Harnessing Persistent Photocurrent in a 2D Semiconductor-Polymer Hybrid Structure: Electron Trapping and Fermi Level Modulation for Optoelectronic Memory.

Recently, 2D semiconductor-based optoelectronic memory has been explored to overcome the limitations of conventional von Neumann architectures by integrating optical sensing and data storage into one device. Persistent photocurrent (PPC), essential for optoelectronic memory, originates from charge carrier trapping according to the Shockley-Read-Hall (SRH) model in 2D semiconductors. The quasi-Fermi level position influences the activation of charge-trapping sites. However, the correlation between quasi-Fermi level modulations and PPC in 2D semiconductors has not been extensively studied. In this study, we demonstrate optoelectronic memory based on a 2D semiconductor-polymer hybrid structure and confirm that the underlying mechanism is charge trapping, as the SRH model explains. Under light illumination, electrons transfer from polyvinylpyrrolidone to p-type tungsten diselenide, resulting in high-level injection and majority carrier-type transitions. The quasi-Fermi level shifts upward with increasing temperature, improving PPC and enabling optoelectronic memory at 433 K. Our findings offer valuable insights into optimizing 2D semiconductor-based optoelectronic memory.

Role of Chalcogenides in Sensitive Therapeutic Drug Monitoring Using Laser Desorption and Ionization.

This study investigates the applicability of six transition metal dichalcogenides to efficient therapeutic drug monitoring of ten antiepileptic drugs using laser desorption/ionization-mass spectrometry. We found that molybdenum ditelluride and tungsten ditelluride are suitable for the sensitive quantification of therapeutic drugs. The contribution of tellurium to the enhanced efficiency of laser desorption ionization was validated through theoretical calculations utilizing an integrated model that incorporates transition-metal dichalcogenides and antiepileptic drugs. The results of our theoretical calculations suggest that the relatively low surface electron density for the tellurium-containing transition metal dichalcogenides induces stronger Coulombic interactions, which results in enhanced laser desorption and ionization efficiency. To demonstrate applicability, up to 120 patient samples were analyzed to determine drug concentrations, and the results were compared with those of immunoassay and liquid chromatography-tandem mass spectrometry. Agreements among these methods were statistically evaluated using the Passing-Bablok regression and Bland-Altman analysis. Furthermore, our method has been shown to be applicable to the simultaneous detection and multiplexed quantification of antiepileptic drugs.

Mitigating substrate effects of van der Waals semiconductors using perfluoropolyether self-assembled monolayers.

The properties of transition metal dichalcogenides (TMDCs) are critically dependent on the dielectric constant of substrates, which significantly limits their application. To address this issue, we used a perfluorinated polyether (PFPE) self-assembled monolayer (SAM) with low surface energy to increase the van der Waals (vdW) gap between TMDCs and the substrate, thereby reducing the interaction between them. This resulted in a reduction in the subthreshold swing value, an increase in the photoluminescence intensity of excitons, and a decrease in the doping effect by the substrate. This work will provide a new way to control the TMDC/dielectric interface and contribute to expanding the applicability of TMDCs.

Divergent Vibrational Property Induced by an Anomalous Layer Sequence in Two-Dimensional GaPS4.

Recently, various fundamental properties of GaPS4 such as anisotropy and strain-induced properties have been reported, but the impacts of the stacking sequence in layered materials remain ambiguous. This ambiguity is evident in the inconsistent Raman scattering data reported for GaPS4, suggesting a significant influence of stacking order on its physical properties. To demonstrate the discrepancies, this study investigates the vibrational characteristics of 2D GaPS4 under different stacking sequences using both experimental observations and theoretical models (AA and AB sequences) through density functional theory calculations. The results of our theoretical calculations revealed that the identical stacking sequence structure significantly influences the vibrational configurations of GaPS4, which results in divergent configurations of Raman scattering spectra including unidentified Raman peaks. Our study addresses not only the clarification of the ambiguity of experimental observations but also qualitative criteria to evaluate the degree of each stacking sequence.

