All-Optical Valley Polarization Switch via Controlling Spin-Triplet and Spin-Singlet Interlayer Exciton Emission in WS2/WSe2 Heterostructure.

Although selective singlet and triplet interlayer exciton (IX) emission of transition metal dichalcogenides (TMD) heterostructures can be achieved by applying an electric or magnetic field, the device structure is complex and a low temperature is usually required. Here, we demonstrate a simple all-optical approach to selectively enhance the emission of singlet and triplet IX by selectively coupling singlet or triplet IX of a WS2/WSe2 heterostructure to a SiO2 microsphere cavity. Angle-resolved photoluminescene reveals that the transition dipole of triplet IX is almost along the out-of-plane direction, while singlet IX only has 69% out-of-plane dipole moment contribution. Since the out-of-plane dipole presents a higher Purcell factor within the cavity, we can simultaneously enhance the emission intensity of IX and control the emissive IX species at room temperature in an all-optical route. Importantly, we demonstrate an all-optical valley polarization switch with a record high on/off ratio of 35.

Generation of Tunable Terahertz Waves from Tailored Versatile Spintronic Meta-Antenna Arrays.

Broadband spintronic terahertz (THz) radiation can be efficiently generated by spin-to-charge current conversion in a ferromagnetic/nonmagnetic heterostructure. There had been many studies on realizing the enhancement or the modulation of spintronic terahertz waves. However, reported devices so far focus on implementing certain specific modulation methods, either related to the spintronic stacks or related to the metamaterial structures. In this study, a set of femtosecond laser-driven versatile spintronic terahertz devices are proposed by integrating meta-antenna structures with W/CoFeB/Pt nanolayer stacks. These monolithic integrated devices exhibit spintronic terahertz wave emission, spectral modulation, and polarization manipulation simultaneously. The terahertz pulses are generated within the ferromagnetic heterostructure interfaces and transmitted along the metallic structures, leading to the modulation of the spintronic terahertz waves. Results have shown that the center-frequency shift is up to 140 GHz and the value of ellipticity can reach 0.6, demonstrating a set of integrated and efficient spintronic terahertz devices to modulate the emitted wave. In addition, compared with the slotline antenna, the maximum peak value of the bandpass band is enhanced up to 1.63 times by carefully designing the metamaterial structure. The spintronic meta-antenna array proposed here paves an integrated way for the manipulation of spintronic terahertz optoelectronic devices.

Identifying the contributions of root and foliage gaseous/particle uptakes to indoor plants for phthalates, OPFRs and PAHs.

Understanding the uptake pathways of organic chemicals in plants can help us use plants as biosentinels for human exposure, and as remediation tools for contaminated sites. Herein, we investigated the relative contributions of root and foliar (gas and particle) uptake pathways to indoor ornamental plants for phthalates (PAEs), organophosphorus flame retardants (OPFRs), and polycyclic aromatic hydrocarbons (PAHs). We looked at different kinds of indoor ornamental plants via pot and hydroponic control experiments, comparing the levels between their leaves and indoor air gaseous and particle phases, floor dust, and window film. Contributions of soil and foliage uptakes were calculated based on chemical concentrations in leaves of hydroponic and soil cultured plants and their mass uptake rates. Across all compounds, the contributions of root uptake to the chemicals in soil cultured plants ranged from 47.5 % to 88.5 %. We used binary first-order mass conservation equations to calculate the contributions of foliage uptake via gaseous and particle phases to the chemicals with similar Kow in plant leaves. Foliar uptake of PAEs occurred mainly via particle adsorption, for light PAHs via gaseous absorption, and for OPFRs via both particle and gaseous uptakes. Negative correlations between chemicals' foliage uptake ratios and their Kow and Koa values suggest that foliage uptake may be influenced by both chemical hydrophilicity and lipophilicity.

Layer-Number Engineered Momentum-Indirect Interlayer Excitons with Large Spectral Tunability.

