Polarization-Switchable Electrochemistry of 2D Layered Bi2O2Se Bifunctional Microreactors by Ferroelectric Modulation.

Ferroelectric catalysts are known for altering surface catalytic activities by changing the direction of their electric polarizations. This study demonstrates polarization-switchable electrochemistry using layered bismuth oxyselenide (L-Bi2O2Se) bifunctional microreactors through ferroelectric modulation. A selective-area ionic liquid gating is developed with precise control over the spatial distribution of the dipole orientation of L-Bi2O2Se. On-chip microreactors with upward polarization favor the oxygen evolution reaction, whereas those with downward polarization prefer the hydrogen evolution reaction. The microscopic origin behind polarization-switchable electrochemistry primarily stems from enhanced surface adsorption and reduced energy barriers for reactions, as examined by nanoscale scanning electrochemical cell microscopy. Integrating a pair of L-Bi2O2Se microreactors consisting of upward or downward polarizations demonstrates overall water splitting in a full-cell configuration based on a bifunctional catalyst. The ability to modulate surface polarizations on a single catalyst via ferroelectric polarization switching offers a pathway for designing catalysts for water splitting.

High-Performance Monolithic 3D Integrated Complementary Inverters Based on Monolayer n-MoS2 and p-WSe2.

Herein, the structure of integrated M3D inverters are successfully demonstrated where a chemical vapor deposition (CVD) synthesized monolayer WSe2 p-type nanosheet FET is vertically integrated on top of CVD synthesized monolayer MoS2 n-type film FET arrays (2.5 × 2.5 cm) by semiconductor industry techniques, such as transfer, e-beam evaporation (EBV), and plasma etching processes. A low temperature (below 250 °C) is employed to protect the WSe2 and MoS2 channel materials from thermal decomposition during the whole fabrication process. The MoS2 NMOS and WSe2 PMOS device fabricated show an on/off current ratio exceeding 106 and the integrated M3D inverters indicate an average voltage gain of ≈9 at VDD = 2 V. In addition, the integrated M3D inverter demonstrates an ultra-low power consumption of 0.112 nW at a VDD of 1 V. Statistical analysis of the fabricated inverters devices shows their high reliability, rendering them suitable for large-area applications. The successful demonstration of M3D inverters based on large-scale 2D monolayer TMDs indicate their high potential for advancing the application of 2D TMDs in future integrated circuits.

Embedment of Multiple Transition Metal Impurities into WS2 Monolayer for Bandstructure Modulation.

Band structure by design in 2D layered semiconductors is highly desirable, with the goal to acquire the electronic properties of interest through the engineering of chemical composition, structure, defect, stacking, or doping. For atomically thin transition metal dichalcogenides, substitutional doping with more than one single type of transition metals is the task for which no feasible approach is proposed. Here, the growth of WS2 monolayer is shown codoped with multiple kinds of transition metal impurities via chemical vapor deposition controlled in a diffusion-limited mode. Multielement embedment of Cr, Fe, Nb, and Mo into the host lattice is exemplified. Abundant impurity states thus generate in the bandgap of the resultant WS2 and provide a robust switch of charging/discharging states upon sweep of an electric filed. A profound memory window exists in the transfer curves of doped WS2 field-effect transistors, forming the basis of binary states for robust nonvolatile memory. The doping technique presented in this work brings one step closer to the rational design of 2D semiconductors with desired electronic properties.

Unexpected Huge Dimerization Ratio in One-Dimensional Carbon Atomic Chains.

Peierls theory predicted atomic distortion in one-dimensional (1D) crystal due to its intrinsic instability in 1930. Free-standing carbon atomic chains created in situ in transmission electron microscope (TEM)1-3 are an ideal example to experimentally observe the dimerization behavior of carbon atomic chain within a finite length. We report here a surprisingly huge distortion found in the free-standing carbon atomic chains at 773 K, which is 10 times larger than the value expected in the system. Such an abnormally distorted phase only dominates at the elevated temperatures, while two distinct phases, distorted and undistorted, coexist at lower or ambient temperatures. Atom-by-atom spectroscopy indeed shows considerable variations in the carbon 1s spectra at each atomic site but commonly observes a slightly downshifted π* peak, which proves its sp1 bonding feature. These results suggest that the simple model, relaxed and straight, is not fully adequate to describe the realistic 1D structure, which is extremely sensitive to perturbations such as external force or boundary conditions.

