The stability of Cr, V, Al carbide MAX phases, materials of interest for a variety of magnetic as well as high temperature applications, has been studied using density-functional-theory first-principles calculations. The enthalpy of mixing predicts these alloys to be unstable towards unmixing at 0 K. The calculations also predict, however, that these phases would be thermally stabilised by configurational entropy at temperatures well below the values used for synthesis. The temperature Ts below which they become unstable is found to be quite sensitive to the presence of magnetic moments on Cr ions, as well as to the material's magnetic order, in addition to chemical order and composition. Allowing for magnetism, the value of Ts for helf V and half Cr with chemically disordered Cr and V atoms, is estimated to be between 516 K and 645 K depending on the level of theory, while, if constrained to spin-paired, Ts drops to 142 K. Antiferromagnetic spin arrangements are found to be favoured at low temperatures, but they are most likely lost at synthesis temperatures, and probably at room temperature as well. However, the combination of antiferromagnetic frustration and configurational disorder should give rise to interesting spin textures at low temperatures.
Density functional calculations are used to investigate the electronic structure of two-dimensional 5d tantalum carbides with honeycomb-like lattice structures. We focus on changes in the low-energy bands near the Fermi level with dimensionality. We find that the Ta 5d states dominate, but the extended nature of the wavefunctions makes them weakly correlated. The carbide sheets are prone to long range magnetic order. We evaluate the stability of these states to enhanced electron--electron interactions through a Hubbard U correction. Lastly, we find spin orbit interactions strongly renormalize …
Electronic structures of carbides with the rocksalt structure were calculated by full potential electronic codes solving the Kohn-Sham equation. Bonding characters were analyzed by constructing tight-binding Hamiltonian based on maximally-localized Wannier functions. It was found that the cations in these compounds act as an electron provider and the frame is formed by the carbon atoms. The electronic states in the vicinity of the Fermi level are mainly from the p-orbitals of C. Pressure and doping are two efficient ways to tune the magnetic and electronic properties of these compounds. It tur…
Cementite-type carbides are of interest for magnetocaloric applications owing to their temperature- or pressure-induced magnetic phase transition. Here, using first-principles calculations, we investigate the magnetism and the magnetic phase transition in iron carbide (Fe3C) with the substitution of Cr atoms at Fe sites with the strain effect. The presence of Cr atoms is found to give rise to a second-order magnetic phase transition from a ferromagnetic phase for Fe3C to a nonmagnetic phase in chromium carbide (Cr3C).While the ternary Fe2CrC and Cr2FeC compounds prefer the ferrimagnetic ground…
We report the observation of local superconductivity induced at the point contact formed between a normal metal tip and WC -- a triple point topological semimetal with super hardness. Remarkably, the maximum critical temperature is up to near 12 K but insensitive to the tip's magnetism. The lateral dimensions of the superconducting puddles were evaluated and the temperature dependencies of superconducting gap and upper critical field were also obtained. These results put constraints on the explanation of the induced superconductivity and pave a pathway for exploring topological superconductivi…
Herein, we compare the thermal vibrations of atoms in select ternary carbides with the formula Mn+1AXn ("MAX phases," M = Ti, Cr; A = Al, Si, Ge; X = C, N) as determined from first principles phonon calculations to those obtained from high-temperature neutron powder diffraction studies. The transition metal carbides TiC, TaC, and WC are also studied to test our methodology on simpler carbides. Good qualitative and quantitative agreement is found between predicted and experimental values for the binary carbides. For all the MAX phases studied - Ti3SiC2, Ti3GeC2, Ti2AlN, Cr2GeC and Ti4AlN3 - den…
The interesting properties of Kagome bands, consisting of Dirac bands and a flat band, have attracted extensive attention. However, the materials with only one Kagome band around the Fermi level cannot possess physical properties of Dirac fermions and strong correlated fermions simultaneously. Here, we propose a new type of band structure --- double Kagome bands, which can realize coexistence of the two kinds of fermions. Moreover, the new band structure is found to exist in a new two-dimensional material, phosphorus carbide P2C3. The carbide material shows good stability and unusual electroni…
In this article, a detailed study of the recently synthesized MAX phase borides M2SB (M = Zr, Hf and Nb) has been performed via first principles technique. Investigation of mechanical hardness, elastic anisotropy, optical properties, dynamical stability and thermal properties are considered for the first time. The estimated values of stiffness constants and elastic moduli are found in good agreement with available results. The micro and macro hardness (Hmicro and Hmacro) parameters are calculated. The Vickers hardness is also calculated using Mulliken population analysis. The electronic densit…
