Self-Trapped Exciton Emission in Highly Polar 0D Hybrid Ammonium/Hydronium-Based Perovskites Triggered by Antimony Doping.

Various monovalent cations are employed to construct metal halide perovskites with various structures and functionalities. However, perovskites based on highly polar A-site cations have seldom been reported. Here, a novel hybrid 0D (NH4)x(OH3)3-xInCl6 perovskite with highly polar hydronium OH3+ cations is introduced in this study. Upon doping with Sb3+, hybrid 0D (NH4)x(OH3)3-xInCl6 single crystals exhibited highly efficient broadband yellowish-green (550 nm) and red (630 nm) dual emissions with a PLQY of 86%. The dual emission arises due to Sb3+ occupying two sites within the crystal lattice that possess different polarization environments, leading to distinct Stokes shift energies. The study revealed that lattice polarity plays a significant role in the self-trapped exciton emission of Sb3+-doped perovskites, contributing up to 25% of the Stokes shift energy for hybrid 0D (NH4)x(OH3)3-xInCl6:Sb3+ as a secondary source, in addition to the Jahn-Teller deformation. These findings highlight the potential of Sb3+-doped perovskites for achieving tunable broadband emission and underscore the importance of lattice polarity in determining the emission properties of perovskite materials.

Identifying atomically thin isolated-band channels for intrinsic steep-slope transistors by high-throughput study.

Developing low-power FETs holds significant importance in advancing logic circuits, especially as the feature size of MOSFETs approaches sub-10 nanometers. However, this has been restricted by the thermionic limitation of SS, which is limited to 60 mV per decade at room temperature. Herein, we proposed a strategy that utilizes 2D semiconductors with an isolated-band feature as channels to realize sub-thermionic SS in MOSFETs. Through high-throughput calculations, we established a guiding principle that combines the atomic structure and orbital interaction to identify their sub-thermionic transport potential. This guides us to screen 192 candidates from the 2D material database comprising 1608 systems. Additionally, the physical relationship between the sub-thermionic transport performances and electronic structures is further revealed, which enables us to predict 15 systems with promising device performances for low-power applications with supply voltage below 0.5 V. This work opens a new way for the low-power electronics based on 2D materials and would inspire extensive interests in the experimental exploration of intrinsic steep-slope MOSFETs.

Cascaded compression of size distribution of nanopores in monolayer graphene.

Monolayer graphene with nanometre-scale pores, atomically thin thickness and remarkable mechanical properties provides wide-ranging opportunities for applications in ion and molecular separations1, energy storage2 and electronics3. Because the performance of these applications relies heavily on the size of the nanopores, it is desirable to design and engineer with precision a suitable nanopore size with narrow size distributions. However, conventional top-down processes often yield log-normal distributions with long tails, particularly at the sub-nanometre scale4. Moreover, the size distribution and density of the nanopores are often intrinsically intercorrelated, leading to a trade-off between the two that substantially limits their applications5-9. Here we report a cascaded compression approach to narrowing the size distribution of nanopores with left skewness and ultrasmall tail deviation, while keeping the density of nanopores increasing at each compression cycle. The formation of nanopores is split into many small steps, in each of which the size distribution of all the existing nanopores is compressed by a combination of shrinkage and expansion and, at the same time as expansion, a new batch of nanopores is created, leading to increased nanopore density by each cycle. As a result, high-density nanopores in monolayer graphene with a left-skewed, short-tail size distribution are obtained that show ultrafast and ångström-size-tunable selective transport of ions and molecules, breaking the limitation of the conventional log-normal size distribution9,10. This method allows for independent control of several metrics of the generated nanopores, including the density, mean diameter, standard deviation and skewness of the size distribution, which will lead to the next leap in nanotechnology.

Bi2O2Se-Based Bimode Noise Generator for the Application of Generative Adversarial Networks.

In the emerging technology, the generative aversive networks (GANs), randomness, and unpredictability of inputting noises are the keys to the uniqueness, diversity, robustness, and security of the generated images. Compared with deterministic software-based noise generation, hardware-based noise generation introduces physical entropy sources, such as electronic and photonic noises, to add unpredictability. In this study, bimode Bi2O2Se-based noise generators have been demonstrated for the application of GANs. Harnessing its ultrahigh carrier mobility, excellent air stability, marvelous optoelectronic performance, as well as the unique surface resistive switching effect and defect locations in the energy diagram, Bi2O2Se provides a good material platform to easily integrate with multiple device architectures for generating noises in different physical sources. The noise of the black current mode in a photodetector architecture and the random telegraph noise in a memristor mode were measured, characterized, compared, and analyzed. A method of Markov chain equipped with K-means clustering was carried out to calculate the discrete noise states and the transition probability matrix between them. To evaluate the generated properties of the GANs based on the hardware noise source, the inception score and Fréchet inception distance were evaluated.

