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At least 343 records · Page 19

Spin–Phonon Coupling and Magnetic Transition in an Organic Molecule Intercalated Cr 2 Ge 2 Te 6

The manipulation of spin–phonon coupling in both formations and explorations of magnetism in two-dimensional van der Waals ferromagnetic semiconductors facilitates unprecedented prospects for spintronic devices. The interlayer engineering with spin–phonon coupling promises controllable magnetism via organic cation intercalation. Here, in this study, spectroscopic evidence reveals the intercalation effect on the intrinsic magnetic and electronic transitions in quasi-two-dimensional Cr 2 Ge 2 Te 6 using tetrabutyl ammonium (TBA + ) as the intercalant. The temperature evolution of Raman modes, E g 3 and A g 1 , along with the magnetization measurements, unambiguously captures the enhancement of the ferromagnetic Curie temperature in the intercalated heterostructure. Moreover, the E g 4 mode highlights the increased effect of spin–phonon interaction in magnetic-order-induced lattice distortion. Combined with the first-principle calculations, we observed a substantial number of electrons transferred from TBA + to Cr through the interface. The interplay between spin–phonon coupling and magnetic ordering in van der Waals magnets appeals for further understanding of the manipulation of magnetism in layered heterostructures.

2D magnet↗

Single-Layer Magnet Phase in Intrinsic Magnetic Topological Insulators, [MnTe][Bi 2 Te 3 ] n , Far beyond the Thermodynamic Limit

The intrinsic magnetic topological insulator (IMTI) family [MnTe][Bi 2 Te 3 ]n has demonstrated magneto-topological properties dependent on n, making it a promising platform for advanced electronics and spintronics. However, due to technical barriers in sample synthesis, their properties in the large n limit remain unknown. To overcome this, we utilized the atomic layer-by-layer molecular beam epitaxy (ALL-MBE) technique and achieved IMTIs with n as large as 15, far beyond that previously reported in bulk crystals or thin films. Then, we discover that the “single-layer magnet (SLM)” phase, primarily determined by intralayer ferromagnetic coupling, emerges for n > ∼4 and remains little affected up to n = 15. Nonetheless, still, nonzero, interlayer ferromagnetic coupling is necessary to stabilize the SLM phase, suggesting that the SLM phase eventually disappears in the n → ∞ limit. This study uncovers the secrets of IMTIs beyond the thermodynamic limit and opens a door to diverse magneto-topological applications.

2D ferromagnets↗

High Magnetic Anisotropy and Magnetocaloric Effects in Single-Crystal Cr 2 Te 3

Here, we report a systematic investigation of anisotropic magnetocaloric effects in single-crystal Cr 2 Te 3 . Single-crystal samples are synthesized by chemical vapor transport and characterized by X-ray and Laue diffraction methods. The maximum magnetic entropy change –ΔS M max is 4.50 J kg –1 K –1 for the easy c-axis (3.36 J kg –1 K –1 for the hard axis along ab-plane), and the relative cooling power (RCP) is 296.7 J kg –1 for the easy c-axis (183.84 J kg –1 for the hard axis along ab-plane) for a magnetic field change of 9 T near the Curie temperature. The magneto-crystalline anisotropy constant K u is estimated to be 580.12 kJ m –3 at 140 K, decreasing to 148.60 kJ m –3 at 168 K. Meanwhile, the maximum of the rotational magnetic entropy change –ΔS M R (T, H) between the c-axis and the ab-plane is about 1.14 J kg –1 K –1 for magnetic-field change of 9 T. The critical exponents are estimated by analyzing magnetocaloric effects, which indicate a 2D-Ising type magnetic system. The accuracy of estimated critical exponents is verified by scaling analysis. The maximum magnetic entropy change –ΔS M max ≈ 5.25 J kg –1 K –1 (along the c-axis) and the corresponding adiabatic temperature change ΔT ad ≈ 3.31 K (along the c-axis) are estimated by analyzing heat capacity measurements with a magnetic field up to 9 T.

