Large Anisotropy Research Articles

The Birefringence Modulation in Short‐Wave Ultraviolet Sulfates with Functional π‐Conjugated Cations and Polymerized Heteroleptic Tetrahedral Anions

AbstractSulfates with a large bandgap are always promising optical candidates. However, due to insufficient birefringence, their applications are restricted. Here, in terms of this deficiency, two strategies are proposed to rationally modulate the optical anisotropy of sulfates by cations and anions, respectively. For the cation modulation, the [C(NH2)3]Al(SO4)2·6H2O crystal is investigated, which exhibits an unprecedented birefringence (0.098 @ 546 nm) compared with other deep‐ultraviolet transparent sulfates, resulting from the synergy of π‐conjugated [C(NH2)3]+ and non‐π‐conjugated [SO4]2− groups. For the anion modulation, a novel functional group, [S3O6]2−, with a large polarizability anisotropy, is designed. Thus, a new crystal, NaKS3O6, is obtained, which exhibits a large birefringence of 0.130 @ 546 nm with a short ultraviolet absorption cutoff edge of 215 nm. These results confirm the validity of the strategies. Therefore, the strategies play an important role in improving sulfate's birefringence and then promoting their potential applications in advanced optical systems.

Tunable magnetic anisotropy of Os-Ru dimer on 2D transition metal chalcogenides substrates

The precise manipulation of atoms enables the creation of distinct materials from the bottom up to construct devices with breakthrough performance, especially in the field of quantum technologies. A large magnetic anisotropy energy (MAE) is important to realize bit storage of information in magnetic memory devices. As the smallest magnetic nanostructure, substrate-supported transition metal dimers are potential atomic-scale storage medium to obtain large MAEs. Using high-throughput first-principles calculations, we have performed a systematic investigation of the MAE of 76 heterodimensional systems consisting of zero-dimensional Os-Ru dimer and experimentally synthesized two-dimensional transition metal dichalcogenides (TMDs). Huge MAEs in the range of 102.09–247.69 meV were found in 13 of these heterodimensional systems. In particular, the Os-Ru@T-ZrSe2 with the largest MAE of 247.69 meV corresponds to a theoretical blocking temperature (67 K) in terms of a relaxation time of 10 years and a storage density of 281 Tb·inch−2. The underlying mechanism for the significant enhancement of MAE is attributed to the rearrangement of the in-plane molecular orbitals near the Fermi level, which is closed relative to the electron transfer capability between the Os-Ru dimer and the TMD substrates. In addition, we have also constructed a heat map for TMD-supported Os-Ru dimer, showing the degree of correlation between MAEs and feature descriptors. Our work not only suggests an effective way to improve MAE of transition metal dimers but also extracts relatively simple rules for substrate selection.

Heat-Assisted Magnetization Switching in Flexible Spin-Orbit Torque Devices.

Heat-assisted magnetic anisotropy engineering has been successfully used in selective magnetic writing and microwave amplification due to a large interfacial thermal resistance between the MgO barrier and the adjacent ferromagnetic layers. However, in spin-orbit torque devices, the writing current does not flow through the tunnel barrier, resulting in a negligible heating effect due to efficient heat dissipation. Here, we report a dramatically reduced switching current density of ∼2.59 MA/cm2 in flexible spin-orbit torque heterostructures, indicating a 98% decrease in writing energy consumption compared with that on a silicon substrate. The reduced driving current density is enabled by the dramatically decreased magnetic anisotropy due to Joule dissipation and the lower thermal conductivity of the flexible substrate. The large magnetic anisotropy could be fully recovered after the impulse, indicating retained high stability. These results pave the way for flexible spintronics with the otherwise incompatible advantages of low power consumption and high stability.

GdFe-based nanostructured thin films with large perpendicular magnetic anisotropy for spintronic applications

In this study, we investigated the impact of geometric factors on the magnetic anisotropy of Gd-Fe alloy thin films deposited on nanoporous alumina membranes. By synthesizing Gd-Fe alloy nanostructure thin films with different hole diameters (ranging from 45 to 90 nm) and keeping the layer thickness and lattice parameters fixed at 45 nm and 105 nm, respectively, we observed a significant perpendicular magnetic anisotropy (PMA) in samples with hole diameter above 65 nm. The transition from in-plane to out-of-plane magnetization in Gd-Fe alloy nanostructure thin films occurred at a critical antidot hole diameter of 75 nm. The observed variations in coercivity and remanence with the nanohole diameter are attributed to substantial changes in the magnetization mechanisms induced by the nanoholes. This novel induction of PMA in Gd-Fe alloy nanostructure thin films through the manipulation of geometric parameters in the antidot arrays opens new possibilities for tailoring the magnetic behavior of ferromagnetic metals with pronounced PMA.