Postsynthesis of h-BN/Graphene Heterostructures Inside a STEM.

Combinations of 2D materials with different physical properties can form heterostructures with modified electrical, mechanical, magnetic, and optical properties. The direct observation of a lateral heterostructure synthesis is reported by epitaxial in-plane graphene growth from the step-edge of hexagonal BN (h-BN) within a scanning transmission electron microscope chamber. Residual hydrocarbon in the chamber is the carbon source. The growth interface between h-BN and graphene is atomically identified as largely N-C bonds. This postgrowth method can form graphene nanoribbons connecting two h-BN domains with different twisting angles, as well as isolated carbon islands with arbitrary shapes embedded in the h-BN layer. The electronic properties of the vertically stacked h-BN/graphene heterostructures are investigated by electron energy-loss spectroscopy (EELS). Low-loss EELS analysis of the dielectric response suggests a robust coupling effect between the graphene and h-BN layers.

Structural and Chemical Dynamics of Pyridinic-Nitrogen Defects in Graphene.

High density and controllable nitrogen doping in graphene is a critical issue to realize high performance graphene-based devices. In this paper, we demonstrate an efficient method to selectively produce graphitic-N and pyridinic-N defects in graphene by using the mixture plasma of ozone and nitrogen. The atomic structure, electronic structure, and dynamic behavior of these nitrogen defects are systematically studied at the atomic level by using a scanning transmission electron microscopy. The pyridinic-N exhibits higher chemical activity and tends to trap a series of transition metal atoms (Mg, Al, Ca, Ti, Cr, Mn, and Fe) as individual atoms.

Exploring the Single Atom Spin State by Electron Spectroscopy.

To control the spin state of an individual atom is an ultimate goal for spintronics. A single atom magnet, which may lead to a supercapacity memory device if realized, requires the high-spin state of an isolated individual atom. Here, we demonstrate the realization of well isolated transition metal (TM) atoms fixed at atomic defects sparsely dispersed in graphene. Core-level electron spectroscopy clearly reveals the high-spin state of the individual TM atoms at the divacancy or edge of the graphene layer. We also show for the first time that the spin state of single TM atoms systematically varies with the coordination of neighboring nitrogen or oxygen atoms. These structures can be thus regarded as the smallest components of spintronic devices with controlled magnetic behavior.

Synthesis of pentameric chlorotin carboxylate clusters for high resolution EUV photoresists under small doses.

This work reports the synthesis and characterization of a novel pentameric tin chloro cluster, (vinylSn)3Sn2Cl5O2(OH)2(t-BuCO2)6 (1), and explores its application as an efficient negative-tone photoresist in a 1 : 2 weight ratio blend with [(n-BuSn)12O14(OH)6](BF4)2 (2). Through e-beam lithography, a small high-resolution pattern (HP = 20 nm) is achieved for the blend photoresist (3) at a dose of 2080 µC cm-2. Additionally, EUV lithography demonstrates the development of a high-resolution pattern (HP = 16 nm) at an EUV dose of 70 mJ cm-2. Mechanistic studies by reflective FTIR indicate a significant decomposition of Sn-carbon and SnO2(t-Bu) moieties starting at J = 35 mJ cm-2, which is accompanied by growth of the Sn-O absorption intensity. A collapse of the cluster frameworks of clusters (1) and (2) is observed at J > 70 mJ cm-2. High-resolution X-ray photoelectron spectroscopy (HRXPS) reveals that low EUV light predominantly decomposes Sn-butyl and Sn-Cl bonds. As EUV doses increase, primary photolytic reactions involve cleavage of Sn-butyl, Sn-O2CBut, and Sn-vinyl bonds. Notably, the photolytic decomposition of Sn-Cl bonds is distinctive, with only two out of five bonds being cleaved, even at high EUV doses, resulting in a break in film growth at J = 27-35 mJ cm-2 in the EUV contrast curve. Moreover, HRXPS analysis suggests that radical propagation on the vinyltin end of the blend is unlikely, providing concise mechanistic insights into the photochemical processes governing the behavior of this advanced photoresist.