Oriented lateral growth of two-dimensional materials on c-plane sapphire.

Two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs) represent the ultimate thickness for scaling down channel materials. They provide a tantalizing solution to push the limit of semiconductor technology nodes in the sub-1 nm range. One key challenge with 2D semiconducting TMD channel materials is to achieve large-scale batch growth on insulating substrates of single crystals with spatial homogeneity and compelling electrical properties. Recent studies have claimed the epitaxy growth of wafer-scale, single-crystal 2D TMDs on a c-plane sapphire substrate with deliberately engineered off-cut angles. It has been postulated that exposed step edges break the energy degeneracy of nucleation and thus drive the seamless stitching of mono-oriented flakes. Here we show that a more dominant factor should be considered: in particular, the interaction of 2D TMD grains with the exposed oxygen-aluminium atomic plane establishes an energy-minimized 2D TMD-sapphire configuration. Reconstructing the surfaces of c-plane sapphire substrates to only a single type of atomic plane (plane symmetry) already guarantees the single-crystal epitaxy of monolayer TMDs without the aid of step edges. Electrical results evidence the structural uniformity of the monolayers. Our findings elucidate a long-standing question that curbs the wafer-scale batch epitaxy of 2D TMD single crystals-an important step towards using 2D materials for future electronics. Experiments extended to perovskite materials also support the argument that the interaction with sapphire atomic surfaces is more dominant than step-edge docking.

Interfacial Reconstructed Layer Controls the Orientation of Monolayer Transition-Metal Dichalcogenides.

Growing continuous monolayer films of transition-metal dichalcogenides (TMDs) without the disruption of grain boundaries is essential to realize the full potential of these materials for future electronics and optoelectronics, but it remains a formidable challenge. It is generally believed that controlling the TMDs orientations on epitaxial substrates stems from matching the atomic registry, symmetry, and penetrable van der Waals forces. Interfacial reconstruction within the exceedingly narrow substrate-epilayer gap has been anticipated. However, its role in the growth mechanism has not been intensively investigated. Here, we report the experimental conformation of an interfacial reconstructed (IR) layer within the substrate-epilayer gap. Such an IR layer profoundly impacts the orientations of nucleating TMDs domains and, thus, affects the materials' properties. These findings provide deeper insights into the buried interface that could have profound implications for the development of TMD-based electronics and optoelectronics.

Epitaxial substitution of metal iodides for low-temperature growth of two-dimensional metal chalcogenides.

The integration of various two-dimensional (2D) materials on wafers enables a more-than-Moore approach for enriching the functionalities of devices1-3. On the other hand, the additive growth of 2D materials to form heterostructures allows construction of materials with unconventional properties. Both may be achieved by materials transfer, but often suffer from mechanical damage or chemical contamination during the transfer. The direct growth of high-quality 2D materials generally requires high temperatures, hampering the additive growth or monolithic incorporation of different 2D materials. Here we report a general approach of growing crystalline 2D layers and their heterostructures at a temperature below 400 °C. Metal iodide (MI, where M = In, Cd, Cu, Co, Fe, Pb, Sn and Bi) layers are epitaxially grown on mica, MoS2 or WS2 at a low temperature, and the subsequent low-barrier-energy substitution of iodine with chalcogens enables the conversion to at least 17 different 2D crystalline metal chalcogenides. As an example, the 2D In2S3 grown on MoS2 at 280 °C exhibits high photoresponsivity comparable with that of the materials grown by conventional high-temperature vapour deposition (~700-1,000 °C). Multiple 2D materials have also been sequentially grown on the same wafer, showing a promising solution for the monolithic integration of different high-quality 2D materials.

Bi2O2Se-based integrated multifunctional optoelectronics.

