Reversible Transition of Semiconducting PtSe2 and Metallic PtTe2 for Scalable All-2D Edge-Contacted FETs.

Two-dimensional (2D) transition metal dichalcogenide (TMD) layers are highly promising as field-effect transistor (FET) channels in the atomic-scale limit. However, accomplishing this superiority in scaled-up FETs remains challenging due to their van der Waals (vdW) bonding nature with respect to conventional metal electrodes. Herein, we report a scalable approach to fabricate centimeter-scale all-2D FET arrays of platinum diselenide (PtSe2) with in-plane platinum ditelluride (PtTe2) edge contacts, mitigating the aforementioned challenges. We realized a reversible transition between semiconducting PtSe2 and metallic PtTe2 via a low-temperature anion exchange reaction compatible with the back-end-of-line (BEOL) processes. All-2D PtSe2 FETs seamlessly edge-contacted with transited metallic PtTe2 exhibited significant performance improvements compared to those with surface-contacted gold electrodes, e.g., an increase of carrier mobility and on/off ratio by over an order of magnitude, achieving a maximum hole mobility of ∼50.30 cm2 V-1 s-1 at room temperature. This study opens up new opportunities toward atomically thin 2D-TMD-based circuitries with extraordinary functionalities.

Boosting the Hydrogen Evolution Reaction Performance of P-Doped PtTe2 Nanocages via Spontaneous Defects Formation.

PtTe2 , a member of the noble metal dichalcogenides (NMDs), has aroused great interest in exploring its behavior in the hydrogen evolution reaction (HER) due to the unique type-II topological semimetallic nature. In this work, a simple template-free hydrothermal method to obtain the phosphorus-doped (P-doped) PtTe2 nanocages with abundant amorphous and crystalline interface (A/C-P-PtTe2 ) is developed. Revealed by density functional theory calculations, the atomic Te vacancies can spontaneously form on the basal planes of PtTe2 by the P doping, which results in the unsaturated Pt atoms exposed as the active sites in the amorphous layer for HER. Owing to the defective structure, the A/C-P-PtTe2 catalysts have the fast Tafel step determined kinetics in HER, which contributes to an ultralow overpotential (η = 28 mV at 10 mA cm-2 ) and a small Tafel slope of 37 mV dec-1 . More importantly, benefiting from the inner stable crystalline P-PtTe2 nanosheets, limited decay of the performance is observed after chronopotentiometry test. This work reveals the important role of the inherent relationship between structure and activity in PtTe2 for HER, which may bring another enlightenment for the design of efficient catalysts based on NMDs in the near future.

Temperature dependent studies on centimeter-scale MoS2and vdW heterostructures.

Transition metal dichalcogenides is an emerging 2D semiconducting material group which has excellent physical properties in the ultimately scaled thickness dimension. Specifically, van der Waals heterostructures hold the great promise in further advancing both the fundamental scientific knowledge and practical technological applications of 2D materials. Although 2D materials have been extensively studied for various sensing applications, temperature sensing still remains relatively unexplored. In this work, we experimentally study the temperature-dependent Raman spectroscopy and electrical conductivity of molybdenum disulfide (MoS2) and its heterostructures with platinum dichalcogenides (PtSe2and PtTe2) to explore their potential to become the next-generation temperature sensor. It is found that the MoS2-PtX2heterostructure shows the great promise as the high-sensitivity temperature sensor.

Thickness-Tunable Synthesis of Ultrathin Type-II Dirac Semimetal PtTe2 Single Crystals and Their Thickness-Dependent Electronic Properties.