We report the first observation of stable single photon sources in silicon carbide (SiC). These sources are extremely bright and operate at room temperature demonstrating that SiC is a viable material in which to realize various quantum information, computation and photonic applications. The maximum single photon count rate detected is 700k counts/s with an inferred quantum efficiency around 70%. The single photon sources are due to intrinsic deep level defects constituted of carbon antisite-vacancy pairs. These are shown to be formed controllably by electron irradiation. The variability of th…
MXenes, a new class of two dimensional materials with several novel properties, are usually prepared from their MAX phases by etching out the A element using strong chemical reagents. This results in passivation of the surfaces of MXene with different functional groups like O, -OH, -F, etc., which in many cases tend to degrade their properties. In this work, using first principle density functional theory based calculations, we propose a novel method to synthesize pristine Ti$_2$C and Ti$_3$C$_2$ MXenes from the bulk titanium carbides with corresponding stoichiometry. Based on the values of cl…
We report magnetism in carbon doped ZnO. Our first-principles calculations based on density functional theory predicted that carbon substitution for oxygen in ZnO results in a magnetic moment of 1.78 $μ_B$ per carbon. The theoretical prediction was confirmed experimentally. C-doped ZnO films deposited by pulsed laser deposition with various carbon concentrations showed ferromagnetism with Curie temperatures higher than 400 K, and the measured magnetic moment based on the content of carbide in the films ($1.5 - 3.0 μ_B$ per carbon) is in agreement with the theoretical prediction. The magnetism …
The present work describes a synthesis route for bulk Ta4AlC3 MAX phase ceramics with high phase purity. Pressure assisted densification was achieved by both hot pressing and spark plasma sintering of tantalum hydride, aluminium and carbon powder mixtures in the 1200-1650°C range. The phases present and microstructures were characterized as a function of the sintering temperature by X-ray diffraction and scanning electron microscopy. High-purity alfa-Ta4AlC3 was obtained by hot pressing at 1500°C for 30 min at 30 MPa. The beta-Ta4AlC3 allotrope was observed in the samples produced by SPS. The …
Cobalt carbide nanoparticles were processed using polyol reduction chemistry that offers high product yields in a cost effective single-step process. Particles are shown to be acicular in morphology and typically assembled as clusters with room temperature coercivities greater than 4 kOe and maximum energy products greater than 20 KJ/m3. Consisting of Co3C and Co2C phases, the ratio of phase volume, particle size, and particle morphology all play important roles in determining permanent magnet properties. Further, the acicular particle shape provides an enhancement to the coercivity via dipola…
Here, we report the first successful exfoliation of two-dimensional Ti$_3$C$_2$T$_x$ MXene through selective etching of silicon from titanium silicon carbide (Ti$_3$SiC$_2$) MAX. The successful etching and exfoliation of MXene is confirmed through the shifting of all (00l) peaks to lower angles along with the increase in c-lattice parameter as determined by X-ray diffraction technique to detail the material structure. The c-lattice parameter of multilayered MXene was found to be 19.34Å which was increased to 26.22 Å after delamination process indicating the successful intercalation of TMA+ ion…
The elemental diversity is crucial to screen out ternary MAX phases with outstanding properties via tuning of bonding types and strength between constitutive atoms. As a matter of fact, the interactions between M and A atoms largely determine the physical and chemical properties of MAX phases. Herein, Se element was experimentally realized to occupy the A site of a MAX phase, Zr2SeC, becoming a new member within this nanolaminated ternary carbide family. Comprehensive characterizations including Rietveld refinement of X-ray Diffraction and atom-resolved transmission electron microscopy techniq…
Nuclear spins in the solid state are both a cause of decoherence and a valuable resource for spin qubits. In this work, we demonstrate control of isolated 29Si nuclear spins in silicon carbide (SiC) to create an entangled state between an optically active divacancy spin and a strongly coupled nuclear register. We then show how isotopic engineering of SiC unlocks control of single weakly coupled nuclear spins and present an ab initio method to predict the optimal isotopic fraction which maximizes the number of usable nuclear memories. We bolster these results by reporting high-fidelity electron…
We study the structural and magnetic properties of La$_{0.7}$Sr$_{0.3}$Mn$_{1-x}$Co$_x$O$_3$ ($0 \leq x \leq 1$). Rietveld refinement of X-ray Diffraction (XRD) pattern suggests phase purity of the polycrystalline samples with R$\bar{3}$c space group. Interplay of Ferromagnetic (FM) and Antiferromagnetic (AFM) interaction upon Co substitution at Mn site in La$_{0.7}$Sr$_{0.3}$MnO$_3$ is evident from magnetic measurements. There is an optimal cobalt substitution at which the coercive field is maximum.
