Beyond the Charge Transfer Mechanism for 2D Materials-Assisted Surface Enhanced Raman Scattering.

Two-dimensional (2D) materials have been extensively implemented as surface-enhanced Raman scattering (SERS) substrates, enabling trace-molecule detection for broad applications. However, the accurate understanding of the mechanism remains elusive because most theoretical explanations are still phenomenological or qualitative based on simplified models and rough assumptions. To advance the development of 2D material-assisted SERS, it is vital to attain a comprehensive understanding of the enhancement mechanism and a quantitative assessment of the enhancement performance. Here, the microscopic chemical mechanism of 2D material-assisted SERS is quantitatively investigated. The frequency-dependent Raman scattering cross sections suggest that the 2D materials' SERS performance is strongly dependent on the excitation wavelengths and the molecule types. By analysis of the microscopic Raman scattering processes, the comprehensive contributions of SERS can be revealed. Beyond the widely postulated charge transfer mechanisms, the quantitative results conclusively demonstrate that the resonant transitions within 2D materials alone are also capable of enhancing the molecular Raman scattering through the diffusive scattering of phonons. Furthermore, all of these scattering routines will interfere with each other and determine the final SERS performance. Our results not only provide a complete picture of the SERS mechanisms but also demonstrate a systematic and quantitative approach to theoretically understand, predict, and promote the 2D materials SERS toward analytical applications.

Functional-Group-Induced Single Quantum Well Dion-Jacobson 2D Perovskite for Efficient and Stable Inverted Perovskite Solar Cells.

In two-dimensional/three-dimensional (2D/3D) perovskite heterostructure, randomly distributed multiple quantum wells (QW) 2D perovskites are frequently generated, which are detrimental to carrier transport and structural stability. Here, the high quality 2D/3D perovskite heterostructure is constructed by fabricating functional-group-induced single QW Dion-Jacobson (DJ) 2D perovskites. The utilization of ─OCH3 in the precursor solution facilitates the formation of colloidal particles with uniform size, resulting in the production of a pure 2D DJ perovskite with an n value of 3. This strategy facilitates the improvement of 3D structural stability and expedites carrier transport. The resultant devices accomplish a power conversion efficiency of 25.26% (certified 25.04%) and 23.56% at a larger area (1 cm2 ) with negligible hysteresis. The devices maintain >96% and >89% of their initial efficiency after continuous maximum power point tracking under simulated AM1.5 illumination for 1300 h and under damp-heat conditions (85 °C and 85% RH) for 1010 h, respectively.

Broadband Near-Infrared Emission from 0D Hybrid Copper Halides.

Metal halides have attracted increasing attention owing to their outstanding optoelectronic properties and tunable emission characteristics. Among these, low-dimensional metal halides have emerged as a novel and efficient luminescent material, primarily attributed to their broad spectral emission induced by self-trapped excitons (STEs). However, achieving highly efficient deep red and near-infrared (NIR) emission in metal halides remains a challenge. In this study, we report a novel zero-dimensional (0D) copper-based metal halide [Na2(DMSO)8]Cu4Br6 as the NIR light source, which exhibits a full width at half-maximum (FWHM) of 195 nm peaking at 685 nm, an impressive quantum efficiency of 68% and a large Stokes shift of 299 nm. Through comprehensive spectral analysis and meticulous data calculations, we substantiate that the emission originates from STEs formed within the 0D structure. Furthermore, we demonstrate the potential application of [Na2(DMSO)8]Cu4Br6 as an invisible light source in night vision by combining it with a commercially available 365 nm ultraviolet (UV) chip. This work not only enriches the family of low-dimensional metal halide materials but also inspires the potential of low-dimensional metal halides in night vision applications.

Water-Molecule-Induced Reversible Fluorescence in a One-Dimensional Mn-Based Hybrid Halide for Anticounterfeiting and Digital Encryption-Decryption.

Hybrid metal halides with reversible transformation of structure and luminescence properties have attracted significant attention in anticounterfeiting. However, their long transition time and slow response rate may hinder the rapid identification of confidential information. Here, a one-dimensional hybrid manganese-based halide, i.e., (C5H11N3)MnCl2Br2·H2O, is prepared and demonstrates the phenomenon of water-molecule-induced reversible photoluminescence transformation. Heating for <40 s induces a dynamic transfer of red-emissive (C5H11N3)MnCl2Br2·H2O to green-emissive (C5H11N3)MnCl2Br2. In addition, the green emission can gradually revert to red emission during a cooling process in a moist environment, demonstrating excellent reversibility. It is found that the water molecule acts as an external stimulus to realize the reversible transition between red and green emission, which also exhibits remarkable stability during repeated cycles. Furthermore, with the assistance of heating and cooling, a complex digital encryption-decryption and an optical "AND" logical gate are achieved, facilitating the development of anticounterfeiting information security.

