Monolayers Of Semiconducting Transition Metal Dichalcogenides Research Articles

(Invited) Wafer-Scale Epitaxy of Transition Metal Dichalcogenides By MOCVD

Monolayer semiconducting transition metal dichalcogenides (MX2, M=W, Mo and X=S, Se) exhibit novel electronic and optical properties. Availability of epitaxial single-crystal monolayers over a wafer scale is a major hurdle in integrating these materials with existing device fabrication processes. Our approach focusses on synthesis of these monolayers using gas source precursors, like those used in traditional III-V semiconductor industry. The precursors are kept in temperature and pressure-controlled bubblers outside the growth chamber and can be metered independently into the growth zone with precision. Uniform epitaxial binary TMD monolayers including MoS2, WS2, WSe2 and MoSe2 have been deposited on 2” sapphire wafers in a cold-wall CVD reactor using metal hexacarbonyl and hydride chalcogen precursors. A multi-step growth process comprising of precursor modulation was developed for WSe2 to independently control nucleation density and the lateral growth rate of monolayer domains on the sapphire substrate [1]. For the sulfides, additional temperature modulation was introduced to increase crystalline quality. Using this approach, uniform, coalesced monolayer and few-layer TMD films were obtained on 2” sapphire substrates. In-plane X-ray diffraction demonstrates that the films are epitaxially oriented with respect to sapphire with narrow X-ray full-width-at-half-maximum indicating minimal rotational misorientation of domains within the basal plane [2]. Deposition of these materials in the same reactor provides insight into the factors controlling their growth, which in essential for the growth of heterostructures and/or alloys. Transmission electron microscopy analysis of these materials revealed additional information about the coalesced film structure. For instance, ~95 % single oriented WS2 domains were observed when the film growth rate was modulated. For WS2, it was also confirmed that despite translational line defects present in the film, mirror boundaries were predominantly absent. WS2 also showed no defect related photoluminescence peak at 80 K, indicating its high quality.In this talk the factors affecting the growth of TMDs (MX2, M=W, Mo and X=S, Se) will be presented. The role of the substrate surface in the nucleation and growth of these TMDs will be discussed. In addition, the structural and optoelectronic characteristics for these films will also be presented.The authors acknowledge financial support of the U.S. National Science Foundation through the Penn State 2D Crystal Consortium – Materials Innovation Platform (2DCC-MIP) under NSF cooperative agreement DMR-1539916 and EFRI 2-DARE Grant EFRI-1433378.[1] Zhang X, Choudhury TH, Chubarov M et al., 2018. Nano Lett. 18(2):1049–56[2] Chubarov M, Choudhury TH, Zhang X et al., 2018. Nanotechnology. 29(5):55706

Band Filling and Cross Quantum Capacitance in Ion-Gated Semiconducting Transition Metal Dichalcogenide Monolayers.

Ionic liquid gated field-effect transistors (FETs) based on semiconducting transition metal dichalcogenides (TMDs) are used to study a rich variety of extremely interesting physical phenomena, but important aspects of how charge carriers are accumulated in these systems are not understood. We address these issues by means of a systematic experimental study of transport in monolayer MoSe2 and WSe2 as a function of magnetic field and gate voltage, exploring accumulated densities of carriers ranging from approximately 1014 cm-2 holes in the valence band to 4 × 1014 cm-2 electrons in the conduction band. We identify the conditions when the chemical potential enters different valleys in the monolayer band structure (the K and Q valley in the conduction band and the two spin-split K-valleys in the valence band) and find that an independent electron picture describes the occupation of states well. Unexpectedly, however, the experiments show very large changes in the device capacitance when multiple valleys are occupied that are not at all compatible with the commonly expected quantum capacitance contribution of these systems, CQ = e2/ (dμ/dn). A theoretical analysis of all terms responsible for the total capacitance shows that under general conditions a term is present besides the usual quantum capacitance, which becomes important for very small distances between the capacitor plates. This term, which we call cross quantum capacitance, originates from screening of the electric field generated by charges on one plate from charges sitting on the other plate. The effect is negligible in normal capacitors but large in ionic liquid FETs because of the atomic proximity between the ions in the gate and the accumulated charges on the TMD, and it accounts for all our experimental observations. Our findings therefore reveal an important contribution to the capacitance of physical systems that had been virtually entirely neglected until now.

