High-Active Surface of Centimeter-Scale ß-In2S3 for Attomolar-Level Hg2+ Sensing.

Recognition layer materials play a crucial role in the functionality of chemical sensors. Although advancements in two-dimensional (2D) materials have promoted sensor development, the controlled fabrication of large-scale recognition layers with highly active sites remains crucial for enhancing sensor sensitivity, especially for trace detection applications. Herein, we propose a strategy for the controlled preparation of centimeter-scale non-layered ultrathin ß-In2S3 materials with tailored high-active sites to design ultrasensitive Hg2+ sensors. Our results reveal that the highly active sites of non-layered ß-In2S3 materials are pivotal for achieving superior sensing performance. Selective detection of Hg2+ at the 1 aM level is achieved via selective Hg-S bonding. Additionally, we evaluate that this sensor exhibits excellent performance in detecting Hg2+ in the tap water matrix. This work provides a proof-of-concept for utilizing non-layered 2D films in high-performance sensors and highlights their potential for diverse analyte sensing applications.

Stepwise One-Shot Borylation Reactions for Intersecting DABNA Substructures Exhibiting Bright Yellow‒Green Electroluminescence with EQE Beyond 40% and Mild Roll-Off.

Boron/nitrogen (B/N)-doped polycyclic aromatic hydrocarbons (PAHs) with the multiple resonance (MR) effect are promising for organic light-emitting diodes (OLEDs) because of their narrowband emission and thermally activated delayed fluorescence (TADF) characteristics. Nevertheless, exploring the variety of such emitters is challenging because of the tricky and limited synthetic protocols. Herein, we designed a novel B/N-doped PAH, L-DABNA-1, whose backbone (L-DABNA) could not be achieved via conventional routes (e.g., one-pot borylation or one-shot borylation). We successfully synthesized it through stepwise one-shot borylations with precisely introducing decorations. The unique MR backbone with intersecting DABNA substructures sharing an aniline group, avoiding any para-N-π-B motif, allows L-DABNA-1 to maintain narrowband TADF emission while significantly redshifting to the yellow-green region with a reverse intersystem crossing rate (kRISC) of 1.28 × 105 s-1. An L-DABNA-1-based OLED device achieved a maximum external quantum efficiency (EQE) of over 40% and maintained a high EQE of 36.3% at 1000 cd m-2, with a current efficiency reaching ~170 cd A-1. This work not only demonstrated the great potential of stepwise borylations in synthesizing B/N-doped PAH backbones, expanding their chemical space, but also provided a promising pathway for exploring MR-TADF emitters at longer wavelengths.

High-pressure effects on the electronic properties and photoluminescence of Ag-doped CsCu2I3.

CsCu2I3 is a popular lead-free metal halide perovskite with good thermal and air stability. To facilitate its applications in optoelectronics, Ag doping and high pressure are employed in this work to improve the optoelectronic properties of CsCu2I3. Using first-principles calculations and experiments, the structural phase change of 10% Ag-doped CsCu2I3 is found to occur at about 4.0 GPa. This reveals the regulation of band structures by hydrostatic pressure. In addition, the high pressure not only increases the emission energy of photoluminescence of 10% Ag-doped CsCu2I3 by more than 0.2 eV, but also increases the emission intensity by multiple times. Finally, the origin of luminescence in 10% Ag-doped CsCu2I3 is attributed to the I vacancies. This work provides insight into the structure and optoelectronic properties of 10% Ag-doped CsCu2I3, and offers significant guidance for the design and manufacturing of future luminescence devices.

High-Performance Broadband Image Sensing Photodetector Based on MnTe/WS2 van der Waals Epitaxial Heterostructures.

Two-dimensional transition metal dichalcogenide (TMDC) heterostructure is receiving considerable attention due to its novel electronic, optoelectronic, and spintronic devices with design-oriented and functional features. However, direct design and synthesis of high-quality TMDC/MnTe heterostructures remain difficult, which severely impede further investigations of semiconductor/magnetic semiconductor devices. Herein, the synthesis of high-quality vertically stacked WS2/MnTe heterostructures is realized via a two-step chemical vapor deposition method. Raman, photoluminescence, and scanning transmission electron microscopy characterizations reveal the high-quality and atomically sharp interfaces of the WS2/MnTe heterostructure. WS2/MnTe-based van der Waals field effect transistors demonstrate high rectification behavior with rectification ratio up to 106, as well as a typical p-n electrical transport characteristic. Notably, the fabricated WS2/MnTe photodetector exhibits sensitive and broadband photoresponse ranging from UV to NIR with a maximum responsivity of 1.2 × 103 A/W, a high external quantum efficiency of 2.7 × 105%, and fast photoresponse time of ∼50 ms. Moreover, WS2/MnTe heterostructure photodetectors possess a broadband image sensing capability at room temperature, suggesting potential applications in next-generation high-performance and broadband image sensing photodetectors.

