CaAl2Si2-type Structure Research Articles

Thermoelectric Properties of Zn-Doped YbMg1.85-xZnxBi1.98.

Bi-based YbMg2Bi1.98 Zintl compounds represent promising thermoelectric materials. Precise composition and appropriate doping are of great importance for this complex semiconductor. Here, the influence of Zn substitution for Mg on the microstructure and thermoelectric properties of p-type YbMg1.85-xZnxBi1.98 (x = 0, 0.05, 0.08, 0.13, 0.23) was investigated. Polycrystalline samples were prepared using induction melting and densified with spark plasma sintering. X-ray diffraction confirmed that the major phase of the samples possesses the trigonal CaAl2Si2-type crystal structure, and SEM/EDS indicated the presence of minor secondary phases. The electrical conductivity increases and the lattice thermal conductivity decreases with more Zn doping in YbMg1.85-xZnxBi1.98, whereas the Seebeck coefficient has a large reduction. The band gap decreases with increasing Zn concentration and leads to bipolar conduction, resulting in an increase in the thermal conductivity at higher temperatures. Figure of merit ZT values of 0.51 and 0.49 were found for the samples with x = 0 and 0.05 at 773 K, respectively. The maximum amount of Zn doping is suggested to be less than x = 0.1.

Magnetic properties and magnetocaloric effect of a metallic triangular lattice antiferromagnetic DyAl2Ge2 single crystal

We report the synthesis, magnetic susceptibility, magnetization, electrical resistivity, heat capacity, and magnetocaloric properties of the metallic triangular lattice antiferromagnetic DyAl2Ge2 single crystal. High-quality rare-earth intermetallic compound DyAl2Ge2 single crystals were synthesized by the metallic flux method. DyAl2Ge2 crystallizes in a trigonal CaAl2Si2-type structure with Dy atoms forming a triangular lattice in the ab plane. The paramagnetic-antiferromagnetic transition occurs at 8 K, as determined by temperature dependencies of magnetic susceptibility and heat capacity. No observable hysteresis was found in the field-induced antiferromagnetic to the ferromagnetic metamagnetic transition of DyAl2Ge2. The electrical resistivity shows an overall metallic behavior with an upturn at the ordering temperature. For a magnetic field change of 0–70 kOe, the maximum magnetic-entropy change is −14.2 J kg−1 K−1 at 11 K and the relative cooling power is 327 J kg−1 with the applied magnetic field along the ab plane.

Abrupt change reflected by the van Hove singularity in the optical spectra of CaMn2P2

The trigonal CaAl2Si2-type structure CaMn2P2 has been reported undergoing an exotic first order phase transition at the critical temperature T K. In this paper, we present the optical spectra for the ab-plane of CaMn2P2 single crystal from 300 K to 10 K for the first time. In the real part of the optical conductivity spectra σ 1(ω), a direct gap could be determined at all temperatures without any Drude term visible, i.e., the sample goes through the first order phase transition from one insulator state to the other insulator state. At higher energy, an asymmetric sharp interband transition peak appears in all σ 1(ω) spectra, which indicates a divergence of the joint density of states. This sharp peak could be well described by the two dimensional van Hove singularity function. In particular, this peak is very sensitive to the first order phase transition, especially the peak position E whose the most prominent blue shift occurs only when the first order transition happens. Our data and analysis reveal that the first order phase transition leads to a weak partial re-normalization of the band structure. Our study will be useful in further investigations about the mechanism of the first order phase transition in the insulator.

