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The exotic electronic properties of topological semimetals (TSs) have opened new pathways for innovative photonic and optoelectronic devices, especially in the highly pursuit terahertz (THz) band. However, in most cases Dirac fermions lay far above or below the Fermi level, thus hindering their successful exploitation for the low-energy photonics. Here, low-energy type-II Dirac fermions in kitkaite (NiTeSe) for ultrasensitive THz detection through metal-topological semimetal-metal heterostructures are exploited. Furthermore, a heterostructure combining two Dirac materials, namely, graphene and NiTeSe, is implemented for a novel photodetector exhibiting a responsivity as high as 1.22 A W-1 , with a response time of 0.6 µs, a noise-equivalent power of 18 pW Hz-0.5 , with outstanding stability in the ambient conditions. This work brings to fruition of Dirac fermiology in THz technology, enabling self-powered, low-power, room-temperature, and ultrafast THz detection.
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The knowledge of the thermal expansion coefficient is of crucial importance to prevent the poor performance of devices, especially when these are made up of several layers of different materials, as in the case of 2D heterostructures. Helium atom scattering is a suitable tool for the direct measurement of the surface thermal expansion coefficient of materials. This information can be obtained directly from the position of the helium diffraction peaks, which allows determining the surface lattice constant at different temperatures by merely applying Bragg's law. We present new data for PdTe2 which confirm a trend observed for several 2D dichalcogenides, namely, that the in-plane lattice constant remains unchanged (within experimental error) in the temperature range of interest for applications, which enables setting an upper limit for the lateral thermal expansion coefficients of these materials.
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Recent years have witnessed rapid progresses made in the photoelectric performance of two-dimensional materials represented by graphene, black phosphorus, and transition metal dichalcogenides. Despite significant efforts, a photodetection technique capable for longer wavelength, higher working temperature as well as fast responsivity, is still facing huge challenges due to a lack of best among bandgap, dark current, and absorption ability. Exploring topological materials with nontrivial band transport leads to peculiar properties of quantized phenomena such as chiral anomaly, and magnetic-optical effect, which enables a novel feasibility for an advanced optoelectronic device working at longer wavelength. In this work, the direct generation of photocurrent at low energy terahertz (THz) band at room temperature is implemented in a planar metal-PtTe2 -metal structure. The results show that the THz photodetector based on PtTe2 with bow-tie-type planar contacts possesses a high photoresponsivity (1.6 A W-1 without bias voltage) with a response time less than 20 µs, while the PtTe2 -graphene heterostructure-based detector can reach responsivity above 1.4 kV W-1 and a response time shorter than 9 µs. Remarkably, it is already exploitable for large area imaging applications. These results suggest that topological semimetals such as PtTe2 can be ideal materials for implementation in a high-performing photodetection system at THz band.
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Transition-metal dichalcogenides showing type-II Dirac fermions are emerging as innovative materials for nanoelectronics. However, their excitation spectrum is mostly unexplored yet. By means of high-resolution electron energy loss spectroscopy and density functional theory, here, we identify the collective excitations of type-II Dirac fermions (3D Dirac plasmons) in PtTe_{2} single crystals. The observed plasmon energy in the long-wavelength limit is â¼0.5 eV, which makes PtTe_{2} suitable for near-infrared optoelectronic applications. We also demonstrate that interband transitions between the two Dirac bands in PtTe_{2} give rise to additional excitations at â¼1 and â¼1.4 eV. Our results are crucial to bringing to fruition type-II Dirac semimetals in optoelectronics.
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Transition metal dichalcogenides, by virtue of their two-dimensional structures, could provide the largest active surface for reactions with minimal materials consumed, which has long been pursued in the design of ideal catalysts. Nevertheless, their structurally perfect basal planes are typically inert; their surface defects, such as under-coordinated atoms at the surfaces or edges, can instead serve as catalytically active centers. Here we show a reaction probability > 90 % for adsorbed methanol (CH3OH) on under-coordinated Pt sites at surface Te vacancies, produced with Ar+ bombardment, on layered PtTe2 - approximately 60 % of the methanol decompose to surface intermediates CHxO (x = 2, 3) and 35 % to CHx (x = 1, 2), and an ultimate production of gaseous molecular hydrogen, methane, water and formaldehyde. The characteristic reactivity is attributed to both the triangular positioning and varied degrees of oxidation of the under-coordinated Pt at Te vacancies.