36 MATERIALS SCIENCE↗

A Ba 6 Cu 31 Te 22 ( A = K, Rb, Cs) Featuring Polyanionic Copper–Telluride Frameworks with Ultralow Thermal Conductivity

In this study, hree polyanionic tellurides, ABa 6 Cu 31 Te 22 (A = K, Rb, Cs), were synthesized in salt flux. The isostructural tellurides crystallize in a new structure type, in the cubic Pa$\overline{3}$ space group with a Wyckoff sequence of d 10 c 2 b 1 and large unit cell volumes of over 5500 Å 3 . The structures feature a framework of [CuTe 4 ] tetrahedra and [CuTe 3 ] trigonal pyramids with disorder in the Cu sites. The polyanionic frameworks have large square antiprism and cuboctahedral voids where Ba and alkali metal cations are situated, forming [BaTe 8 ] and [ATe 12 ], respectively. The overall compositions are close to being charge balanced. The large [ATe 12 ] cuboctahedra allowed for significant anisotropic displacement of the A cations, as observed from both single crystal X-ray diffraction and heat capacity studies. Alkali cations rattling together with Cu atom displacement and disorder leads to the dispersion of phonons, thus softening the lattice and subsequently reducing the thermal conductivity. Evaluations of the electronic band structure revealed the occurrence of a narrow bandgap together with the presence of a flat band near the valence band maximum, giving rise to the high thermopower. The Cs and Rb analogues show a slope change in the temperature dependence of electrical resistivity around room temperature, which is typical for semimetals or degenerate semiconductors. For the as-synthesized and unoptimized materials, high values of the thermoelectric figure-of-merit of ~0.2 were observed at 623 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Surface Oxidation and Crystal Thickness on the Magnetic Properties and Magnetic Domain Structures of Cr 2 Ge 2 Te 6

van der Waals (vdW) magnetic materials, such as Cr 2 Ge 2 Te 6 (CGT), show promise for memory and logic applications. This is due to their broadly tunable magnetic properties and the presence of topological magnetic features such as skyrmionic bubbles. A systematic study of thickness and oxidation effects on magnetic domain structures is important for designing devices and vdW heterostructures for practical applications. Here, we investigate thickness effects on magnetic properties, magnetic domains, and bubbles in oxidation-controlled CGT crystals. We find that CGT exposed to ambient conditions for 5 days forms an oxide layer approximately 5 nm thick. This oxidation leads to a significant increase in the oxidation state of the Cr ions, indicating a change in local magnetic properties. This is supported by real-space magnetic texture imaging through Lorentz transmission electron microscopy. By comparing the thickness-dependent saturation field of oxidized and pristine crystals, we find that oxidation leads to a nonmagnetic surface layer that is thicker than the oxide layer alone. We also find that the stripe domain width and skyrmionic bubble size are strongly affected by the crystal thickness in pristine crystals. Finally, these findings underscore the impact of thickness and surface oxidation on the properties of CGT, such as saturation field and domain/skyrmionic bubble size, and suggest a pathway for manipulating magnetic properties through a controlled oxidation process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Intrinsic exchange biased anomalous Hall effect in an uncompensated antiferromagnet MnBi 2 Te 4

Achieving spin-pinning at the interface of hetero-bilayer ferromagnet/antiferromagnet structures in conventional exchange bias systems can be challenging due to difficulties in interface control and the weakening of spin-pinning caused by poor interface quality. In this work, we propose an alternative approach to stabilize the exchange interaction at the interface of an uncompensated antiferromagnet by utilizing a gradient of interlayer exchange coupling. We demonstrate this exchange interaction through a designed field training protocol in the odd-layer topological antiferromagnet MnBi 2 Te 4 . Our results reveal a remarkable field-trained exchange bias of up to ~ 400 mT, which exhibits high repeatability and can be easily reset by a large training field. Notably, this field-trained exchange bias effect persists even with zero-field initialization, presenting a stark contrast to the traditional field-cooled exchange bias. The highly tunable exchange bias observed in this single antiferromagnet compound, without the need for an additional magnetic layer, provides valuable insight into the exchange interaction mechanism. These findings pave the way for the systematic design of topological antiferromagnetic spintronics.