The recent discovery of topological semimetals has stimulated extensive research interest due to their unique electronic properties and novel transport properties related to a chiral anomaly. However, the studies to date are largely limited to bulk crystals and exfoliated flakes. Here, we report the controllable synthesis of ultrathin two-dimensional (2D) platinum telluride (PtTe2) nanosheets with tunable thickness and investigate the thickness-dependent electronic properties. We show that PtTe2 nanosheets can be readily grown, using a chemical vapor deposition approach, with a hexagonal or triangular geometry and a lateral dimension of up to 80 µm, and the thickness of the nanosheets can be systematically tailored from over 20 to 1.8 nm by reducing the growth temperature or increasing the flow rate of the carrier gas. X-ray-diffraction, transmission-electron microscopy, and electron-diffraction studies confirm that the resulting 2D nanosheets are high-quality single crystals. Raman spectroscopic studies show characteristics Eg and A1g vibration modes at ∼109 and ∼155 cm-1, with a systematic red shift with increasing nanosheet thickness. Electrical transport studies show the 2D PtTe2 nanosheets display an excellent conductivity up to 2.5 × 106 S m-1 and show strong thickness-tunable electrical properties, with both the conductivity and its temperature dependence varying considerably with the thickness. Moreover, 2D PtTe2 nanosheets show an extraordinary breakdown current density up to 5.7 × 107 A/cm2, the highest breakdown current density achieved in 2D metallic transition-metal dichalcogenides to date.

Silicon Waveguide-Integrated Platinum Telluride Midinfrared Photodetector with High Responsivity and High Speed.

The detection of mid-infrared light, covering a variety of molecular vibrational spectra, is critical for both civil and military purposes. Recent studies have highlighted the potential of two-dimensional topological semimetals for mid-infrared detection due to their advantages, including van der Waals (vdW) stacking and gapless electronic structures. Among them, mid-infrared photodetectors based on type-II Dirac semimetals have been less studied. In this paper, we present a silicon waveguide integrated type-II Dirac semimetal platinum telluride (PtTe2) mid-infrared photodetector, and further improve detection performance by using PtTe2-graphene heterostructure. For the fabricated silicon waveguide-integrated PtTe2 photodetector, with an external bias voltage of -10 mV and an input optical power of 86 nW, the measured responsivity is 2.7 A/W at 2004 nm and a 3 dB bandwidth of 0.6 MHz is realized. For the fabricated silicon waveguide-integrated PtTe2-graphene photodetector, as the external bias voltage and input optical power are 0.5 V and 0.13 µW, a responsivity of 5.5 A/W at 2004 nm and a 3 dB bandwidth of 35 MHz are obtained. An external quantum efficiency of 119% can be achieved at an input optical power of 0.376 µW.

Evaluating the Hydrogen Evolution Reaction Activity of Colloidally Prepared PtSe2 and PtTe2 Catalysts in an Alkaline Medium.

The hydrogen evolution reaction (HER) in alkaline electrolytes using transition metal dichalcogenides is a research area that is not tapped into. Alkaline HER ( 2 H 2 O + 2 e - → H 2 + O H - ${{2H}_{2}O+2{e\ }^{-}\to {H}_{2}+{OH}^{-}{\rm \ }}$ ) is harder to achieve relative to acidic HER ( H + + 2 e - → H 2 ${{H}^{+}+2{e\ }^{-}\to \ {H}_{2}}$ ), this is attributed to the additional water dissociation step that occurs in basic HER to generate H+ ions. In fact, for most catalysts, their HER activity decreases tremendously when the electrolyte is changed from acidic to basic conditions. Platinum dichalcogenides, PtX2 (X=S, Se, Te), are an interesting member of transition metal dichalcogenides (TMDs) as these show an immense hybridization of the Pt d orbitals and chalcogen p orbitals because of closely correlated orbital energies. The trend in electronic properties of these materials changes drastically as the chalcogen is changed, with PtS2 reported to exhibit semi-conductor properties, PtSe2 is semi-metallic or semi-conductive, depending on the number of layers, while PtTe2 is metallic. The effect of varying the chalcogen atom on the HER activity of Pt dichalcogenides will be studied. Pt dichalcogenides have previously been prepared by direct high-temperature chalcogen deposition of Pt substrate and evaluated as electrocatalysts for HER in H2SO4. The previously employed synthesis procedures for PtX2 limit these compounds' mass production and post-synthesis treatment. In this study, we demonstrated, for the first time the preparation of PtSe2 and PtTe2 by colloidal synthesis. Colloidal synthesis offers the possibility of large-scale synthesis of materials and affords the employment of the colloids at various concentrations in ink formulation. The electrochemical HER results acquired in 1 M KOH indicate that PtTe2 has a superior HER catalytic activity to PtSe2. A potential of 108 mV for PtTe2 and 161 mV for PtSe2 is required to produce a current density of -10 mA cm-2 from these catalysts. PtTe2 has a low Tafel slope of 79 mVdec-1, indicating faster HER kinetics on PtTe2. Nonetheless, the stability of these catalysts in an alkaline medium needs to be improved to render them excellent HER electrocatalysts.

