Phase Modulation of Self-Gating in Ionic Liquid-Functionalized InSe Field-Effect Transistors.

Understanding the Coulomb interactions between two-dimensional (2D) materials and adjacent ions/impurities is essential to realizing 2D material-based hybrid devices. Electrostatic gating via ionic liquids (ILs) has been employed to study the properties of 2D materials. However, the intrinsic interactions between 2D materials and ILs are rarely addressed. This work studies the intersystem Coulomb interactions in IL-functionalized InSe field-effect transistors by displacement current measurements. We uncover a strong self-gating effect that yields a 50-fold enhancement in interfacial capacitance, reaching 550 nF/cm2 in the maximum. Moreover, we reveal the IL-phase-dependent transport characteristics, including the channel current, carrier mobility, and density, substantiating the self-gating at the InSe/IL interface. The dominance of self-gating in the rubber phase is attributed to the correlation between the intra- and intersystem Coulomb interactions, further confirmed by Raman spectroscopy. This study provides insights into the capacitive coupling at the InSe/IL interface, paving the way to developing liquid/2D material hybrid devices.

Engineering an Indium Selenide van der Waals Interface for Multilevel Charge Storage.

As the continuous miniaturization of floating-gate transistors approaches a physical limit, new innovations in device architectures, working principles, and device materials are in high demand. This study demonstrated a nonvolatile memory structure with multilevel data storage that features a van der Waals gate architecture made up of a partially oxidized surface layer/indium selenide (InSe) van der Waals interface. The key functionality of this proof-of-concept device is provided through the generation of charge-trapping sites via an indirect oxygen plasma treatment on the InSe surface layer. In contrast to floating-gate nonvolatile memory, these sites have the ability to retain charge without the help of a gate dielectric. Together with the layered structure, the surface layer with charge-trapping sites facilitates continual electrostatic doping in the underlying InSe layers. The van der Waals gating effect is further supported by trapped charge-induced core-level energy shifts and relative work function variations obtained from operando scanning X-ray photoelectron spectroscopy and Kelvin probe microscopy, respectively. On modulating the amount of electric field-induced trapped electrons by the electrostatic gate potential, eight distinct storage states remained over 3000 s. Moreover, the device exhibits a high current switching ratio of 106 within 11 cycles. The demonstrated characteristics suggest that the engineering of an InSe interface has potential applications for nonvolatile memory.

Magnetotransport in hybrid InSe/monolayer graphene on SiC.

The magnetotransport properties of a hybrid InSe/monolayer graphene in a SiC system are systematically studied. Compared to those of its bare graphene counterpart, in InSe/graphene, we can effectively modify the carrier density, mobility, effective mass, and electron-electron (e-e) interactions enhanced by weak disorder. We show that in bare graphene and hybrid InSe/graphene systems, the logarithmic temperature (lnT) dependence of the Hall slope R H = Î´R xy /δB = Î´ρ xy /δB can be used to probe e-e interaction effects at various temperatures even when the measured resistivity does not show a lnT dependence due to strong electron-phonon scattering. Nevertheless, one needs to be certain that the change of R H is not caused by an increase of the carrier density by checking the magnetic field position of the longitudinal resistivity minimum at different temperatures. Given the current challenges in gating graphene on SiC with a suitable dielectric layer, our results suggest that capping a van der Waals material on graphene is an effective way to modify the electronic properties of monolayer graphene on SiC.

Unprecedented random lasing in 2D organolead halide single-crystalline perovskite microrods.

