Exciton Valley Polarization Research Articles

Epitaxy of wafer-scale single-crystal MoS2 monolayer via buffer layer control

Monolayer molybdenum disulfide (MoS2), an emergent two-dimensional (2D) semiconductor, holds great promise for transcending the fundamental limits of silicon electronics and continue the downscaling of field-effect transistors. To realize its full potential and high-end applications, controlled synthesis of wafer-scale monolayer MoS2 single crystals on general commercial substrates is highly desired yet challenging. Here, we demonstrate the successful epitaxial growth of 2-inch single-crystal MoS2 monolayers on industry-compatible substrates of c-plane sapphire by engineering the formation of a specific interfacial reconstructed layer through the S/MoO3 precursor ratio control. The unidirectional alignment and seamless stitching of MoS2 domains across the entire wafer are demonstrated through cross-dimensional characterizations ranging from atomic- to centimeter-scale. The epitaxial monolayer MoS2 single crystal shows good wafer-scale uniformity and state-of-the-art quality, as evidenced from the ~100% phonon circular dichroism, exciton valley polarization of ~70%, room-temperature mobility of ~140 cm2v−1s−1, and on/off ratio of ~109. Our work provides a simple strategy to produce wafer-scale single-crystal 2D semiconductors on commercial insulator substrates, paving the way towards the further extension of Moore’s law and industrial applications of 2D electronic circuits.

Control of the valley polarization of monolayer WSe2 by Dexter-like coupling

Intervalley scattering mechanisms strongly affect the dynamics of excitonic complexes in transition metal dichalcogenide monolayers. Here, we investigate the excitation energy dependence of the valley polarization of excitons in a WSe2 monolayer. We observe that the valley polarization drastically decreases when the excitation is resonant with the B 1s resonance. This behavior can be explained by a Dexter-like coupling in the momentum space between exciton states residing in opposite valleys but with the same spin configuration. This induces a net transfer of the exciton population from the optically driven valley towards the opposite, undriven valley. We observe the long-term fingerprints of this population transfer as a vanishing valley polarization for the neutral exciton, and a negative valley polarization for biexcitonic complexes, in qualitative agreement with theoretical predictions based on a fully microscopic many-particle approach. This, together with a decrease of the PL energy when the excitation is resonant with the B 1s state, points to the prominent role of the Dexter-like coupling in the exciton dynamics of atomically thin semiconductors.

Interlayer exciton valley polarization dynamics in large magnetic fields

In van der Waals heterostructures (HS) consisting of stacked MoSe$_2$ and WSe$_2$ monolayers, optically bright interlayer excitons (ILE) can be observed when the constituent layers are crystallographically aligned. The symmetry of the monolayers allows for two different types of alignment, in which the momentum-direct interlayer transitions are either valley-conserving (R-type alignment) or changing the valley index (H-type anti-alignment). Here, we study the valley polarization dynamics of ILE in magnetic fields up to 30~Tesla by time-resolved photoluminescence (PL). For all ILE types, we find a finite initial PL circular degree of polarization ($DoP$) after unpolarized excitation in applied magnetic fields. For ILE in H-type HS, we observe a systematic increase of the PL $DoP$ with time in applied magnetic fields, which saturates at values close to unity for the largest fields. By contrast, for ILE in R-type HS, the PL $DoP$ shows a decrease and a zero crossing before saturating with opposite polarization. This unintuitive behavior can be explained by a model considering the different ILE states in H- and R-type HS and their selection rules coupling PL helicity and valley polarization.

Trap induced long exciton intervalley scattering and population lifetime in monolayer WSe2

Monolayer transition metal dichalcogenides (TMDCs) hold the best promise for next generation optoelectronic and valleytronic devices. However, their actual performance is usually largely affected by the presence of inevitable defects. Therefore, a detailed understanding of the influence of defects on the dynamic properties is crucial for optimizing near future implementations. Here, the exciton population and valley scattering dynamics in a chemical vapor deposition grown large size monolayer WSe2 with naturally abundant vacancy and boundary defects were systematically investigated using polarization controlled heterodyned transient grating spectroscopy at different excitation wavelengths and temperatures. Slow and multi-exponential decay dynamics of the exciton population were observed while no sign of any micron scale diffusive transport was identified, consistent with the effect of exciton trapping by defects. In general, two different kinds of exciton species were identified: one with short population lifetime (∼10 ps) and extremely fast intervalley scattering dynamics (<200 fs) and in contrast another one with a long population lifetime (>1 ns) and very slow intervalley scattering dynamics exceeding 100 ps. We assign the former to non-trapped excitons in the nanometer scale and the latter to defect-bound excitons. Temperature dependent intervalley scattering dynamics of the trapped excitons can be understood in terms of a two optical phonon dominated process at the K point in momentum space. Our findings highlight the importance of the intrinsic defects in monolayer TMDCs for manipulating exciton valley polarization and population lifetimes, which is key for future device applications.

