We screened six cobalt-based 18-VEC systems CoVSi, CoNbSi, CoTaSi (Si-group) and CoVGe, CoNbGe, CoTaGe (Ge-group) by the first-principles approach, with the motivation of stabilizing these orthorhombic phases into the cubic symmetry -- favorable for thermoelectrics. Remarkably, it was found that the Ge-group is energetically more favorable in the cubic symmetry than the hitherto orthorhombic phase. We account the cubic ground state of the Si-group to the interplay of internal pressure and covalent interactions. The principle of covalent interactions will provide an insight and could be vital in speeding the search of missing cubic half-Heusler alloys. Meanwhile, the calculated transport properties of all the systems on \textit{p}-type doping, except CoVSi, are more promising than the well-known CoTiSb. We also provide conservative estimates of the figure of merit, exceeding the CoTiSb. Based on our findings, we suggest possible new phases of ternary compounds for thermoelectric applications.
We propose a scheme to fabricate the cobalt nitride CoN4 monolayer, a magnetic graphene-like two-dimensional material, in which all Co and N atoms are in a plane. Under the pressure above 40 GPa, the bulk CoN4 is stabilized in a triclinic phase. With the pressure decreasing, the triclinic phase of CoN4 is transformed into an orthorhombic phase, and the latter is a layered compound with large interlayer spacing. At ambient condition, the weak interlayer couplings are so small that single CoN4 layer can be exfoliated by the mechanical method.
We report the synthesis, crystal structure, superconductivity and physical property characterizations of the ternary equiatomic compound ScRuSi. Polycrystalline samples of ScRuSi were prepared by an arc-melting method. The as-prepared samples were identified as the orthorhombic Co2P-type o-ScRuSi by the powder X-ray diffraction analysis. Electrical resistivity measurement shows o-ScRuSi to be a metal which superconducts below a Tc of 3.1 K, and the upper critical field μ0Hc2(0) is estimated to be 0.87 T. The magnetization and specific heat measurements confirm the bulk type-II superconductivit…
The triple "magnetic-transport-structural" transition versus temperature in three series of "114" cobaltites - Y1-xYbxBaCo4O7, Y1-xCaxBaCo4O7 and Yb1-xCaxBaCo4O7 - has been studied using magnetic, transport and differential scanning calorimetric measurements. The effect of the size mismatch σ2, due to cationic disordering at the Ln sites upon such a transition is shown for the first time in a triangular lattice. We show that increasing <rLn> has an effect of increasing TS dramatically, while the size mismatch σ2 at the Ln sites decreases TS substantially. Moreover, the cationic mismatch at the…
High-entropy concept introduced with a promising paradigm to obtain exotic physical properties has motivated us to explore the thermoelectric properties of Sr-substituted high-entropy rare-earth cobaltates i.e., (LaNdPrSmEu)$_{1-x}$Sr$_x$CoO3 (0 \leq x \leq 0.10). The structural analysis of the samples synthesized using the standard solid-state route, confirms the orthorhombic structure with the Pbnm space group. The Seebeck coefficient and electrical resistivity decrease with rising Sr concentration as well as with an increase in temperature. The multiple A-site ions in high-entropy rare-eart…
We have investigated the structure of Co$_2$CO$_3$(OH)$_2$ using Density Functional Theory (DFT) simulations as well as Powder X-Ray Diffraction (PXRD) measurements on samples synthesized via deposition from aqueous solution. We consider two possible monoclinic phases, with closely related but symmetrically different crystal structures, based on those of the minerals malachite and rosasite, as well as an orthorhombic phase that can be seen as a common parent structure for the two monoclinic phases, and a triclinic phase with the structure of the mineral kolwezite. Our DFT simulations predict t…
Cobalt carbonate hydroxide (CCH) is a pseudocapacitive material with remarkably high capacitance and cycle stability. Previously, it was reported that CCH pseudocapacitive materials are orthorhombic in nature. Recent structural characterization has revealed that they are hexagonal in nature; however, their H positions still remain unclear. In this work, we carried out first-principles simulations to identify the H positions. Through the simulations, we could consider various fundamental deprotonation reactions inside the crystal and computationally evaluate the electromotive forces (EMF) of th…
A first cobalt boride with the Co:B ratio below 1:1, Co5B16, was synthesized under high-pressure high-temperature conditions. It has a unique orthorhombic structure (space group Pmma, a = 19.1736(12), b = 2.9329(1), and c = 5.4886(2) Å, R1 (all data) = 0.037). The material is hard, paramagnetic, with a weak temperature dependence of magnetic susceptibility.