Three-dimensional organic-inorganic hybrid halide perovskites have been demonstrated as great materials for applications in optoelectronics and photonics. However, their inherent instabilities in the presence of moisture, light, and heat may hinder their commercialization. Alternatively, emerging two-dimensional (2D) organic-inorganic hybrid perovskites have recently attracted increasing attention owing to their great environmental stability and inherent natural quantum-well structure. In this work, we have synthesized a high-quality long-chain organic diammonium spacer assisted 2D hybrid perovskite FA-(N-MPDA)PbBr4 (FA = formamidinium and N-MPDA = N-methylpropane-1,3-diammonium) by the slow evaporation at constant temperature method. The millimeter-sized single-crystalline microrods demonstrate low threshold random lasing behavior at room temperature. The single-crystalline 2D hybrid perovskite random laser achieved a very narrow linewidth (∼0.1 nm) with a low threshold (∼0.5 µJ cm-2) and a high quality factor (∼5350). Furthermore, the 2D hybrid microrod laser shows stable lasing emission with no measurable degradation after at least 2 h under continuous illumination, which substantially proves the stability of 2D perovskites. Our results demonstrate the promise of 2D organic-inorganic microrod-shaped perovskites and provide an important step toward the realization of high-performance optoelectronic devices.

Femtosecond time-evolution of mid-infrared spectral line shapes of Dirac fermions in topological insulators.

Mid-infrared (MIR) light sources have much potential in the study of Dirac-fermions (DFs) in graphene and topological insulators (TIs) because they have a low photon energy. However, the topological surface state transitions (SSTs) in Dirac cones are veiled by the free carrier absorption (FCA) with same spectral line shape that is always seen in static MIR spectra. Therefore, it is difficult to distinguish the SST from the FCA, especially in TIs. Here, we disclose the abnormal MIR spectrum feature of transient reflectivity changes (ΔR/R) for the non-equilibrium states in TIs, and further distinguish FCA and spin-momentum locked SST using time-resolved and linearly polarized ultra-broadband MIR spectroscopy with no environmental perturbation. Although both effects produce similar features in the reflection spectra, they produce completely different variations in the ΔR/R to show their intrinsic ultrafast dynamics.

Modulating Charge Separation with Hexagonal Boron Nitride Mediation in Vertical Van der Waals Heterostructures.

Tuning the optical and electrical properties by stacking different layers of two-dimensional (2D) materials enables us to create unusual physical phenomena. Here, we demonstrate an alternative approach to enhance charge separation and alter physical properties in van der Waals heterojunctions with type-II band alignment by using thin dielectric spacers. To illustrate our working principle, we implement a hexagonal boron nitride (h-BN) sieve layer in between an InSe/GeS heterojunction. The optical transitions at the junctions studied by photoluminescence and the ultrafast pump-probe technique show quenching of emission without h-BN layers exhibiting an indirect recombination process. This quenching effect due to strong interlayer coupling was confirmed with Raman spectroscopic studies. In contrast, h-BN layers in between InSe and GeS show strong enhancement in emission, giving another degree of freedom to tune the heterojunction property. The two-terminal photoresponse study supports the argument by showing a large photocurrent density for an InSe/h-BN/GeS device by avoiding interlayer charge recombination. The enhanced charge separation with h-BN mediation manifests a photoresponsivity and detectivity of 9 × 102 A W-1 and 3.4 × 1014 Jones, respectively. Moreover, a photogain of 1.7 × 103 shows a high detection of electrons for the incident photons. Interestingly, the photovoltaic short-circuit current is switched from positive to negative, whereas the open-circuit voltage changes from negative to positive. Our proposed enhancement of charge separation with 2D-insulator mediation, therefore, provides a useful route to manipulate the physical properties of heterostructures and for the future development of high-performance optoelectronic devices.

Ultralow Schottky Barriers in Hexagonal Boron Nitride-Encapsulated Monolayer WSe2 Tunnel Field-Effect Transistors.

