Dzyaloshinskii-Moriya interaction (DMI) plays a crucial role in stabilizing the exotic topologically stable skyrmion spin textures in the noncentrosymmetric crystals. The recent discovery of biskyrmions and skyrmions in the globally centrosymmetric crystals has raised debate about the role of the DMI in causing the spin textures, since DMI vanishes in such crystal structures. Theoretical studies, on the other hand, suggest non-vanishing DMI even if there is local inversion symmetry breaking in an otherwise globally centrosymmetric crystal structure. Motivated by such theoretical predictions, we present here the results of a systematic crystal structure study of two skyrmion-hosting Ni2In-type centrosymmetric hexagonal compounds, MnNiGa and MnPtGa, using the atomic pair distribution function (PDF) technique. Our result provides information about structural correlations in the short-range (SR), medium-range (MR) and long-range (LR) regimes simultaneously. The analysis of the experimental PDFs, obtained from high flux, high energy, and high Q synchrotron x-ray powder diffraction patterns, reveals that the local SR structure of both MnNiGa and MnPtGa compounds corresponds to the noncentrosymmetric trigonal space group P3m1, while the structure in the MR+LR regimes remains hexagonal in the centrosymmetric P63/mmc space group. These findings are also supported by theoretical DFT calculations. Our results, in conjunction with the previous theoretical predictions, provide a rationale for the genesis of skyrmions in centrosymmetric materials in terms of non-vanishing DMI due to local inversion symmetry breaking. We believe that our findings would encourage a systematic search of skyrmionic textures and other topological phenomena in a vast family of centrosymmetric materials.

Here, the experimentally observed thermoelectric (TE) properties of Fe2VAl are understood through electronic structure calculations in the temperature range of 300–800 K. The Seebeck coefficient (S) is observed as ∼−138μV/K at 300 K. Then, the |S| decreases with increase in temperature, with a value of ∼−18μV/K at 800 K. The temperature dependence of electrical conductivity, σ (thermal conductivity, κ) exhibits the increasing (decreasing) trend with values of ∼1.2× 105 Ω−1 m−1 (∼23.7 W/m K) and ∼2.2× 105 Ω−1 m−1 (∼15.3 W/m K) at 300 K and 800 K, respectively. In order to understand these transport properties, the DFT based semi-classical Boltzmann theory is used. The contributions of multi-band electron and hole pockets are found to be mainly responsible for the temperature dependent trend of these properties. The present study suggests that DFT based calculations provide reasonably good explanations of experimental TE properties of Fe2VAl in the high-temperature range of 300–800 K.

Magnetic skyrmions are nanometer-sized whirling spin textures in the magnetic material, which have the potential to revolutionize the field of spintronics. This study explores the influence of pressure on the structural properties of the PtMnGa hexagonal system, recognized for hosting N & eacute;el skyrmions. By employing pressure- dependent synchrotron x-ray powder diffraction (SXRPD), we reveal an isostructural phase transition in this system at approximately 6 GPa. The isostructural transition is evidenced by a deviation of the lattice parameter from the linear dependence, change of trend in the in-plane to out-of-plane lattice parameter ratio, and a description of the pressure-unit cell volume data by two distinct second-order Birch-Muraghan equation of states. The PtMnGa system, however, exhibits reversible structural behavior when pressure is released. Analysis of combined pressure and temperature-dependent SXRPD data provides indirect evidence that the application of moderate pressure (0.8-1.09 GPa) shifts the thermodynamically stable skyrmion regime near to room temperature in the N & eacute;el skyrmion-host PtMnGa system. Theoretical calculations on band structure, magnetic moment, and density of states (DOS) under pressure further corroborate the experimental findings, offering a comprehensive understanding of the material's response to pressure changes. The combination of experimental findings and theoretical calculations demonstrates the potential for engineering materials supporting stable skyrmions even at elevated temperatures and nominal pressures, which can be attained in the materials using chemical substitution or epitaxial thin films by strain controlling of the substrate-film lattice parameter mismatch.