Highly efficient copper-based halide single crystals with violet emission for visible light communication.

K2CuBr3 single crystals (SCs) are synthesized using a cooling-induced crystallization method with violet emission due to self-trapped excitons (STEs) under photoexcitation. The prepared K2CuBr3 SCs exhibit a high photoluminescence quantum yield (PLQY, 79.2%) and excellent stability against moisture, heat and UV light. When the K2CuBr3 SCs are used as a light source for visible light communication the data transmission rate reaches a striking 248 Mbps, which is more than 33-fold the -3 dB bandwidth.

Flexible perovskite scintillators and detectors for X-ray detection.

X-ray detection and imaging technology has been rapidly developed for various fields since 1895, offering great opportunities to scientific and industrial communities. Particularly, flexible X-ray detectors have drawn numerous attention in medical-related applications, solving the uniform issues of traditional rigid X-ray detectors. Out of all the potential materials, metal halide perovskites (MHPs) have been emerged as excellent candidates as flexible X-ray scintillators and detectors owing to the advantages including low temperature solution processable, strong X-ray absorption coefficient, large mobility lifetime product and tunable bandgap. In this review, the recent advances of MHP-based flexible X-ray detectors are comprehensively summarized, focusing on the scalable synthesis technologies of materials and diverse device architectures, and covering both direct and indirect X-ray detection. A brief outlook that highlights the current challenges impeding the commercialization of flexible MHP-based X-ray detectors is also included with possible solutions to those problem being provided.

Flexible and stable copper-based halide scintillator for high-performance X-ray imaging.

Rb2CuBr3 nanocrystals with a high photoluminescence quantum yield (PLQY) of 75% were synthesized and then further mixed with polymethyl methacrylate to form flexible scintillators. The scintillators maintain a high PLQY, even after bending for 2000 cycles and storing in air for 28 days. X-Ray imaging of targeted objects was demonstrated based on the flexible scintillators, which exhibits a detection limit of 63 nGyair s-1 and a spatial resolution of 27.9 lp mm-1.

Significant performance enhancement of UV-Vis self-powered CsPbBr3 quantum dot-based photodetectors induced by ligand modification and P3HT embedding.

In this work, we report a novel, to the best of our knowledge, strategy to improve the performance of UV-Vis self-powered CsPbBr3 quantum dot (QD) based photodetectors (PDs) by ligand modification and poly(3-hexylthiophene) (P3HT) embedding. Compared with those based on pure QDs, modified PDs show a shortened response time by nearly ten times, and increases of maximum responsivity and specific detectivity by nearly 45 and 97 times, respectively. Such PDs also show a high stability with 90% of the initial photocurrent being maintained even after storage in ambient air without any encapsulation for 30 days.

Photoluminescence Induced by Substitutional Nitrogen in Single-Layer Tungsten Disulfide.

The electronic and optical properties of two-dimensional materials can be strongly influenced by defects, some of which can find significant implementations, such as controllable doping, prolonged valley lifetime, and single-photon emissions. In this work, we demonstrate that defects created by remote N2 plasma exposure in single-layer WS2 can induce a distinct low-energy photoluminescence (PL) peak at 1.59 eV, which is in sharp contrast to that caused by remote Ar plasma. This PL peak has a critical requirement on the N2 plasma exposure dose, which is strongest for WS2 with about 2.0% sulfur deficiencies (including substitutions and vacancies) and vanishes at 5.6% or higher sulfur deficiencies. Both experiments and first-principles calculations suggest that this 1.59 eV PL peak is caused by defects related to the sulfur substitutions by nitrogen, even though low-temperature PL measurements also reveal that not all the sulfur vacancies are remedied by the substitutional nitrogen. The distinct low-energy PL peak suggests that the substitutional nitrogen defect in single-layer WS2 can potentially serve as an isolated artificial atom for creating single-photon emitters, and its intensity can also be used to monitor the doping concentrations of substitutional nitrogen.

Two-Dimensional Gallium Oxide Monolayer for Gas-Sensing Application.