Probing Inherent Optical Anisotropy in Substrates via Direct Nanoimaging of Mie Scattering.

In this study, we investigated the optical properties of a transition metal dichalcogenide (TMD) substrate via Mie-scattering-induced surface analysis (MISA). Employing near-field optical microscopy and finite-difference time-domain (FDTD) simulations, we systemically prove and directly visualize the Mie scattering of superspherical gold nanoparticles (s-AuNPs) at the nanoscale. Molybdenum disulfide substrates exhibited optical isotropy, while rhenium disulfide (ReS2) substrates showed anisotropic behavior attributed to the interaction with incident light's electric field. Our study revealed substantial anisotropic trends in Mie scattering, particularly in the near-infrared energy range, with ReS2 exhibiting more pronounced spectral and angular responses in satellite peaks. Our results emphasize the application of Mie scattering, exploring the optical properties of substrates and contributing to a deeper understanding of nanoscale light-matter interactions.

Ultrahigh Photosensitivity Based on Single-Step Lay-on Integration of Freestanding Two-Dimensional Transition-Metal Dichalcogenide.

Two-dimensional transition-metal dichalcogenides have attracted significant attention because of their unique intrinsic properties, such as high transparency, good flexibility, atomically thin structure, and predictable electron transport. However, the current state of device performance in monolayer transition-metal dichalcogenide-based optoelectronics is far from commercialization, because of its substantial strain on the heterogeneous planar substrate and its robust metal deposition, which causes crystalline damage. In this study, we show that strain-relaxed and undamaged monolayer WSe2 can improve a device performance significantly. We propose here an original point-cell-type photodetector. The device consists in a monolayer of an absorbing TMD (i.e., WSe2) simply deposited on a structured electrode, i.e., core-shell silicon-gold nanopillars. The maximum photoresponsivity of the device is found to be 23.16 A/W, which is a significantly high value for monolayer WSe2-based photodetectors. Such point-cell photodetectors can resolve the critical issues of 2D materials, leading to tremendous improvements in device performance.

Structural phase transition and resistive switching properties of CuxO films during post-thermal annealing.

We studied the phase change and resistive switching characteristics of copper oxide (CuxO) films through post-thermal annealing. This investigation aimed to assess the material's potential for a variety of electrical devices, exploring its versatility in electronic applications. The CuxO films deposited by RF magnetron sputtering were annealed at 300, 500, and 700 °C in ambient air for 4 min by rapid thermal annealing (RTA) method, and then it was confirmed that the structural phase change from Cu2O to CuO occurred with increasing annealing temperature. Resistive random-access memory (ReRAM) devices with Au/CuxO/p+-Si structures were fabricated, and the ReRAM properties appeared in CuO-based devices, while Cu2O ReRAM devices did not exhibit resistive switching behavior. The CuO ReRAM device annealed at 500 °C showed the best properties, with a on/off ratio of 8 × 102, good switching endurance of ∼100 cycles, data retention for 104s, and stable uniformity in the cumulative probability distribution. This characteristic change could be explained by the difference in the grain size and density of defects between the Cu2O and CuO films. These results demonstrate that superior and stable resistive switching properties of RF-sputtered CuxO films can be obtained by low-temperature RTA.

Uncertainty evaluation of photoluminescence quantum yield measurement in an integrating hemisphere-based instrument.

We present an integrating hemisphere-based (i.e., a variant of integrating spheres) implementation of the indirect illumination method for absolute photoluminescence quantum yield measurements, which is a recommended method in the international standard IEC 62607-3-1:2014. We rigorously formulated a mathematical model and a measurement procedure for the absolute photoluminescence quantum yield measurement in the integrating hemisphere-based system. The measurement system was calibrated using an Hg-Ar discharge lamp and spectral irradiance standard lamps for wavelength and relative spectral radiant flux scales, respectively. Furthermore, we identified and evaluated uncertainty components involved in the photoluminescence quantum yield (PLQY) measurement. To validate our measurement system, we applied it to the two de facto standard dyes: quinine bisulfate (QBS) and fluorescein (FLS). Consequently, their PLQY values were determined to be 0.563±0.024 (k=2) and 0.876±0.032 (k=2) for, respectively, QBS and FLS, which are consistent with previous reports.