Heusler type compounds have long been recognized as potential thermoelectric (TE) materials. Here, the experimentally observed TE properties of Fe_2VAl are understood through electronic structure calculations in the temperature range of 300-800 K. The observed value of S is ∼-138 μV/K at 300 K. Then, the |S| decreases with increase in temperature up to the highest temperature with the value of ∼-18 μV/K at 800 K. The negative sign of S in the full temperature window signifies the dominating n-type character of the compound. The temperature dependent of electrical conductivity, σ (thermal conductivity, κ) exhibits the increasing (decreasing) trend with the values of ∼1.2 × 10^5 Ω^-1m^-1 (∼23.7 W/m-K) and ∼2.2 × 10^5 Ω^-1m^-1 (∼15.3 W/m-K) at 300 K and 800 K, respectively. In order to understand these transport properties, the DFT based semi-classical Boltzmann theory is used. The contributions of multi-band electron and hole pockets are found to be mainly responsible for the temperature dependent trend of these properties. The decrement of |S| and increment of σ/τ & κ_e/τ (τ is relaxation time) with temperature is directly related with the contribution of multiple hole pockets. Present study suggests that DFT based electronic calculations provide reasonably good explanations of experimental TE properties of Fe_2VAl in the high temperature range of 300-800 K.

Magnetic force microscopy (MFM) is a scanning microscopy technique that is commonly employed to probe the sample’s magnetostatic stray fields via their interaction with a magnetic probe tip. In this work, a quantitative, single-pass MFM technique is presented that maps one magnetic stray-field component and its spatial derivative at the same time. This technique uses a special cantilever design and a special high-aspect-ratio magnetic interaction tip that approximates a monopole-like moment. Experimental details, such as the control scheme, the sensor design, which enables simultaneous force and force gradient measurements, as well as the potential and limits of the monopole description of the tip moment are thoroughly discussed. To demonstrate the merit of this technique for studying complex magnetic samples it is applied to the examination of polycrystalline MnNiGa bulk samples. In these experiments, the focus lies on mapping and analyzing the stray-field distribution of individual bubble-like magnetization patterns in a centrosymmetric [001] MnNiGa phase. The experimental data is compared to calculated and simulated stray-field distributions of 3D magnetization textures, and, furthermore, bubble dimensions including diameters are evaluated. The results indicate that the magnetic bubbles have a significant spatial extent in depth and a buried bubble top base.

Molecular spins are emerging platforms for quantum information processing. By chemically tuning their molecular structure, it is possible to prepare a robust environment for electron spins and drive the assembly of a large number of qubits in atomically precise spin-architectures. The main challenges in the integration of molecular qubits into solid-state devices are (i) minimizing the interaction with the supporting substrate to suppress quantum decoherence and (ii) controlling the spatial distribution of the spins at the nanometer scale to tailor the coupling among qubits. Herein, we provide a nanofabrication method for the realization of a 2D patterned array of individually addressable Vanadyl Phthalocyanine (VOPc) spin qubits. The molecular nanoarchitecture is crafted on top of a diamagnetic monolayer of Titanyl Phthalocyanine (TiOPc) that electronically decouples the electronic spin of VOPc from the underlying Ag(100) substrate. The isostructural TiOPc interlayer also serves as a template to regulate the spacing between VOPc spin qubits on a scale of a few nanometers, as demonstrated using scanning tunneling microscopy, X-ray circular dichroism, and density functional theory. The long-range molecular ordering is due to a combination of charge transfer from the metallic substrate and strain in the TiOPc interlayer, which is attained without altering the pristine VOPc spin characteristics. Our results pave a viable route towards the future integration of molecular spin qubits into solid-state devices.

The hexagonal compound MnNiGa with Ni2In-type structure has emerged as an important biskyrmion-host system in which these textures are super-stable over a wide temperature range extending from 16 K to the Curie temperature TC-350 K under moderate fields. Both the intensity of the external magnetic field and the presence of magnetoelastic coupling are known to play key role in the stability of the skyrmionic textures. Here we present the results of the first comprehensive investigation of the order of the phase transitions and its field dependence along with magnetoelastic (i.e., spin-lattice) coupling using a combined magnetization and high-resolution synchrotron x-ray powder diffraction (SXRPD) study of MnNiGa. The temperature dependence of the magnetization M(T) exhibits a paramagnetic to collinear ferromagnetic (FM) transition at TC (-347 +/- 0.5 K) with thermal hysteresis and negative slope in the Arrott plots across the TC suggesting its first order character. The M(T) plot in the collinear FM phase exhibits an anomalously decreasing behaviour after reaching its peak value at 300 K followed by a step-like change below 210 K due to an additional spin reorientation transition (SRT) to a non-collinear FM phase with TSRT-20 0 +/- 1 K. The SRT also shows thermal hysteresis characteristic of a first order phase transition. Our field dependent studies reveal stabilization of the collinear FM phase to higher temperatures and destabilization of the SRT transition setting an upper limit on the magnetic field for the observation of biskyrmions in this system. The Rietveld analysis of the SXRPD data reveals anomalies in the unit cell parameters at TC and TSRT without any change in the crystal symmetry. The modelling of the temperature dependence of the unit cell volume in terms of the Debye-Gruneisen equation reveals significant deviation from phonon contributions and the presence of the quadratic spin-lattice coupling below the FM TC, in the precursor SRT regime as well as below TSRT. The present results on the magnetoelastic coupling in the hexagonal MnNiGa may provide the necessary insight towards understanding the extreme sensitivity of the magnetic skyrmionic textures to external stresses.(c) 2023 Elsevier B.V. All rights reserved.

