Atomistic Compositional Details and Their Importance for Spin Qubits in Isotope-Purified Silicon Quantum Wells.

Understanding crystal characteristics down to the atomistic level increasingly emerges as a crucial insight for creating solid state platforms for qubits with reproducible and homogeneous properties. Here, isotope concentration depth profiles in a SiGe/28Si/SiGe heterostructure are analyzed with atom probe tomography (APT) and time-of-flight secondary-ion mass spectrometry down to their respective limits of isotope concentrations and depth resolution. Spin-echo dephasing times T 2 echo = 128 µ s $T_2^\mathbf {echo}=128 \,\umu\mathrm{s}$ and valley energy splittings EVS around 200 µ e V $200 \,\umu\mathrm{e\mathrm{V}}$ have been observed for single spin qubits in this quantum well (QW) heterostructure, pointing toward the suppression of qubit decoherence through hyperfine interaction with crystal host nuclear spins or via scattering between valley states. The concentration of nuclear spin-carrying 29Si is 50 ± 20ppm in the 28Si QW. The resolution limits of APT allow to uncover that both the SiGe/28Si and the 28Si/SiGe interfaces of the QW are shaped by epitaxial growth front segregation signatures on a few monolayer scale. A subsequent thermal treatment, representative of the thermal budget experienced by the heterostructure during qubit device processing, broadens the top SiGe/28Si QW interface by about two monolayers, while the width of the bottom 28Si/SiGe interface remains unchanged. Using a tight-binding model including SiGe alloy disorder, these experimental results suggest that the combination of the slightly thermally broadened top interface and of a minimal Ge concentration of 0.3 $0.3$ % in the QW, resulting from segregation, is instrumental for the observed large E VS = 200 µ e V $E_\mathrm{VS}=200 \,\umu\mathrm{e\mathrm{V}}$ . Minimal Ge additions <1%, which get more likely in thin QWs, will hence support high EVS without compromising coherence times. At the same time, taking thermal treatments during device processing as well as the occurrence of crystal growth characteristics into account seems important for the design of reproducible qubit properties.

Spin Polarization Enhances the Catalytic Activity of Monolayer MoSe2 for Oxygen Reduction Reaction.

The key factors in achieving high energy efficiency for proton exchange membrane fuel cells are reducing overpotential and increasing the oxygen reduction rate. Based on first-principles calculations, we induce H atom adsorption on 4 × 4 × 1 monolayer MoSe2 to induce spin polarization, thereby improving the catalytic performance. In the calculation of supercells, the band unfolding method is used to address the band folding effect in doped systems. Furthermore, it is evident from analyzing the unique energy band configuration of MoSe2 that a higher valley splitting value has better catalytic effects on the oxygen reduction reaction. We believe that the symmetries of the distinct adsorption site result in different overpotentials. In addition, when an even number of hydrogen atoms is adsorbed, the monolayer MoSe2 has no spin polarization. The spin can affect the electron transfer process and alter the hybrid energy with the reaction products, thereby regulating its catalytic performance.

Phase-Dependent Magnetic Proximity Modulations on Valley Polarization and Splitting.

Proximate-induced magnetic interactions present a promising strategy for precise manipulation of valley degrees of freedom. Taking advantage of the splendid valleytronic platform of transition metal dichalcogenides, magnetic two-dimensional VSe2 with different phases are introduced to intervene in the spin of electrons and modulate their valleytronic properties. When constructing the heterostructures, 1T-VSe2/WX2 (X = S and Se) showcases significant improvement in the valley polarizations at room temperature, while 2H-VSe2/WX2 exhibits superior performance at low temperatures and demonstrates heightened sensitivity to the external magnetic field. Simultaneously, considerable valley splitting with a large geff factor up to -29.0 is observed in 2H-VSe2/WS2, while it is negligible in 1T-VSe2/WX2. First-principles calculations reveal a phase-dependent magnetic proximity mechanism on the valleytronic modulations, which is dominated by interfacial charge transfer in 1T-VSe2/WX2 and the proximity exchange field in 2H-VSe2/WX2 heterostructures. The effective control over valley degrees of freedom will bridge the valleytronic physics and devices, rendering enormous potential in the field of valley quantum applications.