Terahertz and Infrared Plasmon Polaritons in PtTe2 Type-II Dirac Topological Semimetal.

Surface plasmon polaritons (SPPs) are electromagnetic excitations existing at the interface between a metal and a dielectric. SPPs provide a promising path in nanophotonic devices for light manipulation at the micro and nanoscale with applications in optoelectronics, biomedicine, and energy harvesting. Recently, SPPs are extended to unconventional materials like graphene, transparent oxides, superconductors, and topological systems characterized by linearly dispersive electronic bands. In this respect, 3D Dirac and Weyl semimetals offer a promising frontier for infrared (IR) and terahertz (THz) radiation tuning by topologically-protected SPPs. In this work, the THz-IR optical response of platinum ditelluride (PtTe2) type-II Dirac topological semimetal films grown on Si substrates is investigated. SPPs generated on microscale ribbon arrays of PtTe2 are detected in the far-field limit, finding an excellent agreement among measurements, theoretical models, and electromagnetic simulation data. The far-field measurements are further supported by near-field IR data which indicate a strong electric field enhancement due to the SPP excitation near the ribbon edges. The present findings indicate that the PtTe2 ribbon array appears an ideal active layout for geometrically tunable SPPs thus inspiring a new fashion of optically tunable materials in the technologically demanding THz and IR spectrum.

Uncooled Broadband Photodetection via Light Trapping in Conformal PtTe2-Silicon Nanopillar Heterostructures.

Dirac semimetals have demonstrated significant attraction in the field of optoelectronics due to their unique bandgap structure and high carrier mobility. Combining them with classical semiconductor materials to form heterojunctions enables broadband optoelectronic conversion at room temperature. However, the low light absorption of layered Dirac semimetals substantially limits the device's responsivity in the infrared band. Herein, a three-dimensional (3D) heterostructure, composed of silicon nanopillars (SiNPs) and a conformal PtTe2 film, is proposed and demonstrated to enhance the photoresponsivity for uncooled broadband detection. The light trapping effect in the 3D heterostructure efficiently promotes the interaction between light and PtTe2, while also enhancing the light absorption efficiency of silicon, which enables the enhancement of the device responsivity across a broadband spectrum. Experimentally, the PtTe2-SiNPs heterojunction device demonstrates excellent photoelectric conversion behavior across the visible, near-infrared, and long-wave infrared (LWIR) bands, with its responsivity demonstrating an order-of-magnitude improvement compared to the counterparts with planar silicon heterojunctions. Under 11 µm laser irradiation, the noise equivalent power (NEP) can reach 1.76 nW·Hz-1/2 (@1 kHz). These findings offer a strategic approach to the design and fabrication of high-performance broadband photodetectors based on Dirac semimetals.

High Mobility Transistors and Flexible Optical Synapses Enabled by Wafer-Scale Chemical Transformation of Pt-Based 2D Layers.

Electronic devices employing two-dimensional (2D) van der Waals (vdW) transition-metal dichalcogenide (TMD) layers as semiconducting channels often exhibit limited performance (e.g., low carrier mobility), in part, due to their high contact resistances caused by interfacing non-vdW three-dimensional (3D) metal electrodes. Herein, we report that this intrinsic contact issue can be efficiently mitigated by forming the 2D/2D in-plane junctions of 2D semiconductor channels seamlessly interfaced with 2D metal electrodes. For this, we demonstrated the selectively patterned conversion of semiconducting 2D PtSe2 (channels) to metallic 2D PtTe2 (electrodes) layers by employing a wafer-scale low-temperature chemical vapor deposition (CVD) process. We investigated a variety of field-effect transistors (FETs) employing wafer-scale CVD-2D PtSe2/2D PtTe2 heterolayers and identified that silicon dioxide (SiO2) top-gated FETs exhibited an extremely high hole mobility of ∼120 cm2 V-1 s-1 at room temperature, significantly surpassing performances with previous wafer-scale 2D PtSe2-based FETs. The low-temperature nature of the CVD method further allowed for the direct fabrication of wafer-scale arrays of 2D PtSe2/2D PtTe2 heterolayers on polyamide (PI) substrates, which intrinsically displayed optical pulse-induced artificial synaptic behaviors. This study is believed to vastly broaden the applicability of 2D TMD layers for next-generation, high-performance electronic devices with unconventional functionalities.