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Charge density waves (CDWs) involved with electronic and phononic subsystems simultaneously are a common quantum state in solid-state physics, especially in low-dimensional materials. However, CDW phase dynamics in various dimensions are yet to be studied, and their phase transition mechanism is currently moot. Here we show that using the distinct temperature evolution of orientation-dependent ultrafast electron and phonon dynamics, different dimensional CDW phases are verified in CuTe. When the temperature decreases, the shrinking of c-axis length accompanied with the appearance of interchain and interlayer interactions causes the quantum fluctuations (QF) of the CDW phase until 220 K. At T < 220 K, the CDWs on the different ab-planes are finally locked with each other in anti-phase to form a CDW phase along the c-axis. This study shows the dimension evolution of CDW phases in one CDW system and their stabilized mechanisms in different temperature regimes.
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Layered van der Waals crystals exhibit unique properties making them attractive for applications in nanoelectronics, optoelectronics, and sensing. The integration of two-dimensional materials with complementary metal-oxide-semiconductor (CMOS) technology requires controllable n- and p-type doping. In this work, we demonstrate the fabrication of vertical p-n heterojunctions made of p-type tin monoselenide (SnSe) and n-type tin diselenide (SnSe2). The p-n heterojunction is created in a single flake by the NH3-plasma-assisted phase transformation from SnSe2 to SnSe. We show that the transformation rate and crystal quality strongly depend on plasma parameters like plasma power, temperature, partial pressure, NH3 flow, and duration of plasma treatment. With optimal plasma parameters, the full transformation of SnSe2 flakes into SnSe is achieved within a few seconds. The crystal quality and the topography of the fabricated SnSe-SnSe2 heterostructures are investigated using micro-Raman spectroscopy and cross-sectional transmission electron microscopy. The formation of a p-n junction is verified by current-voltage measurements.
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Silicon (Si), the dominant semiconductor in microelectronics yet lacking optoelectronic functionalities in UV regions, has been researched extensively to make revolutionary changes. In this study, the inherent drawback of Si on optoelectronic functionalities in UV regions is potentially overcome through heterostructure coupling of delaminated p-type MnPS3, having bulk, multiple-layer, and few-layer features, with n-type Si. By artificially mimicking the architectures of shrubs with unique UV shading phenomena, the revolutionary multiple-layer MnPS3 structures with staggered stacking configurations trigger outstanding UV photosensing performances, displaying an average EQE value of 1.1 × 103%, average photoresponsivity of 3.1 × 102 A/W, average detectivity of 1.9 × 1014 cm Hz1/2W1-, and average on/off ratio of 1.8 × 103 under 365 nm light. To the best of our knowledge, this is the first attempt toward realizing gate-free MnPS3-based UV photodetectors, while all of the photodetection outcomes are better than those of more sophisticated field-effect transistor (FET) designs, which have remarkable impacts on the practicality and functionality of next-generation UV optoelectronics.
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Hydrogen production from methanol decomposition to syngas (H2 + CO) is a promising alternative route for clean energy transition. One major challenge is related to the quest for stable, cost-effective, and selective catalysts operating below 400 °C. We illustrate an investigation of the surface reactivity of a Ni3Sn4 catalyst working at 250 °C, by combining density functional theory, operando X-ray absorption spectroscopy, and high-resolution transmission electron microscopy. We discovered that the catalytic reaction is driven by surface tin-oxide phases, which protects the underlying Ni atoms from irreversible chemical modifications, increasing the catalyst durability. Moreover, we found that Sn content plays a key role in enhancing the H2 selectivity, with respect to secondary products such as CO2. These findings open new perspectives for the engineering of scalable and low-cost catalysts for hydrogen production.
