WSe2 Single Crystals Research Articles

Flexible p-Type WSe2 Transistors with Alumina Top-Gate Dielectric.

Tungsten diselenide (WSe2) field-effect transistors (FETs) are promising for emerging electronics because of their tunable polarity, enabling complementary transistor technology, and their suitability for flexible electronics through material transfer. In this work, we demonstrate flexible p-type WSe2 FETs with absolute drain currents |ID| up to 7 μA/μm. We achieve this by fabricating flexible top-gated FETs with a combined WSe2 and metal contact transfer approach using WSe2 grown by metal-organic chemical vapor deposition on sapphire. Despite moderate WSe2 crystal grain size, our devices show similar or higher |ID| and ID on/off ratio (∼105) compared to most devices with exfoliated single-crystal WSe2 from the literature. We analyze charge trapping in our devices using pulsed and bias stress measurements. Notably, the high |ID| values are preserved during pulsing, where charge trapping is minimized. Overall, we demonstrate a fabrication approach advantageous for high drain currents in flexible 2D transistors.

Synthesis of 2D single crystal WSe2/C nanostripe array as anode material for Na-ion batteries

2D single crystal WSe2 nanostripe array and its carbon composite WSe2/C material were synthesized. In each piece of the material, WSe2 nanostripes with a uniform width of 7–8 nm were parallelly arranged with a fixed gap of 3.7 nm to form a 2D sheet-like morphology. The entire piece of one WSe2 sheet is a single crystal WSe2 with its c-axis perpendicular to the sheet plane, making all the side surface of the nanostripes fully covered with crystal edge sites. After coating with carbon, 2D WSe2/C composite material displays much better electrochemical properties than the non-porous WSe2 particles, which suggests that 2D WSe2/C nanostripe array may be a promising candidate for reversible storage of Na-ion batteries.

Low-Temperature Raman Investigations and Photoresponse of a Detector Based on High-Quality WSe2 Crystals

The WSe2 single crystals were grown by a high-yield vapor-phase synthesis technique. The grown crystals have 2H-hexagonal lattice structure with a P63/mmc space group. Excitonic resonances A′ and B′ are observed due to splitting of the ground and excited states of A and B transitions, respectively, resulting from inter- and intralayer perturbation of the d-electron band of the W atom by p orbitals of the Se atom. Raman spectroscopy over the temperature range of 77 to 298 K shows that the A1g and E2g modes exhibit a linear dependence on temperature. The shifting of frequency from 251.46 to 253.71 cm–1 follows the first-order temperature coefficient of 9.8 × 10–3 cm–1 K–1. The width of the Raman peaks at half maxima also exhibits a systematic linear dependence on temperature. On the basis of the semiquantitative model, it is stated that the thermal expansion contribution mainly dominates in WSe2 single crystals. Subsequently, the photodetector was analyzed in the temperature range of 200 to 298 K under periodic exposure of 670 nm light of 5 mW/cm2 power intensity. The device exhibits a photoresponsivity of 43.92 mA/W and a response time of 0.85 s.

Electronic structure of exfoliated millimeter-sized monolayer WSe2 on silicon wafer

The monolayer WSe2 is interesting and important for future application in nanoelectronics, spintronics and valleytronics devices, because it has the largest spin splitting and longest valley coherence time among all the known monolayer transition-metal dichalcogenides (TMDs). To obtain the large-area monolayer TMDs' crystal is the first step to manufacture scalable and high-performance electronic devices. In this letter, we have successfully fabricated millimeter-sized monolayer WSe2 single crystals with very high quality, based on our improved mechanical exfoliation method. With such superior samples, using standard high resolution angle-resolved photoemission spectroscopy, we did comprehensive electronic band structure measurements on our monolayer WSe2. The overall band features point it to be a 1.2eV direct band gap semiconductor. Its spin-splitting of the valence band at K point is found as 460 meV, which is 30 meV less than the corresponding band splitting in its bulk counterpart. The effective hole masses of valence bands are determined as 2.344 me at Gamma, and 0.529 me as well as 0.532 me at K for the upper and lower branch of splitting bands, respectively. And screening effect from substrate is shown to substantially impact on the electronic properties. Our results provide important insights into band structure engineering in monolayer TMDs. Our monolayer WSe2 crystals may constitute a valuable device platform.