Efficient, narrow-band, and stable electroluminescence from organoboron-nitrogen-carbonyl emitter.

Organic light-emitting diodes (OLEDs) exploiting simple binary emissive layers (EMLs) blending only emitters and hosts have natural advantages in low-cost commercialization. However, previously reported OLEDs based on binary EMLs hardly simultaneously achieved desired comprehensive performances, e.g., high efficiency, low efficiency roll-off, narrow emission bands, and high operation stability. Here, we report a molecular-design strategy. Such a strategy leads to a fast reverse intersystem crossing rate in our designed emitter h-BNCO-1 of 1.79×105 s-1. An OLED exploiting a binary EML with h-BNCO-1 achieves ultrapure emission, a maximum external quantum efficiency of over 40% and a mild roll-off of 14% at 1000 cd·m-2. Moreover, h-BNCO-1 also exhibits promising operational stability in an alternative OLED exploiting a compact binary EML (the lifetime reaching 95% of the initial luminance at 1000 cd m-2 is ~ 137 h). Here, our work has thus provided a molecular-design strategy for OLEDs with promising comprehensive performance.

Interlayer-coupling-engineerable flat bands in twisted MoSi2N4bilayers.

The two-dimensional layered semiconductor MoSi2N4, which has several advantages including high strength, excellent stability, high hole mobility, and high thermal conductivity, was recently successfully synthesized using chemical vapor deposition. Based on first-principles calculations, we investigate the effects of the twist angle and interlayer distance variation on the electronic properties of twisted bilayer MoSi2N4. The flat bands are absent for twisted bilayer MoSi2N4when the twist angleθis reduced to 3.89°. Taking twisted bilayer MoSi2N4withθof 5.09° as an example, we find that flat bands emerge as the interlayer distance decreases. As the interlayer distance can be effectively modulated by hydrostatic pressure, we propose hydrostatic pressure as a knob for tailoring the flat bands in twisted bilayer MoSi2N4. Our findings provide theoretical support for extending the applications of MoSi2N4in strong correlation physics and superconductivity.

Self-Powered Programmable van der Waals Photodetectors with Nonvolatile Semifloating Gate.

Tunable photovoltaic photodetectors are of significant relevance in the fields of programmable and neuromorphic optoelectronics. However, their widespread adoption is hindered by intricate architectural design and energy consumption challenges. This study employs a nonvolatile MoTe2/hexagonal boron nitride/graphene semifloating photodetector to address these issues. Programed with pulsed gate voltage, the MoTe2 channel can be reconfigured from an n+-n to a p-n homojunction and the photocurrent transition changes from negative to positive values. Scanning photocurrent mapping reveals that the negative and positive photocurrents are attributed to Schottky junction and p-n homojunction, respectively. In the p-n configuration, the device demonstrates self-driven, linear, rapid response (∼3 ms), and broadband sensitivity (from 405 to 1500 nm) for photodetection, with typical performances of responsivity at ∼0.5 A/W and detectivity ∼1.6 × 1012 Jones under 635 nm illumination. These outstanding photodetection capabilities emphasize the potential of the semifloating photodetector as a pioneering approach for advancing logical and nonvolatile optoelectronics.

Integrating the atomically separated frontier molecular orbital distribution of two multiple resonance frameworks through a single bond for high-efficiency narrowband emission.