A two-dimensional (2D) Ga2O3 monolayer with an asymmetric quintuple-layer configuration was reported as a novel 2D material with excellent stability and strain tunability. This unusual asymmetrical structure opens up new possibilities for improving the selectivity and sensitivity of gas sensors by using selected surface orientations. In this study, the surface adsorptions of nine molecular gases, namely, O2, CO2, CO, SO2, NO2, H2S, NO, NH3, and H2O, on the 2D Ga2O3 monolayer are systematically investigated through first-principles calculations. The intrinsic dipole of the system leads to different adsorption energies and changes in the electronic structures between the top- and bottom-surface adsorptions. Analyses of electronic structures and charge transport calculations indicate a potential application of the 2D Ga2O3 monolayer as a room-temperature NO gas-sensing device with high sensitivity and tunable adsorption energy using plenary strain-induced lattice distortion.

Chirality-Dependent Second Harmonic Generation of MoS2 Nanoscroll with Enhanced Efficiency.

Materials with high second harmonic generation (SHG) efficiency and reduced dimensions are favorable for integrated photonics and nonlinear optical applications. Here, we fabricate MoS2 nanoscrolls with different chiralities and study their SHG performances. As a 1D material, MoS2 nanoscroll shows reduced symmetry and strong chirality dependency in the polarization-resolved SHG characterizations. This SHG performance can be well explained by the superposition theory of second harmonic field of the nanoscroll walls. MoS2 nanoscrolls with certain chiralities and diameters in our experiment can have SHG intensity up to 95 times stronger than that of monolayer MoS2, and the full potential can still be further exploited. The same chirality-dependent SHG can be expected for nanoscrolls or nanotubes composed of other noncentrosymmetric 2D materials, such as WS2, WSe2, and hBN. The characterization and analysis results presented here can also be exploited as a nondestructive technique to determine the chiralities of these nanoscrolls and nanotubes.

Tunable Properties of Novel Ga2O3 Monolayer for Electronic and Optoelectronic Applications.

A novel two-dimensional (2D) Ga2O3 monolayer was constructed and systematically investigated by first-principles calculations. The 2D Ga2O3 has an asymmetric configuration with a quintuple-layer atomic structure, the same as the well-studied α-In2Se3, and is expected to be experimentally synthesized. The dynamic and thermodynamic calculations show excellent stability properties of this monolayer material. The relaxed Ga2O3 monolayer has an indirect band gap of 3.16 eV, smaller than that of ß-Ga2O3 bulk, and shows tunable electronic and optoelectronic properties with biaxial strain engineering. An attractive feature is that the asymmetric configuration spontaneously introduces an intrinsic dipole and thus the electrostatic potential difference between the top and bottom surfaces of the Ga2O3 monolayer, which helps to separate photon-generated electrons and holes within the quintuple-layer structure. By applying compressive strain, the Ga2O3 monolayer can be converted to a direct band gap semiconductor with a wider gap reaching 3.5 eV. Also, enhancement of hybridization between orbitals leads to an increase of electron mobility, from the initial 5000 to 7000 cm2 V-1 s-1. Excellent optical absorption ability is confirmed, which can be effectively tuned by strain engineering. With superior stability, as well as strain-tunable electronic properties, carrier mobility, and optical absorption, the studied novel Ga2O3 monolayer sheds light on low-dimensional electronic and optoelectronic device applications.

Coherent Lattice Wobbling and Out-of-Phase Intensity Oscillations of Friedel Pairs Observed by Ultrafast Electron Diffraction.

The inspection of Friedel's law in ultrafast electron diffraction (UED) is important to gain a comprehensive understanding of material atomic structure and its dynamic response. Here, monoclinic gallium telluride (GaTe), as a low-symmetry, layered crystal in contrast to many other 2D materials, is investigated by mega-electronvolt UED. Strong out-of-phase oscillations of Bragg peak intensities are observed for Friedel pairs, which does not obey Friedel's law. As evidenced by the preserved mirror symmetry and supported by both kinematic and dynamic scattering simulations, the intensity oscillations are provoked by the lowest-order longitudinal acoustic breathing phonon. Our results provide a generalized understanding of Friedel's law in UED and demonstrate that by designed misalignment of surface normal and primitive lattice vectors, coherent lattice wobbling and effective shear strain can be generated in crystal films by laser pulse excitation, which is otherwise hard to achieve and can be further utilized to dynamically tune and switch material properties.

Defect creation in WSe2 with a microsecond photoluminescence lifetime by focused ion beam irradiation.