Heusler type compounds have long been recognized as potential thermoelectric (TE) materials. Here, the experimentally observed TE properties of Fe 2 VAl are understood through electronic structure calculations in the temperature range of 300 − 800 K. The observed value of S is ∼ − 138 µ V/K at 300 K. Then, the | S | decreases with increase in temperature up to the highest temperature with the value of ∼ − 18 µ V/K at 800 K. The negative sign of S in the full temperature window signifies the dominating n -type character of the compound. The temperature dependent of electrical conductivity, σ (thermal conductivity, κ ) exhibits the increasing (decreasing) trend with the values of ∼ 1.2 × 10 5 Ω − 1 m − 1 ( ∼ 23.7 W/m-K) and ∼ 2.2 × 10 5 Ω − 1 m − 1 ( ∼ 15.3 W/m-K) at 300 K and 800 K, respectively. In order to understand these transport properties, the DFT based semi-classical Boltzmann theory is used. The contributions of multi-band electron and hole pockets are found to be mainly responsible for the temperature dependent trend of these properties. The decrement of | S | and increment of σ/τ & κ e /τ ( τ is relaxation time) with temperature is directly related with the contribution of multiple hole pockets. Present study suggests that DFT based electronic calculations provide reasonably good explanations of experimental TE properties of Fe 2 VAl in the high temperature range of 300 − 800 K.

Magnetic skyrmions are vortex-like spin textures, which can be manipulated by external stress or pressure via magnetoelastic effects. Here, we present the observation of isostructural phase transition in a biskyrmion host hexagonal MnNiGa at a pressure around 4 GPa using pressure-dependent synchrotron x-ray powder diffraction (XRD) data analysis. Our XRD data reveals anisotropic compression behavior with pressure with different compression rates of the a-axis in the basal plane and the c-axis in the prismatic plane. However, the hexagonal symmetry remains unchanged for pressure up to 14 GPa. Fitting of unit cell volume with pressure using a second-order Birch-Murnagan equation of state reveals that the data to fall into two distinct curves for those above and below 4 GPa. The present study contributes to the understanding of crystal structure with the application of hydrostatic pressure in the biskyrmion host MnNiGa, wherein the skyrmion textures can be manipulated by pressure due to their magnetoelastic character.

Understanding the excitonic processes at the interfaces of fluorescent π-conjugated molecules and metal electrodes is important for both fundamental studies and emerging applications. Adsorption configurations of molecules on metal surfaces significantly affect the physical characteristics of junctions as well as molecules. Here, the electronic structures and optical properties of molecular assemblies/Au interfaces were investigated using scanning probe and photoluminescence microscopy techniques. Scanning tunneling microscopy images and tunneling conductance spectra suggested that the self-assembled molecules were physisorbed on the Au surface. Visible-range photoluminescence studies showed that Au thin films modified the emission spectra and reduced the lifetime of excitons. Surface potential maps, obtained by Kelvin probe force microscopy, could visualize electron transfer from the molecules to Au under illumination, which could explain the decreased lifetime of excitons at the molecule/Au interface.

We present the effect of substitution-induced pressure on the reversibility of the magnetocaloric effect (MCE) in Ni2CrxMn1.4-xIn0.6 (x = 0.1, 0.2, 0.3) alloys, through characterization in pulsed magnetic fields. We measured the adiabatic temperature change Delta T-ad directly during applied magnetic field pulses of 2 and 6 T. We paid special attention to the reversibility of Delta T-ad. The substitution of Mn by Cr in Ni2Mn1.4In0.6 leads to a negative pressure, as evidence by the increase of the lattice parameters, which shifts the martensitic transition towards lower temperatures and enhances the ferromagnetism of the martensite phase. We found a large value of Delta T-ad = -7 K at T = 270 K for the sample with x = 0.1 for a field change of 6 T. We discuss the reversibility of the MCE in these alloys in terms of the Clausius-Clapeyron equation.