To explore the potential of field-effect transistors (FETs) based on monolayers (MLs) of the two-dimensional semiconducting channel (SC) for spintronics, the two most important issues are to ensure the formation of variable low-resistive tunnel ferromagnetic contacts (FCs) and to preserve intrinsic properties of the SC during fabrication. Large Schottky barriers lead to the formation of high resistive contacts, and methods adopted to control the barriers often alter the intrinsic properties of the SC. This work aims at addressing both issues in fully encapsulated ML WSe2 FETs using bilayer hexagonal boron nitride (h-BN) as a tunnel barrier at the FC/SC interface. We investigate the electrical transport in ML WSe2 FETs with the current-in-plane geometry that yields hole mobilities of ∼38.3 cm2 V-1 s-1 at 240 K and on/off ratios of the order of 107, limited by the contact regions. We have achieved an ultralow effective Schottky barrier (∼5.34 meV) with an encapsulated tunneling device as opposed to a nonencapsulated device in which the barrier heights are considerably higher. These observations provide an insight into the electrical behavior of the FC/h-BN/SC/h-BN heterostructures, and such control over the barrier heights opens up the possibilities for WSe2-based spintronic devices.

Selenium nanoparticle prepared by femtosecond laser-induced plasma shock wave.

A novel approach for the production of both amorphous and crystalline selenium nanoparticles (SeNPs) using femtosecond laser-induced plasma shock wave on the surface of Bi2Se3 topological insulators at room temperature and ambient pressure is demonstrated. The shape and size of SeNPs can be reliably controlled via the kinetic energy obtained from laser pulses, so these are applicable as active components in nanoscale applications. Importantly, the rapid, low-cost and eco-friendly synthesis strategy developed in this study could also be extendable to other systems.

Crystal Growth and Magnetic Properties of Topological Nodal-Line Semimetal GdSbTe with Antiferromagnetic Spin Ordering.

We report crystal growth, AC and DC magnetic susceptibilities [χ(T, H)], magnetization [M(T, H)], and heat capacity [CP(T, H)] measurement results of GdSbTe single crystal. GdSbTe is isostructural to the confirmed nonmagnetic nodal-line semimetal ZrSiS of noncentrosymmetric tetragonal crystal structure in space group P4/nmm (No. 129), but it shows additional long-range antiferromagnetic spin ordering for the Gd spins of S = 7/2 below TN. Both χ(T, H) and CP(T, H) measurements confirm the existence of a long-range antiferromagnetic (AFM) spin ordering of Gd spins below TN ∼ 12 K, and an additional spin reorientation/recovery (sr) behavior is identified from the change of on-site spin anisotropy between Tsr1 ∼ 7 and Tsr2 ∼ 4 K. The anisotropic magnetic susceptibilities of χ(T, H) below TN clearly demonstrate that the AFM long-range spin ordering of GdSbTe has an easy axis parallel to the ab-plane direction. The field- and orientation-dependent magnetization of M(T, H) at 2 K shows two plateaus to indicate the spin-flop transition for H||ab near ∼2.1 T and a metamagnetic state near ∼5.9 T having ∼1/3 of the fully polarized magnetization by the applied field. The heat capacity measurement results yield Sommerfeld coefficient of γ ∼ 7.6(4) mJ/mol K2 and θD ∼ 195(2) K being less than half of that for the nonmagnetic ZrSiS. A three-dimensional (3D) AFM spin structure is supported by the ab initio calculations for Gd having magnetic moment of 7.1 µB and the calculated AFM band structure indicates that GdSbTe is a semimetal with bare density of states (0.36 states/eV fu) at the Fermi level, which is 10 times smaller than the measured one to suggest strong spin-fluctuation.

Sn-Doping Enhanced Ultrahigh Mobility In1-xSnxSe Phototransistor.