Structures of Three Alkaline-Earth Metal Germanides Refined from Single-Crystal X-ray Diffraction Data

The calcium- and strontium- alumo-germanides SrxCa1–xAl2Ge2 (x ≈ 0.4) and SrAl2Ge2 have been synthesized and structurally characterized. Additionally, a binary calcium germanide CaGe has also been identified as a byproduct. All three crystal structures have been established from single-crystal X-ray diffraction methods and refined with high accuracy and precision. The binary CaGe crystallizes with a CrB-type structure in the orthorhombic space group Cmcm (no. 63; Z = 4; Pearson symbol oC8), where the germanium atoms are interconnected into infinite zigzag chains, formally [Ge]2−. The calcium atoms are arranged in monocapped trigonal prisms, centered by Ge atoms. SrxCa1−xAl2Ge2 (x ≈ 0.4) and SrAl2Ge2 have been confirmed to crystallize with a CaAl2Si2-type structure in the trigonal space group P3¯m1 (no. 164; Z = 1; Pearson symbol hP5), where the germanium and aluminum atoms form puckered double-layers, formally [Al2Ge2]2−. The calcium atoms are located between the layers and reside inside distorted octahedra of Ge atoms. All presented structures have a valence electron count satisfying the octet rules (e.g., Ca2+Ge2− and Ca2+[Al2Ge2]2−) and can be regarded as Zintl phases.

Prediction of topological Dirac semimetal in Ca-based Zintl layered compounds CaM2X2 (M\u2009=\u2009Zn or Cd; X\u2009=\u2009N, P, As, Sb, or Bi)

Topological Dirac materials are attracting a lot of attention because they offer exotic physical phenomena. An exhaustive search coupled with first-principles calculations was implemented to investigate 10 Zintl compounds with a chemical formula of CaM2X2 (M = Zn or Cd, X = N, P, As, Sb, or Bi) under three crystal structures: CaAl2Si2-, ThCr2Si2-, and BaCu2S2-type crystal phases. All of the materials were found to energetically prefer the CaAl2Si2-type structure based on total ground state energy calculations. Symmetry-based indicators are used to evaluate their topological properties. Interestingly, we found that CaM2Bi2 (M = Zn or Cd) are topological crystalline insulators. Further calculations under the hybrid functional approach and analysis using k · p model reveal that they exhibit topological Dirac semimetal (TDSM) states, where the four-fold degenerate Dirac points are located along the high symmetry line in-between Г to A points. These findings are verified through Green's function surface state calculations under HSE06. Finally, phonon spectra calculations revealed that CaCd2Bi2 is thermodynamically stable. The Zintl phase of AM2X2 compounds have not been identified in any topological material databases, thus can be a new playground in the search for new topological materials.

Discovering the desirable physical properties of arsenic compounds AB2As2 and their alloys: a theoretical study.

In the current study, the stability, elastic, electronic, and optical properties of AB2As2 (A = Ca, Sr; B = Mg, Zn, Cd) and their alloys with a trigonal CaAl2Si2-type structure are thoroughly examined for the first time based on the first-principles calculations. The optimized structural parameters are highly consistent with the experimental data. The dynamic stability of four alloys is demonstrated by computing their phonon spectra. All compounds are mechanically stable and brittle materials. The results imply that both CaMg2As2 and SrMg2As2 exhibit indirect band gaps at the Γ-M symmetry point, while AZn2As2 and ACd2As2 at the Γ point exhibit direct bandgap features. Moreover, the trend of band gap reduction (∼1 eV) is presented from AMg2As2 to ACd2As2. The allowed transition from an indirect band gap to a direct band gap is observed from AMg2As2 to A(Mg0.5B0.5)2As2. Four alloys display more suitable direct band gaps (1.2-1.5 eV) for potential optoelectronic applications. In addition, these compounds possess high carrier mobility. The analysis of various optical properties is discussed in detail. This finding demonstrates that some novel compounds can be potential candidates for possible optoelectronic devices.