Revealing exciton masses and dielectric properties of monolayer semiconductors with high magnetic fields

In semiconductor physics, many essential optoelectronic material parameters can be experimentally revealed via optical spectroscopy in sufficiently large magnetic fields. For monolayer transition-metal dichalcogenide semiconductors, this field scale is substantial—tens of teslas or more—due to heavy carrier masses and huge exciton binding energies. Here we report absorption spectroscopy of monolayer {{rm{MoS}}}_{2},{{rm{MoSe}}}_{2},{{rm{MoTe}}}_{2}, and {{rm{WS}}}_{2} in very high magnetic fields to 91 T. We follow the diamagnetic shifts and valley Zeeman splittings of not only the exciton’s 1s ground state but also its excited 2s,3s,ldots ,ns Rydberg states. This provides a direct experimental measure of the effective (reduced) exciton masses and dielectric properties. Exciton binding energies, exciton radii, and free-particle bandgaps are also determined. The measured exciton masses are heavier than theoretically predicted, especially for Mo-based monolayers. These results provide essential and quantitative parameters for the rational design of opto-electronic van der Waals heterostructures incorporating 2D semiconductors.

Spectroscopic studies of atomic defects and bandgap renormalization in semiconducting monolayer transition metal dichalcogenides

Assessing atomic defect states and their ramifications on the electronic properties of two-dimensional van der Waals semiconducting transition metal dichalcogenides (SC-TMDs) is the primary task to expedite multi-disciplinary efforts in the promotion of next-generation electrical and optical device applications utilizing these low-dimensional materials. Here, with electron tunneling and optical spectroscopy measurements with density functional theory, we spectroscopically locate the mid-gap states from chalcogen-atom vacancies in four representative monolayer SC-TMDs—WS2, MoS2, WSe2, and MoSe2—, and carefully analyze the similarities and dissimilarities of the atomic defects in four distinctive materials regarding the physical origins of the missing chalcogen atoms and the implications to SC-mTMD properties. In addition, we address both quasiparticle and optical energy gaps of the SC-mTMD films and find out many-body interactions significantly enlarge the quasiparticle energy gaps and excitonic binding energies, when the semiconducting monolayers are encapsulated by non-interacting hexagonal boron nitride layers.

Ballistic thermoelectric properties of monolayer semiconducting transition metal dichalcogenides and oxides

Combining first-principles calculations with Landauer-B\"uttiker formalism, ballistic thermoelectric transport properties of semiconducting two-dimensional transition metal dichalcogenides (TMDs) and oxides (TMOs) (namely ${\mathrm{MX}}_{2}$ with M = Cr, Mo, W, Ti, Zr, Hf; X = O, S, Se, Te) are investigated in their 2H and 1T phases. Having computed structural, as well as ballistic electronic and phononic transport properties for all structures, we report the thermoelectric properties of the semiconducting ones. We find that 2H phases of four of the studied structures have very promising thermoelectric properties, unlike their 1T phases. The maximum room temperature $p$-type thermoelectric figure of merit ($ZT$) of 1.57 is obtained for $2\mathrm{H}\ensuremath{-}{\mathrm{HfSe}}_{2}$, which can be as high as 3.30 at $T=800$ K. Additionally, $2\mathrm{H}\ensuremath{-}{\mathrm{ZrSe}}_{2}, 2\mathrm{H}\ensuremath{-}{\mathrm{ZrTe}}_{2}$, and $2\mathrm{H}\ensuremath{-}{\mathrm{HfS}}_{2}$ have considerable $ZT$ values (both $n$- and $p$-type), that are above 1 at room temperature. The 1T phases of Zr and Hf-based oxides possess relatively high power factors, however their high lattice thermal conductance values limit their $ZT$ values to below 1 at room temperature.

Optical orientation with linearly polarized light in transition metal dichalcogenides

We study the optical properties of semiconducting transition metal dichalcogenide monolayers under the influence of strong out-of-plane magnetic fields, using the effective massive Dirac model. We pay attention to the role of spin-orbit coupling effects, doping level and electron-electron interactions, treated at the Hartree-Fock level. We find that optically-induced valley and spin imbalance, commonly attained with circularly polarized light, can also be obtained with linearly polarized light in the doped regime. Additionally, we explore an exchange-driven mechanism to enhance the spin-orbit splitting of the conduction band, in n-doped systems, controlling both the carrier density and the intensity of the applied magnetic field.

