remove B₂O₃. After rinsing, we succeeded in stably generating temperatures higher than 2000°C. We also improved a molding process of different-sized GBC tubes for convenient use and tested the molded GBC heater. It was free from the B₂O₃ problem. The electromotive force of the W/Re thermocouple was successfully monitored up to 2400°C.     

Magnetic property and Mössbauer analysis of SrSn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Bold">x</Emphasis></Subscript>O<Subscript>3</Subscript> prepared by a sol-gel method

The dilute magnetic properties of SrSn_1?xFe_xO₃ (x = 0.01 ? 0.15) prepared by sol-gel and thermal decomposition methods were investigated by ⁵⁷Fe Mössbauer spectrometry, magnetometry, and X-ray diffractometry. It was found that SrSnO₃ doped with 2–8 % Fe show weak ferromagnetism although only paramagnetic doublets are observed in ⁵⁷Fe Mössbauer spectra at room temperature (RT), whereas SrSnO₃ doped with 10–15 % Fe show relatively strong ferromagnetism, and the sextets are additionally observed in the ⁵⁷Fe Mössbauer spectra at RT. The weak ferromagnetism by doping 2–8 % Fe is considered to be caused by the induced magnetic defects, and the ferromagnetism by doping 10–15 % Fe are considered mainly due to the magnetic coupling between dilute Fe ³⁺ partially substituted at Sn ⁴⁺ sites in the orthorhombic structure of SrSnO_3?δ accompanying the oxygen deficiencies. It is further remarkable that poor crystalline 8 % Fe doped SrSnO_3?δ obtained by annealing at 600 ^°C shows relatively high saturation magnetization and low coercivity.