Alkali metal bilayer intercalation in graphene.

Alkali metal (AM) intercalation between graphene layers holds promise for electronic manipulation and energy storage, yet the underlying mechanism remains challenging to fully comprehend despite extensive research. In this study, we employ low-voltage scanning transmission electron microscopy (LV-STEM) to visualize the atomic structure of intercalated AMs (potassium, rubidium, and cesium) in bilayer graphene (BLG). Our findings reveal that the intercalated AMs adopt bilayer structures with hcp stacking, and specifically a C6M2C6 composition. These structures closely resemble the bilayer form of fcc (111) structure observed in AMs under high-pressure conditions. A negative charge transferred from bilayer AMs to graphene layers of approximately 1~1.5×1014 e-/cm-2 was determined by electron energy loss spectroscopy (EELS), Raman, and electrical transport. The bilayer AM is stable in BLG and graphite superficial layers but absent in the graphite interior, primarily dominated by single-layer AM intercalation. This hints at enhancing AM intercalation capacity by thinning the graphite material.

Enhanced Electrical Transport Properties of Molybdenum Disulfide Field-Effect Transistors by Using Alkali Metal Fluorides as Dielectric Capping Layers.

The electronic properties of 2D materials are highly influenced by the molecular activity at their interfaces. A method was proposed to address this issue by employing passivation techniques using monolayer MoS2 field-effect transistors (FETs) while preserving high performance. Herein, we have used alkali metal fluorides as dielectric capping layers, including lithium fluoride (LiF), sodium fluoride (NaF), and potassium fluoride (KF) dielectric capping layers, to mitigate the environmental impact of oxygen and water exposure. Among them, the LiF dielectric capping layer significantly improved the transistor performance, specifically in terms of enhanced field effect mobility from 74 to 137 cm2/V·s, increased current density from 17 µA/µm to 32.13 µA/µm at a drain voltage of Vd of 1 V, and decreased subthreshold swing to 0.8 V/dec The results have been analytically verified by X-ray photoelectron spectroscopy (XPS) and Raman, and photoluminescence (PL) spectroscopy, and the demonstrated technique can be extended to other transition metal dichalcogenide (TMD)-based FETs, which can become a prospect for cutting-edge electronic applications. These findings highlight certain important trade-offs and provide insight into the significance of interface control and passivation material choice on the electrical stability, performance, and enhancement of the MoS2 FET.

Nonvolatile Modulation of Bi2O2Se/Pb(Zr,Ti)O3 Heteroepitaxy.

The pursuit of high-performance electronic devices has driven the research focus toward 2D semiconductors with high electron mobility and suitable band gaps. Previous studies have demonstrated that quasi-2D Bi2O2Se (BOSe) has remarkable physical properties and is a promising candidate for further exploration. Building upon this foundation, the present work introduces a novel concept for achieving nonvolatile and reversible control of BOSe's electronic properties. The approach involves the epitaxial integration of a ferroelectric PbZr0.2Ti0.8O3 (PZT) layer to modify BOSe's band alignment. Within the BOSe/PZT heteroepitaxy, through two opposite ferroelectric polarization states of the PZT layer, we can tune the Fermi level in the BOSe layer. Consequently, this controlled modulation of the electronic structure provides a pathway to manipulate the electrical properties of the BOSe layer and the corresponding devices.

Graphene annealing: how clean can it be?