Atomically separated frontier molecular orbital (FMO) distribution plays a crucial role in achieving narrowband emissions for multiple resonance (MR)-type thermally activated delayed fluorescence emitters. Directly peripherally decorating a MR framework with donor or acceptor groups is a common strategy for developing MR emitters. However, this approach always induces bonding features and thus spectral broadening as a side effect. How direct donor/acceptor decoration enhances atomic FMO separation while avoiding bonding features has not been explored. For this aim, two MR derivatives are synthesized by integrating two MR frameworks at different sites. Following resonance alignment, DOBNA-m-CzBN avoids breaking nonbonding FMO features at the single connecting bond and shows enhanced MR characteristics, with a sharp emission at 491 nm and a full width at half maximum (FWHM) of 24 nm/118 meV. Conversely, DOBNA-p-CzBN emerges as a bonding feature due to its continuous π-conjugation extension, with a broadened FWHM of 26 nm/132 meV peaking at 497 nm. Impressively, both emitters exhibit outstanding external quantum efficiencies of 37.8-38.6% in organic light-emitting diodes (OLEDs), demonstrating improved performance with rigid acceptor decoration. Distinctly, the electroluminescence of DOBNA-m-CzBN shows a narrower FWHM than that of DOBNA-p-CzBN. This work for the first time reports the enhancement of atomic FMO separation for MR emitters via peripheral decoration through a single bond and provides a more comprehensive illustration for further development of MR emitters.

A Quadruple-Borylated Multiple-Resonance Emitter with para/meta Heteroatomic Patterns for Narrowband Orange-Red Emission.

Hindered by spectral broadening issues with redshifted emission, long-wavelength (e.g., maxima beyond 570 nm) multiple resonance (MR) emitters with full width at half maxima (FWHMs) below 20 nm remain absent. Herein, by strategically embedding diverse boron (B)/nitrogen (N) atomic pairs into a polycyclic aromatic hydrocarbon (PAH) skeleton, we propose a hybrid pattern for the construction of a long-wavelength narrowband MR emitter. The proof-of-concept emitter B4N6-Me realized orange-red emission with an extremely small FWHM of 19 nm (energy unit: 70 meV), representing the narrowest FWHM among all reported long-wavelength MR emitters. Theoretical calculations revealed that the cooperation of the applied para B-π-N and para B-π-B/N-π-N patterns is complementary, which gives rise to both narrowband and redshift characteristics. The corresponding organic light-emitting diode (OLED) employing B4N6-Me achieved state-of-the-art performance, e.g., a narrowband orange-red emission with an FWHM of 27 nm (energy unit: 99 meV), an excellent maximum external quantum efficiency (EQE) of 35.8 %, and ultralow efficiency roll-off (EQE of 28.4 % at 1000 cd m-2 ). This work provides new insights into the further molecular design and synthesis of long-wavelength MR emitters.

Combining Carbazole Building Blocks and ν-DABNA Heteroatom Alignment for a Double Boron-Embedded MR-TADF Emitter with Improved Performance.

Building blocks and heteroatom alignments are two determining factors in designing multiple resonance (MR)-type thermally activated delayed fluorescence (TADF) emitters. Carbazole-fused MR emitters, represented by CzBN derivatives, and the heteroatom alignments of ν-DABNA are two star series of MR-TADF emitters that show impressive performances from the aspects of building blocks and heteroatom alignments, respectively. Herein, a novel CzBN analog, Π-CzBN, featuring ν-DABNA heteroatom alignment is developed via facile one-shot lithium-free borylation. Π-CzBN exhibits superior photophysical properties with a photoluminescence quantum yield close to 100 % and narrowband sky blue emission with a full width at half maximum (FWHM) of 16 nm/85 meV. It also gives efficient TADF properties with a small singlet-triplet energy offset of 40 meV and a fast reverse intersystem crossing rate of 2.9×105  s-1 . The optimized OLED using Π-CzBN as the emitter achieves an exceptional external quantum efficiency of 39.3 % with a low efficiency roll-off of 20 % at 1000 cd m-2 and a narrowband emission at 495 nm with FWHM of 21 nm/106 meV, making it one of the best reported devices based on MR emitters with comprehensive performance.

Monolayer Iron Oxychloride with a Resonant Band Structure for Ultrasensitive Molecular Sensing.

Two-dimensional layered materials (2DLMs) are expected to be next-generation commercial sensors for surface-enhanced Raman scattering (SERS) sensing owing to their unique structural features and physicochemical properties. The low sensitivity and poor universality of 2DLMs are the dominant barriers toward their practical applications. Herein, we report that monolayer iron oxychloride (FeOCl) with a naturally suitable band structure is a promising candidate for ultrasensitive SERS sensing. The generally boosted Raman scattering cross section of different analyte-FeOCl systems benefits from the resonant photoinduced charge transfer processes and strong ground-state interactions. In addition, the strong adsorption ability of monolayer FeOCl is crucial for rapid detection in practical applications, which is proven to be much better than those of conventional SERS sensors. Consequently, monolayer FeOCl enables diverse SERS applications, including multicomponent analysis, chemical reaction monitoring, and indirect ion sensing.