Interlayer excitons (IXs) in type II van der Waals (vdW) heterostructures are equipped with an oriented permanent dipole moment and long lifetime and thus would allow promising applications in excitonic and optoelectronic devices. However, based on the widely studied heterostructures of transition-metal dichalcogenides (TMDs), IX emission is greatly influenced by the lattice mismatch and geometric misalignment between the constituent layers, increasing the complexity of the device fabrication. Here, we report on the robust momentum-indirect IX emission in TMD/two-dimensional (2D) perovskite vdW heterostructures, which were fabricated without considering the orientation arrangement or momentum mismatch. The IXs show a large diffusion coefficient of ∼10 cm2 s-1, and importantly the IX emission energy can be widely tuned from 1.3 to 1.6 eV via changing the layer number of the 2D perovskite or the thickness of TMD flakes, shedding light on the applications of vdW interface engineering to broad-spectrum optoelectronics.

Light-Controlled Reconfigurable Optical Synapse Based on Carbon Nanotubes/2D Perovskite Heterostructure for Image Recognition.

Two-dimensional (2D) halide perovskite material is characterized by a mixed conducting behavior that possesses both electronic and ionic conductivity. The study on the influence of the light on ion migration in the 2D perovskite is helpful to improve the performance of perovskite-based optoelectronic devices. Here, we constructed an exfoliated 2D perovskite/carbon nanotubes (CNTs) heterostructure optical synapse, in which CNTs can be used as nanoprobes to qualitatively observe the ion aggregation or dissipation process in 2D perovskite, and found that light significantly changes the memory curve of the reconfigurable optical synapses. Through the molecular dynamic simulation, the dynamic process of ion migration in the heterostructure was simulated and the electrostatic interaction effect of nonequilibrium charge distribution of CNTs on iodide ion was demonstrated. Finally, an effective light-controlled process was realized through the synapses, which in situ regulated the performance of the weight-value discretized BP (WD-BP) neural network. This work lays a foundation for the future development of intelligent nano-optoelectronic devices.

Nonvolatile electrical switching of optical and valleytronic properties of interlayer excitons.

Long-lived interlayer excitons (IXs) in van der Waals heterostructures (HSs) stacked by monolayer transition metal dichalcogenides (TMDs) carry valley-polarized information and thus could find promising applications in valleytronic devices. Current manipulation approaches for valley polarization of IXs are mainly limited in electrical field/doping, magnetic field or twist-angle engineering. Here, we demonstrate an electrochemical-doping method, which is efficient, in-situ and nonvolatile. We find the emission characteristics of IXs in WS2/WSe2 HSs exhibit a large excitonic/valley-polarized hysteresis upon cyclic-voltage sweeping, which is ascribed to the chemical-doping of O2/H2O redox couple trapped between WSe2 and substrate. Taking advantage of the large hysteresis, a nonvolatile valley-addressable memory is successfully demonstrated. The valley-polarized information can be non-volatilely switched by electrical gating with retention time exceeding 60 min. These findings open up an avenue for nonvolatile valley-addressable memory and could stimulate more investigations on valleytronic devices.

Self-Powered Filterless On-Chip Full-Stokes Polarimeter.

The detection of polarization states of light is essential in photonic and optoelectronic devices. Currently, the polarimeters are usually constructed with the help of waveplates or a comprehensive metasurface, which will inevitably increase the fabrication complexity and unnecessary energy loss. Here, we have successfully demonstrated a self-powered filterless on-chip full-Stokes polarimeter based on a single-layer MoS2/few-layer MoS2 homojunction. Combining the built-in electric field enhanced circular photogalvanic effect with the intrinsic optical anisotropy of MoS2 between in-plane and out-of-plane directions, the device is able to conveniently sense four Stokes parameters of incident light at zero bias without requiring an extra filtering layer and can function in the wavelength range of 650-690 nm with acceptable average errors. Besides, this homojunction device is easy to integrate with silicon-based chips and could have much smaller sizes than metasurface based polarimeters. Our study thus provides an excellent paradigm for high-performance on-chip filterless polarimeters.