Surface contamination by polymer residues has long been a critical problem in probing graphene's intrinsic properties and in using graphene for unique applications in surface chemistry, biotechnology, and ultrahigh speed electronics. Poly(methyl methacrylate) (PMMA) is a macromolecule commonly used for graphene transfer and device processing, leaving a thin layer of residue to be empirically cleaned by annealing. Here we report on a systematic study of PMMA decomposition on graphene and of its impact on graphene's intrinsic properties using transmission electron microscopy (TEM) in combination with Raman spectroscopy. TEM images revealed that the physisorbed PMMA proceeds in two steps of weight loss in annealing and cannot be removed entirely at a graphene susceptible temperature before breaking. Raman analysis shows a remarkable blue-shift of the 2D mode after annealing, implying an anneal-induced band structure modulation in graphene with defects. Calculations using density functional theory show that local rehybridization of carbons from sp(2) to sp(3) on graphene defects may occur in the random scission of polymer chains and account for the blue-shift of the Raman 2D mode.

Remote catalyzation for direct formation of graphene layers on oxides.

Direct deposition of high-quality graphene layers on insulating substrates such as SiO(2) paves the way toward the development of graphene-based high-speed electronics. Here, we describe a novel growth technique that enables the direct deposition of graphene layers on SiO(2) with crystalline quality potentially comparable to graphene grown on Cu foils using chemical vapor deposition (CVD). Rather than using Cu foils as substrates, our approach uses them to provide subliming Cu atoms in the CVD process. The prime feature of the proposed technique is remote catalyzation using floating Cu and H atoms for the decomposition of hydrocarbons. This allows for the direct graphitization of carbon radicals on oxide surfaces, forming isolated low-defect graphene layers without the need for postgrowth etching or evaporation of the metal catalyst. The defect density of the resulting graphene layers can be significantly reduced by tuning growth parameters such as the gas ratios, Cu surface areas, and substrate-to-Cu distance. Under optimized conditions, graphene layers with nondiscernible Raman D peaks can be obtained when predeposited graphite flakes are used as seeds for extended growth.

Novel hexameric tin carboxylate clusters as efficient negative-tone EUV photoresists: high resolution with well-defined patterns under low energy doses.

Synthesis of two novel tin carboxylate clusters (RSn)6(R'CO2)8O4Cl2 is described, and their structures have been characterized by X-ray diffraction. These clusters have irregular ladder geometry to form very smooth films with small surface roughness (RMS <0.7 nm) over a large domain. EUV lithography can be used to resolve half pitches (HPs) in the order of 15-16 nm with line width roughness (LWR = 4.5-6.0 nm) using small doses (20-90 mJ cm-2). Cluster 1 (R = n-butyl; R'CO2 = 2-methyl-3-butenoate) contains only a radical precursor and cluster 2 (R = vinyl, R'CO2 = 2-methylbutyrate) bears both a radical precursor and an acceptor; the latter is much better than the former in EUV and e-beam photosensitivity. For these clusters, the mechanisms of EUV irradiation have been elucidated with high resolution X-ray photoelectron spectroscopy (HRXPS) and reflective Fourier-transform infrared spectroscopy (FTIR). At low EUV doses, two clusters undergo a Sn-Cl bond cleavage together with a typical decarboxylation to generate carbon radicals. The n-butyl groups of cluster 1 are prone to cleavage whereas the vinyl-Sn bonds of species 2 are inert toward EUV irradiation; participation of radical polymerization is evident for the latter.

Highly hydroxylated hafnium clusters are accessible to high resolution EUV photoresists under small energy doses.

This work reports the success in accessing high-resolution negative-tone EUV photoresists without radical chain growth in the aggregation mechanism. The synthesis of a highly hydroxylated Hf6O4(OH)8(RCO2)8 cluster 3 (R = s-butyl or s-Bu) is described; its EUV performance enables high resolution patterns HP = 18 nm under only 30 mJ cm-2. This photoresist also achieves high resolution patterns for e-beam lithography. Our new photoresist design to increase hydroxide substitutions of carboxylate ligands in the Hf6O4(OH)4(RCO2)12 clusters improves the EUV resolution and also greatly reduces EUV doses. Mechanistic analysis indicates that EUV light not only enables photolytic decomposition of carboxylate ligands, but also enhances the Hf-OH dehydration. One additional advantage of cluster 3 is a very small loss of film thickness (ca. 13%) after the EUV pattern development.