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In recent years, the correlation between the existence of topological electronic states in materials and their catalytic activity has gained increasing attention, due to the exceptional electron conductivity and charge carrier mobility exhibited by quantum materials. However, the physicochemical mechanisms ruling catalysis with quantum materials are not fully understood. Here, we investigate the chemical reactivity, ambient stability, and catalytic activity of the topological nodal-line semimetal AuSn4. Our findings reveal that the surface of AuSn4 is prone to oxidation, resulting in the formation of a nanometric SnO2 skin. This surface oxidation significantly enhances the material's performance as a catalyst for the hydrogen evolution reaction in acidic environments. We demonstrate that the peculiar atomic structure of oxidized AuSn4 enables the migration of hydrogen atoms through the Sn-O layer with a minimal energy barrier of only 0.19 eV. Furthermore, the Volmer step becomes exothermic in the presence of Sn vacancies or tin-oxide skin, as opposed to being hindered in the pristine sample, with energy values of -0.62 and -1.66 eV, respectively, compared to the +0.46 eV energy barrier in the pristine sample. Our model also suggests that oxidized AuSn4 can serve as a catalyst for the hydrogen evolution reaction in alkali media. Additionally, we evaluate the material's suitability for the carbon dioxide reduction reaction, finding that the presence of topologically protected electronic states enhances the migration of hydrogen atoms adsorbed on the catalyst to carbon dioxide.
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Methanol (CH3OH) oxidation offers a promising avenue for transitioning to clean energy, particularly in the field of direct methanol fuel cells (DMFCs). However, the development of efficient and cost-effective catalysts for the methanol oxidation reaction (MOR) remains a critical challenge. Herein, we report the exceptional electrocatalytic activity and stability of Ni3Sn4 toward MOR in acidic media, achieving a performance comparable to that of commercial Pt/C catalysts. Our catalyst design incorporates Earth-abundant Ni and Sn elements, resulting in a material that is 1800 times more cost-effective than Pt/C. Density functional theory (DFT) modeling substantiates our experimental findings, shedding light on the favorable reaction mechanisms and kinetics on the Ni3Sn4 surface. Additionally, the as-synthesized Ni3Sn4 electrocatalyst demonstrates commendable durability, maintaining its electrocatalytic activity even after prolonged exposure to harsh acidic conditions.
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Layered transition metal dichalcogenides (TMDs) are two-dimensional materials exhibiting a variety of unique features with great potential for electronic and optoelectronic applications. The performance of devices fabricated with mono or few-layer TMD materials, nevertheless, is significantly affected by surface defects in the TMD materials. Recent efforts have been focused on delicate control of growth conditions to reduce the defect density, whereas the preparation of a defect-free surface remains challenging. Here, we show a counterintuitive approach to decrease surface defects on layered TMDs: a two-step process including Ar ion bombardment and subsequent annealing. With this approach, the defects, mainly Te vacancies, on the as-cleaved PtTe2 and PdTe2 surfaces were decreased by more than 99%, giving a defect density <1.0 × 1010 cm-2, which cannot be achieved solely with annealing. We also attempt to propose a mechanism behind the processes.
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The zero-magnetic-field nonlinear Hall effect (NLHE) refers to the second-order transverse current induced by an applied alternating electric field; it indicates the topological properties of inversion-symmetry-breaking crystals. Despite several studies on the NLHE induced by the Berry-curvature dipole in Weyl semimetals, the direct current conversion by rectification is limited to very low driving frequencies and cryogenic temperatures. The nonlinear photoresponse generated by the NLHE at room temperature can be useful for numerous applications in communication, sensing, and photodetection across a high bandwidth. In this study, observations of the second-order NLHE in type-II Dirac semimetal CoTe2 under time-reversal symmetry are reported. This is determined by the disorder-induced extrinsic contribution on the broken-inversion-symmetry surface and room-temperature terahertz rectification without the need for semiconductor junctions or bias voltage. It is shown that remarkable photoresponsivity over 0.1 A W-1 , a response time of approximately 710 ns, and a mean noise equivalent power of 1 pW Hz-1/2 can be achieved at room temperature. The results open a new pathway for low-energy photon harvesting via nonlinear rectification induced by the NLHE in strongly spin-orbit-coupled and inversion-symmetry-breaking systems, promising a considerable impact in the field of infrared/terahertz photonics.