Thermally Assisted Rashba Splitting and Circular Photogalvanic Effect in Aqueously Synthesized 2D Dion-Jacobson Perovskite Crystals.

Recently, a two-dimensional Dion-Jacobson (DJ) perovskite (AMP)PbI4 (AMP = 4-(aminomethyl)piperidinium) is emerging with remarkable Rashba effect and ferroelectricity. However, the origin of the giant Rashba splitting remains elusive and the current synthetic strategy via slow cooling is time- and power-consuming, hindering its future applications. Here, we report on an economical aqueous method to obtain (AMP)PbI4 crystals and clarify the origin of the giant Rashba effect by temperature- and polarization-dependent photoluminescence (PL) spectroscopy. The strong temperature-dependent PL helicity indicates the thermally assisted structural distortion as the main origin of the Rashba effect, suggesting that valley polarization still preserves at high temperatures. The Rashba effect was further confirmed by the circular photogalvanic effect near the indirect bandgap. Our study not only optimizes the synthetic strategies of this DJ perovskite but also sheds light on its potential applications in room/high-temperature spintronics and valleytronics.

Exciton-Phonon Interaction-Induced Large In-Plane Optical Anisotropy in Two-Dimensional All-Inorganic Perovskite Crystals.

Two-dimensional (2D) perovskites are an emerging class of layered materials with unique optoelectronic properties. To date, most 2D perovskites with Ruddlesden-Popper (RP) phase reported are organic- inorganic hybrid perovskites with long organic spacers. Here, we report a high-quality all-inorganic 2D perovskite, Cs2PbI2Cl2, synthesized by an aqueous method. The as-synthesized perovskite crystals exhibit large in-plane emission and reflection optical anisotropy. The maximum in-plane linear dichroic ratio is up to 9.6 for exciton emission and 2.0 for reflection at 77 K. The large in-plane optical anisotropy may be ascribed to the strong electron-phonon interaction-induced lattice distortion. The large optical anisotropy enables us to construct a polarization-sensitive photodetector based on this perovskite, for which the linear dichroic ratio of photoresponse is about 1.2. Our study provides an alternative avenue to achieve in-plane optical anisotropy in an isotropy structure and thus would be of great importance for polarization-associated applications.

Multistate Memory Enabled by Interface Engineering Based on Multilayer Tungsten Diselenide.

The diversification of data types and the explosive increase of data size in the information era continuously required to miniaturize the memory devices with high data storage capability. Atomically thin two-dimensional (2D) transition metal dichalcogenides (TMDs) are promising candidates for flexible and transparent electronic and optoelectronic devices with high integration density. Multistate memory devices based on TMDs could possess high data storage capability with a large integration density and thus exhibit great potential applications in the field of data storage. Here, we report the multistate data storage based on multilayer tungsten diselenide (WSe2) transistors by interface engineering. The multiple resistance states of the WSe2 transistors are achieved by applying different gate voltage pulses, and the switching ratio of the memory can be as large as 105 with high cycling endurance. The water and oxygen molecules (H2O/O2) trapped at the interface between the SiO2 substrate and WSe2 introduce the trap states and thus the large hysteresis of the transfer curves, which leads to the multistate data storage. In addition, the laminated Au thin film electrodes make the contact interface between the electrodes and WSe2 free of dangling bond and Fermi level pinning, thus giving rise to the excellent performance of memory devices. Importantly, the interface trap states can be easily controlled by a simple oxygen plasma treatment of the SiO2 substrate, and subsequently, the performance of the multistate memory devices can be manipulated. Our findings provide a simple and efficient strategy to engineer the interface states for the multistate data storage applications and would motivate more investigations on the trap state-associated applications.

Manipulation of Valley Pseudospin by Selective Spin Injection in Chiral Two-Dimensional Perovskite/Monolayer Transition Metal Dichalcogenide Heterostructures.