Anomalous displacement reaction for synthesizing above-room-temperature and air-stable vdW ferromagnet PtTe2Ge1/3.

Emerging van der Waals (vdW) magnets provide a paradise for the exploration of magnetism in the ultimate two-dimensional (2D) limit, and the construction of integrated spintronic devices, and have become a research frontier in the field of low-dimensional materials. To date, prototypical vdW magnets based on metals of the first transition series (e.g. V, Cr, Mn and Fe) and chalcogen elements suffer from rapid oxidation restricted by the Hard-Soft-Acid-Base principle, as well as low Curie temperatures (T C), which has become a generally admitted challenge in 2D spintronics. Here, starting from air-unstable Cr2Ge2Te6 vdW thin flakes, we synthesize Ge-embedded PtTe2 (namely PtTe2Ge1/3) with superior air stability, through the displacement reaction in the Cr2Ge2Te6/Pt bilayer. In this process, the anomalous substitution of Cr with Pt in the thermal diffusion is inverse to the metal activity order, which can be attributed to the compatibility between soft-acid (Pt) and soft-base (Te) elements. Meanwhile, the layered uniform insertion of Ge unbalances Pt-Te bonds and introduces long-range ordered ferromagnetism with perpendicular magnetic anisotropy and a Curie temperature above room temperature. Our work demonstrates the anti-metal-activity-order reaction tendency unique in 2D transition-metal magnets and boosts progress towards practical 2D spintronics.

Triggering Pt Active Sites in Basal Plane of Van der Waals PtTe2 Materials by Amorphization Engineering for Hydrogen Evolution.

Exposing active sites and optimizing their binding strength to reaction intermediates are two essential strategies to significantly improve the catalytic performance of 2D materials. However, pursuing an efficient way to achieve these goals simultaneously remains a considerable challenge. Here, using 2D PtTe2 van der Waals material with a well-defined crystal structure and atomically thin thickness as a model catalyst, it is observed that a moderate calcination strategy can promote the structural transformation of 2D crystal PtTe2 nanosheets (c-PtTe2 NSs) into oxygen-doped 2D amorphous PtTe2 NSs (a-PtTe2 NSs). The experimental and theoretical investigations cooperatively reveal that oxygen dopants can break the inherent Pt-Te covalent bond in c-PtTe2 NSs, thereby triggering the reconfiguration of interlayer Pt atoms and exposing them thoroughly. Meanwhile, the structural transformation can effectively tailor the electronic properties (e.g., the density of state near the Fermi level, d-band center, and conductivity) of Pt active sites via the hybridization of Pt 5d orbitals and O 2p orbitals. As a result, a-PtTe2 NSs with large amounts of exposed Pt active sites and optimized binding strength to hydrogen intermediates exhibit excellent activity and stability in hydrogen evolution reaction.

Multiwavelength Optoelectronic Synapse with 2D Materials for Mixed-Color Pattern Recognition.