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Sc5Rh6Sn18with a cage-type quasiskutterudite crystal lattice and type II superconductivity, with superconducting transition temperatureTc= 4.99 K, was investigated under hydrostatic high-pressure (HP) using electrical transport, synchrotron x-ray diffraction (XRD) and Raman spectroscopy. Our data show that HP enhance the metallic nature andTcof the system.Tcis found to show a continuous increase reaching to 5.24 K at 2.5 GPa. Although the system is metallic in nature, Raman spectroscopy investigations at ambient pressure revealed the presence of three weak modes at 165.97, 219.86 and 230.35 cm-1, mostly related to the rattling atom Sc. The HP-XRD data revealed that the cage structure was stable without any structural phase transition up to â¼7 GPa. The lattice parameters and volume exhibited a smooth decrease without any anomalies as a function of pressure in this pressure range. In particular, a second order Birch-Murnaghan equation of state can describe the pressure dependence of the unit cell volume well, yielding a bulk modulus of â¼97 GPa. HP Raman investigations revealed a linear shift of all the three Raman modes to higher wavenumbers with increasing pressure up to â¼8 GPa. As the pressure enhances the bond overlap, thus inducing more electronic charges into the system, HP-XRD and Raman results may indicate the possibility of obtaining higherTcwith increasing pressures in this pressure range.
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Tin diselenide (SnSe2) is a layered semiconductor with broad application capabilities in the fields of energy storage, photocatalysis, and photodetection. Here, we correlate the physicochemical properties of this van der Waals semiconductor to sensing applications for detecting chemical species (chemosensors) and millimeter waves (terahertz photodetectors) by combining experiments of high-resolution electron energy loss spectroscopy and X-ray photoelectron spectroscopy with density functional theory. The response of the pristine, defective, and oxidized SnSe2 surface towards H2, H2O, H2S, NH3, and NO2 analytes was investigated. Furthermore, the effects of the thickness were assessed for monolayer, bilayer, and bulk samples of SnSe2. The formation of a sub-nanometric SnO2 skin over the SnSe2 surface (self-assembled SnO2/SnSe2 heterostructure) corresponds to a strong adsorption of all analytes. The formation of non-covalent bonds between SnO2 and analytes corresponds to an increase of the magnitude of the transferred charge. The theoretical model nicely fits experimental data on gas response to analytes, validating the SnO2/SnSe2 heterostructure as a suitable playground for sensing of noxious gases, with sensitivities of 0.43, 2.13, 0.11, 1.06 [ppm]-1 for H2, H2S, NH3, and NO2, respectively. The corresponding limit of detection is 5 ppm, 10 ppb, 250 ppb, and 400 ppb for H2, H2S, NH3, and NO2, respectively. Furthermore, SnSe2-based sensors are also suitable for fast large-area imaging applications at room temperature for millimeter waves in the THz range.
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Despite the considerable effort, fast and highly sensitive photodetection is not widely available at the low-photon-energy range (~meV) of the electromagnetic spectrum, owing to the challenging light funneling into small active areas with efficient conversion into an electrical signal. Here, we provide an alternative strategy by efficiently integrating and manipulating at the nanoscale the optoelectronic properties of topological Dirac semimetal PtSe2 and its van der Waals heterostructures. Explicitly, we realize strong plasmonic antenna coupling to semimetal states near the skin-depth regime (λ/104), featuring colossal photoresponse by in-plane symmetry breaking. The observed spontaneous and polarization-sensitive photocurrent are correlated to strong coupling with the nonequilibrium states in PtSe2 Dirac semimetal, yielding efficient light absorption in the photon range below 1.24 meV with responsivity exceeding â¼0.2 A/W and noise-equivalent power (NEP) less than ~38 pW/Hz0.5, as well as superb ambient stability. Present results pave the way to efficient engineering of a topological semimetal for high-speed and low-energy photon harvesting in areas such as biomedical imaging, remote sensing or security applications.