Monolayer two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted great interest in spintronics and valleytronics due to the spin-valley locking effect. To efficiently control and manipulate the valley pseudospin is of paramount importance for valley-based electronics and optoelectronics. A variety of strategies have been developed to address the valley pseudospin including optical, electrical, and magnetic methods; nonetheless, they involve either below liquid-nitrogen temperature or an external magnetic field, which increases the cost and complexity of the devices. Here, we report a straightforward way to manipulate valley polarization in monolayer TMDs via selective spin injection in chiral 2D perovskite/monolayer TMD (e.g., MoS2 and WSe2) van der Waals heterostructures without requiring an external magnetic field or specially designed device structures. We show the dangling-bond-free vdW interface can allow an impressive average spin injection efficiency of 78% to produce persistent valley polarization in monolayer MoS2 (WSe2) over 10% from liquid-nitrogen temperature to above 200 K. We attribute the valley polarization of monolayer MoS2 (WSe2) to selective spin injection from chiral 2D perovskites, which can effectively introduce population imbalance between valleys in monolayer MoS2 (WSe2). Our findings provide an alternative strategy to manipulate the valley polarization in TMDs without requiring circularly polarized light excitation, below liquid-nitrogen temperature, or external magnetic field, and thus would promote the development of perovskite-based spintronic and valleytronic devices.

Robust Interlayer Coupling in Two-Dimensional Perovskite/Monolayer Transition Metal Dichalcogenide Heterostructures.

Interlayer excitons have been extensively studied in monolayer transition metal dichalcogenide (TMD) heterobilayers mainly due to the long lifetime, which is beneficial for a wide range of optoelectronic applications. To date, the majority of investigations of interlayer excitons in TMD heterobilayers have been focusing on the geometric arrangement of structures, spin-valley lifetime, and interlayer valley excitons with interlayer hopping rules. Nevertheless, interlayer excitons in TMD heterobilayers strongly depend on the local atomic registry and coupling strength, which increase the complexity of the device fabrication. Here, we report pronounced interlayer exciton emission in two-dimensional (2D) perovskite/monolayer TMD heterostructures without the need of thermal annealing or specific geometric arrangements, and the interlayer exciton emission is rather general among 2D perovskites and monolayer TMDs. Such interlayer exciton emission completely dominates the emission spectrum at 78 K regardless of the stacking sequence, suggesting the robust interlayer coupling in 2D perovskite/monolayer TMD heterostructures. Furthermore, the interlayer exciton emission shows a large blue-shift with increasing laser intensity due to the repulsive dipole-dipole interaction and can persist above 220 K. Importantly, the interlayer exciton emission also possesses robust circular polarization in chiral 2D perovskite/monolayer WSe2 heterostructures, which can be applied to manipulate the valley degree of freedom for valleytronic devices. Our findings would provide a favorable platform to explore interlayer coupling and related physical processes in 2D perovskites and TMDs and further provoke more investigations into the understanding and controlling of excitonic effects and associated optoelectronic applications in van der Waals heterostructures over a broad-range spectral response.

Reversible luminescent humidity chromism of organic-inorganic hybrid PEA2MnBr4 single crystals.

Organic-inorganic hybrids have drawn great attention for gas sensors due to their high sensitivity, good selectivity and acceptable stability at room temperature. There are two main approaches by which organic-inorganic hybrids convert gas information to electric or optical signals (vapochromism). Here, we have reported a new organic-inorganic hybrid PEA2MnBr4 for humidity detection by luminescent visible chromism. PEA2MnBr4 single crystals were grown by the solution method and determined by single-crystal X-ray diffraction. Luminescent humidity chromism was found on PEA2MnBr4 from green emission at the water-desorption state to pink emission at the water-adsorption state within 18 s at a relative humidity of 38% RH. This obviously visible chromism was further used to check the water content in toluene with a low detection limit between 0.02 and 0.05 vol%.

Circularly Polarized Luminescence from Chiral Tetranuclear Copper(I) Iodide Clusters.