A TADF Emitter with Dual Para-Positioned Donors Enables OLEDs with Improved Efficiency and CIE Coordinates Close to the Rec. 2020 Red Standard.

Developing red thermally activated delayed fluorescence (TADF) emitters concurrently with high efficiency and emission color close to the BT.2020 red standard is an ongoing challenge. Herein, we developed a new red TADF emitter BCN-TPA, in which two identical donors are attached at the para-positions of one fused phenyl ring in the acceptor framework. Such an arrangement mode can lead the donors with an obvious superimposed effect comparing the conventional arrangement with edge-capped donors on the acceptor. Thus, BCN-TPA yields enhanced overall donor strength with numerous superiorities, such as high oscillator strength and narrow singlet-triplet energy difference, thus giving rise to red-shifted emission with improved overall exciton utilization. In an organic light-emitting diode, BCN-TPA presents efficient deep-red electroluminescence with a maximum external quantum efficiency of 27.6% and a peak at 656 nm, corresponding to CIE coordinates of (0.686, 0.304), which are very close to the red primary in the BT.2020 standard. To the best of our knowledge, this is one of the topmost efficiencies in the field of deep-red TADF OLEDs. This work exemplifies an easy design principle for constructing high-performance deep-red TADF emitters, providing unique molecular-level insights toward improving color quality and elevating efficiency based on conventional D-A type molecular frameworks.

Strain Tunability of Perpendicular Magnetic Anisotropy in van der Waals Ferromagnets VI3.

Layered ferromagnets with strong magnetic anisotropy energy (MAE) have special applications in nanoscale memory elements in electronic circuits. Here, we report a strain tunability of perpendicular magnetic anisotropy in van der Waals (vdW) ferromagnets VI3 using magnetic circular dichroism measurements. For an unstrained flake, the M-H curve shows a rectangular-shaped hysteresis loop with a large coercivity (1.775 T at 10 K) and remanent magnetization. Furthermore, the coercivity can be enhanced to a maximum of 2.6 T under a 3.8% external in-plane tensile strain. Our DFT calculations show that the increased MAE under strain contributes to the enhancement of coercivity. Meanwhile, the strain tunability on the coercivity of CrI3, with a similar crystal structure, is limited. The main reason is the strong spin-orbit coupling in V3+ in VI6 octahedra in comparison with that in Cr3+. The strain tunability of coercivity in VI3 flakes highlights its potential for integration into vdW heterostructures.

Stable antiferromagnetism and semiconducting-to-metal transition in ALaCuOsO6 (A = Ba and Sr): strain modulations.

Double perovskite oxides (DPO) with antiferromagnetic ground state have received much consideration as they exhibit small stray-field and ultra-fast spin dynamics, which is extremely convenient for high-density and high-frequency data storage devices. It is a well-established fact that strain can easily tune the physical properties of the materials; therefore, the electronic and magnetic properties of recently synthesized ordered ALaCuOsO6 (A = Ba and Sr) DPO under biaxial ([110]) strain are investigated using ab initio calculations. Our results revealed that the unstrained systems exhibit semiconducting states having energy band gaps (Eg) of 0.28 and 0.39 eV for A = Ba and Sr, respectively. Along with this, both structures exhibit AFM ground state due to a strong AFM coupling between partially filled high-energy Cu+ e1g↑ and low-energy empty Os+5 t02g↓ orbitals. The calculated partial spin moments of Cu and Os ions are 0.65/0.66 and 1.58/1.60µB in a Ba-/Sr-doped system having electronic configurations of 3d9 (t32g↑t32g↓e2g↑e1g↓) with S = 0.5 and 5d3 (t32g↑) with S = 1.5, respectively. The robustness of AFM spin ordering is affirmed under the strain effects. The most striking feature of the present study is that Ba- and Sr-doped systems demonstrate an electronic transition from semiconductor to metal at critical tensile strains of +4% and +5% along with improved magnetism as well as Néel temperature, respectively. However, the magnetic ground state remains robust against applied strains in both cases. Hence, the present study shows that strain engineering could be a practical tool to modulate the electronic and magnetic properties of DPO to further enhance their technological applications in spintronics.

A Highly Twisted Carbazole-Fused DABNA Derivative as an Orange-Red TADF Emitter for OLEDs with Nearly 40 % EQE.