Gain without inversion and enhancement of refractive index via intervalley quantum coherence transfer in hybrid WS2 -metallic nanoantenna systems

We theoretically study formation of gain without inversion and resonant enhancement of refractive index with suppressed absorption in a system consisting of a monolayer of transition metal dichalcogenide (${\mathrm{WS}}_{2}$) and a metallic nanoantenna. We show that these processes happen when the hybrid system interacts with a right-circularly polarized laser beam, allowing quantum coherence transfer to happen from the K to ${\mathrm{K}}^{\ensuremath{'}}$ valley. Our results show that the quantum coherence transfer can convert the ${\mathrm{K}}^{\ensuremath{'}}$ valley into a conjugated system wherein the real and imaginary parts of its polarization become similar to the imaginary and real parts of the K valley polarization, respectively. This allows the maximum refractive index in the ${\mathrm{K}}^{\ensuremath{'}}$ valley to occur as the absorption becomes zero. We characterize the conjugated valley system by inspecting the evolution of its Bloch vector as the incident laser frequency varies. The theoretical approach includes density matrix formalism while considering a pure dephasing rate that represents the fast decay of exciton valley polarization in transition metal dichalcogenide monolayers.

Control of the exciton valley dynamics in atomically thin semiconductors by tailoring the environment

The exciton valley dynamics in van der Waals heterostructures with transition metal dichalcogenides monolayers is driven by the long-range exchange interaction between the electron and the hole in the exciton. It couples the states active in the opposite circular polarizations resulting in the longitudinal-transverse splitting of excitons propagating in the monolayer plane. Here we study theoretically the effect of the dielectric environment on the long-range exchange interaction and demonstrate how the encapsulation in the hexagonal boron nitride modifies the exciton longitudinal-transverse splitting. We calculate the exciton spin/valley polarization relaxation due to the long-range exchange interaction and demonstrate that the variation of the monolayer environment results in significant, up to five-fold, enhancement of the exciton valley polarization lifetime.

Machine-Learning Analysis to Predict the Exciton Valley Polarization Landscape of 2D Semiconductors.

We demonstrate the applicability of employing machine-learning-based analysis to predict the low-temperature exciton valley polarization landscape of monolayer tungsten diselenide (1L-WSe2) using position-dependent information extracted from its photoluminescence (PL) spectra at room temperature. We performed low- and room-temperature polarization-resolved PL mapping and used the obtained experimental data to create regression models for the prediction using the Random Forest machine-learning algorithm. The local information extracted from the room-temperature PL spectra and the low-temperature exciton valley polarization was used as the input and output data for the machine-learning process, respectively. The spatial distribution of the exciton valley polarization in a 1L-WSe2 sample that was not used for the learning of the decision trees was successfully predicted. Furthermore, we numerically obtained the degree of importance for each input variable and demonstrated that this parameter provides helpful information for examining the physics that shape the spatially heterogeneous valley polarization landscape of 1L-WSe2.

Continuous Control and Enhancement of Excitonic Valley Polarization in Monolayer WSe2 by Electrostatic Doping

AbstractEnhancement and continuous control of the excitonic valley polarization in electrostatically doped monolayer WSe2 are demonstrated. Under excitation with circularly polarized light, 20% valley polarization of excitons around the charge neutrality condition at 70 K is increased to 40% by modulating the electron/hole density up to 2 × 1012 cm−2. This increase originates from slow valley relaxation for neutral exciton between the K and −K valleys owing to screening of long‐range e–h exchange interactions by doped carriers. The gate‐dependences of the exciton valley polarization at various temperatures are reproduced by theoretical calculations, which holds potential for next‐generation valleytronic devices continuously controlled by an applied bias voltage.

Zeeman-Induced Valley-Sensitive Photocurrent in Monolayer MoS_{2}.