Neuromorphic visual systems emulating biological retina functionalities have enormous potential for in-sensor computing, with prospects of making artificial intelligence ubiquitous. Conventionally, visual information is captured by an image sensor, stored by memory units, and eventually processed by the machine learning algorithm. Here, we present an optoelectronic synapse device with multifunctional integration of all the processes required for real time object identification. Ultraviolet-visible wavelength-sensitive MoS2 FET channel with infrared sensitive PtTe2/Si gate electrode enables the device to sense, store, and process optical data for a wide range of the electromagnetic spectrum, while maintaining a low dark current. The device exhibits optical stimulation-controlled short-term and long-term potentiation, electrically driven long-term depression, synaptic weight update for multiple wavelengths of light ranging from 300 nm in ultraviolet to 2 µm in infrared. An artificial neural network developed using the extracted weight update parameters of the device can be trained to identify both single wavelength and mixed wavelength patterns. This work demonstrates a device that could potentially be used for realizing a multiwavelength neuromorphic visual system for pattern recognition and object identification.

Mid-Infrared Photodetection of Type-II Dirac Semimetal 1T-PtTe2 Grown by Molecular Beam Epitaxy.

Mid-infrared (MIR) photodetection is of significance in civil and military applications because it shows superiority in absorbing the vibration of various molecules and covering atmospheric transmission windows. Recently, the PtTe2, a typical type-II Dirac semimetal, has come under the spotlight due to its unique photodetection sensibility in the MIR region and robust stability in the atmosphere. Here, the high-quality and large-scale 1T-PtTe2 thin films with air stability were grown by molecular beam epitaxy. Broadband photoresponse of the photodetectors of PtTe2 from 420 nm to 10.7 µm shows high responsivity and detectivity of 0.2 mA W-1 and 2.6 × 107 Jones at 10.7 µm and 1.6 mA W-1 and 2.2 × 108 Jones at 4.7 µm under the atmosphere, respectively. Moreover, the photodetectors exhibit high sensitivity in visible and near-infrared regions (8.2 mA W-1 at 650 nm and 15.6 mA W-1 at 960 nm). The power- and polarization-dependent photoresponse measurements reveal the linear relationship of power photoresponse and obvious anisotropic photoresponse (the ratio of anisotropy ellipse is 8.3 at 10.7 µm), respectively. These results suggest that the PtTe2 could be expected to be an advanced photodetection material for polarization angle-sensitive detection, infrared imaging, and photodetection from the visible to MIR range.

Electrochemically Exfoliated Platinum Dichalcogenide Atomic Layers for High-Performance Air-Stable Infrared Photodetectors.

Platinum dichalcogenide (PtX2), an emergent group-10 transition metal dichalcogenide (TMD) has shown great potential in infrared photonic and optoelectronic applications due to its layer-dependent electronic structure with potentially suitable bandgap. However, a scalable synthesis of PtSe2 and PtTe2 atomic layers with controlled thickness still represents a major challenge in this field because of the strong interlayer interactions. Herein, we develop a facile cathodic exfoliation approach for the synthesis of solution-processable high-quality PtSe2 and PtTe2 atomic layers for high-performance infrared (IR) photodetection. As-exfoliated PtSe2 and PtTe2 bilayer exhibit an excellent photoresponsivity of 72 and 1620 mA W-1 at zero gate voltage under a 1540 nm laser illumination, respectively, approximately several orders of magnitude higher than that of the majority of IR photodetectors based on graphene, TMDs, and black phosphorus. In addition, our PtSe2 and PtTe2 bilayer device also shows a decent specific detectivity of beyond 109 Jones with remarkable air-stability (>several months), outperforming the mechanically exfoliated counterparts under the laser illumination with a similar wavelength. Moreover, a high yield of PtSe2 and PtTe2 atomic layers dispersed in solution also allows for a facile fabrication of air-stable wafer-scale IR photodetector. This work demonstrates a new route for the synthesis of solution-processable layered materials with the narrow bandgap for the infrared optoelectronic applications.

Scalable Van der Waals Two-Dimensional PtTe2 Layers Integrated onto Silicon for Efficient Near-to-Mid Infrared Photodetection.

