Efficient and tunable one-dimensional charge transport in layered lanthanide metal?organic framework
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Tailoring electron transfer dynamics across solid–liquid interfaces is fundamental to the interconversion of electrical and chemical energy. Stacking atomically thin layers with a small azimuthal misorientation to produce moiré superlattices enables the controlled engineering of electronic band structures and the formation of extremely flat electronic bands. Here, we report a strong twist-angle dependence of heterogeneous charge transfer kinetics at twisted bilayer graphene electrodes with the greatest enhancement observed near the ‘magic angle’ (~1.1°). Furthermore, this effect is driven by the angle-dependent tuning of moiré-derived flat bands that modulate electron transfer processes with the solution-phase redox couple. Combined experimental and computational analysis reveals that the variation in electrochemical activity with moiré angle is controlled by a structural relaxation of the moiré superlattice at twist angles of <2°, and ‘topological defect’ AA stacking regions, where flat bands are localized, produce a large anomalous local electrochemical enhancement that cannot be accounted for by the elevated local density of states alone.
Assembling colloidal particles using site-selective directional interactions into predetermined colloidal superlattices with desired properties is broadly sought-after, but challenging to achieve. Here in this paper, we exploit regioselective depletion interactions to engineer the directional bonding and assembly of non-spherical colloidal hybrid microparticles. We report that the crystallization of a binary colloidal mixture can be regulated by tuning the depletion conditions. Subsequently, we fabricate triblock biphasic colloids with controlled aspect ratios to achieve regioselective bonding. Without any surface treatment, these biphasic colloids assemble into various colloidal superstructures and superlattices featuring optimized pole-to-pole or center-to-center interactions. Additionally, we observe polymorphic crystallization, quantify the abundancy of each form using algorithms we developed, and investigate the crystallization process in real time. We demonstrate selective control of attractive interactions between specific regions on an anisotropic colloid with no need of site-specific surface functionalization, leading to a general method for achieving colloidal structures with yet unforeseen arrangements and properties.
Magnetism and spin-orbit coupling are two quintessential ingredients underlying topological transport phenomena in itinerant ferromagnets. When spin-polarized bands support nodal points/lines with band degeneracy that can be lifted by spin-orbit coupling, the nodal structures become a source of Berry curvature, leading to a large anomalous Hall effect. However, two-dimensional systems can possess stable nodal structures only when proper crystalline symmetry exists. Here, in this study, we show that two-dimensional spin-polarized band structures of perovskite oxides generally support symmetry-protected nodal lines and points that govern both the sign and the magnitude of the anomalous Hall effect. To demonstrate this, we performed angle-resolved photoemission studies of ultrathin films of SrRuO 3 , a representative metallic ferromagnet with spin-orbit coupling. We show that the sign-changing anomalous Hall effect upon variation in the film thickness, magnetization and chemical potential can be well explained by theoretical models. Our work may facilitate new switchable devices based on ferromagnetic ultrathin films.
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The interaction between distinct excitations in solids is of both fundamental interest and technological importance. One example of such interactions is coupling between an exciton, a Coulomb bound electron-hole pair, and a magnon, a collective spin excitation. The recent emergence of van der Waals magnetic semiconductors1 provides a powerful platform for exploring these exciton-magnon interactions and their fundamental properties, such as strong correlation2, as well as their photo-spintronic and quantum transduction3 applications. Here we demonstrate precise control of coherent exciton-magnon interactions in the layered magnetic semiconductor CrSBr. We show that by controlling the direction of applied magnetic fields relative to the crystal axes, and thus the rotational symmetry of the magnetic system4, we can tune not only the exciton coupling to the bright magnon, but also to an optically dark mode via magnon hybridization. The exciton-magnon coupling and associated magnon dispersion curves can be further modulated by applying a uniaxial strain. At the critical strain, a dispersionless dark magnon band emerges. Our results demonstrate unprecedented control of the opto-mechanical-magnonic coupling, and a step towards the predictable and controllable implementation of hybrid quantum magnonics.
Coherent heterojunctions, quantum wells and multiple quantum wells are needed for high-performance devices; these are generally grown via a dedicated vapour phase epitaxy process. Here we demonstrate the growth of coherent perovskite heterojunctions and quantum wells made of mixed-dimensional perovskites using a solution process. By exploiting the solubility difference of methylammonium (MA + ) and 4-(aminomethyl)piperidinium (4AMP 2+ ), we assemble layered perovskites with different layer numbers. The resulting 4AMP-MA n–1 Pb n I 3n+1 materials each with different layer numbers or bandgaps form quantum wells. Heterojunctions and quantum wells made of 4AMP-MA 2 Pb 3 I 10 (n = 3) and 4AMP-MAPb 2 I 7 (n = 2) with various barrier thickness are tailored by the solution temperature profile during crystal growth. Multiple quantum wells have been formed by cycling temperature profiles. The planar heterojunction and quantum wells have lattice matching without interfacial defects, and exhibit strong thermal stability. Type I band alignment at the n = 2/n = 3 heterojunction is confirmed by both computation and optical studies. In conclusion, this study opens a new direction for the development of sophisticated perovskite heterojunction and quantum well devices.
Correlated topological materials often maintain a delicate balance among physical symmetries. Many topological orders are symmetry protected, whereas most correlated phenomena arise from spontaneous symmetry breaking. Cases where symmetry breaking induces a non-trivial topological phase are rare. Here we demonstrate the presence of two such phases in Ta 2 Pd 3 Te 5 , where Coulomb interactions form excitons that condense below 100 K, one with zero and the other with finite momentum. We observed a full spectral bulk gap, which stems from exciton condensation. This topological excitonic insulator state spontaneously breaks mirror symmetries but involves a weak structural coupling. Scanning tunnelling microscopy shows gapless boundary modes in the bulk insulating phase. Their magnetic field response, together with theoretical modelling, indicates a topological origin. These observations establish Ta 2 Pd 3 Te 5 as a topological excitonic insulator in a three-dimensional crystal. Finally, our results manifest a unique sequence of topological exciton condensations in a bulk crystal, offering exciting opportunities to study critical behaviour and excitations.
Quasicrystals are characterized by atomic arrangements having long-range order without periodicity. Van der Waals bilayers provide an opportunity to controllably vary the atomic alignment between two layers from a periodic moiré crystal to an aperiodic quasicrystal. Here, in this work, we reveal that in a dodecagonal WSe 2 quasicrystal, two separate valleys in separate layers are brought arbitrarily close in momentum space through higher-order Umklapp scatterings. A modest perpendicular electric field is then sufficient to induce strong interlayer valley hybridization, manifested as another hybrid excitonic doublet. Concurrently, we observe the disappearance of the trion that exists at low field, which we attribute to a modified spatial distribution of the wavefunction due to the quasicrystal potential. This is possibly a precursor to localization. Our findings highlight the ability of incommensurate systems to bring any pair of momenta into close proximity, thereby introducing opportunities for valley engineering.
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