On the electronic and spin-valley coupling of vanadium doped MoS2(1-x)Se2xmonolayers.

Monolayers of MoS2with tunable bandgap and valley positions are highly demanding for their applications in opto-spintronics. Herein, selenium (Se) and vanadium (V) co-doped MoS2monolayers (vanadium doped MoS2(1-x)Se2x(V-MoSSe)) are developed and showed their variations in the electronic and optical properties with dopant content. Vanadium gets substitutionally (in place of Mo) doped within the MoS2lattice while selenium doped in place of sulfur, as shown by a detailed microstructure and spectroscopy analyses. The bandgap tunability with selenium doping can be achieved while valley shift is occurred due to the doping of vanadium. Chemical vapor deposition assisted grown MoS2(also selenium doped MoS2as shown here) is known for its n-type transport behavior while vanadium doping is found to be changing its nature to p-doping. Chirality dependent photoexcitation studies indicate a room temperature valley splitting in V-MoSSe (∼8 meV), where such a valley splitting is verified using density functional theory based calculations.

Tunable Valley Splitting and Bipolar Operation in Graphene Quantum Dots.

Quantum states in graphene are 2-fold degenerate in spins, and 2-fold in valleys. Both degrees of freedom can be utilized for qubit preparations. In our bilayer graphene quantum dots, we demonstrate that the valley g-factor gv, defined analogously to the spin g-factor gs for valley splitting in a perpendicular magnetic field, is tunable by over a factor of 4 from 20 to 90, by gate voltage adjustments only. Larger gv results from larger electronic dot sizes, determined from the charging energy. On our versatile device, bipolar operation, charging our quantum dot with charge carriers of the same or the opposite polarity as the leads, can be performed. Dots of both polarities are tunable to the first charge carrier, such that the transition from an electron to a hole dot by the action of the plunger gate can be observed. Addition of gates easily extends the system to host tunable double dots.

Synthesis of Co-Doped MoS2 Monolayers with Enhanced Valley Splitting.

Internal magnetic moments induced by magnetic dopants in MoS2 monolayers are shown to serve as a new means to engineer valley Zeeman splitting (VZS). Specifically, successful synthesis of monolayer MoS2 doped with the magnetic element Co is reported, and the magnitude of the valley splitting is engineered by manipulating the dopant concentration. Valley splittings of 3.9, 5.2, and 6.15 meV at 7 T in Co-doped MoS2 with Co concentrations of 0.8%, 1.7%, and 2.5%, respectively, are achieved as revealed by polarization-resolved photoluminescence (PL) spectroscopy. Atomic-resolution electron microscopy studies clearly identify the magnetic sites of Co substitution in the MoS2 lattice, forming two distinct types of configurations, namely isolated single dopants and tridopant clusters. Density functional theory (DFT) and model calculations reveal that the observed enhanced VZS arises from an internal magnetic field induced by the tridopant clusters, which couples to the spin, atomic orbital, and valley magnetic moment of carriers from the conduction and valence bands. The present study demonstrates a new method to control the valley pseudospin via magnetic dopants in layered semiconducting materials, paving the way toward magneto-optical and spintronic devices.

Enhanced Valley Splitting of Transition-Metal Dichalcogenide by Vacancies in Robust Ferromagnetic Insulating Chromium Trihalides.

Recently, single-layer CrI3, a member of the chromium trihalides CrX3 (where X = Cl, Br, or I), has been exfoliated and experimentally demonstrated as an atomically thin material suitable for two-dimensional spintronics. Valley splitting due to the magnetic proximity effect has been demonstrated in a WSe2/CrI3 van der Waals heterojunction. However, the understanding of the mechanisms behind the favorable performance of CrI3 is still limited. Here, we systematically study the carrier mobility and the intrinsic point defects in CrX3 and assess their influence on valley splitting in WSe2/CrI3 by first-principles calculations. The flat-band nature induces extremely large carrier mass and ultralow carrier mobility. In addition, intrinsic point defects-localized states in the middle of the band gap-show deep transition energy levels and act as carrier recombination centers, further lowering the carrier mobility. Moreover, vacancies in CrI3 can enhance ferromagnetism and valley splitting in a WSe2/CrI3 heterojunction, proving that chromium trihalides are excellent ferromagnetic insulators for spintronic and valleytronic applications.