Generation of highly anisotropic physical properties in ferromagnetic thin films controlled by their differently oriented nano-sheets

We fabricated ferromagnetic nano-crystalline thin films of Co, Fe, Co–Fe and Co-rich and Fe-rich, Co–MT and Fe–MT (MT = transition metal), constituted by nano-sheets with a controlled slant. Visualization of these nano-sheets by Scanning Tunneling Microscopy and High-Resolution Transmission Electron Microscopy (HRTEM) showed typically tilt angles ≈56° with respect to the substrate plane, and nano-sheets ≈3.0–4.0 nm thick, ≈30–100 nm wide, and ≈200–300 nm long, with an inter-sheet distance of ≈0.9–1.2 nm, depending on their constitutive elements. Induced by this nano-morphology, these films exhibited large uniaxial magnetic anisotropy in the plane, the easy direction of magnetization being parallel to the longitudinal direction of the nano-sheets. In the as-grown films, typical values of the anisotropy field were between Hk ≈ 48 and 110 kA/m depending on composition. The changes in the nano-morphology caused by thermal treatments, and hence in the anisotropic properties, were also visualized by HRTEM, including chemical analysis at the nano-scale. Some films retained their nano-sheet morphology and increased their anisotropies by up to three times after being heated to at least 500 °C: for example, the thermal treatments produced crystallization processes and the growth of CoV and CoFe magnetic phases, maintaining the nano-sheet morphology. In contrast, other annealed films, Co, Fe, CoZn, CoCu… lost their nano-sheet morphology and hence their anisotropies. This work opens a path of study for these new magnetically anisotropic materials, particularly with respect to the nano-morphological and structural changes related to the increase in magnetic anisotropy.

Large anomalous transverse transport properties in atomically thin 2D Fe3GaTe2

Anomalous transverse conductivities, such as anomalous Hall conductivity (AHC), anomalous Nernst conductivity (ANC), and anomalous thermal Hall conductivity (ATHC), play a crucial role in the emerging field of spintronics. Motivated by the recent fabrication of two-dimensional (2D) ferromagnetic thin film Fe3GaTe2, we investigate the thickness-dependent anomalous transverse conductivities of the 2D Fe3GaTe2 system (from one to four layers). The atomically ultrathin 2D Fe3GaTe2 system shows above-room-temperature ferromagnetism with a large perpendicular magnetic anisotropy energy. Furthermore, we obtain a large AHC of −485 S/cm in the four-layer thickness, and this is further enhanced to −550 S/cm with small electron doping. This AHC is seven times larger than the measured AHC in thicker 2D Fe3GaTe2 (178 nm). The ANC also reaches 0.55 A/K.m in the four-layer structure. Along with these, the four-layer system exhibits a large ATHC (−0.105 ~ −0.135 W/K.m). This ATHC is comparable to the large ATHC found in Weyl semimetal Co3Sn2S2. Based on our results, the atomically ultrathin 2D Fe3GaTe2 system shows outstanding anomalous transverse conductivities and can be utilized as a potential platform for future spintronics and spin caloritronic device applications.

Polysulfide Anions [Sx]2- (x=2, 3, 4, 5): Promising Functional Building Units for Infrared Nonlinear Optical Materials.

Infrared nonlinear optical (IR NLO) materials play significant roles in laser technology. The novel functional building units (FBUs) are of great importance in constructing NLO materials with strong second harmonic generation (SHG). Herein, polysulfide anion [Sx]2- (x=2, 3, 4, 5) units are investigated on NLO-related properties and structure-performance relationships. Theoretical calculations uncover that the [Sx]2- (x=2, 3, 4, 5) units are potential IR NLO FBUs with large polarizability anisotropy (δ), hyperpolarizability (β) and wide HOMO-LUMO gap. Fourteen crystals including [Sx]2- (x=2, 3, 4, 5) units are calculated and analyzed. The results show that these units can result in a wide IR transmittance range, significant SHG effects, wide band gap Eg (Na2S4: Eg=3.09eV), and large birefringence Δn [BaS3 (P21212): Δn=0.70]. More importantly, it is highlighted that the crystal materials including with [Sx]2- (x=2, 3, 4, 5) groups are good candidates for the exploration of the outstanding IR NLO materials.