We present here the improved crystallographic/geometric compatibility and magnetocaloric reversibility by measurement of magnetic entropy change using different protocols in 10% Pt substituted Ni2Mn1.4In0.6 magnetic shape memory alloy. The substitution of Pt reduces the thermal hysteresis about 50% to the Ni2Mn1.4In0.6. The origin of the reduced thermal hysteresis is investigated by the crystallographic compatibility of the austenite and martensite phases. The calculated middle eigenvalue of the transformation matrix turned out to be 0.9982, which is very close to 1 (deviation is only 0.18%) suggests for the crystallographic compatibility between the austenite and martensite phases in Ni1.9Pt0.1Mn1.4In0.6. A very small thermal hysteresis and crystallographic compatibility between two phases in this alloy system indicate a stress-free transition layer (i.e. perfect habit plane) between the austenite and martensite phase, which is expected to give reversible martensite phase transition and therefore reversible magnetocaloric effect (MCE) as well. The calculated value of the isothermal entropy change (Delta S-iso) using the magnetization curve under three different measurement protocols (i.e. isothermal, loop, and isofield measurement protocol) is found to be nearly same indicating a reversible MCE in the present alloy system. Our work provides a path to design new magnetic shape memory Heusler alloys for magnetic refrigeration and also suggest that any of the above measurement protocol can be used for the calculation of Delta S-iso for materials satisfying geometrical compatibility condition.

Given renewed interest in the electronic properties of semimetallic compounds with varying degrees of spin orbit coupling we have grown single crystals of SrAgSb and SrAuSb, measured their temperature and field dependent electrical resistivity and magnetization and performed density functional theory (DFT) band structure calculations. Magnetization measurements are consistent with a diamagnetic host with a small amount of local moment bearing impurities. Although the residual resistivity ratio (RRR) for all samples studied was relatively low, ranging between 2.4 and 3.4, the compounds had non-saturating magnetoresistance (MR), reaching values of $\sim$ 17% and $\sim$ 70% at 4 K and 9 T for SrAgSb and SrAuSb respectively. Band structure calculations, using the experimentally determined Wyckoff positions for the Sr, Ag/Au, and Sb atoms, show that whereas SrAgSb is a topologically trivial, but compensated, semimetal; SrAuSb is a topologically non-trivial, Dirac semimetal.

We report an improved reversibility of magnetostriction and inverse magnetocaloric effect (MCE) for the magnetic shape-memory Heusler alloy Ni1.8Mn1.8In0.4. We show that the magnetostriction and MCE crucially depends on the geometrical compatibility of the austenite and martensite phases. Detailed information on the compatibility of both phases has been obtained from the transformation matrix calculated from x-ray diffraction data. The uniqueness of the lattice parameters results in an improved reversibility of the magnetostriction and the MCE. In the thermal hysteresis region of the martensitic transformation, the maximum relative length change is 0.3% and the adiabatic temperature change Delta T-ad approximate to -10 K in pulsed magnetic fields. Our results reveal that the approach of geometric compatibility will allow one to design materials with reversible magnetostriction and reversible inverse MCE at a first-order magnetostructural phase transition in shape-memory Heusler alloys.

Over the past decade the family of chiral noncollinear spin textures has continued to expand with the observation in metallic compounds of Bloch-like skyrmions in several B20 compounds, and antiskyrmions in a tetragonal inverse Heusler. Néel like skyrmions in bulk crystals with broken inversion symmetry have recently been seen in two distinct nonmetallic compounds, GaV4 S8 and VOSe2 O5 at low temperatures (below ≈13 K) only. Here, the first observation of bulk Néel skyrmions in a metallic compound PtMnGa and, moreover, at high temperatures up to ≈220 K is reported. Lorentz transmission electron microscopy reveals the chiral Néel character of the skyrmions. A strong variation is reported of the size of the skyrmions on the thickness of the lamella in which they are confined, varying by a factor of 7 as the thickness is varied from ≈90 nm to ≈4 µm. Moreover, the skyrmions are highly robust to in-plane magnetic fields and can be stabilized in a zero magnetic field using suitable field-cooling protocols over a very broad temperature range to as low as 5 K. These properties, together with the possibility of manipulating skyrmions in metallic PtMnGa via current induced spin-orbit torques, make them extremely exciting for future spintronic applications.