First-order antiferromagnetic transitions of SrMn2P2 and CaMn2P2 single crystals containing corrugated-honeycomb Mn sublattices

SrMn2P2 and CaMn2P2 are insulators that adopt the trigonal CaAl2Si2-type structure containing corrugated Mn honeycomb layers. Magnetic susceptibility χ and heat capacity versus temperature T data reveal a weak first-order antiferromagnetic (AFM) transition at the Néel temperature [Formula: see text] K for SrMn2P2 and a strong first-order AFM transition at [Formula: see text] K for CaMn2P2 Both compounds exhibit isotropic and nearly T-independent [Formula: see text], suggesting magnetic structures in which nearest-neighbor moments are aligned at [Formula: see text] to each other. The 31P NMR measurements confirm the strong first-order transition in CaMn2P2 but show critical slowing down above [Formula: see text] for SrMn2P2, thus also evidencing second-order character. The 31P NMR measurements indicate that the AFM structure of CaMn2P2 is commensurate with the lattice whereas that of SrMn2P2 is incommensurate. These first-order AFM transitions are unique among the class of (Ca, Sr, Ba)Mn2 (P, As, Sb, Bi)2 compounds that otherwise exhibit second-order AFM transitions. This result challenges our understanding of the circumstances under which first-order AFM transitions occur.

Optoelectronic, thermodynamic and vibrational properties of intermetallic MgAl2Ge2: a first-principles study

Intermetallic compounds with CaAl2Si2-type structure have been studied extensively due to their exciting set of physical properties. Among various alumo-germanides, MgAl2Ge2 is the new representative of CaAl2Si2-type structures. Our previous study explores the structural aspects, mechanical behaviors and electronic features of intermetallic MgAl2Ge2. The present work discloses the results of optoelectronic, thermodynamic and vibrational properties of MgAl2Ge2 via density functional theory-based investigations. The band structure calculations suggest that MgAl2Ge2 possesses slight electronic anisotropy and the compound is metallic. The Fermi surface topology reveals that both electron- and hole-like sheets are present in MgAl2Ge2. The electron charge density map indicates toward the dominance of covalent bonding in MgAl2Ge2. The optical parameters are found to be independent of the state of the polarization of incident electric field. The large value of the reflectivity in the visible-to-ultraviolet region up to ~ 15 eV suggests that MgAl2Ge2 might be a good candidate as coating material to avoid solar heating. The thermodynamic properties have been calculated using the quasi-harmonic Debye approximation. We have found indications of lattice instability at the Brillouin zone boundary in the trigonal Poverline{3}m1 phase from the phonon dispersion curves. However, the compound might be stable at elevated temperature and as a function of pressure. All the theoretical findings herein have been compared with the reported results (where available). Various implications of our results have been discussed in detail.Graphic abstract

Zintl Phase Yb1–xBaxMg2Bi1.98 Compounds with Enhanced Thermoelectric Performance Caused by Cation Substitution

Contributing to the unique structural and chemical characteristics, AM2X2 Zintl compounds with the CaAl2Si2-type structure present advanced thermoelectric properties. In the present work, for YbMg2...

Enhanced thermoelectric properties of Zintl phase YbMg2Bi1.98 through Bi site substitution with Sb

Benefiting from the unique “Phonon-Glass, Electron-Crystal” (PGEC) characteristic, Zintl phases have been considered as a kind of promising thermoelectric materials. For the typical AM2X2 compounds with the CaAl2Si2-type structure, YbMg2Bi2 has shown competitive thermoelectric performance recently. Nevertheless, the optimization of YbMg2Bi2 compounds is primarily focused on the substitution on Yb or Mg site. Herein, the Bi site is substituted by isoelectric Sb and the effect on the thermoelectric transport behavior is investigated. The partial substitution reduces the carrier concentration and induces the lattice deformation caused by the different atomic radius and mass between Bi and Sb, further leading to the decreased power factor and thermal conductivity. Fortunately, the reduction extent of the thermal conductivity outperforms that of power factor. Finally, the Sb substitution successfully results in a better thermoelectric performance compared with that of the pristine YbMg2Bi1.98. Especially, the calculated energy conversion efficiency (η) of YbMg2Bi1.88Sb0.1 which also possesses a relatively high output power density reaches the maximum value of 9.8 % when Th = 873 K, and Tc = 300 K, respectively. This work demonstrates that the idea of substitution on anionic site should be a new strategy to achieve better ZT values for AM2X2 compounds.