High Coercivity and Magnetization in WSe2 by Codoping Co and Nb.

Introducing ferromagnetism in transition metal dichalcogenides has attracted lots of attention due to the possible applications in spintronics devices. Generally, single magnetic element doping is used to introduce magnetism. However, mostly, weak ferromagnetism is observed. In this work, codoping of two kinds of transition metals (Nb and Co) into WSe2 is used to study its magnetic properties. In detail, single crystal WSe2 is codoped with 4 at% Co and various concentrations of Nb by employing the physical ion implantation method. Raman, X-ray diffraction and X-ray photoelectron spectroscopy results reveal the effective substitutional doping of implanted elements (Co and Nb). Magnetic measurements illustrate that both un-doped and 4 at% Co doped WSe2 show weak ferromagnetism whereas magnetization is strongly enhanced when Co and Nb are codoped into WSe2 . The magnetization is comparable with a ferromagnet, which may be attributed to Co, Nb doping and defects. In addition, a large coercivity of ≈1.2 kOe is observed in the 1 at% Nb-4 at% Co codoped WSe2 sample, which may be ascribed to the combined effect of doping-induced stress, defect-dictated pinning and anisotropy of NbSe bond owing to the charge transfer between Nb and Se ions.

Growth and application of WSe2 single crystal synthesized by DVT in thin film hetero-junction photodetector

Tungsten di-selenide (WSe2) belonging to the family of layered transition metal di-chalcogenides (TMDCs) is at present widely used in optoelectronic devices due to their adequate energy band gap suitable for photosensing applications. In the present investigation, WSe2 single crystals are grown by direct vapor transport (DVT) technique in a dual zone horizontal furnace maintaining a temperature difference of 50 K between source zone (SZ) and growth zone (GZ). The crystals thus obtained were thin, shiny and with an average thickness of 30 mm. The surface topography of crystals studied by optical microscope revealed hexagonal spirals on the crystal surface which seemed to arise due to screw dislocation defect. The structural properties of the as grown crystals studied by powder X-ray diffraction (XRD) elucidated good crystallinity, hexagonal structure and confirmed the orientation of crystals along crystallographic c-axis. P-type semiconductor nature of the crystals was affirmed by thermoelectric power (TEP) measurement. Optical and vibrational properties of the grown crystals were studied by UV–Visible, photoluminescence (PL) and Raman spectroscopy. An optical direct band gap of 1.41 eV was determined for the crystals which were micromechanically exfoliated upto few layers. The excitonic mechanism of the grown WSe2 crystal was explained by PL spectroscopy. The results of Raman spectroscopy disclosed A1g and E2g vibrational modes present in the crystals. The current–voltage characteristics of nSnSe/pWSe2 hetero-structure studied using Keithley 2400 SMU showed rectification behavior at low bias voltage in dark and illuminated conditions. The diode parameters like ideality factor and barrier potential were determined to be 2.54 and 0.4 eV, respectively, by following conventional lnI–V method. The photodetection properties of the fabricated device were studied using a Laser source (670 nm) having an intensity of 3 mWcm−2at different bias voltage ranging from 0.3 V to 3 V. Parameters such as responsivity, detectivity and external quantum efficiency (EQE) were calculated to substantiate the excellent detection properties shown by the prepared photodetector using time resolved pulsed photoresponse. Value of responsivity and EQE increased from 42.22 mA W−1 to 533.77 mA W−1 and 7% to 95%, respectively, with increase in bias voltage from 0.3 V to 3 V. Also, detectivity values were found to be of the order of 107 Jones.

A Double Support Layer for Facile Clean Transfer of Two-Dimensional Materials for High-Performance Electronic and Optoelectronic Devices.