We report the effects of Al-doping on the structure and magnetic properties in CaBa(Co$_{1-x}$Al$_{x}$)$_4$O$_7$ (0$\leq$x$\leq$0.25). The system exhibits a structural transition from an orthorhombic symmetry to a hexagonal symmetry when the Al content exceeds $x =$ 0.1. The Curie temperature and the value of the magnetization decrease with increasing Al doping level, indicating that the ferrimagnetic ground state is gradually suppressed. The ground state eventually transits into a spin-glass state for $x >$ 0.1. Moreover, the short-range magnetic correlations, which occur at high temperatures…
We report on the high-temperature (350 K <T< 1000 K) thermoelectric properties of the ternary compounds LuNiSb (cubic) and LuNiSn (orthorhombic) and a composite material (LuNiSb)$_{0.5}$(LuNiSn)$_{0.5}$. The electrical conductivity in LuNiSn is metallic, while it is semiconducting-like in LuNiSb. The Seebeck coefficient reaches -5.5 $μ$V/K at 700 K for the former compound and 66 $μ$V/K at 607 K for the latter one. The composite sample (LuNiSb)$_{0.5}$(LuNiSn)$_{0.5}$ constructed from orthorhombic matrix with cubic inclusions combines the electrical conductivity of LuNiSn with the thermoelectri…
We report on the effect of ligand exchange of copper sulphide selenide as well as copper selenide nanocrystals with the organic pi-system Cobalt beta-tetraaminophthalocyanine and analyse changes in the structural, optical as well as electric properties of thin films of these hybrid materials. A strong ligand interaction with the surface of the nanocrystals is revealed by UV-vis absorption and Raman spectroscopy. Grazing-incidence small-angle X-ray scattering studies show a significant contraction in the interparticle distance upon ligand exchange. For copper-deficient copper selenide, this con…
We have performed angle-resolved photoemission spectroscopy of layered ternary telluride Ta3SiTe6 which is predicted to host nodal lines associated with nonsymmorphic crystal symmetry. We found that the energy bands in the valence-band region show Dirac-like dispersions which present a band degeneracy at the R point of the bulk orthorhombic Brillouin zone. This band degeneracy extends one-dimensionally along the whole SR high-symmetry line, forming the nodal lines protected by the glide mirror symmetry of the crystal. We also observed a small band splitting near EF which supports the existence…
In 2006, a novel cobalt-based superalloy was discovered [1] with mechanical properties better than some conventional nickel-based superalloys. As with conventional superalloys, its high performance arises from the precipitate-hardening effect of a coherent L1$_2$ phase, which is in two-phase equilibrium with the fcc matrix. Inspired by this unexpected discovery of an L1$_2$ ternary phase, we performed a first-principles search through 2224 ternary metallic systems for analogous precipitate-hardening phases of the form $X_{3}$[$A_{0.5}, B_{0.5}$], where $X$ = Ni, Co, or Fe, and [$A,B$] = Li, Be…
The substitution of cobalt and nickel for manganese in the perovskite manganate LaBiMn2O6+d; has been realized, leading to the perovskites LaBiMn2-x(M)xO6+d, with M = Co, Ni and x =0-2/3. In contrast to the literature those phases are found to be orthorhombic with Pnma symmetry. More importantly, it is shown that ferromagnetism is enhanced, TC being increased from 80 K for the parent compound (x = 0) to 97 K for Ni-phase, and to 130 K for the Co-phase. Moreover, a strong competition between ferromagnetism and a glassy-ferromagnetic state in the case of nickel or a spin-glass behaviour in the c…
Combining theory with experiments, we study the phase stability, elastic properties, electronic structure and hardness of layered ternary borides AlCr2B2, AlMn2B2, AlFe2B2, AlCo2B2, and AlNi2B2. We find that the first three borides of this series are stable phases, while AlCo2B2 and AlNi2B2 are metastable. We show that the elasticity increases in the boride series, and predict that AlCr2B2, AlMn2B2, and AlFe2B2 are more brittle, while AlCo2B2 and AlNi2B2 are more ductile. We propose that the elasticity of AlFe2B2 can be improved by alloying it with cobalt or nickel, or a combination of them. W…