Ni-Mn-In magnetic shape-memory Heusler alloys exhibit generally a large thermal hysteresis at their first-order martensitic phase transition which hinder a technological application in magnetic refrigeration. By optimizing the Cu content in Ni_2Cu_xMn_1.4-xIn_0.6, we obtained a thermal hysteresis of the martensitic phase transition in Ni_2Cu_0.2Mn_1.2In_0.6 of only 6 K. We can explain this very small hysteresis by an almost perfect habit plane at the interface of martensite and austenite phases. Application of hydrostatic pressure does not reduce the hysteresis further, but shifts the martensitic transition close to room temperature. The isothermal entropy change does not depend on warming or cooling protocols and is pressure independent. Experiments in pulsed-magnetic fields on Ni_2Cu_0.2Mn_1.2In_0.6 find a reversible magnetocaloric effect with a maximum adiabatic temperature change of -13 K.

Heusler-type Fe2VAl compound is a promising thermoelectric candidate with non-magnetic ground state. The present work investigates the Seebeck coefficient (S) of Fe2VAl in the temperature region 300 to 620 K with the help of experimental and theoretical tools. The experimental value of S is observed ∼−130 μV/K at 300 K. Afterthat, the magnitude of S decreases gradually as the temperature increases. At T = 620 K, the value of S is found to be ∼−26 μV/K. In order to understand the behaviour of the experimentally observed S value, the band-structure and density of states calculations are performed by using LDA, PBE, PBEsol, mBJ and SCAN within density functional theory. All the above mentioned exchange-correlation (XC) functionals (except mBJ) predict the semi-metal like behaviour of the compound, whereas the mBJ gives the indirect band gap of ∼0.22 eV having the well agreement with experimentally observed value. The temperature dependence of S for Fe2VAl is also calculated with the help of all the five mentioned functionals individually. The best XC functional is investigated for searching the new thermoelectric materials by taking Fe2VAl as a case example through this study. The best matching between experimental and calculated values of S as a function of temperature is observed by setting the mBJ band gap with the band-structure of PBEsol or SCAN. Therefore, the present study suggests that the band-structure of PBEsol or SCAN with mBJ band gap can be used for searching the new thermoelectric materials.

The large magnetocaloric effect (MCE) observed in Ni-Mn based shape-memory Heusler alloys put them forward to use in magnetic refrigeration technology. It is associated with a first-order magnetostructural (martensitic) phase transition. We conducted a comprehensive study of the MCE for the off-stoichiometric Heusler alloy Ni_2.2Mn_0.8Ga in the vicinity of its first-order magnetostructural phase transition. We found a reversible MCE under repeated magnetic field cycles. The reversible behavior can be attributed to the small thermal hysteresis of the martensitic phase transition. Based on the analysis of our detailed temperature dependent X-ray diffraction data, we demonstrate the geometric compatibility of the cubic austenite and tetragonal martensite phases. This finding directly relates the reversible MCE behavior to an improved geometric compatibility condition between cubic austenite and tetragonal martensite phases. The approach will help to design shape-memory Heusler alloys with a large reversible MCE taking advantage of the first-order martensitic phase transition.

The origin of incommensurate structural modulation in Ni-Mn based Heusler type magnetic shape memory alloys (MSMAs) is still an unresolved issue inspite of intense focus on this due to its role in the magnetic field induced ultra-high strains. In the archetypal MSMA Ni2MnGa, the observation of non-uniform displacement of atoms from their mean positions in the modulated martensite phase, premartensite phase and charge density wave as well as the presence of phason broadening of satellite peaks have been taken in support of the electronic instability model linked with a soft acoustic phonon. We present here results of a combined high resolution synchrotron x-ray powder diffraction (SXRPD) and neutron powder diffraction (NPD) study on Ni2Mn1.4In0.6 using (3+1)D superspace group approach, which reveal not only uniform atomic displacements in the modulated structure of the martensite phase with physically acceptable ordered magnetic moments in the antiferromagnetic phase at low temperatures but also the absence of any premartensite phase and phason broadening of the satellite peaks. Our HRTEM studies and first principles calculations of the ground state also support uniform atomic displacements predicted by powder diffraction studies. All these observations suggest that the structural modulation in the martensite phase of Ni2Mn1.4In0.6 MSMA can be explained in terms of the adaptive phase model. The present study underlines the importance of superspace group analysis using complimentary SXRPD and NPD in understanding the physics of the origin of modulation as well as the magnetic and the modulated ground states of the Heusler type MSMAs. Our work also highlights the fact that the mechanism responsible for the origin of modulated structure in different Ni-Mn based MSMAs may not be universal and it must be investigated thoroughly in different alloy compositions.