36 MATERIALS SCIENCE↗

High-temperature concomitant metal-insulator and spin-reorientation transitions in a compressed nodal-line ferrimagnet Mn 3 Si 2 Te 6

Symmetry-protected band degeneracy, coupled with a magnetic order, is the key to realizing novel magnetoelectric phenomena in topological magnets. While the spin-polarized nodal states have been identified to introduce extremely-sensitive electronic responses to the magnetic states, their possible role in determining magnetic ground states has remained elusive. Here, taking external pressure as a control knob, we show that a metal-insulator transition, a spin-reorientation transition, and a structural modification occur concomitantly when the nodal-line state crosses the Fermi level in a ferrimagnetic semiconductor Mn 3 Si 2 Te 6 . These unique pressure-driven magnetic and electronic transitions, associated with the dome-shaped Tc variation up to nearly room temperature, originate from the interplay between the spin-orbit coupling of the nodal-line state and magnetic frustration of localized spins. Our findings highlight that the nodal-line states, isolated from other trivial states, can facilitate strongly tunable magnetic properties in topological magnets.

36 MATERIALS SCIENCE↗

Observation of dimension-crossover of a tunable 1D Dirac fermion in topological semimetal NbSi x Te 2

Condensed matter systems in low dimensions exhibit emergent physics that does not exist in three dimensions. When electrons are confined to one dimension (1D), some significant electronic states appear, such as charge density wave, spin-charge separations, and Su-Schrieffer-Heeger (SSH) topological state. However, a clear understanding of how the 1D electronic properties connects with topology is currently lacking. Here we systematically investigated the characteristic 1D Dirac fermion electronic structure originated from the metallic NbTe 2 chains on the surface of the composition-tunable layered compound NbSi x Te 2 (x = 0.40 and 0.43) using angle-resolved photoemission spectroscopy. We found the Dirac fermion forms a Dirac nodal line structure protected by the combined $\widetilde {M_y}$ and time-reversal symmetry T and proves the NbSi x Te2 system as a topological semimetal, in consistent with the ab-initio calculations. As x decreases, the interaction between adjacent NbTe 2 chains increases and Dirac fermion goes through a dimension-crossover from 1D to 2D, as evidenced by the variation of its Fermi surface and Fermi velocity across the Brillouin zone in consistence with a Dirac SSH model. Our findings demonstrate a tunable 1D Dirac electron system, which offers a versatile platform for the exploration of intriguing 1D physics and device applications.

36 MATERIALS SCIENCE↗

An antiferromagnetic diode effect in even-layered MnBi 2 Te 4

In a p–n junction, the separation of positive and negative charges leads to diode transport, in which charge flows in only one direction. Non-centrosymmetric polar conductors are intrinsic diodes that could be of use in the development of nonlinear applications. Such systems have recently been extended to non-centrosymmetric superconductors, and the superconducting diode effect has been observed. Here, in this paper, we report an antiferromagnetic diode effect in a centrosymmetric crystal without directional charge separation. We observed large second-harmonic transport in a nonlinear electronic device enabled by the compensated antiferromagnetic state of even-layered MnBi 2 Te 4 . We show that this antiferromagnetic diode effect can be used to create in-plane field-effect transistors and microwave-energy-harvesting devices. We also show that electrical sum-frequency generation can be used as a tool to detect nonlinear responses in quantum materials.

electronic properties and materials↗

Dynamic signatures of spin-lattice coupling in the layered ferrimagnet Mn 3 Si 2 Te 6

Magnetic van der Waals (vdW) materials exhibit a profound interconnectedness between their various degrees of freedom, pointing to a wealth of potential applications in low-power and high-speed spintronic devices. Recently, light-matter interactions have been leveraged as robust, dynamic pathways to gain control over the properties of vdW magnets through the use of ultrafast pulses of light. Here, we utilize ultrafast photoexcitation to drive coherent lattice oscillations in the layered ferrimagnetic crystal Mn 3 Si 2 Te 6 , which significantly stiffen below the magnetic ordering temperature. We suggest that this is due to an exchange-mediated contraction of the lattice, stemming from strong magneto-structural coupling in this material. Furthermore, simulations of the transient incoherent response uncover the critical role of the spin-mediated electronic relaxation pathways. These results underscore the importance of spin-lattice coupling in vdW magnets and demonstrate a promising strategy for their dynamic optical control via their entangled degrees of freedom.