We present self flux growth and characterization of single crystalline AlMn$_2$B$_2$. It is an orthorhombic (space group Cmmm), layered material with a plate like morphology. The anisotropic bulk magnetization data, electrical transport and $^{11}$B nuclear magnetic resonance(NMR) data revealed an antiferromagnetic (AFM) transition at 313 $\pm$ 2 K. In the magnetization data, there is also a broad local maximum significantly above the AFM transition that could be a signature of low dimensional magnetic interactions in AlMn$_2$B$_2$.
The potential of a wide range of layered ternary carbide and nitride MAX phases as conductors in interconnect metal lines in advanced CMOS technology nodes has been evaluated using automated first principles simulations based on density functional theory. The resistivity scaling potential of these compounds, i.e. the sensitivity of their resistivity to reduced line dimensions, has been benchmarked against Cu and Ru by evaluating their transport properties within a semiclassical transport formalism. In addition, their cohesive energy has been assessed as a proxy for the resistance against elect…
We demonstrate the electrical and optical control of ferromagnetism in semiconductor heterostructures at high temperatures of 100-117 K. The heterostructures consist of Mn delta-doped GaAs and p-type AlGaAs, where the overlap of the hole wavefunction with the Mn delta-doping profile leads to high ferromagnetic transition temperature TC of over 100 K (max. 172 K). We are able to isothermally change the paramagnetic state to the ferromagnetic state and vice versa, by applying a gate electric-field or by light irradiation. The large modulation of TC (DTC ~15 K) at high temperatures (> ~100 K) dem…
MXenes are 2D transition metal carbides with high potential for overcoming limitations of conventional two-dimensional electronics. In this context, various MXenes have shown magnetic properties suitable for applications in spintronics, yet the number of MXenes reported so far is far smaller than their parental MAX phases. Therefore, we have studied the structural, electronic and magnetic properties of bimetallic and vacancy-ordered MXenes derived from a new $(V_{2/3}Zr_{1/3})_2AlC $ MAX phase to assess whether MXene exfoliation would return stable magnetic materials. In particular, we have in…
Using a synergistic combination of experimental and computational methods, we shed light on the unusual solubility of (Cr,Ti)3AlC2 MAX phase, showing that it may accommodate Cr only at very low concentrations (<2at%) or at the exact Cr/(Cr+Ti) ratio of 2/3, even when the ratio of reactants is far from this stoichiometry (1/2 < Cr/(Cr+Ti) < 5/6). In both phases Cr exclusively occupies the 4f sites, bridging carbide layers with the Al layer. Despite this, the peculiar stability of (Cr2/3Ti1/3)3AlC2 is attributed to the formation of strong, spin-polarised Cr-C bonds, which result in volume reduct…
An interesting class of ternary metallic borides, known as the 212 MAX phase borides, is the recent advancement of the MAX phase family. In this article, results from ab-initio calculations on unexplored Ti$_2$PB$_2$, Zr$_2$PbB$_2$, and Nb$_2$AB$_2$ [A = P, S] are reported wherein Ti$_2$PB$_2$ along with its 211 boride phase Ti$_2$PB are predicted for the first time. The stability was confirmed by calculating the formation energy, phonon dispersion curve, and elastic stiffness constants. The obtained elastic constants, elastic moduli, and Vickers hardness values of Ti$_2$PB$_2$, Zr$_2$PbB$_2$,…
Thin epitaxial films of Tb metal were grown on a clean W(110) substrate in ultra-high vacuum and studied in-situ by low-energy electron microscopy. Annealed films present magnetic contrast in spin-polarized low-energy electron microscopy. The energy dependence of the electron reflectivity was determined and a maximum value of its spin asymmetry of about 1\% was measured. The magnetization direction of the Tb films is in-plane. Upon raising the temperature, no change in the domain distribution is observed, while the asymmetry in the electron reflectivity decreases when approaching the critical …
MAX phases are a family of layered, hexagonal-structure ternary carbides or nitrides of a transitional metal and an A-group element. What makes this type of material fascinating and potentially useful is their remarkable combinations of metallic and ceramic characteristics; as well as the indispensable role in 'top-down' synthesis of their 2D counterparts, MXenes. To enhance the efficiency in the successful search for potential novel MAX phases, the main efforts could go toward creating an informationprediction system incorporating all MAX phases' databases, as well as generally valid principl…
Recent chemical exfoliation of layered MAX phase compounds to novel two-dimensional transition metal carbides and nitrides, so called MXenes, has brought new opportunity to materials science and technology. This review highlights the computational attempts that have been made to understand the physics and chemistry of this very promising family of advanced two-dimensional materials, and to exploit their novel and exceptional properties for electronic and energy harvesting applications.