Layered Li(Ni,Mn,Co,)O$_2$ (NMC) presents an intriguing ternary alloy design space for optimization as a cathode material in Li-ion batteries. Recently, the high cost and resource limitations of Co have added a new design constraint and high Ni-containing NMC alloys have gained enormous attention despite possible performance trade-offs. It is not fully understood if this material space is a disordered solid solution at room temperature and any arbitrary combination can be used or if there exist distinct transition metal orderings to which meta-stable solid solutions will decay during cycling a…
Using density functional theory calculations, we have investigated the structural, energetic, and electronic properties of ternary graphite intercalation compounds (GICs) containing alkali atoms (AM) and normal alkylamine molecules (nC$x$), denoted as AM-nC$x$-GICs (AM=Li, Na, K, $x$=1, 2, 3, 4). The orthorhombic unit cells have been used to build the models for crystalline stage-I AM-nC$x$-GICs. By performing the variable cell relaxations and the analysis of results, we have found that with the increase in the atomic number of alkali atoms the layer separations decreases in contrast to AM-GIC…
Rhodium-containing compounds offer a fertile playground to explore novel materials with superconductivity and other fantastic electronic correlation effects. A new ternary rhodium-antimonide La$_2$Rh$_{3+δ}$Sb$_4$ ($δ\approx 1/8$) has been synthesized by a Bi-flux method. It crystallizes in the orthorhombic Pr$_2$Ir$_3$Sb$_4$-like structure, with the space group $Pnma$ (No. 62). The crystalline structure appears as stacking the two dimensional RhSb$_4$- and RhSb$_5$-polyhedra networks along $\mathbf{b}$ axis, and the La atoms embed in the cavities of these networks. Band structure calculations…
Rietveld profiles, Moessbauer spectra and x-ray absorption fine structure (XAFS) were analyzed through the structural phase transition at Ts = 355 K in HoBaCo4O7. Excess of the oxygen content over O7 was avoided via annealing the samples in argon flow at 600 degree C. Space groups (S.G.) Pbn21c and P63mc were used to refine the structure parameters in the low- and high-temperature phases, respectively. Additionally, the Cmc21 symmetry was considered as a concurrent model of structure of the low-temperature phase. In the high-temperature phase, severe anisotropy of thermal motion of the major p…
We propose a design scheme for potential electrides derived from conventional materials. Starting with rare-earth-based ternary halides, we exclude halogens and perform global structure optimization to obtain thermodynamically stable or metastable phases but having an excess of electrons confined inside interstitial cavities. Then, spin-polarized interstitial states are induced by chemical substitution with magnetic lanthanides. To demonstrate the capability of our approach, we test with 11 ternary halides and successfully predict 30 stable and metastable phases of nonmagnetic electrides subje…
Canfieldite, Ag$_8$SnS$_6$, is a semiconducting mineral notable for its high ionic conductivity, photosensitivity, and low thermal conductivity. We report the solution growth of large single crystals of Ag$_8$SnS$_6$ of mass up to 1 g from a ternary Ag-Sn-S melt. On cooling from high temperature, Ag$_8$SnS$_6$ undergoes a known cubic (F-43m) to orthorhombic (Pna2$_1$) phase transition at $\approx$ 460 K. By studying the magnetization and thermal expansion between 5-300 K, we discover a second structural transition at $\approx$ 120 K. Single crystal X-ray diffraction reveals the low temperature…
In this work, we present the formation and characterization of a quaternary (pseudo ternary) icosahedral quasicrystal in Al65Ga5Pd17Mn13 alloy. The X ray diffraction and transmission electron microscopy confirmed the formation of icosahedral B2 type and O crystalline (orthorhombic structure) phases in as cast alloy. The icosahedral phase gets formed after annealing at 800 C for 60 hours. The formation of icosahedral phase in AlGaPdMn quaternary alloy by present technique has been studied for the first time. The Energy dispersive X-ray analysis investigations suggest the presence of Ga (5 at) i…