Anisotropic magnetic properties of trigonal ErAl2Ge2 single crystal

We report the anisotropic magnetic properties of the ternary compound ErAl2Ge2. Single crystals of this compound were grown by high temperature solution growth technique,using Al:Ge eutectic composition as flux. From the powder x-ray diffraction we confirmed that ErAl2Ge2 crystallizes in the trigonal CaAl2Si2-type crystal structure. The anisotropic magnetic properties of a single crystal were investigated by measuring the magnetic susceptibility, magnetization, heat capacity and electrical resistivity. A bulk antiferromagnetic ordering occurs around 4 K as inferred from the magnetic susceptibility and the heat capacity. The susceptibility is larger along the ab-plane and flattens out below the magnetic transition temperature () and the magnetization in the ordered state increases more rapidly along the ab-plane than along the c-axis suggesting that the moments are inclined more towards the ab-plane. The magnetic susceptibility, magnetization and the 4f -derived part of the heat capacity in the paramagnetic regime analysed based on the point charge model of the crystalline electric field (CEF) indicate a relatively low CEF energy level splitting.

Synthesis, structure and physical properties of layered quaternary sulfides NaLiMS2 (M = Mn, Fe, Co)

Three layered quaternary sulfides, NaLiMS2 (M = Mn, Fe, Co) were synthesized by solid-state reactions. They adopt a trigonal CaAl2Si2-type structure (S.G. P-3m1) with Li and M randomly distributed at the tetrahedral metal site. Magnetic measurements reveal spin-glass ground states for these compounds, in contrast to the long-range antiferromagnetic order in the ternary counterpart NaFe1.6S2. As evidenced by electrical resistivity and optical measurements, all these three compounds show semiconducting nature, consistent with the results of first-principles calculations. The measured band gaps are 3.4 eV and 1.25 eV for NaLiMnS2 and NaLiCoS2, respectively. Photoelectric measurements on NaLiCoS2 demonstrate its potential application in photovoltaic devices.

Chemical bonding origin of the unexpected isotropic physical properties in thermoelectric Mg3Sb2 and\xa0related materials

The Mg3Sb2 structure is currently being intensely scrutinized due to its outstanding thermoelectric properties. Usually, it is described as a layered Zintl phase with a clear distinction between covalent [Mg2Sb2]2− layers and ionic Mg2+ layers. Based on the quantitative chemical bonding analysis, we unravel instead that Mg3Sb2 exhibits a nearly isotropic three-dimensional bonding network with the interlayer and intralayer bonds being mostly ionic and surprisingly similar, which results in the nearly isotropic structural and thermal properties. The isotropic three-dimensional bonding network is found to be broadly applicable to many Mg-containing compounds with the CaAl2Si2-type structure. Intriguingly, a parameter based on the electron density can be used as an indicator measuring the anisotropy of lattice thermal conductivity in Mg3Sb2-related structures. This work extends our understanding of structure and properties based on chemical bonding analysis, and it will guide the search for and design of materials with tailored anisotropic properties.

Quaternary rare-earth transition-metal phosphides REMnCuP2 (RE = Y, La–Nd, Sm, Gd–Tm, Lu) with CaAl2Si2-type structure and a polymorph of LaMnCuP2 with BaCu2S2-type structure

The series of quaternary rare-earth phosphides REMnCuP2 (RE = Y, La–Nd, Sm, Gd–Tm, Lu), which had previously been limited to the Yb member, has been prepared by reaction of the elements at 800 °C. These phosphides adopt the CaAl2Si2-type structure (trigonal, space group P3¯m1 , Z = 1) with Mn and Cu atoms disordered over the tetrahedral M sites within [M2P2] slabs. However, single-crystal X-ray diffraction studies, carried out on some of these members (RE = Tb, Dy, Er, Tm), provide evidence for an interstitial octahedral site being partially occupied by Cu atoms, resulting in the nonstoichiometric formulation REMnCu1+xP2 (x = 0.10–0.16). A second polymorph of LaMnCuP2 adopting the BaCu2S2-type structure (orthorhombic, space group Pnma, Z = 4) was also identified in the course of these investigations. Electronic structure calculations on a ordered superstructure model of YMnCuP2 indicate the absence of a band gap.