We study the composition dependent evolution of geometric and magnetic structures of MnO clusters within density functional theory. A systematic and extensive search through the potential energy surface is performed to identify the correct ground state, and significant isomers. We find that the magnetic structures in these MnO clusters are complex, which has been explained using the intrinsic electronic structure of the cluster, and analyzed using model Hamiltonian with parameters obtained from maximally localized Wannier functions. The calculated vertical displacement energies of off-stoichio…
We have studied the atomic ordering of B-site transition metals and magnetic properties in the pulsed-laser deposited films of La2CrFeO6 (LCFO) and La2VMnO6 (LVMO), whose bulk materials are known to be single perovskites with random distribution of the B-site cations. Despite similar ionic characters of constituent transition metals in each compound, the maximum B-site order attained was surprisingly high, ~90% for LCFO and ~80% for LVMO, suggesting a significant role of epitaxial stabilization in the spontaneous ordering process. Magnetization and valence state characterizations revealed that…
Sigma-phase intermetallic compound of Fe54Cr46 was investigated using DC and AC magnetic susceptibility techniques. A clear-cut evidence was found that the sample orders magnetically at Tc=23.5 K and its ground magnetic state is constituted by a spin glass. The temperature at which the zero-field cooled magnetization has its maximum decreases with an external magnetic field in line with the Gabay-Toulouse prediction. The temperature at which the AC magnetic susceptibility has its maximum does not depend on frequency which, in the light of the mean-field theory, testifies to very long magnetic …
Layered nanolaminate ternary carbides, nitrides and carbonitrides with general formula Mn+1AXn or MAX (n = 1, 2, or 3, M is an early transition metal, A is mostly group 13 or 14 element, and X is C and/or N) has revolutionized the world of nanomaterials, due to the coexistence of both ceramic and metallic nature, giving rise to exceptional mechanical, thermal, electrical, chemical properties and wide range of applications. Although several solid-state bulk synthesis methods have been developed to produce a variety of MAX phases, however, for certain applications, the growth of MAX phases, espe…
Anomalies in the temperature dependences of the recoil-free factor, f, and the average center shift, <CS>, measured by 57-Fe Mossbauer Spectroscopy, were observed for the first time in the archetype of the σ-phase alloys system, Fe-Cr. In both cases the anomaly started at the temperature close to the magnetic ordering temperature, and in both cases it was indicative of lattice vibrations hardening. As no magnetostrictive effects were found, the anomalies seem to be entirely due to a spin-phonon coupling. The observed changes in f and in <CS> were expressed in terms of the underlying changes in…
Co-rich Co$_{1-x}$Mn$_x$ alloys have hcp or fcc disordered phases and those ferromagnetic orderings are significantly deteriorated with increasing Mn concentration $x$ in bulk. On the other hand, those metastable bcc phases show properties attractive to spintronics, e.g., high tunnel magnetoresistance (TMR) ratio of more than 200% (600%) at 300 K (10 K) in magnetic tunnel junctions (MTJs) with the $x$ = 0.25 bcc alloy electrodes [Kunimatsu et al., Appl. Phys. Express 13, 083007 (2020)]. Here, we report systematic study of structure and magnetism for epitaxial thin films as well as the TMR effe…
A fundamental issue concerning iron-based superconductivity is the roles of electronic nematicity and magnetism in realising high transition temperature ($T_{\rm c}$). To address this issue, FeSe is a key material, as it exhibits a unique pressure phase diagram involving nonmagnetic nematic and pressure-induced antiferromagnetic ordered phases. However, as these two phases in FeSe overlap with each other, the effects of two orders on superconductivity remain perplexing. Here we construct the three-dimensional electronic phase diagram, temperature ($T$) against pressure ($P$) and isovalent S-su…
The term "MAX phase" refers to a very interesting and important class of layered ternary transition-metal carbides and nitrides with a novel combination of both metal and ceramic-like properties that have made these materials highly regarded candidates for numerous technological and engineering applications. Using (Cr2Hf)2Al3C3 as an example, we demonstrate the possibility of incorporating more types of elements into a MAX phase while maintaining the crystallinity, instead of creating solid-solution phases. The crystal structure and elastic properties of MAX-like (Cr2Hf)2Al3C3 are studied usin…