Defect engineering is important for tailoring the electronic and optical properties of two-dimensional materials, and the capability of generating defects of certain types at specific locations is meaningful for potential applications such as optoelectronics and quantum photonics. In this work, atomic defects are created in single-layer WSe2 using focused ion beam (FIB) irradiation, with defect densities spanning many orders of magnitude. The influences of defects are systematically characterized. Raman spectroscopy can only discern defects in WSe2 for a FIB dose higher than 1 × 1013 cm-2, which causes blue shifts of both A'1 and E' modes. Photoluminescence (PL) of WSe2 is more sensitive to defects. At cryogenic temperature, the low-energy PL induced by defects can be revealed, which shows redshifts and broadenings with increased FIB doses. Similar Raman shifts and PL spectrum changes are observed for the WSe2 film grown by chemical vapor deposition (CVD). A four microsecond-long lifetime is observed in the PL dynamics and is three orders of magnitude longer than the often observed delocalized exciton lifetime and becomes more dominant for WSe2 with increasing FIB doses. The ultra-long lifetime of PL in single-layer WSe2 is consistent with first-principles calculation results considering the creation of both chalcogen and metal vacancies by FIB, and can be valuable for photo-catalytic reactions, valleytronics and quantum light emissions owing to the longer carrier separation/manipulation time.

Interface Engineering of Monolayer MoS2/GaN Hybrid Heterostructure: Modified Band Alignment for Photocatalytic Water Splitting Application by Nitridation Treatment.

Interface engineering is a key strategy to deal with the two-dimensional (2D)/three-dimensional (3D) hybrid heterostructure, since the properties of this atomic-layer-thick 2D material can easily be impacted by the substrate environment. In this work, the structural, electronic, and optical properties of the 2D/3D heterostructure of monolayer MoS2 on wurtzite GaN surface without and with nitridation interfacial layer are systematically investigated by first-principles calculation and experimental analysis. The nitridation interfacial layer can be introduced into the 2D/3D heterostructure by remote N2 plasma treatment to GaN sample surface prior to stacking monolayer MoS2 on top. The calculation results reveal that the 2D/3D integrated heterostructure is energetically favorable with a negative formation energy. Both interfaces demonstrate indirect band gap, which is a benefit for longer lifetime of the photoexcited carriers. Meanwhile, the conduction band edge and valence band edge of the MoS2 side increases after nitridation treatment. The modification to band alignment is then verified by X-ray photoelectron spectroscopy measurement on MoS2/GaN heterostructures constructed by a modified wet-transfer technique, which indicates that the MoS2/GaN heterostructure without nitridation shows a type-II alignment with a conduction band offset (CBO) of only 0.07 eV. However, by the deployment of interface nitridation, the band edges of MoS2 move upward for ∼0.5 eV as a result of the nitridized substrate property. The significantly increased CBO could lead to better electron accumulation capability at the GaN side. The nitridized 2D/3D heterostructure with effective interface treatment exhibits a clean band gap and substantial optical absorption ability and could be potentially used as practical photocatalyst for hydrogen generation by water splitting using solar energy.

In Situ Resonant Raman Spectroscopy to Monitor the Surface Functionalization of MoS2 and WSe2 for High-k Integration: A First-Principles Study.

Surface functionalization of the dangling-bond-free MoS2, WSe2, and other TMDs (transition metal dichalcogenides) is of large practical importance, for example, in providing nucleation sites for the subsequent high-k dielectric integration. Of the surface functionalization methods, the reversible O or N atom adsorption on top of the chalcogen atoms is most promising. However, hazards such as severe oxidation or nitridation persist when the adsorption coverage is high. An in situ characterization technique, which can be integrated with the surface functionalization and dielectric deposition chamber, becomes valuable to enable the real-time monitoring of surface adsorption conditions. Raman spectroscopy, as a nondestructive characterization method without vacuum requirement, is a strong candidate. By utilizing first-principles calculations, Raman spectra of single-layer MoS2 and WSe2 with various O/N adsorption coverages are studied. The calculations suggest that the low-coverage O/N adsorbates will act as perturbations to the periodic lattice and activate the acoustic-phonon Raman scatterings. While high-coverage adsorptions will further activate and intensify the optical-phonon Raman scatterings of previously silent A2u and E1g modes, due to the breaking of reflection symmetry in the z direction, new phonon modes associated with the adatom oscillations are also introduced. All these pieces of evidence, together with the peak shifts of previously active A1g and E2g1 modes, suggest that in situ resonant Raman spectroscopy is capable of providing important information to quantify the O/N adsorption coverage and can be used as a valuable real-time characterization technique to monitor and control the surface functionalization conditions of MoS2 and WSe2.

Carboxylesterase Inhibitors: An Update.