Thermoelectric properties of (Ba,K)Cd2As2 crystallized in the CaAl2Si2-type structure

As-Based Zintl compounds Ba1-xKxCd2As2 crystallized in the CaAl2Si2-type structure (space group P3[combining macron]m1) were prepared using solid-state reactions followed by hot-pressing. We have successfully substituted K for Ba up to x = 0.08, producing hole-carrier doping with concentrations up to 1.60 × 1020 cm-3. We have determined the band-gap value of non-doped BaCd2As2 to be 0.40 eV from the temperature dependence of the electrical resistivity. Both the electrical resistivity and the Seebeck coefficient decrease with hole doping, leading to a power factor value of 1.28 mW m-1 K-2 at 762 K for x = 0.04. A first-principles band calculation shows that the relatively large power factor mainly originates from the two-fold degeneracy of the bands comprising As px,y orbitals and from the anisotropic band structure at the valence-band maximum. The lattice thermal conductivity is suppressed by the K doping to 0.46 W m-1 K-1 at 773 K for x = 0.08, presumably due to randomness. The effect of randomness is compensated by an increase in the electronic thermal conductivity, which keeps the total thermal conductivity approximately constant. In consequence, the dimensionless figure-of-merit ZT reaches a maximum value of 0.81 at 762 K for x = 0.04.

Single crystal growth and anisotropic magnetic properties of HoAl2Ge2

We have grown a single crystal of HoAl2Ge2, which crystallizes in the hexagonal CaAl2Si2 type structure with Ho ions in the trigonal coordination in the ab plane. The data obtained from the bulk measurement techniques of magnetization, heat capacity and transport reveal that HoAl2Ge2 orders antiferromagnetically at TN ∼6.5 K. The susceptibility below TN and isothermal magnetization at 2 K indicate the ab plane as the easy plane of magnetization. Heat capacity data reveal a prominent Schottky anomaly with a broad peak centered around 25 K, suggesting a relatively low crystal electric field (CEF) splitting. The electrical resistivity reveals the occurrence of a superzone gap below TN. The point charge model of the CEF is applied to the magnetization and the heat capacity data. While a good fit to the paramagnetic susceptibility is obtained, the CEF parameters do not provide a satisfactory fit to the isothermal magnetization at 2 K and the Schottky anomaly.

Structure Evolution and Spin-Glass Transition of Layered Compounds ALiFeSe2 (A = Na, K, Rb).

Three new layered compounds, namely NaLiFeSe2, KLiFeSe2, and RbLiFeSe2, have been discovered. NaLiFeSe2 adopts a trigonal CaAl2Si2-type structure with space group P3̅m1, while the other two possess a tetragonal ThCr2Si2-type structure with space group I4/mmm. Structural refinements reveal that Li and Fe atoms randomly occupy the same sites in all these compounds without ordering. It is found that the radius of the alkali metals plays a vital role in determining the symmetry of this series of compounds. The substitution of Li at the Fe site shortens the layer spacing and elongates the A-Se bond length in the ThCr2Si2-type structure. The elongated Na-Se bond length would destabilize the ThCr2Si2-type structure in NaLiFeSe2, suggesting that NaxFe2-ySe2 lies at the border of ThCr2Si2-type and CaAl2Si2-type structures. Magnetic and resistivity measurements demonstrate that these compounds exhibit anisotropic spin-glass and narrow-band-gap semiconducting characteristics. First-principles calculations indicate that the introduction of Li enhances strong localization and weakens the correlation of the 3d electrons of Fe, which are responsible for the observed spin-glass transition and semiconducting conductions.