Collective excitations in a two-component one-dimensional massless Dirac plasma

We study spectra of long wavelength plasma oscillations in a system of two energy splitted one-dimensional (1D) massless Dirac fermion subbands coupled by spin-orbit interaction. Such a system may be formed by edge subbands in semiconducting transition metal dichalcogenide monolayers. Intrasubband transitions of massless Dirac fermions give rise to optical and acoustic gapless branches of intrasubband 1D plasmons. We reveal that the optical branch is of quantum character with group velocity being inverse proportional to square root of the Planck constant, whereas the acoustic branch is classical one with group velocity proportional to geometric mean of the edge subband velocities. Spin-orbit interaction, allowing intersubband transitions in the system, results in emergence of two branches of intersubband 1D plasmons: upper and lower ones. The upper and lower branches are gapped at small wave vectors and evolve with positive and negative group velocities, respectively, from energy splitting of the edge subbands at Fermi-level. The both intersubband branches adjoin intersubband single particle excitation continuum from above, while in case of the edge subbands with unequal velocities the lower one experiences Landau damping at small wave vectors. In addition, the lower branch, attaining zero frequency at a non-zero wave vector, alters its group velocity from negative to positive one.

Tight-binding piezoelectric theory and electromechanical coupling correlations for transition metal dichalcogenide monolayers

The lack of inversion symmetry in semiconducting transition metal dichalcogenide monolayers (TMDMs) enables a considerable molecular-level intrinsic piezoelectricity, which opens prospects for atomically-thin piezotronics and optoelectronics. Here, based on the tight-binding (TB) approach and Berry phase polarization theory, we establish an atomic-scale TB theory for demonstrating piezoelectric physics in TMDMs. Using the TB piezoelectric theory, we predict their electronic Gr\"{u}neisen parameters (EGP) which measure the electron-phonon couplings. By virtue of the constructed analytical piezoelectric model, we further reveal the correlation between the electronic contribution to piezoelectric coefficients and strain-induced pseudomagnetic gauge field (PMF). These predicted EGP and PMF for TMDMs are experimentally testable, and hence the TB piezoelectric model is an alternative theoretical framework for calculating electron-phonon interactions and PMF.

A gate-free monolayer WSe2 pn diode

Interest in bringing p- and n-type monolayer semiconducting transition metal dichalcogenides (TMD) into contact to form rectifying pn diode has thrived since it is crucial to control the electrical properties in two-dimensional (2D) electronic and optoelectronic devices. Usually this involves vertically stacking different TMDs with pn heterojunction or, laterally manipulating carrier density by gate biasing. Here, by utilizing a locally reversed ferroelectric polarization, we laterally manipulate the carrier density and created a WSe2 pn homojunction on the supporting ferroelectric BiFeO3 substrate. This non-volatile WSe2 pn homojunction is demonstrated with optical and scanning probe methods and scanning photoelectron micro-spectroscopy. A homo-interface is a direct manifestation of our WSe2 pn diode, which can be quantitatively understood as a clear rectifying behavior. The non-volatile confinement of carriers and associated gate-free pn homojunction can be an addition to the 2D electron–photon toolbox and pave the way to develop laterally 2D electronics and photonics.

1D/2D Materials, Flexible Substrates and Surfaces

There has been a growing interest in two dimensional (2D) crystals beyond graphene, exhibiting novel properties and potential applications in next generation electronic and photonic devices. Graphene has superior properties, including high carrier mobility, ultrahigh surface area and excellent thermal conductivity. Whereas the lack of a band gap is a critical limitation for the use of graphene in electronic devices, monolayer semiconducting transition metal dichalcogenides (TMDs) have shown highly promising prospects in electronics and optoelectronics. Therefore, non-graphene 2D atomic layers, such as hexagonal boron nitride (hBN) and TMDs, have been integrated into research scale devices, thereby probing mechanical, chemical, electrical and optoelectrical functions. This abstract reports on our investigation of chemical vapour deposition (CVD)-growth, achieving localized, patterned, single crystalline or polycrystalline monolayers of TMDs, including MoS2, WS2, WSe2 and MoSe2, as well as their heterostructures. Particular focus is on enabling the fabrication of epitaxially grown TMDs on other van der Waals materials towards synthesizing TMDs with an ultralow-defect density. Furthermore the growth of TMD homobilayers with well-ordered stacking angles is demonstrated using the control of edge structures of the underlying TMD layer. Other nanomaterials, including vertically aligned carbon nanotubes for stretchable supercapacitors, are also investigated toward combining 2D materials with flexible substrates. Smart polymer functional surfaces using dodecylbenzenesulfonate-doped polypyrrole (PPy(DBS)) are also investigated to demonstrate in situ control of droplet pinning on the polymer surface, enabling the control of droplet adhesion from strongly pinned to extremely slippery (and vice versa). The pinning of organic droplets on the surfaces is dramatically controlled in situ, presenting great potential for manipulation and control of liquid droplets for various applications including oil separation, water treatment and anti-bacterial surfaces. We believe that our work represents a major advance in materials science and engineering, especially pertaining to those topics that involve functional and tunable surfaces.