36 MATERIALS SCIENCE↗

Understanding the thermally activated charge transport in NaPb m SbQ m+2 (Q = S, Se, Te) thermoelectrics: weak dielectric screening leads to grain boundary dominated charge carrier scattering

Many thermoelectric materials feature irregular electrical conductivity with thermally activated transport below ~600 K and metallic behavior at high temperatures, despite possessing degenerate carrier concentrations. The suppression of the electrical conductivity ultimately degrades the thermoelectric performance on the cold side and limits the device energy conversion efficiency. As such, establishing the origin of the low temperature scattering and developing strategies to mitigate its effect are paramount issues. To date, the correct microscopic description of the low temperature carrier scattering remains an open issue, and there is little work addressing why some thermoelectric materials are more susceptible to the deleterious behavior. Here, we use the promising thermoelectric alloys of PbQ and NaSbQ 2 (Q = S, Se, Te) as model systems to address these concerns. We directly show the thermally activated transport stems from the scattering of charge carriers by the grain boundaries (GBs), and that the expected metallic electrical conductivity is recovered by preparing large grained samples with reduced densities of GBs. We furthermore study the electrical properties NaPb m SbSe m+2 as a function of NaSbSe 2 fraction, as well as those of the chalcogenide analogues, PbTe–NaSbTe 2 and PbS–NaSbS 2 , and demonstrate that the strength of GB scattering can be understood by utilizing simple chemical principles. By considering the polarizability of the host atoms, we directly relate the magnitude of GB scattering to the relative degree of charge carrier screening in each material, and demonstrate that GB scattering is strongest in the ionic NaSbQ 2 -rich compounds and weakest in more polarizable PbQ-rich phases. We finally show how these chemical arguments elegantly explain the strong GB scattering in numerous other thermoelectric materials. By uniting the deleterious charge transport properties exhibited by many different compounds into a common picture, we discuss how our work gives design principles for proper microstructure engineering in emerging thermoelectric materials.

36 MATERIALS SCIENCE↗

Ultralow thermal conductivity in diamondoid lattices: high thermoelectric performance in chalcopyrite Cu 0.8+y Ag 0.2 In 1–y Te 2

Because of its unique transport properties, CuInTe 2 has been considered as a promising p-type material for thermoelectric applications. However, its diamondoid structure gives it a high intrinsic lattice thermal conductivity that greatly limits its thermoelectric performance. In this study, we demonstrate that Ag alloying gives rise to an extremely low lattice thermal conductivity of 0.47 W m –1 K –1 for Cu 0.8 Ag 0.2 InTe 2 at 850 K. Moreover, we found Cu doping significantly improves the carrier mobility while simultaneously increasing the carrier concentraton. As a result, the power factor of Cu 0.8 Ag 0.2 InTe 2 increases and a maximum ZT of ~1.6 is achieved at 850 K. Both DFT calculations and low temperature heat capacity measurements suggest a strong interaction between low frequency optical phonons and heat carrying acoustic phonons, which is derived from the weak Ag–Te bonding. Here, this strong phonon coupling decreases the Debye temperature and induces a low sound velocity.

36 MATERIALS SCIENCE↗

Plasma-jet printing of colloidal thermoelectric Bi 2 Te 3 nanoflakes for flexible energy harvesting

Thermoelectric generators (TEGs) convert temperature differences into electrical power and are attractive among energy harvesting devices due to their autonomous and silent operation. While thermoelectric materials have undergone substantial improvements in material properties, a reliable and cost-effective fabrication method suitable for microgravity and space applications remains a challenge, particularly as commercial space flight and extended crewed space missions increase in frequency. This paper demonstrates the use of plasma-jet printing (PJP), a gravity-independent, electromagnetic field-assisted printing technology, to deposit colloidal thermoelectric nanoflakes with engineered nanopores onto flexible substrates at room temperature. We observe substantial improvements in material adhesion and flexibility with less than 2% and 11% variation in performance after 10 000 bending cycles over 25 mm and 8 mm radii of curvature, respectively, as compared to previously reported TE films. Our printed films demonstrate electrical conductivity of 2.5 × 10 3 S m -1 and a power factor of 70 μW m -1 K -2 at room temperature. To our knowledge, these are the first reported values of plasma-jet printed thermoelectric nanomaterial films. This advancement in plasma jet printing significantly promotes the development of nanoengineered 2D and layered materials not only for energy harvesting but also for the development of large-scale flexible electronics and sensors for both space and commercial applications.

99 GENERAL AND MISCELLANEOUS↗