The prominent light-matter interaction in 2D materials has become a pivotal research area that involves either an archetypal study of inherent mechanisms to explore such interactions or specific applications to assess the efficacy of such novel phenomena. With scientifically controlled light-matter interactions, various applications have been developed. Here, we report four diverse applications on a single structure utilizing the efficient photoresponse of Bi2O2Se with precisely tuned multiple optical wavelengths. First, the Bi2O2Se-based device performs the function of optoelectronic memory using UV (λ = 365 nm, 1.1 mW cm-2) for the write-in process with SiO2 as the charge trapping medium followed by a +1 V bias for read-out. Second, associative learning is mimicked with wavelengths of 525 nm and 635 nm. Third, using similar optical inputs, functions of logic gates "AND", "OR", "NAND", and "NOR" are realized with response current and resistance as outputs. Fourth is the demonstration of a 4 bit binary to the decimal converter using wavelengths of 740 nm (LSB), 595 nm, 490 nm, and 385 nm (MSB) as binary inputs and output response current regarded as equivalent decimal output. Our demonstration is a paradigm for Bi2O2Se-based devices to be an integral part of future advanced multifunctional electronic systems.

Statistical Assessment of High-Performance Scaled Double-Gate Transistors from Monolayer WS2.

Scaling of monolayer transition metal dichalcogenide (TMD) field-effect transistors (FETs) is an important step toward evaluating the application space of TMD materials. Although some work on ultrashort channel monolayer (ML) TMD FETs has been published, there exist no comprehensive studies that assess their performance in a statistically relevant manner, providing critical insights into the impact of the device geometry. Part of the reason for the absence of such a study is the substantial variability of TMD devices when processes are not carefully controlled. In this work, we show a statistical study of ultrashort channel double-gated ML WS2 FETs exhibiting excellent device performance and limited device-to-device variations. From a detailed analysis of cross-sectional scanning transmission electron microscopy (STEM) images and careful technology computer aided design (TCAD) simulations, we evaluated, in particular, an unexpected deterioration of the subthreshold characteristics for our shortest devices. Two potential candidates for the observed behavior were identified, i.e., buckling of the TMD on the substrate and loss of gate control due to the source geometry and the high-k dielectric between the metal gate and the metal source electrode.

Graphdiyne-Based Nanofilms for Compliant On-Skin Sensing.

Thin-film electronics pliably laminated onto the epidermis for noninvasive, specific, and multifunctional sensing are ideal wearable systems for health monitoring and information technologies. However, it remains a critical challenge to fabricate ultrathin and compliant skin-like sensors with high imperceptibility and sensitivities. Here we report a design of conductive hydrogen-substituted graphdiyne (HsGDY) nanofilms with conjugated porous structure and inherent softness for on-skin sensors that allow minimization of stress and discomfort with wear. Dominated by the subtle deformation-induced changes in the interdomain tunneling conductance, the engineered HsGDY sensors show continuous and accurate results. Real-time noninvasive spatial mapping of dynamic/static strains in both tensile/compressive directions monitors various body motions with high sensitivity (GF ∼22.6, under 2% strain), fast response (∼60 ms), and long-term durability (∼5000 cycles). Moreover, such devices can dynamically distinguish between the temperature difference and frequency of air inhaled and exhaled through the nostril, revealing a quantitative assessment of the movement/health of the human body. The proof-of-concept strategy provides an alternative route for the design of next-generation wearable organic bioelectronics with multiple electronic functionalities.

Fast water transport and molecular sieving through ultrathin ordered conjugated-polymer-framework membranes.

The development of membranes that block solutes while allowing rapid water transport is of great importance. The microstructure of the membrane needs to be rationally designed at the molecular level to achieve precise molecular sieving and high water flux simultaneously. We report the design and fabrication of ultrathin, ordered conjugated-polymer-framework (CPF) films with thicknesses down to 1 nm via chemical vapour deposition and their performance as separation membranes. Our CPF membranes inherently have regular rhombic sub-nanometre (10.3 × 3.7 Å) channels, unlike membranes made of carbon nanotubes or graphene, whose separation performance depends on the alignment or stacking of materials. The optimized membrane exhibited a high water/NaCl selectivity of ∼6,900 and water permeance of ∼112 mol m-2 h-1 bar-1, and salt rejection >99.5% in high-salinity mixed-ion separations driven by osmotic pressure. Molecular dynamics simulations revealed that water molecules quickly and collectively pass through the membrane by forming a continuous three-dimensional network within the hydrophobic channels. The advent of ordered CPF provides a route towards developing carbon-based membranes for precise molecular separation.

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.

High-κ perovskite membranes as insulators for two-dimensional transistors.