Circularly polarized luminescent (CPL) materials are promising in applications such as 3D displays and quantum communication. Hybrid organic-inorganic copper(I) iodides have been rapidly developed due to their intense photoluminescence and structural diversity; nevertheless, the reported Cu-I clusters rarely show CPL activities. In this study, we introduced chiral organic molecules R/S-methylbenzylammonium (R/S-MBA) into Cu-I inorganic skeletons to achieve chiral tetranuclear (R/S-MBA)4Cu4I4 clusters with intense orange luminescence and CPL activity at room temperature. These enantiomeric (R/S-MBA)4Cu4I4 clusters show oppositely signed circular dichroism (CD) signals, which agree well with their simulated electronic CD spectra. The crystallization-induced helical arrangement of (R/S-MBA)4Cu4I4 clusters and their largely distorted polynuclear configuration demonstrate a new platform for the study of chiral-related properties.

Anisotropy of Excitons in Two-Dimensional Perovskite Crystals.

Two-dimensional (2D) perovskites show great potential for optoelectronic applications due to their bandgap tunability, extremely large excition binding energy, and large crystal anisotropy compared with their three-dimensional counterparts. To fully explore exciton-based applications and improve their performance, it is essential to understand the exciton behavior in 2D perovskites. Here, we investigate exciton anisotropy within the crystallographic plane and cross plane of (C4H9NH3)2PbI4 2D perovskite crystals by polarization-resolved photoluminescence, reflection, and photoconductivity studies. We observe a polarization-dependent emission evolution and an enhanced self-trapped exciton emission with an oblique incident excitation from the cross plane. Furthermore, the anisotropy of excitons in (C4H9NH3)2PbI4 2D perovskite crystals is identified by polarization-resolved photoluminescence and photoconductivity measurement, and a completely opposite polarization-dependent behavior was observed for free excitons and self-trapped excitons. We attribute this different anisotropy to the existence of out-of-plane excitons and different optical selection rule for free excitons and self-trapped excitons. Our findings will shed light on designing and improving the performance of exciton-based optoelectronic devices in 2D perovskites.

Self-trapped excitons in two-dimensional perovskites.

With strong electron-phonon coupling, the self-trapped excitons are usually formed in materials, which leads to the local lattice distortion and localized excitons. The self-trapping strongly depends on the dimensionality of the materials. In the three-dimensional case, there is a potential barrier for self-trapping, whereas no such barrier is present for quasi-one-dimensional systems. Two-dimensional (2D) systems are marginal cases with a much lower potential barrier or nonexistent potential barrier for the self-trapping, leading to the easier formation of self-trapped states. Self-trapped excitons emission exhibits a broadband emission with a large Stokes shift below the bandgap. 2D perovskites are a class of layered structure material with unique optical properties and would find potential promising optoelectronic. In particular, self-trapped excitons are present in 2D perovskites and can significantly influence the optical and electrical properties of 2D perovskites due to the soft characteristic and strong electron-phonon interaction. Here, we summarized the luminescence characteristics, origins, and characterizations of self-trapped excitons in 2D perovskites and finally gave an introduction to their applications in optoelectronics.

Light-Enhanced Ion Migration in Two-Dimensional Perovskite Single Crystals Revealed in Carbon Nanotubes/Two-Dimensional Perovskite Heterostructure and Its Photomemory Application.