Plasmon-exciton couplings in the MoS2/AuNP plasmonic hybrid structure.

The understanding and engineering of the plasmon-exciton coupling are necessary to control the innovative optoelectronic device platform. In this study, we investigated the intertwined mechanism of each plasmon-exciton couplings in monolayer molybdenum disulfide (MoS2) and plasmonic hybrid structure. The results of absorption, simulation, electrostatics, and emission spectra show that interaction between photoexcited carrier and exciton modes are successfully coupled by energy transfer and exciton recombination processes. Especially, neutral exciton, trion, and biexciton can be selectively enhanced by designing the plasmonic hybrid platform. All of these results imply that there is another degree of freedom to control the individual enhancement of each exciton mode in the development of nano optoelectronic devices.

Regenerating MXene by a Facile Chemical Treatment Method.

A popular substance in the MXene family, titanium carbide (Ti3C2Tx), has received substantial attention mainly due to its high metallic conductivity, easy solution processability, and environment friendliness. However, the poor oxygen resistance nature of MXene has prevented its practical applications from being realized. Despite significant attempts to improve the oxidative stability of MXenes, a comprehensive understanding of the oxidation mechanism is still elusive, thus leaving an optimal strategy for recycling oxidized MXene in question. Here, by developing a facile hydrofluoric acid (HF) post-treatment, we have unraveled the regeneration kinetics of the oxidized Ti3C2Tx. A systematic and extensive investigation using a combination of Raman spectroscopy, scanning electron microscopy, X-ray diffractometer, and X-ray photoelectron spectroscopy revealed that HF post-treatment is critical for restoring the structure/morphology and surface composition of MXene nanosheets. These are ascribed to the oxidizing agent removal kinetics, while the generation of amorphous carbon and Ti(III) in fluorinated derivatives provides efficient electrical conductivity. Our findings suggested that HF post-treatment is sufficient to evade and reduce the degradation process while maintaining the conductivity for a longer time, which will not only be economically advantageous but also a step forward for the rational design of Ti3C2Tx-based devices and functional coatings.

Inductive Effect of Lewis Acidic Dopants on the Band Levels of Perovskite for a Photocatalytic Reaction.

Band-edge modulation of halide perovskites as photoabsorbers plays significant roles in the application of photovoltaic and photochemical systems. Here, Lewis acidity of dopants (M) as the new descriptor of engineering the band-edge position of the perovskite is investigated in the gradiently doped perovskite along the core-to-surface (CsPbBr3-CsPb1-xMxBr3). Reducing M-bromide bond strength with an increase in hardness of acidic M increases the electron ability of basic Br, thus strengthening the Pb-Br orbital coupling in M-Pb-Br, noted as the inductive effect of dopants. Especially, the highly hard Lewis acidic Mg localized in the outer position of the perovskite induces the increase of work function and then shifts band edge upward along the core-to-surface of the perovskite. Thus, charge separation driven by the dopant-induced internal electric field induces the slow annihilation of the excited holes, improving the slow aromatic Csp3-H dissociation in the photocatalytic oxidation process by ∼211% (491.39 µmol g-1 h-1) enhancements, compared with undoped nanocrystals.

Improved Stability of MAPbI3 Perovskite Solar Cells Using Two-Dimensional Transition-Metal Dichalcogenide Interlayers.

Perovskite solar cells (PSCs) have been receiving considerable attention as next-generation solar cells. However, their short lifetime is a major obstacle to their commercialization. In addition to the properties of the materials used in PSCs, their interfaces play an important role in device stability by maintaining their initial design. In this study, we developed a transition-metal dichalcogenide (TMD) as a stable and efficient interlayer. MoS2 and WSe2 were applied to both the hole and electron transport sides of the PSCs with general FTO/TiO2/MAPbI3/Spiro-OMeTAD/Au structures, respectively. Owing to efficient charge transfer by TMD interlayers, our PSCs achieved a 19.24% efficiency, which is higher than the efficiency of the control devices (18.22%). Furthermore, the device stability was markedly improved by the passivation and strain-release effects of the TMD interlayers. Thus, the PSCs with TMD interlayers demonstrated a stable performance over 1000 h under damp heat (85 °C and 85% relative humidity) conditions.