Clean transfer of two-dimensional (2D) materials grown by chemical vapor deposition is critical for their application in electronics and optoelectronics. Although rosin can be used as a support layer for the clean transfer of graphene grown on Cu, it has not been usable for the transfer of 2D materials grown on noble metals or for large-area transfer. Here, we report a poly(methyl methacrylate) (PMMA)/rosin double support layer that enables facile ultraclean transfer of large-area 2D materials grown on different metals. The bottom rosin layer ensures clean transfer, whereas the top PMMA layer not only screens the rosin from the transfer conditions but also improves the strength of the transfer layer to make the transfer easier and more robust. We demonstrate the transfer of monolayer WSe2 and WS2 single crystals grown on Au as well as large-area graphene films grown on Cu. As a result of the clean surface, the transferred WSe2 retains the intrinsic optical properties of the as-grown sample. Moreover, it does not require annealing to form good ohmic contacts with metal electrodes, enabling high-performance field effect transistors with mobility and ON/OFF ratio ∼10 times higher than those made by PMMA-transferred WSe2. The ultraclean graphene film is found to be a good anode for flexible organic photovoltaic cells with a high power conversion efficiency of ∼6.4% achieved.

An approach to high-throughput growth of submillimeter transition metal dichalcogenide single crystals.

High-throughput growth of large size transition metal dichalcogenide (TMD) single crystals is an important challenge for their applications in the next generation electronic and optoelectronic integration devices. Here we report the high-throughput growth of submillimeter monolayer TMD single crystals by two-stage space confined chemical vapor deposition, where the nucleation density of TMD crystals is significantly decreased for the growth of large size monolayer crystals by the space confinement effect. Moreover, high-throughput growth of submillimeter TMD crystals is also achieved by stacking the substrates along the perpendicular direction to the flow of the reaction gases. The mobilities of the TMD materials produced in this way are up to 1.2, 17.0 and 25.0 cm2 (V s)-1 for monolayer WS2, WSe2 and MoS2 single crystals, respectively. The results demonstrate that two-stage space confined growth is a highly promising method for high-throughput fabrication of high-quality submillimeter monolayer TMD single crystals, which will pave a new pathway to large-scale production of TMD-based electronic and optoelectronic devices.

Removing Defects in WSe2 via Surface Oxidation and Etching to Improve Solar Conversion Performance

Layered metal dichalcogenide materials (MX2) have great potential for solar energy conversion. However, as-grown MX2 materials often contain edge and terrace defects that degrade semiconducting properties and hinder their solar performance. Herein, we demonstrate a simple approach to removing surface defects and improving the solar performance by using UV-generated ozone to oxidize the surface of WSe2 nanoplates and single crystals, followed by a simple soak in aqueous solutions to remove the oxide. Structural characterizations reveal that defective edges and basal plane defect sites are selectively oxidized and subsequently etched, and the ratio of the nonstoichiometric WSex species is reduced. After this treatment, p-type WSe2 single crystals show increased electron accumulation on the surface and significantly enhanced photoelectrochemical solar conversion efficiency. These results and insights will be useful in the improvement and utilization of layered MX2 materials based on both Se and S for solar energy conversion and other device applications.

Ultimate limit in size and performance of WSe2 vertical diodes

Precise doping-profile engineering in van der Waals heterostructures is a key element to promote optimal device performance in various electrical and optical applications with two-dimensional layered materials. Here, we report tungsten diselenide- (WSe2) based pure vertical diodes with atomically defined p-, i- and n-channel regions. Externally modulated p- and n-doped layers are respectively formed on the bottom and the top facets of WSe2 single crystals by direct evaporations of high and low work-function metals platinum and gadolinium, thus forming atomically sharp p–i–n heterojunctions in the homogeneous WSe2 layers. As the number of layers increases, charge transport through the vertical WSe2 p–i–n heterojunctions is characterized by a series of quantum tunneling events; direct tunneling, Fowler–Nordheim tunneling, and Schottky emission tunneling. With optimally selected WSe2 thickness, our vertical heterojunctions show superb diode characteristics of an unprecedentedly high current density and low turn-on voltages while maintaining good current rectification.