The scaling of silicon metal-oxide-semiconductor field-effect transistors has followed Moore's law for decades, but the physical thinning of silicon at sub-ten-nanometre technology nodes introduces issues such as leakage currents1. Two-dimensional (2D) layered semiconductors, with an atomic thickness that allows superior gate-field penetration, are of interest as channel materials for future transistors2,3. However, the integration of high-dielectric-constant (κ) materials with 2D materials, while scaling their capacitance equivalent thickness (CET), has proved challenging. Here we explore transferrable ultrahigh-κ single-crystalline perovskite strontium-titanium-oxide membranes as a gate dielectric for 2D field-effect transistors. Our perovskite membranes exhibit a desirable sub-one-nanometre CET with a low leakage current (less than 10-2 amperes per square centimetre at 2.5 megavolts per centimetre). We find that the van der Waals gap between strontium-titanium-oxide dielectrics and 2D semiconductors mitigates the unfavourable fringing-induced barrier-lowering effect resulting from the use of ultrahigh-κ dielectrics4. Typical short-channel transistors made of scalable molybdenum-disulfide films by chemical vapour deposition and strontium-titanium-oxide dielectrics exhibit steep subthreshold swings down to about 70 millivolts per decade and on/off current ratios up to 107, which matches the low-power specifications suggested by the latest International Roadmap for Devices and Systems5.

Nanoscale Electronic Transparency of Wafer-Scale Hexagonal Boron Nitride.

Monolayer hexagonal boron nitride (hBN) has attracted interest as an ultrathin tunnel barrier or environmental protection layer. Recently, wafer-scale hBN growth on Cu(111) was developed for semiconductor chip applications. For basic research and technology, understanding how hBN perturbs underlying electronically active layers is critical. Encouragingly, hBN/Cu(111) has been shown to preserve the Cu(111) surface state (SS), but it was unknown how tunneling into this SS through hBN varies spatially. Here, we demonstrate that the Cu(111) SS under wafer-scale hBN is homogeneous in energy and spectral weight over nanometer length scales and across atomic terraces. In contrast, a new spectral feature─not seen on bare Cu(111)─varies with atomic registry and shares the spatial periodicity of the hBN/Cu(111) moiré. This work demonstrates that, for some 2D electron systems, an hBN overlayer can act as a protective yet remarkably transparent window on fragile low-energy electronic structure below.

Directly Visualizing Photoinduced Renormalized Momentum-Forbidden Electronic Quantum States in an Atomically Thin Semiconductor.

Resolving the momentum degree of freedom of photoexcited charge carriers and exploring the excited-state physics in the hexagonal Brillouin zone of atomically thin semiconductors have recently attracted great interest for optoelectronic technologies. We demonstrate a combination of light-modulated scanning tunneling microscopy and the quasiparticle interference (QPI) technique to offer a directly accessible approach to reveal and quantify the unexplored momentum-forbidden electronic quantum states in transition metal dichalcogenide (TMD) monolayers. Our QPI results affirm the large spin-splitting energy at the spin-valley-coupled Q valleys in the conduction band (CB) of a tungsten disulfide monolayer. Furthermore, we also quantify the photoexcited carrier density-dependent band renormalization at the Q valleys. Our findings directly highlight the importance of the excited-state distribution at the Q valley in the band renormalization in TMDs and support the critical role of the CB Q valley in engineering the quantum electronic valley degree of freedom in TMD devices.

Unusual Activity of Rationally Designed Cobalt Phosphide/Oxide Heterostructure Composite for Hydrogen Production in Alkaline Medium.

Design and development of an efficient, nonprecious catalyst with structural features and functionality necessary for driving the hydrogen evolution reaction (HER) in an alkaline medium remain a formidable challenge. At the root of the functional limitation is the inability to tune the active catalytic sites while overcoming the poor reaction kinetics observed under basic conditions. Herein, we report a facile approach to enable the selective design of an electrochemically efficient cobalt phosphide oxide composite catalyst on carbon cloth (CoP-CoxOy/CC), with good activity and durability toward HER in alkaline medium (η10 = -43 mV). Theoretical studies revealed that the redistribution of electrons at laterally dispersed Co phosphide/oxide interfaces gives rise to a synergistic effect in the heterostructured composite, by which various Co oxide phases initiate the dissociation of the alkaline water molecule. Meanwhile, the highly active CoP further facilitates the adsorption-desorption process of water electrolysis, leading to extremely high HER activity.

Bi2O2Se-Based True Random Number Generator for Security Applications.