Fractionation as a Tool to Control Mn/Al Site Mixing and Magnetism in CaMn_{2+x}Al_{10-x}
Ames National Laboratory, U.S. Department of Energy, Iowa State University（艾姆斯国家实验室，美国能源部，爱荷华州立大学）；Department of Physics and Astronomy, Iowa State University（爱荷华州立大学物理与天文系）；Faculty of Applied Physics and Mathematics and Advanced Materials Center, Gdansk University of Technology（格但斯克理工大学应用物理与数学学院及先进材料中心）
MAX phases are nanolaminated ternary materials that combine metallic and ceramic properties. Currently, the A-site elements replacement in traditional ones by later transition-metals opens a door to explore new types of MAX phases. In this work, we performed a systematic first-principle study to explore trends in stability, electronic structure and mechanical properties of 288 compositions of M2AX phases (M=Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W; A=Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, Tl, Pb, Bi, Mn, Fe, Co, Ni, Cu, Zn, Tc, Ru, Rh, Pd, Ag, Cd, Os, Ir, Pt, Au, Hg; X=C). Such a dataset, combi…
Magnetism is a very relevant subject that permeates our everyday lives. However, magnetism keeps taking us from surprise to surprise which seems to indicate that it is a phenomenon not well understood. For example, we found that bulk amorphous palladium becomes magnetic; so, naturally one should ask, could defective palladium develop magnetism? In particular, would amorphous porous palladium become magnetic? Here we show that the answer to that question is affirmative, this defective topology of Pd is magnetic, with a magnetism that depends on the amount of sample porosity and on the topology …
Fermi level dependence of magnetism and magnetotransport in the magnetic topological insulators Bi$_{2}$Te$_{3}$ and BiSbTe$_{3}$ containing self-organized MnBi$_{2}$Te$_{4}$ septuple layers
The dynamics of magnetic moments in iron-chromium alloys with different levels of Cr clustering show unusual features resulting from the fact that even in a perfect body-centred cubic structure, magnetic moments experience geometric magnetic frustration resembling that of a spin glass. Due to the long range exchange coupling and configuration randomness, magnetic moments of Cr solutes remain non-collinear at all temperatures. To characterise magnetic properties of Fe-Cr alloys, we explore the temperature dependence of magnetisation, susceptibility, Curie temperature and spin-spin correlations …
We report the results of measurements of $^{27}$Al and $^{55}$Mn NMR spectra, the related spin-lattice relaxation rates, and the dc magnetic susceptibility of the stable decagonal quasicrystal Al$_{69.8}$Pd$_{12.1}$Mn$_{18.2}$. The temperature-variation of the magnetic susceptibility $χ(T)$ reveals that the Mn ions carry only an average magnetic moment of approximately $2μ_{\mathrm{B}}$, and confirms a spin-glass type freezing of the Mn-moments at $T_f=12$K. The NMR spectra reveal two partially resolved lines for the $^{27}$Al-nuclei, indicating that there are two different sets of environment…
Using density functional calculations we have investigated the local spin moment formation and lattice deformation in graphene when an isolated vacancy is created. We predict two competing equilibrium structures: a ground state planar configuration with a saturated local moment of 1.5 $μ_B$, and a metastable non-planar configuration with a vanishing magnetic moment, at a modest energy expense of ~50 meV. Though non-planarity relieves the lattice of vacancy-induced strain, the planar state is energetically favored due to maximally localized defect states (v$σ$, v$π$). In the planar configuratio…
A substantial magnetodielectric effect is often an indication of coupled magnetic and elastic order, such as is found in the multiferroics. However, it has recently been shown that magnetism is not necessary to produce either a magnetoresistance or a magnetocapacitance when the material is inhomogeneous [M. M. Parish and P. B. Littlewood, Phys. Rev. Lett. 101, 166602 (2008)]. Here, we will investigate the characteristic magnetic-field-dependent dielectric response of such an inhomogeneous system using exact calculations and numerical simulations of conductor-dielectric composites. In particula…
The magnetic interactions in La{0.70}Ca{0.30}Mn{1-x}Cr{x}O{3} (x = 0.15, 0.50 and 0.70) are investigated by x-ray absorption spectroscopy (XAS), x-ray magnetic circular dichroism (XMCD), high-resolution x-ray powder diffraction, and bulk magnetization measurements. XAS in the Mn and Cr L{2,3} edges support stable single valent Cr{3+} ions and a varying Mn valence state with x, while the O K edge XAS spectrum reveals local maxima in the O 2p density of states close to the Fermi level due to mixing with Mn and Cr 3d states. A robust antiferromagnetic state is found for x=0.70 below TN = 258 K. F…