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Here, we discuss the key features of electrocatalysis with mitrofanovite (Pt3Te4), a recently discovered mineral with superb performances in hydrogen evolution reaction. Mitrofanovite is a layered topological metal with spin-polarized topological surface states with potential applications for spintronics. However, mitrofanovite is also an exceptional platform for electrocatalysis, with costs of the electrodes suppressed by 47% owing to the partial replacement of Pt with Te. Remarkably, the Tafel slope in nanostructured mitrofanovite is just 33 mV/dec, while reduced mitrofanovite has the same Tafel slope (36 mV/dec) as state-of-the-art electrodes of pure Pt. Mitrofanovite also affords surface stability and robustness to CO poisoning. Accordingly, these findings pave the way for the advent of mitrofanovite for large-scale hydrogen production.
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Monolayer transition metal dichalcogenides offer an appropriate platform for developing advanced electronics beyond graphene. Similar to two-dimensional molecular frameworks, the electronic properties of such monolayers can be sensitive to perturbations from the surroundings; the implied tunability of electronic structure is of great interest. Using scanning tunneling microscopy/spectroscopy, we demonstrated a bandgap engineering technique in two monolayer materials, MoS2 and PtTe2, with the tunneling current as a control parameter. The bandgap of monolayer MoS2 decreases logarithmically by the increasing tunneling current, indicating an electric-field-induced gap renormalization effect. Monolayer PtTe2, by contrast, exhibits a much stronger gap reduction, and a reversible semiconductor-to-metal transition occurs at a moderate tunneling current. This unusual switching behavior of monolayer PtTe2, not seen in bulk semimetallic PtTe2, can be attributed to its surface electronic structure that can readily couple to the tunneling tip, as demonstrated by theoretical calculations.
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Due to their peculiar quasiparticle excitations, topological metals have high potential for applications in the fields of spintronics, catalysis, and superconductivity. Here, by combining spin- and angle-resolved photoemission spectroscopy, scanning tunneling microscopy/spectroscopy, and density functional theory, we discover surface-termination-dependent topological electronic states in the recently discovered mitrofanovite Pt3Te4. Mitrofanovite crystal is formed by alternating, van der Waals bound layers of Pt2Te2 and PtTe2. Our results demonstrate that mitrofanovite is a topological metal with termination-dependent (i) electronic band structure and (ii) spin texture. Despite their distinct electronic character, both surface terminations are characterized by electronic states exhibiting strong spin polarization with a node at the Γ point and sign reversal across the Γ point, indicating their topological nature and the possibility of realizing two distinct electronic configurations (both of them with topological features) on the surface of the same material.
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The advent of topological semimetals enables the exploitation of symmetry-protected topological phenomena and quantized transport. Here, we present homogeneous rectifiers, converting high-frequency electromagnetic energy into direct current, based on low-energy Dirac fermions of topological semimetal-NiTe2, with state-of-the-art efficiency already in the first implementation. Explicitly, these devices display room-temperature photosensitivity as high as 251 mA W-1 at 0.3 THz in an unbiased mode, with a photocurrent anisotropy ratio of 22, originating from the interplay between the spin-polarized surface and bulk states. Device performances in terms of broadband operation, high dynamic range, as well as their high sensitivity, validate the immense potential and unique advantages associated to the control of nonequilibrium gapless topological states via built-in electric field, electromagnetic polarization and symmetry breaking in topological semimetals. These findings pave the way for the exploitation of topological phase of matter for high-frequency operations in polarization-sensitive sensing, communications and imaging.