(Invited) Zintl Phase Thermoelectrics: Engineering Transport through Crystal Chemistry

Intermetallic Zintl phases form complex composite structures characterized by covalently-bonded polyanions stabilized by the surrounding cations. The Zintl polyanions occur in an astounding variety of forms, including isolated 0-dimensional clusters, 1-D chains, and 2-D slabs, making this an ideal class of compounds to study structure-property relationships in complex semiconductors. AM 2 X 2 compounds in the CaAl2Si2 structure type are one of the most successful classes of Zintl thermoelectrics - particularly in light of recent reports of zT ~ 1.5 in n-type MgMg2Sb2. This talk will explore the role played by the defect chemistry of AM 2 X 2 compounds. We have shown both experimentally and using first principles calculations that the low formation energy for cation vacancies in this structure type enables tuning of the electronic properties via either alloying or by directly varying the cation content. In addition, by using high pressure, we have investigated the transport properties of AM 2 X 2 compounds synthesized using high pressure. While AM 2 X 2 compounds in the CaAl2Si2 structure are typically narrow gap semiconductors, those in the related tetragonal BaZn2P2 structure type are exclusively metals or semimetals and are known to exhibit superconductivity. In the first example of a phase transition between these two technologically important structures types, we show that SrAl2Si2 (trigonal CaAl2Si2-type structure at ambient pressure) can be obtained as a metastable phase in the tetragonal BaZn2P2 structure type by employing high-pressure, high-temperature synthesis. Our study shows that the changes in the electronic density of states lead to the emergence of phonon-driven superconductivity in the tetragonal polymorph. By accessing structural motifs that are not thermodynamically stable at ambient conditions, we are thus able to directly investigate the relationship between structure and electronic properties in AM 2 X 2 Zintls.

Strong magnetic correlations to 900 K in single crystals of the trigonal antiferromagnetic insulatorsSrMn2As2andCaMn2As2

Crystallographic, electronic transport, thermal and magnetic properties are reported for SrMn2As2 and CaMn2As2 single crystals grown using Sn flux. Rietveld refinements of powder x-ray diffraction data show that the two compounds are isostructural and crystallize in the trigonal CaAl2Si2-type structure (space group P-3m1), in agreement with the literature. Electrical resistivity rho versus temperature T measurements demonstrate insulating ground states for both compounds with activation energies of 85 meV for SrMn2As2 and 61 meV for CaMn2As2. In a local-moment picture, the Mn^{+2} 3d^5 ions are expected to have high-spin S = 5/2 with spectroscopic splitting factor g = 2. Magnetic susceptibility chi and heat capacity measurements versus T reveal antiferromagnetic (AFM) transitions at TN = 120(2) K and 62(3) K for SrMn2As2 and CaMn2As2, respectively. The anisotropic chi(T < TN) data indicate that the hexagonal c axis is the hard axis and hence that the ordered Mn moments are aligned in the ab plane. The chi(T) for both compounds and Cp(T) data for SrMn2As2 show strong dynamic short-range AFM correlations from TN up to at least 900 K, likely associated with quasi-two-dimensional connectivity of strong AFM exchange interactions between the Mn spins within the corrugated honeycomb Mn layers parallel to the ab plane.

(Sr1-xNax)(Cd1-xMnx)2As2: A new charge and spin doping decoupled diluted magnetic semiconductors with CaAl2Si2-type structure

We report the synthesis and characterization of a new bulk diluted ferromagnetic semiconductor via Na and Mn co-doping in SrCd2As2 with a hexagonal CaAl2Si2-type structure. Together with carrier doping via (Sr,Na) substitution, spin doping via (Cd,Mn) substitution results in ferromagnetic order with Curie temperature of TC up to 13 K. Negative magnetoresistance is assigned to weak localization at low temperatures, where the magnetization of samples becomes saturated. The hexagonal structure of (Sr1−xNax)(Cd1−xMnx)2As2 can be acted as a promising candidate for spin manipulations owing to its relatively small coercive field of less than 24 Oe.