Raman Scattering Measurement of Suspended Graphene under Extreme Strain Induced by Nanoindentation.

Graphene is known as a superstiff and extremely strong material. Hence, applying strains greater than 1% to graphene and simultaneously measuring changes in its physical properties has been challenging because of the limited methodologies for measuring both high strain and other physical properties. Here, Raman scattering measurement of suspended graphene under extremely high biaxial strain as large as 6.1% using an atomic force microscopy (AFM)-Raman spectroscopy measurement tool is reported. Nanoindentation is performed using AFM tips machined to have a flat top and a hole shape, resulting in a strained graphene area sufficiently large to enable the acquisition of a Raman signal. At the same time, the laser light is focused on the strained flat area of the graphene membrane. The Raman signals of the G and 2D bands of graphene are redshifted by 282 and 684 cm-1 , respectively, which is unprecedented for graphene. This measurement technique provides an effective methodology to measure variations in the physical properties of atomically thin materials under superhigh strain.

Methylammonium Compensation Effects in MAPbI3 Perovskite Solar Cells for High-Quality Inorganic CuSCN Hole Transport Layers.

Recent studies have demonstrated that copper (I) thiocyanate (CuSCN) has huge potential as a hole extraction material (HEM) for perovskite solar cells. Here, we used CuSCN as a HEM and analyzed its relationships with a methylammonium lead iodide (MAPbI3) perovskite layer. The CuSCN dissolved in diethyl sulfide (DES) was spin-coated on the MAPbI3 layer. For high-quality and dense CuSCN layers, post-annealing was carried out at various temperatures and times. However, the unwanted dissociation of MAPbI3 to PbI2 was observed due to the post-annealing for a long time at elevated temperatures. In addition, DES, which is used as a CuSCN solvent, is a polar solvent that damages the surface of MAPbI3 perovskites and causes poor interfacial properties between the perovskite layer and HEM. To solve this problem, the effect of the molar ratio of methylammonium iodide (MAI) and PbI2 in the MAPbI3 precursor solution was investigated. The excess MAI molar ratio in the MAPbI3 precursor solution reduced MAPbI3 surface damage despite using DES polar solvent for CuSCN solution. In addition, dissociation of MAPbI3 to PbI2 following an adequate post-annealing process was well suppressed. The excess MAI molar ratio in the MAPbI3 precursor could be compensated for the MA loss and effectively suppress phase separation from MAPbI3 to MAI + PbI2 during post-annealing. The efficiency based on the normal planar structure of CuSCN/MAPbI3 (using excess MAI)/TiO2 was approximately 17%. The CuSCN-based MAPbI3 device shows more optimized stability than the conventional spiro-OMeTAD under damp heat (85 °C and 85% relative humidity) conditions because of the robust inorganic HEM.

Large-Area MoS2 via Colloidal Nanosheet Ink for Integrated Memtransistor.

2D transition metal dichalcogenides (TMDs) exhibit intriguing properties for applications in optoelectronics and electronics, among which memtransistors received extensive attention as multifunctional devices. For practical applications of 2D TMDs, large-area fabrication of the materials via reliable processes, which is in trade-off with their quality, has been a long-standing issue. Here, a simple and effective way is proposed to fabricate large-area and high-quality molybdenum disulfide thin films using MoS2 colloidal ink through a spray coating, followed by a postsulfurization process. High-quality MoS2 thin films exhibit excellent optical and electrical properties that can be utilized in field-effect transistors (FETs) and memtransistor arrays. The MoS2 FETs show an average on/off ratio of 5 × 106 and a high electron mobility of 10.34 cm2  V-1  s-1 , which can be understood by the healing of sulfur vacancies, recrystallization, and the removal of the carbon contamination of the MoS2 . These MoS2 -based memtransistors present stable operations with a high switching ratio tuned by back gate and light illumination, which is promising for multiple-levels memory and complex neuromorphic computing. This study demonstrates a new strategy to fabricate 2D TMDs with large-area and high quality for integrated optoelectronic and memory device applications.