Improvement axial dispersion calculation in fibrous garnished fixed beds using the neural method

To determine accurately the physical modeling of flow through porous media and / or in chemical reactors, especially in the field of low Reynolds numbers, it is essential to compute the coefficient of axial dispersion. In prior studies, we employed the neural method to compute axial dispersion within fixed beds with parallelepiped and spherical packings. In the present study we apply the same method of calculation on heterogeneous fixed beds with large anisotropy using data from Poirier and Trinh on fibrous beds. Such an investigation could be however very useful while one has the desire to predict the mixing process to characterize the axial dispersion in fixed beds of anisotropic particles andwhenexperimental measurements are not accessible and / or difficult to implement as for reactors and / or industrial complex porous media. To show also the robustness and applicability of this method, the calculation results obtained will be modeled using expressions similar to those proposed by Poirier and Trinh, so that we can compare our results with those obtained by these authors, under the same operating conditions. Furthermore, our study offers a comprehensive analysis encompassing all three examined fixed bed configurations, namely parallelepiped, spherical, and fibrous arrangements.

Strain-tunable ferromagnetism and skyrmions in two-dimensional Janus Cr2XYTe6 (X, Y = Si, Ge, Sn, and X≠Y) monolayers

By using first-principles calculations and micromagnetic simulations, we investigate the electronic structure, magnetic properties, and skyrmions in two-dimensional Janus Cr2XYTe6 (X,Y = Si, Ge, Sn, X ≠ Y) monolayers. Our findings reveal that the Cr2XYTe6 monolayers are ferromagnetic semiconductors with a high Curie temperature (Tc). The bandgap and Tc can be further increased by applying tensile strain. In addition, there is a transition from the ferromagnetic to the antiferromagnetic state at a compressive strain. Both Cr2SiSnTe6 and Cr2SiGeTe6 exhibit a large magnetic anisotropy energy, which are mainly associated with the significant spin–orbit coupling of the nonmagnetic Te atoms rather than that of the magnetic Cr atoms. Interestingly, the Cr2SiSnTe6 monolayer exhibits a significant Dzyaloshinskii–Moriya interaction of 1.12 meV, which facilitates the formation of chiral domain walls and skyrmions. Furthermore, under tensile strain, chiral DWs can be transformed into skyrmions if applying an external magnetic field. These findings suggest that Janus Cr2XYTe6 monolayers hold promise for spintronic nanodevice applications.

AX·(H2SeO3)n (A = K, Cs; X = Cl, Br; n = 1, 2): A Series of Ionic Cocrystals as Promising UV Birefringent Materials with Large Birefringence and Wide Band Gap.

The design and syntheses of new birefringent crystals will be of great importance in commercial applications and materials science. A series of ultraviolet (UV) birefringent crystals, AX·(H2SeO3)n (A = K, Cs; X = Cl, Br; n = 1, 2), with large sizes up to 23 × 6 × 3 mm3, was successfully synthesized by simple aqueous solution method. These four compounds belong to three different space groups. Isomorphic KCl·(H2SeO3)2 and CsCl·(H2SeO3)2 crystallize in the space group, while CsBr·(H2SeO3)2 and CsCl·H2SeO3 crystallize in the P21/m and P21/c space groups, respectively. They exhibit cocrystal structures composed of [2(H2SeO3)]∞ and [AX]∞ frameworks, ingeniously inheriting the large optical anisotropy of selenite and the wide band gap of alkali metal halide. And it proves that these compounds indeed possess large birefringence (0.1-0.17 at 532 nm) and short UV cutoff edges (227-239 nm), achieving a balance of optical properties. This research affords a simple and viable strategy for the design and syntheses of new UV birefringent crystals. Besides, it is also found that the n value and ionic size (A and X ions) have important influences on the crystal structures and optical properties of AX·(H2SeO3)n. And this will promote further understanding of the alkali metal halide selenite family.