Two-dimensional ternary materials are attracting widespread interest because of the additional degree of freedom available to tailor the material property for a specific application. An In1-xSnxSe phototransistor possessing tunable ultrahigh mobility by Sn-doping engineering is demonstrated in this study. A striking feature of In1-xSnxSe flakes is the reduction in the oxide phase compared to undoped InSe, which is validated by spectroscopic analyses. Moreover, first-principles density functional calculations performed for the In1-xSnxSe crystal system reveal the same effective mass when doped with Sn atoms. Hence, because of an increased lifetime owing to the enhanced crystal quality, the carriers in In1-xSnxSe have higher mobility than in InSe. The internally boosted electrical properties of In1-xSnxSe exhibit ultrahigh mobility of 2560 ± 240 cm2 V-1 s-1 by suppressing the interfacial traps with substrate modification and channel encapsulation. As a phototransistor, the ultrathin In1-xSnxSe flakes are highly sensitive with a detectivity of 1014 Jones. It possesses a large photoresponsivity and photogain (Vg = 40 V) as high as 3 × 105 A W-1 and 0.5 × 106, respectively. The obtained results outperform all previously reported performances of InSe-based devices. Thus, the doping-engineered In1-xSnxSe-layered semiconductor finds a potential application in optoelectronics and meets the demand for faster electronic technology.

The dp type π-bond and chiral charge density waves in 1T-TiSe2.

Based on the atomic electronic configuration and Ti-Se coordination, a valence bond model for the layered transition metal dichalcogenide (TMDC) 1T-TiSe2 is proposed. 1T-TiSe2 is viewed as being composed of edge-sharing TiSe4-plaquettes as TiSe2-ribbon chains in each layer via a directional valence shell electron distribution as chemical bonds, in contrast to the conventional layer view of face-sharing TiSe6-octahedra. The four valence electrons per Ti in the hybridized dsp2-orbitals of square coordination form σ-bonds with the four nearest neighbor Se atoms in the chain. The electrons in the lone pair of the Se-4pz orbital are proposed to form a dp type π-bond via side-to-side orbital overlap with the empty Ti-3dxz/3dyz orbitals within each chain, which is positively supported by quantum chemistry calculations. A study of electron energy loss spectroscopy (EELS) with transmission electron microscopy (TEM) for 1T-TiSe2 is presented to show an energy loss near ∼7 and ∼20 eV, which confirms the existence of collective plasmon oscillations with the predicted effective electron numbers for the π- and (π + σ)-bond electrons, respectively.

Ultra-high performance flexible piezopotential gated In1-xSnxSe phototransistor.

Flexible optoelectronic devices facilitated by the piezotronic effect have important applications in the near future in many different fields ranging from solid-state lighting to biomedicine. Two-dimensional materials possessing extraordinary mechanical strength and semiconducting properties are essential for realizing nanopiezotronics and piezo-phototronics. Here, we report the first demonstration of piezo-phototronic properties in In1-xSnxSe flexible devices by applying systematic mechanical strain under photoexcitation. Interestingly, we discover that the dark current and photocurrent are increased by five times under a bending strain of 2.7% with a maximum photoresponsivity of 1037 AW-1. In addition, the device can act as a strain sensor with a strain sensitivity up to 206. Based on these values, the device outperforms the same class of devices in two-dimensional materials. The underlying mechanism responsible for the discovered behavior can be interpreted in terms of piezoelectric potential gating, allowing the device to perform like a phototransistor. The strain-induced gate voltage assists in the efficient separation of photogenerated charge carriers and enhances the mobility of In1-xSnxSe, resulting in good performance on a freeform surface. Thus, our multifunctional device is useful for the development of a variety of advanced applications and will help meet the demand of emerging technologies.

High-Performance InSe Transistors with Ohmic Contact Enabled by Nonrectifying Barrier-Type Indium Electrodes.