Two-dimensional (2D) hybrid perovskite sandwiched between two long-chain organic layers is an emerging class of low-cost semiconductor materials with unique optical properties and improved moisture stability. Unlike conventional semiconductors, ion migration in perovskite is a unique phenomenon possibly responsible for long carrier lifetime, current-voltage hysteresis, and low-frequency giant dielectric response. While there are many studies of ion migration in bulk hybrid perovskite, not much is known for its 2D counterparts, especially for ion migration induced by light excitation. Here, we construct an exfoliated 2D perovskite/carbon nanotube (CNT) heterostructure field effect transistor (FET), not only to demonstrate its potential in photomemory applications, but also to study the light induced ion migration mechanisms. We show that the FET I-V characteristic curve can be regulated by light and shows two opposite trends under different CNT oxygen doping conditions. Our temperature-dependent study indicates that the change in the I-V curve is probably caused by ion redistribution in the 2D hybrid perovskite. The first principle calculation shows the reduction of the migration barrier of I vacancy under light excitation. The device simulation shows that the increase of 2D hybrid perovskite dielectric constant (enabled by the increased ion migration) can change the I-V curve in the trends observed experimentally. Finally, the so synthesized FET shows the multilevel photomemory function. Our work shows that not only we could understand the unique ion migration behavior in 2D hybrid perovskite, it might also be used for many future memory function related applications not realizable in traditional semiconductors.

Improved Output Power of GaN-based VCSEL with Band-Engineered Electron Blocking Layer.

The vertical-cavity surface-emitting laser (VCSEL) has unique advantages over the conventional edge-emitting laser and has recently attracted a lot of attention. However, the output power of GaN-based VCSEL is still low due to the large electron leakage caused by the built-in polarization at the heterointerface within the device. In this paper, in order to improve the output power, a new structure of p-type composition-graded AlxGa1-xN electron blocking layer (EBL) is proposed in the VCSEL, by replacing the last quantum barrier (LQB) and EBL in the conventional structure. The simulation results show that the proposed EBL in the VCSEL suppresses the leaking electrons remarkably and contributes to a 70.6% increase of the output power, compared with the conventional GaN-based VCSEL.

InGaN/GaN Distributed Feedback Laser Diodes with Surface Gratings and Sidewall Gratings.

A variety of potential applications such as visible light communications require laser sources with a narrow linewidth and a single wavelength emission in the blue light region. The gallium nitride (GaN)-based distributed feedback laser diode (DFB-LD) is a promising light source that meets these requirements. Here, we present GaN DFB-LDs that share growth and fabrication processes and have surface gratings and sidewall gratings on the same epitaxial substrate, which makes LDs with different structures comparable. By electrical pulse pumping, single-peak emissions at 398.5 and 399.95 nm with a full width at half maximum (FWHM) of 0.32 and 0.23 nm were achieved, respectively. The surface and sidewall gratings were fabricated alongside the p-contact metal stripe by electrical beam lithography and inductively coupled plasma etching. DFB LDs with 2.5 µm ridge width exhibit a smaller FWHM than those with 5 and 10 µm ridge widths, indicating that the narrow ridge width is favorable for the narrowing of the line width of the DFB LD. The slope efficiency of the DFB LD with sidewall gratings is higher than that of surface grating DFB LDs with the same ridge width and period of gratings. Our experiment may provide a reliable and simple approach for optimizing gratings and GaN DFB-LDs.

Charge-Accumulation Effect in Transition Metal Dichalcogenide Heterobilayers.

Charge transfer in transition-metal-dichalcogenides (TMDs) heterostructures is a prerequisite for the formation of interlayer excitons, which hold great promise for optoelectronics and valleytronics. Charge accumulation accompanied by a charge-transfer process can introduce considerable effect on interlayer exciton-based applications; nevertheless, this aspect has been rarely studied up to date. This work demonstrates how the charge accumulation affects the light emission of interlayer excitons in van der Waals heterobilayers (HBs) consisting of monolayer WSe2 and WS2 . As excitation power increases, the photoluminescence intensity of interlayer excitons increases more rapidly than that of intralayer excitons. The phenomenon can be explained by charge-accumulation effect, which not only increases the recombination probability of interlayer excitons but also saturates the charge-transfer process. This scenario is further confirmed by a careful examination of trion binding energy of WS2 , which nonlinearly increases with the increase of the excitation power before reaching a maximum of about 75 meV. These investigations provide a better understanding of interlayer excitons and trions in HBs, which may provoke further explorations of excitonic physics as well as TMDs-based devices.