Fragility of the Dirac Cone Splitting in Topological Crystalline Insulator Heterostructures.

The "double Dirac cone" 2D topological interface states found on the (001) faces of topological crystalline insulators such as Pb1-xSnxSe feature degeneracies located away from time reversal invariant momenta and are a manifestation of both mirror symmetry protection and valley interactions. Similar shifted degeneracies in 1D interface states have been highlighted as a potential basis for a topological transistor, but realizing such a device will require a detailed understanding of the intervalley physics involved. In addition, the operation of this or similar devices outside of ultrahigh vacuum will require encapsulation, and the consequences of this for the topological interface state must be understood. Here we address both topics for the case of 2D surface states using angle-resolved photoemission spectroscopy. We examine bulk Pb1-xSnxSe(001) crystals overgrown with PbSe, realizing trivial/topological heterostructures. We demonstrate that the valley interaction that splits the two Dirac cones at each X̅ is extremely sensitive to atomic-scale details of the surface, exhibiting non-monotonic changes as PbSe deposition proceeds. This includes an apparent total collapse of the splitting for sub-monolayer coverage, eliminating the Lifshitz transition. For a large overlayer thickness we observe quantized PbSe states, possibly reflecting a symmetry confinement mechanism at the buried topological interface.

Excitonic Valley Effects in Monolayer WS2 under High Magnetic Fields.

Transition-metal dichalcogenides can be easily produced as atomically thin sheets, exhibiting the possibility to optically polarize and read out the valley pseudospin of extremely stable excitonic quasiparticles present in these 2D semiconductors. Here, we investigate a monolayer of tungsten disulfide in high magnetic fields up to 30 T via photoluminescence spectroscopy at low temperatures. The valley degeneracy is lifted for all optical features, particularly for excitons, singlet and triplet trions, for which we determine the g factor separately. While the observation of a diamagnetic shift of the exciton and trion resonances gives us insight into the real-space extension of these quasiparticles, magnetic field-induced valley polarization effects shed light onto the exciton and trion dispersion relations in reciprocal space. The field dependence of the trion valley polarizations is in line with the predicted trion splitting into singlet and triplet configurations.

Electrostatically Confined Monolayer Graphene Quantum Dots with Orbital and Valley Splittings.

The electrostatic confinement of massless charge carriers is hampered by Klein tunneling. Circumventing this problem in graphene mainly relies on carving out nanostructures or applying electric displacement fields to open a band gap in bilayer graphene. So far, these approaches suffer from edge disorder or insufficiently controlled localization of electrons. Here we realize an alternative strategy in monolayer graphene, by combining a homogeneous magnetic field and electrostatic confinement. Using the tip of a scanning tunneling microscope, we induce a confining potential in the Landau gaps of bulk graphene without the need for physical edges. Gating the localized states toward the Fermi energy leads to regular charging sequences with more than 40 Coulomb peaks exhibiting typical addition energies of 7-20 meV. Orbital splittings of 4-10 meV and a valley splitting of about 3 meV for the first orbital state can be deduced. These experimental observations are quantitatively reproduced by tight binding calculations, which include the interactions of the graphene with the aligned hexagonal boron nitride substrate. The demonstrated confinement approach appears suitable to create quantum dots with well-defined wave function properties beyond the reach of traditional techniques.

Optical Investigation of Monolayer and Bulk Tungsten Diselenide (WSe2) in High Magnetic Fields.

Optical spectroscopy in high magnetic fields B ≤ 65 T is used to reveal the very different nature of carriers in monolayer and bulk transition metal dichalcogenides. In monolayer WSe2, the exciton emission shifts linearly with the magnetic field and exhibits a splitting that originates from the magnetic field induced valley splitting. The monolayer data can be described using a single particle picture with a Dirac-like Hamiltonian for massive Dirac Fermions, with an additional term to phenomenologically include the valley splitting. In contrast, in bulk WSe2 where the inversion symmetry is restored, transmission measurements show a distinctly excitonic behavior with absorption to the 1s and 2s states. Magnetic field induces a spin splitting together with a small diamagnetic shift and cyclotron like behavior at high fields, which is best described within the hydrogen model.