Multiple resonance (MR) type thermally activated delayed fluorescence (TADF) material is currently a research hotspot in organic light-emitting diodes (OLEDs) due to their high color purity and high exciton utilization. However, there are only a handful of MR-TADF emitters with emissions beyond the blue-to-green region. The very limited emission colors for MR-TADF emitters are mainly caused by the fact that so far molecular modifications of MR-TADF do not offer much change in the emission colors. Here, we report a new approach to modifying a prototypical MR core of DABNA by fusing carbazoles to the MR framework. The carbazole-fused molecule (TCZ-F-DABNA) basically maintains the MR-dominated features of DABNA while red-shifting the emission. Its OLED achieves an external quantum efficiency of 39.2 % with a peak at 588 nm, which is a record-high efficiency for OLEDs with peaks beyond 560 nm. This work provides a new approach for significantly tunning emission colors of MR-TADF emitters.

Site-selective growth of two-dimensional materials: strategies and applications.

Over the years, there have been major advances in two-dimensional (2D) materials on account of their excellent and unique properties. Among the various strategies for 2D material fabrication, chemical vapor deposition (CVD) is considered as the most promising method to achieve large-area and high-quality 2D film growth. Furthermore, to realize the potential applications of 2D materials in different fields, the integration of 2D materials into functional devices is essential. However, the materials made by common CVD are randomly distributed on substrates, which is disadvantageous for fabricating arrays of devices. To solve this problem, a site-selective growth method was developed to meet the requirement of batch production for practical applications because it achieves control over the locations of products and benefits the subsequent direct integration. Herein, state-of-the-art methods for site-selective synthesis, including seeded growth and patterned growth, are reviewed. Then, the electronic and optoelectronic applications of the as-grown 2D materials are also reviewed. Finally, the remaining challenges and future prospects regarding site-selective methods and applications are discussed.

Low-defect-density WS2 by hydroxide vapor phase deposition.

Two-dimensional (2D) semiconducting monolayers such as transition metal dichalcogenides (TMDs) are promising channel materials to extend Moore's Law in advanced electronics. Synthetic TMD layers from chemical vapor deposition (CVD) are scalable for fabrication but notorious for their high defect densities. Therefore, innovative endeavors on growth reaction to enhance their quality are urgently needed. Here, we report that the hydroxide W species, an extremely pure vapor phase metal precursor form, is very efficient for sulfurization, leading to about one order of magnitude lower defect density compared to those from conventional CVD methods. The field-effect transistor (FET) devices based on the proposed growth reach a peak electron mobility ~200 cm2/Vs (~800 cm2/Vs) at room temperature (15 K), comparable to those from exfoliated flakes. The FET device with a channel length of 100 nm displays a high on-state current of ~400 µA/µm, encouraging the industrialization of 2D materials.

Pressure Tunable van Hove Singularities of Twisted Bilayer Graphene.

The giant light-matter interaction induced by van Hove singularities (vHSs) of twisted bilayer graphene (tBLG) is responsible for enhanced optical absorption and strong photoresponse. Here, we investigated the evolution of vHSs in tBLG under pressure by using Raman spectroscopy. Pressure not only induces a blue shift of the G/R band but also tunes the intensity of the G/R band. The blue shift of the G/R band is due to the reduction of the in-plane lattice constant, and the variation of the G/R band intensity is due to the vHSs' shift of tBLG. Moreover, the main band in the absorption spectrum of tBLG is attributed to multiple transitions from valence to conduction bands. Because the ratio of R to G band intensity increases under pressure and the origins of R and G bands are different, we claim that pressure enhances intervalley electron scattering. This study paves the way for pressure engineering of vHS and the corresponding photon-electron-phonon interaction in tBLG.

Distinguishing the respective determining factors for spectral broadening and concentration quenching in multiple resonance type TADF emitter systems.

Multiple resonance (MR) type thermally activated delayed fluorescence (TADF) emitters have attracted much recent attention due to their narrow emission spectra and high photoluminescence quantum yields (PLQYs). Spectral broadening and concentration quenching at high doping concentrations are two issues currently limiting the development of MR-TADF emitters. However, the origins of these have not been fully clarified so far. In this work, by investigating emitters with the same MR cores but peripheral groups of different steric types, we distinguished that the spectral broadening and concentration quenching are mainly caused by excimer formation and triplet exciton annihilation, respectively. This understanding on aggregated behaviors of MR emitters provides new insight for the further development of high-performance MR-TADF emitters with low concentration sensitivities.