The electrical contact to two-dimensional (2D) semiconductor materials is decisive to the electronic performance of 2D semiconductor field-effect devices (FEDs). The presence of a Schottky barrier often leads to a large contact resistance, which seriously limits the channel conductance and carrier mobility measured in a two-terminal geometry. In contrast, Ohmic contact is desirable and can be achieved by the presence of a nonrectifying or tunneling barrier. Here, we demonstrate that a nonrectifying barrier can be realized by contacting indium (In), a low work function metal, with layered InSe because of a favorable band alignment at the In-InSe interface. The nonrectifying barrier is manifested by Ohmic contact behavior at T = 2 K and a low barrier height, ΦB = 50 meV. This Ohmic contact enables demonstration of an on-current as large as 410 µA/µm, which is among the highest values achieved in FEDs based on layered semiconductors. A high electron mobility of 3700 and 1000 cm2/V·s is achieved with the two-terminal In-InSe FEDs at T = 2 K and room temperature, respectively, which can be attributed to enhanced quality of both conduction channel and the contacts. The improvement in the contact quality is further proven by an X-ray photoelectron spectroscopy study, which suggests that a reduction effect occurs at the In-InSe interface. The demonstration of high-performance In-InSe FEDs indicates a viable interface engineering method for next-generation, 2D semiconductor-based electronics.

Tuning Rashba Spin-Orbit Coupling in Gated Multilayer InSe.

Manipulating the electron spin with the aid of spin-orbit coupling (SOC) is an indispensable element of spintronics. Electrostatically gating a material with strong SOC results in an effective magnetic field which can in turn be used to govern the electron spin. In this work, we report the existence and electrostatic tunability of Rashba SOC in multilayer InSe. We observed a gate-voltage-tuned crossover from weak localization (WL) to weak antilocalization (WAL) effect in quantum transport studies of InSe, which suggests an increasing SOC strength. Quantitative analyses of magneto-transport studies and energy band diagram calculations provide strong evidence for the predominance of Rashba SOC in electrostatically gated InSe. Furthermore, we attribute the tendency of the SOC strength to saturate at high gate voltages to the increased electronic density of states-induced saturation of the electric field experienced by the electrons in the InSe layer. This explanation of nonlinear gate voltage control of Rashba SOC can be generalized to other electrostatically gated semiconductor nanomaterials in which a similar tendency of spin-orbit length saturation was observed (e.g., nanowire field effect transistors), and is thus of broad implications in spintronics. Identifying and controlling the Rashba SOC in InSe may serve pivotally in devising III-VI semiconductor-based spintronic devices in the future.

Low-Threshold Lasing from 2D Homologous Organic-Inorganic Hybrid Ruddlesden-Popper Perovskite Single Crystals.

Organic-inorganic hybrid two-dimensional (2D) perovskites have recently attracted great attention in optical and optoelectronic applications due to their inherent natural quantum-well structure. We report the growth of high-quality millimeter-sized single crystals belonging to homologous two-dimensional (2D) hybrid organic-inorganic Ruddelsden-Popper perovskites (RPPs) of (BA)2(MA) n-1Pb nI3 n+1 ( n = 1, 2, and 3) by a slow evaporation at a constant-temperature (SECT) solution-growth strategy. The as-grown 2D hybrid perovskite single crystals exhibit excellent crystallinity, phase purity, and spectral uniformity. Low-threshold lasing behaviors with different emission wavelengths at room temperature have been observed from the homologous 2D hybrid RPP single crystals. Our result demonstrates that solution-growth homologous organic-inorganic hybrid 2D perovskite single crystals open up a new window as a promising candidate for optical gain media.

Non-Fermi Liquids as Highly Active Oxygen Evolution Reaction Catalysts.

The oxygen evolution reaction (OER) plays a key role in emerging energy conversion technologies such as rechargeable metal-air batteries, and direct solar water splitting. Herein, a remarkably low overpotential of ≈150 mV at 10 mA cm-2disk in alkaline solutions using one of the non-Fermi liquids, Hg2Ru2O7, is reported. Hg2Ru2O7 displays a rapid increase in current density and excellent durability as an OER catalyst. This outstanding catalytic performance is realized through the coexistence of localized d-bands with the metallic state that is unique to non-Fermi liquids. The findings indicate that non-Fermi liquids could greatly improve the design of highly active OER catalysts.