Effect of Annealing Temperature and Time on the Magnetic Properties and Magnetic Anisotropy of a Temper-Rolled, Semi-processed Non-oriented Electrical Steel

The effect of final annealing temperature and time on the core loss, magnetic permeability, and magnetic anisotropy of a temper-rolled, semi-processed 0.5 wt.% Si non-oriented electrical steel was investigated. The magnetic properties of the steel sheets at 50–400 Hz and 0.5–1.50 T were measured by the Epstein frame method on strips cut along both the rolling (RD) and transverse directions (TD). Optimal magnetic properties were obtained when the annealing temperature was at 800–825°C, and the annealing time was 2–4 h. Relatively large magnetic anisotropy between the RD and TD was observed in samples after recrystallization (~ 10% in core loss and ~ 70% in relative permeability), while deformed and non-recrystallized samples showed small anisotropy in magnetic properties. Regardless of the processing state of the steel, i.e., temper-rolled, recovered, or recrystallized, the core loss followed quadratic polynomial functions with respect to both the frequency and magnetic flux density, while the relative magnetic permeability followed cubic polynomial functions with respect to both the frequency and magnetic flux density. The microstructure and texture of selected samples were characterized by electron backscatter diffraction, which revealed the correlations between the magnetic properties of the steel and the microstructure and texture.

Observing magnetoanisotropic weak antilocalization in near-surface quantum wells

We investigate the effects of an in-plane magnetic field on the weak antilocalization signature of near-surface quantum wells lacking bulk and inversion symmetry. The measured magnetoconductivity, which is conductivity as a function of the out-of-plane magnetic field, exhibits a strong anisotropy with respect to the direction of the in-plane magnetic field. The twofold symmetry of the observed magnetoanisotropy originates from the competition between Rashba and Dresselhaus spin-orbit couplings. The high sensitivity of the weak antilocalization to the spin texture produced by the combined Zeeman and spin-orbit fields results in very large anisotropy ratios, reaching 100%. Using a semiclassical universal model in quantitative agreement with the experimental data, we uniquely determine the values of the Dresselhaus and Rashba parameters as well as the effective in-plane g-factor of the electrons. Understanding these parameters provides prospects for different applications ranging from spintronics to topological quantum computing. Published by the American Physical Society 2024

Theory of electronic structure and effective masses of ultra-wide bandgap wurtzite aluminum nitride

I develop a theory of electronic structure for wurtzite(W)-Aluminium Nitride, based on the three uppermost valence bands and the lowest conduction band at the Γ-point. As distinguished from the Chuang-Chang approach [9], where the Hamiltonian is diagonalised considering all the bands, through an matrix, I follow a different procedure. In my approach, initially I follow a two-band approximation for the matrix, where the Hamiltonian is diagonalised by treating the conduction band and each of the valence bands separately. Thus, I diagonalise three different matrices, for obtaining the dispersions of the valence bands. The conduction band energy is obtained from the first diagonalization, involving band edge states. Effect of other two valence bands on a given valence band is considered through second order perturbation theory. Details of this procedure are outlined in Appendix A. It gives analytic expressions for the dispersion of the bands. I compare the results obtained for W-AlN with recent calculations and note satisfactory agreements. I also calculate the effective masses of holes in the valence bands both at the Γ-point and also as functions of the wavevector. My results agree fairly well with a recent calculation [3]. The hole effective masses for all the bands show large anisotropy. The effective mass of the electron in the conduction band does not show appreciable anisotropy.

A novel high accuracy finite-difference time-domain method

The finite-difference time-domain (FDTD) method is widely used for numerical simulations of electromagnetic waves and acoustic waves. It is known, however, that the Courant condition is restricted in higher dimensions and with higher order differences in space. Although it is possible to relax the Courant condition by utilizing the third-degree difference in space, there remains a large anisotropy in the numerical dispersion at large Courant numbers. This study aims to reduce the anisotropy in the numerical dispersion and relax the Courant condition simultaneously. A new third-degree difference operator including the Laplacian is introduced to the time-development equations of FDTD(2,4) with second- and fourth-order accuracies. The present numerical simulations have demonstrated that numerical oscillations due to the anisotropic dispersion relation are reduced with the new operator.Graphical

Large Magnetic Anisotropy in Mono- and Binuclear cobalt(II) Complexes: The Role of the Distortion of the Coordination Sphere in Validity of the Spin-Hamiltonian Formalism.