The fast development of the Internet of things (IoT) promises to deliver convenience to human life. However, a huge amount of the data is constantly generated, transmitted, processed, and stored, posing significant security challenges. The currently available security protocols and encryption techniques are mostly based on software algorithms and pseudorandom number generators that are vulnerable to attacks. A true random number generator (TRNG) based on devices using stochastically physical phenomena has been proposed for auditory data encryption and trusted communication. In the current study, a Bi2O2Se-based memristive TRNG is demonstrated for security applications. Compared with traditional metal-insulator-metal based memristors, or other two-dimensional material-based memristors, the Bi2O2Se layer as electrode with non-van der Waals interface, high carrier mobility, air stability, extreme low thermal conductivity, as well as vertical surface resistive switching shows intrinsic stochasticity and complexity in a memristive true analogue/digital random number generation. Moreover, those analogue/digital random number generation processes are proved to be resilient for machine learning prediction.

Two-Dimensional Cs2AgBiBr6/WS2 Heterostructure-Based Photodetector with Boosted Detectivity via Interfacial Engineering.

Two-dimensional (2D) transition metal dichalcogenide (TMDC) monolayers have been widely used for optoelectronic devices because of their ultrasensitivity to light detection acquired from their direct gap properties. However, the small cross-section of photon absorption in the atomically thin layer thickness significantly limits the generation of photocarriers, restricting their performance. Here, we integrate monolayer WS2 with 2D perovskites Cs2AgBiBr6, which serve as the light absorption layer, to greatly enhance the photosensitivity of WS2. The efficient charge transfer at the Cs2AgBiBr6/WS2 heterojunction is evidenced by the shortened photoluminescence (PL) decay time of Cs2AgBiBr6. Scanning photocurrent microscopy of Cs2AgBiBr6/WS2/graphene reveals that improved charge extraction from graphene leads to an enhanced photoresponse. The 2D Cs2AgBiBr6/WS2/graphene vertical heterostructure photodetector exhibits a high detectivity (D*) of 1.5 × 1013 Jones with a fast response time of 52.3 µs/53.6 µs and an on/off ratio of 1.02 × 104. It is worth noting that this 2D heterostructure photodetector can realize self-powered light detection behavior with an open-circuit voltage of ∼0.75 V. The results suggest that the 2D perovskites can effectively improve the TMDC layer-based photodetectors for low-power consumption photoelectrical applications.

Wafer-scale single-orientation 2D layers by atomic edge-guided epitaxial growth.

Two-dimensional (2D) layered materials hold tremendous promise for post-Si nanoelectronics due to their unique optical and electrical properties. Significant advances have been achieved in device fabrication and synthesis routes for 2D nanoelectronics over the past decade; however, one major bottleneck preventing their immediate applications has been the lack of a reproducible approach for growing wafer-scale single-crystal films despite tremendous progress in recent experimental demonstrations. In this tutorial review, we provide a systematic summary of the critical factors-including crystal/substrate symmetry and energy consideration-necessary for synthesizing single-orientation 2D layers. In particular, we focus on the discussions of the atomic edge-guided epitaxial growth, which assists in unidirectional nucleation for the wafer-scale growth of single-crystal 2D layers.

2D Materials-Based Static Random-Access Memory.

2D transition-metal dichalcogenide semiconductors, such as MoS2 and WSe2 , with adequate bandgaps are promising channel materials for ultrascaled logic transistors. This scalability study of 2D material (2DM)-based field-effect transistor (FET) and static random-access memory (SRAM) cells analyzing the impact of layer thickness reveals that the monolayer 2DM FET with superior electrostatics is beneficial for its ability to mitigate the read-write conflict in an SRAM cell at scaled technology nodes (1-2.1 nm). Moreover, the monolayer 2DM SRAM exhibits lower cell read access time and write time than the bilayer and trilayer 2DM SRAM cells at fixed leakage power. This simulation predicts that the optimization of 2DM SRAM designed with state-of-the-art contact resistance, mobility, and equivalent oxide thickness leads to excellent stability and operation speed at the 1-nm node. Applying the nanosheet (NS) gate-all-around (GAA) structure to 2DM further reduces cell read access time and write time and improves the area density of the SRAM cells, demonstrating a feasible scaling path beyond Si technology using 2DM NSFETs. In addition to the device design, the process challenges for 2DM NSFETs, including the cost-effective stacking of 2DM layers, formation of electrical contacts, suspended 2DM channels, and GAA structures, are also discussed.