Electrically and Optically Controllable p-n Junction Memtransistor Based on an Al2 O3 Encapsulated 2D Te/ReS2 van der Waals Heterostructure.

The exploration of memtransistors as a combination of a memristor and a transistor has recently attracted intensive attention because it offers a promising candidate for next-generation multilevel nonvolatile memories and synaptic devices. However, the present state-of-the-art memtransistors, which are based on a single material, such as MoS2 or perovskite, exhibit a relatively low switching ratio, require extremely high electric fields to modulate bistable resistance states and do not perform multifunctional operations. Here, the realization of an electrically and optically controllable p-n junction memtransistor using an Al2 O3 encapsulated 2D Te/ReS2 van der Waals heterostructure is reported. The hybrid memtransistor shows a reversible bipolar resistance switching behavior between a low resistance state and a high resistance state with a high switching ratio up to 106 at a low operating voltage (<10 V), high cycling endurance, and long retention time. Moreover, multiple resistance states are achieved by applying different bias voltages, gate voltages, or light powers. In addition, logical operations, including the inverter and AND/OR gates, and synaptic activities are performed by controlling the optical and electrical inputs. The work offers a novel strategy for the reliable fabrication of p-n junction memtransistors for multifunctional devices and neuromorphic applications.

Interface Trap Suppression and Electron Doping in Van der Waals Materials Using Cross-Linked Poly(vinylpyrrolidone).

The instability of van der Waals (vdW) materials leads to spontaneous morphological and chemical transformations in the air. Although the passivation of vdW materials with other resistive materials is often used to solve stability issues, this passivation layer can block carrier injection and thus interfere with charge transfer doping. In this study, a facile method is proposed for n-doping and mediation of Se vacancies in tungsten diselenide (WSe2) by poly(vinylpyrrolidone) (PVP) coating. The major carrier type of the PVP-coated WSe2-based field-effect transistor (FET) was converted from hole (p-type) to electron (n-type). Furthermore, the vacancy-induced interface trap density was reduced by approximately 500 times. This study provides a practical doping and passivation method for the van der Waals materials, as well as a comprehensive understanding of the chemical reaction and electronic transport in these materials.

Investigation of Cation Exchange Behaviors of FAxMA1-xPbI3 Films Using Dynamic Spin-Coating.

In this study, we fabricated and characterized uniform multi-cation perovskite FAxMA1-xPbI3 films. We used the dynamic spin-coating method to control the cation ratio of the film by gradually increasing the FA+, which replaced the MA+ in the films. When the FA+ concentration was lower than xFA ~0.415 in the films, the stability of the multi-cation perovskite improved. Above this concentration, the film exhibited δ-phase FAPbI3 in the FAxMA1-xPbI3 films. The formation of δ-phase FAPbI3 disturbed the homogeneity of the photoluminescence spatial distribution and suppressed the absorption spectral bandwidth with the increasing bandgap. The precise control of the cation ratio of multi-cation perovskite films is necessary to optimize the energy-harvesting performance.

Nano-Thermal Analysis of Defect-Induced Surface Pre-Melting in 2D Tellurium.

Thermal properties, such as thermal conductivity, heat capacity, and melting temperature, influence the efficiency and stability of two-dimensional (2D) material applications. However, existing studies on thermal characteristics-except for thermal conductivity-are insufficient for 2D materials. Here, we investigated the melting temperature of 2D Tellurium (2D Te) using the nano-thermal analysis technique and found anomalous behavior that occurs before the melting temperature is reached. The theoretical calculations present surface pre-melting in 2D Te and Raman scattering measurements suggest that defects in 2D Te accelerate surface pre-melting. Understanding the pre-melting surface characteristics of 2D Te will provide valuable information for practical applications.