Environmental engineering of transition metal dichalcogenide optoelectronics

The explosion of interest in two-dimensional van der Waals materials has been in many ways driven by their layered geometry. This feature makes possible numerous avenues for assembling and manipulating the optical and electronic properties of these materials. In the specific case of monolayer transition metal dichalcogenide semiconductors, the direct band gap combined with the flexibility for manipulation of layers has made this class of materials promising for optoelectronics. Here, we review the properties of these layered materials and the various means of engineering these properties for optoelectronics. We summarize approaches for control that modify their structural and chemical environment, and we give particular detail on the integration of these materials into engineered optical fields to control their optical characteristics. This combination of controllability from their layered surface structure and photonic environment provide an expansive landscape for novel optoelectronic phenomena.

The transport and optical sensing properties of MoS2, MoSe2, WS2 and WSe2 semiconducting transition metal dichalcogenides

In this paper, we investigate the transport and optical properties of the monolayer semiconducting transition metal dichalcogenides (STMDs) in the absence and presence of the NH3, NO, NO2, and O2 gas molecules to assess their potentials as gas sensors. The first-principles calculations based on density functional theory indicate that absorption of the O2, NO2, NO gas molecules on the surface of these materials leads to significant changes in their transmission spectrum. Our calculations predict a charge transfer between the adsorbent gas and any of these STMDs. However, the presence of NH3 molecule has little effect on the transport properties of these materials. The results show that when the STMDs are exposed to NO, NO2, and O2 molecules, the dielectric function changes. Therefore, these materials can be employed as the sensing element in an optical gas sensor.

Microscopic Origin of the Valley Hall Effect in Transition Metal Dichalcogenides Revealed by Wavelength-Dependent Mapping.

The band structure of many semiconducting monolayer transition metal dichalcogenides (TMDs) possesses two degenerate valleys with equal and opposite Berry curvature. It has been predicted that, when illuminated with circularly polarized light, interband transitions generate an unbalanced nonequilibrium population of electrons and holes in these valleys, resulting in a finite Hall voltage at zero magnetic field when a current flows through the system. This is the so-called valley Hall effect that has recently been observed experimentally. Here, we show that this effect is mediated by photogenerated neutral excitons and charged trions and not by interband transitions generating independent electrons and holes. We further demonstrate an experimental strategy, based on wavelength dependent spatial mapping of the Hall voltage, which allows the exciton and trion contributions to the valley Hall effect to be discriminated in the measurement. These results represent a significant step forward in our understanding of the microscopic origin of photoinduced valley Hall effect in semiconducting transition metal dichalcogenides and demonstrate experimentally that composite quasi-particles, such as trions, can also possess a finite Berry curvature.

Valley-Polarized Exciton Dynamics in Exfoliated Monolayer WSe2

Semiconducting transition metal dichalcogenide monolayers have emerged as promising candidates for future valleytronics-based quantum information technologies. Two distinct momentum-states of tightly-bound electron-hole pairs in these materials can be deterministically initialized via irradiation with circularly polarized light. Here, we investigate the ultrafast dynamics of such a valley polarization in monolayer tungsten diselenide by means of time-resolved Kerr reflectometry. The observed Kerr signal in our sample stems exclusively from charge-neutral excitons. Our findings support the picture of a fast decay of the valley polarization of bright excitons due to radiative recombination, intra-conduction-band spin-flip transitions, intervalley-scattering processes, and the formation of long-lived valley-polarized dark states.

Magnetoreflection spectroscopy of monolayer transition-metal dichalcogenide semiconductors in pulsed magnetic fields

The authors describe recent experimental efforts to perform polarization-resolved optical spectroscopy of monolayer transition-metal dichalcogenide semiconductors in very large pulsed magnetic fields to 65 T. The experimental setup and technical challenges are discussed in detail, and temperature-dependent magnetoreflection spectra from atomically thin tungsten disulphide are presented. The data clearly reveal not only the valley Zeeman effect in these two-dimensional semiconductors but also the small quadratic exciton diamagnetic shift from which the very small exciton size can be directly inferred. Finally, the authors present model calculations that demonstrate how the measured diamagnetic shifts can be used to constrain estimates of the exciton binding energy in this new family of monolayer semiconductors.

Atomic-Scale Spectroscopy of Gated Monolayer MoS2.