Polycrystalline samples of ternary rare earth germanides R$_{2}$Co$_{3}$Ge$_{5}$(R = La, Ce and Pr) have been prepared and investigated by means of magnetic susceptibility, isothermal magnetization, electrical resistivity and specific heat measurements. All these compounds crystallize in orthorhombic U$_{2}$Co$_{3}$Si$_{5}$ structure (space group \textit{Ibam}). No evidence of magnetic or superconducting transition is observed in any of these compounds down to 2 K. The unit cell volume of Ce$_{2}$Co$_{3}$Ge$_{5}$ deviates from the expected lanthanide contraction, indicating non trivalent state…
We report on the synthesis and physical properties of the new ternary intermetallic Ce$_2$Rh$_2$Ga. Its formation and dimorphism have been investigated by powder and single crystal X-ray diffractometry, as well as by differential thermal analyses. LT- and HT-Ce$_2$Rh$_2$Ga can be obtained by the chosen respective thermal treatment. The high-temperature form (HT-Ce$_2$Rh$_2$Ga), stable above 864(5)°C, is orthorhombic La2Ni3-type [Cmce, oS20, a=5.851(2) Å, b=9.618 (2) Å, c=7.487 (2) Å, V=421.3(2) Å3]; the low-temperature form (LT-Ce$_2$Rh$_2$Ga), stable below this temperature, is monoclinic Pr2C…
The solid solution Ga1-xGexV4S8 (x = 0 - 1) was synthesized by solid state reactions and characterized by temperature-dependent x-ray powder diffraction and static magnetic susceptibility measurements. The compounds crystallize in the cubic GaMo4S8-type structure (space group F-43m), built up by heterocubane-like [V4S4](5-x)+ cubes and [Ga1-xGexS4](5-x)- tetrahedra arranged in a NaCl-like manner. The successive substitution of Ga3+ by Ge4+ increases the electron count in the molecular orbital (MO) of the V4-cluster gradually from seven to eight. We observe an almost linear increase of the magn…
Contrary to previous studies that identified the ground state crystal structure of the entire R_3Co series (R is a rare earth) as orthorhombic Pnma, we show that Y_3Co undergoes a structural phase transition at T_t=160K. Single crystal neutron diffraction data reveal that at T_t the trigonal prisms formed by a cobalt atom and its six nearest-neighbor yttrium atoms experience distortions accompanied by notable changes of the Y-Co distances. The formation of the low-temperature phase is accompanied by a pronounced lattice distortion and anomalies seen in heat capacity and resistivity measurement…
A new ternary intermetallic compound $\mathrm{Pr_2Rh_2Ga}$ was synthesized by arc-melting and was characterized by powder X-ray diffraction (PXRD), magnetization, heat capacity $\mathrm{C}_p(\textit{T})$, and electrical resistivity $ρ(T)$ measurements. PXRD patterns revealed that $\mathrm{Pr_2Rh_2Ga}$ crystallizes in the $\rm{La_2Ni_3}$-type of orthorhombic structure with the space group $Cmca$. The temperature variation of magnetic susceptibility, $\mathrm {C}_p(\textit{T})$ and $ρ(T)$ confirmed that $\mathrm{Pr_2Rh_2Ga}$ exhibits a ferromagnetic behavior with the transition temperature of 18…
Spin-orbit coupling in heavy 5$d$ metal oxides, in particular, iridates have received tremendous interest in recent years due to the realization of exotic electronic and magnetic phases. Here, we report the synthesis, structural, magnetic, thermodynamic, and optical properties of the ternary iridate Pr$_3$IrO$_7$. Single crystals of Pr$_3$IrO$_7$ have been grown by the KF flux method. Structural analysis shows that Pr$_3$IrO$_7$ crystallizes in an orthorhombic phase with $Cmcm$ symmetry. The electron energy loss spectroscopy study indicates that Pr is in a 3+ valence state, which implies a 5+ …
Temperature-driven sodium-ion dynamical-to-static crossover in the zig-zag ordered phase of Na$_{0.5}$CoO$_2$
Beijing Academy of Quantum Information Sciences（北京量子信息科学研究院）；Key Laboratory of Artificial Structures and Quantum Control (Ministry of Education), School of Physics and Astronomy, Shanghai Jiao Tong University（上海交通大学物理与天文学院人工结构与量子控制教育部重点实验室）；School of Physical Science and Technology, Lanzhou University（兰州大学物理科学与技术学院）；International Center for Quantum Materials, School of Physics, Peking University（北京大学物理学院物质科学量子创新中心）；Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences（中国科学院物理研究所北京凝聚态物理国家实验室）