In recent years, there has been increasing interest in leveraging two-dimensional (2D) van der Waals (vdW) crystals for infrared (IR) photodetection, exploiting their unusual optoelectrical properties. Some 2D vdW materials with small band gap energies such as graphene and black phosphorus have been explored as stand-alone IR responsive layers in photodetectors. However, the devices incorporating these IR-sensitive 2D layers often exhibited poor performances owing to their preparation issues such as limited scalability and air instability. Herein, we explored wafer-scale 2D platinum ditelluride (PtTe2) layers for near-to-mid IR photodetection by directly growing them onto silicon (Si) wafers. 2D PtTe2/Si heterojunctions exhibited wavelength- and intensity-dependent high photocurrents in a spectral range of ∼1-7 µm, significantly outperforming stand-alone 2D PtTe2 layers. The observed superiority is attributed to their excellent Schottky junction characteristics accompanying suppressed carrier recombination as well as optical absorbance competition between 2D PtTe2 layers and Si. The direct and scalable growth of 2D PtTe2 layers was further extended to demonstrate mechanically flexible IR photodetectors.

Wafer-Scale Growth of 2D PtTe2 with Layer Orientation Tunable High Electrical Conductivity and Superior Hydrophobicity.

Platinum ditelluride (PtTe2) is an emerging semimetallic two-dimensional (2D) transition-metal dichalcogenide (TMDC) crystal with intriguing band structures and unusual topological properties. Despite much devoted efforts, scalable and controllable synthesis of large-area 2D PtTe2 with well-defined layer orientation has not been established, leaving its projected structure-property relationship largely unclarified. Herein, we report a scalable low-temperature growth of 2D PtTe2 layers on an area greater than a few square centimeters by reacting Pt thin films of controlled thickness with vaporized tellurium at 400 °C. We systematically investigated their thickness-dependent 2D layer orientation as well as its correlated electrical conductivity and surface property. We unveil that 2D PtTe2 layers undergo three distinct growth mode transitions, i.e., horizontally aligned holey layers, continuous layer-by-layer lateral growth, and horizontal-to-vertical layer transition. This growth transition is a consequence of competing thermodynamic and kinetic factors dictated by accumulating internal strain, analogous to the transition of Frank-van der Merwe (FM) to Stranski-Krastanov (SK) growth in epitaxial thin-film models. The exclusive role of the strain on dictating 2D layer orientation has been quantitatively verified by the transmission electron microscopy (TEM) strain mapping analysis. These centimeter-scale 2D PtTe2 layers exhibit layer orientation tunable metallic transports yielding the highest value of ∼1.7 × 106 S/m at a certain critical thickness, supported by a combined verification of density functional theory (DFT) and electrical measurements. Moreover, they show intrinsically high hydrophobicity manifested by the water contact angle (WCA) value up to ∼117°, which is the highest among all reported 2D TMDCs of comparable dimensions and geometries. Accordingly, this study confirms the high material quality of these emerging large-area 2D PtTe2 layers, projecting vast opportunities employing their tunable layer morphology and semimetallic properties from investigations of novel quantum phenomena to applications in electrocatalysis.

Crossover from 2D metal to 3D Dirac semimetal in metallic PtTe2 films with local Rashba effect.

PtTe2 and PtSe2 with trigonal structure have attracted extensive research interests since the discovery of type-II Dirac fermions in the bulk crystals. The evolution of the electronic structure from bulk 3D topological semimetal to 2D atomic thin films is an important scientific question. While a transition from 3D type-II Dirac semimetal in the bulk to 2D semiconductor in monolayer (ML) film has been reported for PtSe2, so far the evolution of electronic structure of atomically thin PtTe2 films still remains unexplored. Here we report a systematic angle-resolved photoemission spectroscopy (ARPES) study of the electronic structure of high quality PtTe2 films grown by molecular beam epitaxy with thickness from 2 ML to 6 ML. ARPES measurements show that PtTe2 films still remain metallic even down to 2 ML thickness, which is in sharp contrast to the semiconducting property of few layer PtSe2 films. Moreover, a transition from 2D metal to 3D type-II Dirac semimetal occurs at film thickness of 4-6 ML. In addition, Spin-ARPES measurements reveal helical spin textures induced by local Rashba effect in the bulk PtTe2 crystal, suggesting that similar hidden spin is also expected in few monolayer PtTe2 films. Our work reveals the transition from 2D metal to 3D topological semimetal and provides new opportunities for investigating metallic 2D films with local Rashba effect.