Chemical vapor deposition growth of sub-centimeter single crystal WSe2 monolayer by NaCl-assistant

Monolayer WSe2 exhibits unique optical and electronic properties, showing great potential applications in functional integrated devices, such as electronic devices and optoelectronics. Understanding the growth behavior and process are the key points for the salt-assisted growth of large domain WSe2 monolayers, it is also very important for its further application in on-chip laser and opto-devices. Here, we report a NaCl-assistant method for controlled growth of single crystal monolayer WSe2 with a domain size up to 0.57 mm on SiO2/Si substrate. Atomic-resolution scanning transmission electron microscopy reveals that the Se1 and Se2 vacancy point defects are the main defect type of those materials. The growth behavior of the salt-assisted method have been systemly investigated. The loading mass of NaCl powder prefers to be less with the controllable vapor process. The flow of hydrogen gas was also preferred to be suitable with a weak etching effect. The morphology of monolayer WSe2 shows a sensitive temperature dependence evolution with the growth temperature increasing. A screw dislocation growth behavior with 15° angle is also observed with the NaCl-assistant method. The results provide a deep understanding of the mechanism for the NaCl-assistant growth of large size monolayer WSe2.

Magnetic properties of Co doped WSe2 by implantation

In this research, the potential of transition metal doped 2D WSe2 as a 2D dilute magnetic semiconductor has been explored experimentally. Single crystal WSe2 was doped with Co with various concentrations by a physical implantation method. Raman and X-ray diffraction spectra indicate the effective doping of Co in the substitutional sites. Secondary ion mass spectrometry results demonstrate the Gaussian distribution of Co in WSe2. Magnetic measurements show that both un-doped WSe2 and WSe2 doped with Co exhibit weak ferromagnetism at room temperature. The magnetization is increased with Co doping compared to un-doped WSe2 and it tends to be enhanced with increasing doping concentration.

Ultrafast Growth of High-Quality Monolayer WSe2 on Au.

The ultrafast growth of high-quality uniform monolayer WSe2 is reported with a growth rate of ≈26 µm s-1 by chemical vapor deposition on reusable Au substrate, which is ≈2-3 orders of magnitude faster than those of most 2D transition metal dichalcogenides grown on nonmetal substrates. Such ultrafast growth allows for the fabrication of millimeter-size single-crystal WSe2 domains in ≈30 s and large-area continuous films in ≈60 s. Importantly, the ultrafast grown WSe2 shows excellent crystal quality and extraordinary electrical performance comparable to those of the mechanically exfoliated samples, with a high mobility up to ≈143 cm2 V-1 s-1 and ON/OFF ratio up to 9 × 106 at room temperature. Density functional theory calculations reveal that the ultrafast growth of WSe2 is due to the small energy barriers and exothermic characteristic for the diffusion and attachment of W and Se on the edges of WSe2 on Au substrate.

Pressure-induced iso-structural phase transition and metallization in WSe2

We present in situ high-pressure synchrotron X-ray diffraction (XRD) and Raman spectroscopy study, and electrical transport measurement of single crystal WSe2 in diamond anvil cells with pressures up to 54.0–62.8 GPa. The XRD and Raman results show that the phase undergoes a pressure-induced iso-structural transition via layer sliding, beginning at 28.5 GPa and not being completed up to around 60 GPa. The Raman data also reveals a dominant role of the in-plane strain over the out-of plane compression in helping achieve the transition. Consistently, the electrical transport experiments down to 1.8 K reveals a pressure-induced metallization for WSe2 through a broad pressure range of 28.2–61.7 GPa, where a mixed semiconducting and metallic feature is observed due to the coexisting low- and high-pressure structures.

Growth and characterization of WSe2 single crystals using TeCl4 as transport agent

The growth of WSe2 single crystals, using TeCl4 as transport agent was performed successfully from slowly cooled polycrystalline powders as precursors. The resulting single crystals were characterized by X-ray diffraction (XRD) and their surfaces examined by scanning electron microscopy (SEM) presented fewer defects than single crystals prepared from air-quenched polycrystalline powders. Energy Dispersive X-ray microanalysis (EDX), inductively coupled plasma (ICP) spectroscopy and X-ray photoelectron spectroscopy (XPS) revealed that the single crystals are homogeneous and stoichiometric. Electrical conductivity and photocurrent measurements have confirmed the semiconducting character of the single crystals and a photocurrent of 75 mA cm−2 has been reached. In addition, single crystals with areas in the 25–100mm2 range can be obtained under the reported growth conditions.