The control of the valley degree of freedom lies at the core of interest in monolayer transition metal dichalcogenides, where specific valley-spin excitation can be created using circularly polarized light. Measurement and manipulation of the valley index has also been achieved, but mainly with purely optical methods. Here, in monolayer MoS_{2}, we identify a response to the valley polarization of excitons in the longitudinal electrical transport when the valley degeneracy is broken by an out-of-plane magnetic field B_{z}. The spin information is also simultaneously determined with spin-sensitive contacts. In the presence of B_{z}, a significant modulation of the photocurrent is observed as a function of the circular polarization state of the excitation. We attribute this effect to unbalanced transport of valley-polarized trions induced by the opposite Zeeman shifts of two (K and K^{'}) valleys. Our interpretation is supported by the contrasting behavior in bilayer MoS_{2}, as well as the observed doping and spatial dependence of the valley photocurrent.

Evidence for line width and carrier screening effects on excitonic valley relaxation in 2D semiconductors

Monolayers of transition metal dichalcogenides (TMDC) have recently emerged as excellent platforms for exploiting new physics and applications relying on electronic valley degrees of freedom in two-dimensional (2D) systems. Here, we demonstrate that Coulomb screening by 2D carriers plays a critical role in excitonic valley pseudospin relaxation processes in naturally carrier-doped WSe2 monolayers (1L-WSe2). The exciton valley relaxation times were examined using polarization- and time-resolved photoluminescence spectroscopy at temperatures ranging from 10 to 160 K. We show that the temperature-dependent exciton valley relaxation times in 1L-WSe2 under various exciton and carrier densities can be understood using a unified framework of intervalley exciton scattering via momentum-dependent long-range electron–hole exchange interactions screened by 2D carriers that depend on the carrier density and the exciton linewidth. Moreover, the developed framework was successfully applied to engineer the valley polarization of excitons in 1L-WSe2. These findings may facilitate the development of TMDC-based opto-valleytronic devices.

Robust valley polarization of helium ion modified atomically thin MoS2

Atomically thin semiconductors have dimensions that are commensurate with critical feature sizes of future optoelectronic devices defined using electron/ion beam lithography. Robustness of their emergent optical and valleytronic properties is essential for typical exposure doses used during fabrication. Here, we explore how focused helium ion bombardement affects the intrinsic vibrational, luminescence and valleytronic properties of atomically thin . By probing the disorder dependent vibrational response we deduce the interdefect distance by applying a phonon confinement model. We show that the increasing interdefect distance correlates with disorder-related luminscence arising 180 meV below the neutral exciton emission. We perform ab initio density functional theory of a variety of defect related morphologies, which yield first indications on the origin of the observed additional luminescence. Remarkably, no significant reduction of free exciton valley polarization is observed until the interdefect distance approaches a few nanometers, namely the size of the free exciton Bohr radius. Our findings pave the way for direct writing of sub-10 nm nanoscale valleytronic devices and circuits using focused helium ions.

Disorder-dependent valley properties in monolayer WSe2

We investigate the effect on disorder potential on exciton valley polarization and valley coherence in monolayer WSe2. By analyzing polarization properties of photoluminescence, the valley coherence (VC) and valley polarization (VP) is quantified across the inhomogeneously broadened exciton resonance. We find that disorder plays a critical role in the exciton VC, while minimally affecting VP. For different monolayer samples with disorder characterized by their Stokes Shift (SS), VC decreases in samples with higher SS while VP again remains unchanged. These two methods consistently demonstrate that VC as defined by the degree of linearly polarized photoluminescence is more sensitive to disorder potential, motivating further theoretical studies.

Magneto-optics in transition metal diselenide monolayers

We perform photoluminescence experiments at 4 K on two different transition metal diselenide monolayers (MLs), namely MoSe2 and WSe2 in magnetic fields Bz up to 9 T applied perpendicular to the sample plane. In MoSe2 MLs the valley polarization of the neutral and the charged exciton (trion) can be tuned by the magnetic field, independent of the excitation laser polarization. In the investigated WSe2 ML sample the evolution of the trion valley polarization depends both on the applied magnetic field and the excitation laser helicity, while the neutral exciton valley polarization depends only on the latter. Remarkably, we observe a reversal of the sign of the trion polarization between WSe2 and MoSe2. For both systems we observe a clear Zeeman splitting for the neutral exciton and the trion of about ±2 meV at T. The extracted Landé-factors for both exciton complexes in both materials are .