The electronic properties of semiconducting monolayer transition-metal dichalcogenides can be tuned by electrostatic gate potentials. Here we report gate-tunable imaging and spectroscopy of monolayer MoS2 by atomic-resolution scanning tunneling microscopy/spectroscopy (STM/STS). Our measurements are performed on large-area samples grown by metal-organic chemical vapor deposition (MOCVD) techniques on a silicon oxide substrate. Topographic measurements of defect density indicate a sample quality comparable to single-crystal MoS2. From gate voltage dependent spectroscopic measurements, we determine that in-gap states exist in or near the MoS2 film at a density of 1.3 × 10(12) eV(-1) cm(-2). By combining the single-particle band gap measured by STS with optical measurements, we estimate an exciton binding energy of 230 meV on this substrate, in qualitative agreement with numerical simulation. Grain boundaries are observed in these polycrystalline samples, which are seen to not have strong electronic signatures in STM imaging.

Exciton Dynamics in Monolayer Transition Metal Dichalcogenides.

Since the discovery of semiconducting monolayer transition metal dichalcogenides, a variety of experimental and theoretical studies have been carried out seeking to understand the intrinsic exciton population recombination and valley relaxation dynamics. Reports of the exciton decay time range from hundreds of femtoseconds to ten nanoseconds, while the valley depolarization time can exceed one nanosecond. At present, however, a consensus on the microscopic mechanisms governing exciton radiative and non-radiative recombination is lacking. The strong exciton oscillator strength resulting in up to ~ 20% absorption for a single monolayer points to ultrafast radiative recombination. However, the low quantum yield and large variance in the reported lifetimes suggest that non-radiative Auger-type processes obscure the intrinsic exciton radiative lifetime. In either case, the electron-hole exchange interaction plays an important role in the exciton spin and valley dynamics. In this article, we review the experiments and theory that have led to these conclusions and comment on future experiments that could complement our current understanding.

Van der Waals stacked 2D layered materials for optoelectronics

The band gaps of many atomically thin 2D layered materials such as graphene, black phosphorus, monolayer semiconducting transition metal dichalcogenides and hBN range from 0 to 6 eV. These isolated atomic planes can be reassembled into hybrid heterostructures made layer by layer in a precisely chosen sequence. Thus, the electronic properties of 2D materials can be engineered by van der Waals stacking, and the interlayer coupling can be tuned, which opens up avenues for creating new material systems with rich functionalities and novel physical properties. Early studies suggest that van der Waals stacked 2D materials work exceptionally well, dramatically enriching the optoelectronics applications of 2D materials. Here we review recent progress in van der Waals stacked 2D materials, and discuss their potential applications in optoelectronics.

Landau levels and Shubnikov–de Haas oscillations in monolayer transition metal dichalcogenide semiconductors

We study the Landau level (LL) spectrum using a multi-band theory in monolayer transition metal dichalcogenide semiconductors. We find that in a wide magnetic field range the LL can be characterized by a harmonic oscillator spectrum and a linear-in-magnetic field term which describes the valley degeneracy breaking. The effect of the non-parabolicity of the band-dispersion on the LL spectrum is also discussed. Motivated by recent magnetotransport experiments, we use the self-consistent Born approximation and the Kubo formalism to calculate the Shubnikov–de Haas oscillations of the longitudinal conductivity. We investigate how the doping level, the spin-splitting of the bands and the broken valley degeneracy of the LLs affect the magnetoconductance oscillations. We consider monolayer MoS2 and WSe2 as concrete examples and compare the results of numerical calculations and an analytical formula which is valid in the semiclassical regime. Finally, we briefly analyze the recent experimental results (Cui et al 2015 Nat. Nanotechnol. 10 534) using the theoretical approach we have developed.

Visualizing nanoscale excitonic relaxation properties of disordered edges and grain boundaries in monolayer molybdenum disulfide.

Two-dimensional monolayer transition metal dichalcogenide semiconductors are ideal building blocks for atomically thin, flexible optoelectronic and catalytic devices. Although challenging for two-dimensional systems, sub-diffraction optical microscopy provides a nanoscale material understanding that is vital for optimizing their optoelectronic properties. Here we use the ‘Campanile' nano-optical probe to spectroscopically image exciton recombination within monolayer MoS2 with sub-wavelength resolution (60 nm), at the length scale relevant to many critical optoelectronic processes. Synthetic monolayer MoS2 is found to be composed of two distinct optoelectronic regions: an interior, locally ordered but mesoscopically heterogeneous two-dimensional quantum well and an unexpected ∼300-nm wide, energetically disordered edge region. Further, grain boundaries are imaged with sufficient resolution to quantify local exciton-quenching phenomena, and complimentary nano-Auger microscopy reveals that the optically defective grain boundary and edge regions are sulfur deficient. The nanoscale structure–property relationships established here are critical for the interpretation of edge- and boundary-related phenomena and the development of next-generation two-dimensional optoelectronic devices.