Mammalian carboxylesterases are key serine hydrolases that catalyze the hydrolysis of a wide variety of ester compounds in the corresponding carboxylic acids and alcohols. In human, two major carboxylesterases, CES1 and CES2, have been identified and well-studied over the past decade. CES1 inhibitors have potential applications in the treatment of hypertriglyceridaemia, obesity and type 2 diabetes, owing to that this enzyme plays prominent role in the metabolism of cholesteryl esters. CES2 plays crucial roles in the metabolic activation of many prodrugs including anticancer agents capecitabine and CPT-11. Co-administration with CES2 inhibitors may ameliorate CPT-11 associated lifethreatening diarrhea or improve the half-lives of CES2-substrate drugs. The important roles of carboxylesterases in both endogenous and xenobiotic metabolism arouse great interest in the discovery and development of potent and selective inhibitors against these enzymes. This review is focused on the application potentials and recent advances in the discovery and development of carboxylesterases inhibitors. The inhibitory capacities and inhibition mechanism of a variety of carboxylesterases inhibitors including synthetic, semi-synthetic and natural compounds are comprehensively summarized. Furthermore, the key structural features and structure-activity relationships (SARs) of different classes of CES1 and CES2 inhibitors are discussed. All information and knowledge summarized in this review will be very helpful for the medicinal chemists to design and develop more potent and highly selective carboxylesterases inhibitors for potential biomedical applications.

Enhanced dielectric deposition on single-layer MoS2 with low damage using remote N2 plasma treatment.

Using remote N2 plasma treatment to promote dielectric deposition on the dangling-bond free MoS2 is explored for the first time. The N2 plasma induced damages are systematically studied by the defect-sensitive acoustic-phonon Raman of single-layer MoS2, with samples undergoing O2 plasma treatment as a comparison. O2 plasma treatment causes defects in MoS2 mainly by oxidizing MoS2 along the already defective sites (most likely the flake edges), which results in the layer oxidation of MoS2. In contrast, N2 plasma causes defects in MoS2 mainly by straining and mechanically distorting the MoS2 layers first. Owing to the relatively strong MoS2-substrate interaction and chemical inertness of MoS2 in N2 plasma, single-layer MoS2 shows great stability in N2 plasma and only stable point defects are introduced after long-duration N2 plasma exposure. Considering the enormous vulnerability of single-layer MoS2 in O2 plasma and the excellent stability of single-layer MoS2 in N2 plasma, the remote N2 plasma treatment shows great advantage as surface functionalization to promote dielectric deposition on single-layer MoS2.

Improved Gate Dielectric Deposition and Enhanced Electrical Stability for Single-Layer MoS2 MOSFET with an AlN Interfacial Layer.

Transistors based on MoS2 and other TMDs have been widely studied. The dangling-bond free surface of MoS2 has made the deposition of high-quality high-k dielectrics on MoS2 a challenge. The resulted transistors often suffer from the threshold voltage instability induced by the high density traps near MoS2/dielectric interface or inside the gate dielectric, which is detrimental for the practical applications of MoS2 metal-oxide-semiconductor field-effect transistor (MOSFET). In this work, by using AlN deposited by plasma enhanced atomic layer deposition (PEALD) as an interfacial layer, top-gate dielectrics as thin as 6 nm for single-layer MoS2 transistors are demonstrated. The AlN interfacial layer not only promotes the conformal deposition of high-quality Al2O3 on the dangling-bond free MoS2, but also greatly enhances the electrical stability of the MoS2 transistors. Very small hysteresis (ΔVth) is observed even at large gate biases and high temperatures. The transistor also exhibits a low level of flicker noise, which clearly originates from the Hooge mobility fluctuation instead of the carrier number fluctuation. The observed superior electrical stability of MoS2 transistor is attributed to the low border trap density of the AlN interfacial layer, as well as the small gate leakage and high dielectric strength of AlN/Al2O3 dielectric stack.

Trap-state-dominated suppression of electron conduction in carbon nanotube thin-film transistors.

The often observed p-type conduction of single carbon nanotube field-effect transistors is usually attributed to the Schottky barriers at the metal contacts induced by the work function differences or by the doping effect of the oxygen adsorption when carbon nanotubes are exposed to air, which cause the asymmetry between electron and hole injections. However, for carbon nanotube thin-film transistors, our contrast experiments between oxygen doping and electrostatic doping demonstrate that the doping-generated transport barriers do not introduce any observable suppression of electron conduction, which is further evidenced by the perfect linear behavior of transfer characteristics with the channel length scaling. On the basis of the above observation, we conclude that the environmental adsorbates work by more than simply shifting the Fermi level of the CNTs; more importantly, these adsorbates cause a poor gate modulation efficiency of electron conduction due to the relatively large trap state density near the conduction band edge of the carbon nanotubes, for which we further propose quantitatively that the adsorbed oxygen-water redox couple is responsible.