To get a better insight into understanding the factors affecting the enhancement of the magnetic anisotropy in single molecule (single ion) magnets, two cobalt(II) complexes based on a tridentate ligand 2,6-di(thiazol-2-yl)pyridine substituted at the 4-position with N-methyl-pyrrol-2-yl have been synthesized and studied by X-ray crystallography, AC and DC magnetic data, FIRMS and HFEPR spectra, and theoretical calculations. The change of the counteranion in starting Co(II) salts results in the formation of pentacoordinated mononuclear [Co(mpyr-dtpy)Cl2]·2MeCN (1) complex and binuclear [Co(mpyr-dtpy)2][Co(NCS)4] (2) compound. The observed marked distortion of trigonal bipyramid geometry in 1 and cationic octahedral and anionic tetrahedral units in 2 brings up a question about the validity of the spin-Hamiltonian formalism and the possibility of determining the value and sign of the zero-field splitting D parameter. Both complexes exhibit field-induced slow magnetic relaxation with two or three relaxation channels at BDC = 0.3 T. The high-frequency relaxation time in the reciprocal form τ(HF)-1 = CTn develops according to the Raman relaxation mechanism (for 2, n = 8.8) and the phonon-bottleneck-like mechanism (for 1, n = 2.3). The high-frequency relaxation time at T = 2.0 K and BDC = 0.30 T is τ(HF) = 96 and 47 μs for 1 and 2, respectively.

Theoretical prediction of two-dimensional ferromagnetic Mn2X2 (X = As, Sb) with strain-controlled magnetocrystalline anisotropy.

Two-dimensional (2D) magnetic materials with large and tunable magnetocrystalline anisotropy (MCA) provide unique opportunities to develop various spintronic devices. We, herein, propose an experimentally feasible 2D material platform, Mn2X2 (X = As, Sb), which is a family of intrinsic ferromagnet. Using first-principles calculations, we show that 2D Mn2X2 (X = As, Sb) with a robust ferromagnetic ground state exhibits not only a large perpendicular magnetic anisotropy (PMA), but also significant strain-driven modulation behaviors under external biaxial strain. The analysis of the results demonstrates that the dominant contribution to the change of MCA of Mn2As2 and Mn2Sb2 primarily arises from the Mn and Sb atoms, respectively. Moreover, we reveal that the underlying origin is the competitive mechanism for the spin-orbit coupling (SOC) between different orbitals and spin channels. These findings indicate that 2D Mn2X2 (X = As, Sb) provides a promising material platform for the next generation of ultra-low energy memory devices.

Control of the geometry and anisotropy driven by the combination of steric and anion coordination effects in CoII complexes with N6-tripodal ligands: the impact of the size of the ligand on the magnetization relaxation time.

Four mononuclear CoII complexes of formula [Co(L)(SCN)2(CH3OH)0.5(H2O)0.5]·1.5H2O·0.75CH3OH (1), [Co(L1)Cl2]·H2O·2CH3CN (2), [Co(L1)(SCN)2]·1.5H2O·CH3OH (3) and [Co(L1)]ClO4·2CH3OH (4) were prepared from the N6-tripodal Schiff base ligands (S)P[N(Me)NC(H)2-Q]3 (L) and (S)P[N(Me)NC(H)1-ISOQ]3 (L1), where Q and ISOQ represent quinolyl and isoquinolyl moieties, respectively. In 1, the L ligand does not coordinate to the CoII ion in a tripodal manner but using a new N,N,S tridentate mode, which is due to the fact that the N6-tripodal coordination promotes a strong steric hindrance between the quinolyl moieties. However, L1 can coordinate to the CoII ions either in a tripodal manner using CoII salts with poorly coordinating anions to give 4 or in a bisbidentate fashion using CoII salt-containing medium to strongly coordinating anions to afford 2 and 3. In the case of L1, there is no steric hindrance between ISOQ moieties after coordination to the CoII ion. The CoII ion exhibits a distorted octahedral geometry for compounds 1-3, with the anions in cis positions for the former and in trans positions for the two latter compounds. Compound 4 shows an intermediate geometry between an octahedral and trigonal prism but closer to the latter one. DC magnetic properties, HFEPR and FIRMS measurements and ab initio calculations demonstrate that distorted octahedral complexes 1-3 exhibit easy-plane magnetic anisotropy (D > 0), whereas compound 4 shows large easy-axis magnetic anisotropy (D < 0). Comparative analysis of the magneto-structural data underlines the important role that is played not only by the coordination geometry but also the electronic effects in determining the anisotropy of the CoII ions. Compounds 2-3 show a field-induced slow relaxation of magnetization. Despite its large easy-axis magnetic anisotropy, compound 4 does not show significant slow relaxation (SMR) above 2 K under zero applied magnetic fields, but its magnetic dilution with ZnII triggers SMR at zero field. Finally, it is worth remarking that compounds 2-4 show smaller relaxation times than the analogous complexes with the tripodal ligand bearing in its arms pyridine instead of isoquinoline moieties, which is most likely due to the increase of the molecular size in the former one.