The symmetry-resolved electronic structure of 2H-WSe2(0 0 0 1)

The orbital symmetry of the band structure of 2H-WSe2(0 0 0 1) has been investigated by means of angle-resolved photoelectron spectroscopy (ARPES) and density functional theory (DFT). The WSe2(0 0 0 1) experimental band structure is found, by ARPES, to be significantly different for states of even and odd reflection parities along both the – and – lines, in good agreement with results obtained from DFT. The light polarization dependence of the photoemission intensities from the top of the valence band for bulk WSe2(0 0 0 1) is explained by the dominance of W 5 states around the -point and W 5dxy states around the -point, thus dominated, respectively, by states of even and odd symmetry, with respect to the – line. The splitting of the topmost valence band at , due to spin–orbit coupling, is measured to be 0.49 ± 0.01 eV, in agreement with the 0.48 eV value from DFT, and prior measurements for the bulk single crystal WSe2(0 0 0 1), albeit slightly smaller than the 0.513 ± 0.01 eV observed for monolayer WSe2.

Synthesis of Millimeter‐Scale Transition Metal Dichalcogenides Single Crystals

The emergence of semiconducting transition metal dichalcogenide (TMD) atomic layers has opened up unprecedented opportunities in atomically thin electronics. Yet the scalable growth of TMD layers with large grain sizes and uniformity has remained very challenging. Here is reported a simple, scalable chemical vapor deposition approach for the growth of MoSe2 layers is reported, in which the nucleation density can be reduced from 105 to 25 nuclei cm−2, leading to millimeter‐scale MoSe2 single crystals as well as continuous macrocrystalline films with millimeter size grains. The selective growth of monolayers and multilayered MoSe2 films with well‐defined stacking orientation can also be controlled via tuning the growth temperature. In addition, periodic defects, such as nanoscale triangular holes, can be engineered into these layers by controlling the growth conditions. The low density of grain boundaries in the films results in high average mobilities, around ≈42 cm2 V−1 s−1, for back‐gated MoSe2 transistors. This generic synthesis approach is also demonstrated for other TMD layers such as millimeter‐scale WSe2 single crystals.

Gate-Optimized Thermoelectric Power Factor in Ultrathin WSe2 Single Crystals.

We report an electric field tuning of the thermopower in ultrathin WSe2 single crystals over a wide range of carrier concentration by using electric double-layer (EDL) technique. We succeeded in the optimization of power factor not only in the hole but also in the electron side, which has never been chemically accessed. The maximized values of power factor are one-order larger than that obtained by changing chemical composition, reflecting the clean nature of electrostatic doping.

Optical analysis for few TMDC materials

The transition metal dichalcogenides possess layered structure of Se-M-Se (M = Nb, Mo, Ta and W) sandwich interact with each other by van der Waal forces and can also provide sites for intercalation. Because of their technological importance, lubricants, catalysts, battery cathodes and electrodes in the photoelectrochemical solar cells, much attention has gone in the studies of growth of these materials in crystalline and nanocrystalline forms. In the present work we report the growth of NbSe2, MoSe2, TaSe2 and WSe2 single crystals and determine the optical bandgap using optical absorption. The optical absorption of as-grown crystals has been measured at room temperature near the fundamental absorption edge. Both direct and indirect transitions are involved in the absorption process. The indirect transition was found to be allowed with two phonons involved in the process. The direct and indirect energy gaps and phonon energies for all crystals have been estimated. The results obtained are discussed in detail.

Imaging the Anisotropic Reactivity of a Tungsten Diselenide Photocathode

AbstractThe reported activity of a photoelectrode reflects all kinds of reactive sites, good or bad. To understand localized behavior, such as catalytic sites or recombination centers, methods for mapping the anisotropic surface photoreactivity are constantly sought. The layered crystal structure of tungsten diselenide, a small bandgap semiconductor of great importance to solar fuels research, makes it especially prone to step‐edge defects. Such steps are detrimental to photoelectrochemical performance. The first direct mapping of the photoreactivity of p‐doped WSe2 single crystals in solution by using scanning electrochemical microscopy under illumination (photo‐SECM) is presented herein. This nondestructive method reveals the anisotropic reactivity of step edges of p‐WSe2 photocathodes, which serve as sites for both dark oxidation and lowered photoreduction in the dark and under illumination.