Topological Quantum Phase Transition and Superconductivity Induced by Pressure in the Bismuth Tellurohalide BiTeI.

A pressure-induced topological quantum phase transition has been theoretically predicted for the semiconductor bismuth tellurohalide BiTeI with giant Rashba spin splitting. In this work, evolution of the electrical transport properties in BiTeI and BiTeBr is investigated under high pressure. The pressure-dependent resistivity in a wide temperature range passes through a minimum at around 3 GPa, indicating the predicted topological quantum phase transition in BiTeI. Superconductivity is observed in both BiTeI and BiTeBr, while resistivity at higher temperatures still exhibits semiconducting behavior. Theoretical calculations suggest that superconductivity may develop from the multivalley semiconductor phase. The superconducting transition temperature, Tc , increases with applied pressure and reaches a maximum value of 5.2 K at 23.5 GPa for BiTeI (4.8 K at 31.7 GPa for BiTeBr), followed by a slow decrease. The results demonstrate that BiTeX (X = I, Br) compounds with nontrivial topology of electronic states display new ground states upon compression.

Magnetocrystalline two-fold symmetry in CaFe2O4 single crystal.

Understanding of magnetocrystalline anisotropy in CaFe2O4 is a matter of importance for its future applications. A high quality single crystal CaFe2O4 sample is studied by using synchrotron x-ray diffraction, a magnetometer and the electron spin resonance (ESR) technique. A broad feature of the susceptibility curve around room temperature is observed, indicating the development of 1D spin interactions above the on-set of antiferromagnetic transition. The angular dependency of ESR reveals an in-plane two-fold symmetry, suggesting a strong correlation between the room temperature spin structure and magnetocrystalline anisotropy. This finding opens an opportunity for the device utilizing the anisotropy field of CaFe2O4.

Anomalous Acoustic Plasmon Mode from Topologically Protected States.

Plasmons, the collective excitations of electrons in the bulk or at the surface, play an important role in the properties of materials, and have generated the field of "plasmonics." We report the observation of a highly unusual acoustic plasmon mode on the surface of a three-dimensional topological insulator (TI) Bi_{2}Se_{3}, using momentum resolved inelastic electron scattering. In sharp contrast to ordinary plasmon modes, this mode exhibits almost linear dispersion into the second Brillouin zone and remains prominent with remarkably weak damping not seen in any other systems. This behavior must be associated with the inherent robustness of the electrons in the TI surface state, so that not only the surface Dirac states but also their collective excitations are topologically protected. On the other hand, this mode has much smaller energy dispersion than expected from a continuous media excitation picture, which can be attributed to the strong coupling with surface phonons.

Screening limited switching performance of multilayer 2D semiconductor FETs: the case for SnS.

Gate tunable p-type multilayer tin mono-sulfide (SnS) field-effect transistor (FET) devices with SnS thickness between 50 and 100 nm were fabricated and studied to understand their performance. The devices showed anisotropic inplane conductance and room temperature field effect mobilities ∼5-10 cm2 V-1 s-1. However, the devices showed an ON-OFF ratio ∼10 at room temperature due to appreciable OFF state conductance. The weak gate tuning behavior and finite OFF state conductance in the depletion regime of SnS devices are explained by the finite carrier screening length effect which causes the existence of a conductive surface layer from defect induced holes in SnS. Through etching and n-type surface doping by Cs2CO3 to reduce/compensate the not-gatable holes near the SnS flake's top surface, the devices exhibited an order of magnitude improvement in the ON-OFF ratio, and a hole Hall mobility of ∼100 cm2 V-1 s-1 at room temperature is observed. This work suggests that in order to obtain effective switching and low OFF state power consumption, two-dimensional (2D) semiconductor based depletion mode FETs should limit their thickness to within the Debye screening length of the carriers in the semiconductor.