Two-dimensional Cr2GaX4 (X = S, Se, Te) monolayers: half-metallic intrinsic room temperature ferromagnets with large magnetic anisotropy

Based on first-principles calculations, we predict a series of Cr2GaX4 (X = S, Se, Te) monolayers, which exhibit intrinsic ferromagnetic ordering, large magnetic anisotropy energy, and high Curie temperatures above room temperature.

NaMoO3(IO3)(H2O): water molecule introduction induces strong second harmonic generation response, widened band gap and large anisotropy.

Exploring feasible tactics to induce the formation of non-centrosymmetric (NCS) structures, especially from centrosymmetric (CS) structures, is essential for the development of nonlinear optical crystals with more potential. An NCS alkali metal-containing molybdenum iodate hydrate, namely, NaMoO3(IO3)(H2O), was designed based on the CS matrix NaMoO3(IO3) via introducing a water molecule into the structure. The introduction of one crystalline water molecule results in the rearrangement of Λ-shaped cis-[MoO4(IO3)2] units, and the proper array of the cis-[MoO4(IO3)2] units in NaMoO3(IO3)(H2O) results in its strong SHG response of 4.6 × KH2PO4. In addition, NaMoO3(IO3)(H2O) exhibits a wider optical bandgap of 3.44 eV and a larger birefringence of 0.231 than its matrix. Furthermore, the framework of NaMoO3(IO3)(H2O) is highly similar to that of α-KMoO3(IO3), with water molecules assisting Na+ cations in occupying the position of K+. However, due to the extra hydrogen bond of water molecules, the [MoO3(IO3)]∞ layers in NaMoO3(IO3)(H2O) retain a parallel-stacking arrangement, different from the antiparallel arrangement of layers in α-KMoO3(IO3) with a centric structure. This study confirms the feasibility of applying a water molecule to adjust the orientation of basic building block units to assemble an NCS structure based on CS crystals.

Large magnetic anisotropy and enhanced Curie temperature in two-dimensional MnTe2 coupled with β-phase group-VA semiconductor monolayers.

Promoting the Curie temperature (T C) and tunning the magnetocrystalline anisotropy energy (MAE) have been key issues with two-dimensional (2D) ferromagnetic (FM) materials. Here, the structural and magnetic properties of MnTe2/X (X = As, Sb and Bi) heterostructures are investigated through first-principles calculations. We reveal that monolayer MnTe2 weakly interacts with monolayer As or Sb through van der Waals (vdW) forces, but has strong covalent bonds with monolayer Bi, indicated by Bi-Te bond formation. The coupling of MnTe2 with these β-phase group-VA semiconductor monolayers substantially modulates MAE, with MnTe2/As showing a shift to in-plane easy magnetization, and MnTe2/Sb exhibiting a large perpendicular MAE of 4.13 meV per cell. The formation of vdW heterostructures influence on Te spin-orbit coupling matrix elements markedly governs MAE. MnTe2/Bi also has an in-plane MAE, contributed by both Te and Bi atoms. Additionally, coupling MnTe2 with X significantly affects magnetic interactions. It is worth noting that the T C of MnTe2/Sb reaches 233.2 K, significantly larger than that of pure MnTe2. A large perpendicular MAE and a heightened T C makes MnTe2/Sb desired candidates for next-generation spintronic applications. Our work provides a way to modulate the magnetic properties of 2D FM materials.