Ultrafast and Broad-Band Graphene Heterojunction Photodetectors with High Gain.

Graphene possesses an exotic band structure that spans a wide range of important technological wavelength regimes for photodetection, all within a single material. Conventional methods aimed at enhancing detection efficiency often suffer from an extended response time when the light is switched off. The task of achieving ultrafast broad-band photodetection with a high gain remains challenging. Here, we propose a devised architecture that combines graphene with a photosensitizer composed of an alternating strip superstructure of WS2-WSe2. Upon illumination, n+-WS2 and p+-WSe2 strips create alternating electron- and hole-conduction channels in graphene, effectively overcoming the tradeoff between the responsivity and switch time. This configuration allows for achieving a responsivity of 1.7 × 107 mA/W, with an extrinsic response time of 3-4 µs. The inclusion of the superstructure booster enables photodetection across a wide range from the near-ultraviolet to mid-infrared regime and offers a distinctive photogating route for high responsivity and fast temporal response in the pursuit of broad-band detection.

Molybdenum Chloride Nanostructures with Giant Lattice Distortions Intercalated into Bilayer Graphene.

The nanospace of the van der Waals (vdW) gap between structural units of two-dimensional (2D) materials serves as a platform for growing unusual 2D systems through intercalation and studying their properties. Various kinds of metal chlorides have previously been intercalated for tuning the properties of host layered materials, but the atomic structure of the intercalants remains still unidentified. In this study, we investigate the atomic structural transformation of molybdenum(V) chloride (MoCl5) after intercalation into bilayer graphene (BLG). Using scanning transmission electron microscopy, we found that the intercalated material represents MoCl3 networks, MoCl2 chains, and Mo5Cl10 rings. Giant lattice distortions and frequent structural transitions occur in the 2D MoClx that have never been observed in metal chloride systems. The trend of symmetric to nonsymmetric structural transformations can cause additional charge transfer from BLG to the intercalated MoClx, as suggested by our density functional theory calculations. Our study deepens the understanding of the behavior of matter in the confined space of the vdW gap in BLG and provides hints at a more efficient tuning of material properties by intercalation for potential applications, including transparent conductive films, optoelectronics, and energy storage.

Silicon-van der Waals heterointegration for CMOS-compatible logic-in-memory design.

Silicon CMOS-based computing-in-memory encounters design and power challenges, especially in logic-in-memory scenarios requiring nonvolatility and reconfigurability. Here, we report a universal design for nonvolatile reconfigurable devices featuring a 2D/3D heterointegrated configuration. By leveraging the photo-controlled charge trapping/detrapping process and the partially top-gated energy band landscape, the van der Waals heterostacking achieves polarity storage and logic reconfigurable characteristics, respectively. Precise polarity tunability, logic nonvolatility, robustness against high temperature (at 85°C), and near-ideal subthreshold swing (80 mV dec-1) can be done. A comprehensive investigation of dynamic charge fluctuations provides a holistic understanding of the origins of nonvolatile reconfigurability (a trap level of 1013 cm-2 eV-1). Furthermore, we cascade such nonvolatile reconfigurable units into a monolithic circuit layer to demonstrate logic-in-memory computing possibilities, such as high-gain (65 at Vdd = 0.5 V) logic gates. This work provides an innovative 3D heterointegration prototype for future computing-in-memory hardware.

WSe2/WS2 Heterobilayer Nonvolatile Memory Device with Boosted Charge Retention.

A two-dimensional (2D) nonvolatile memory device architecture to improve the long-term charge retention with the minimum charge loss without compromising storage capacity and the extinction ratio for practical applications has been an imminent demand. To address the current issue, we adopted a novel type-II band-aligned heterobilayer channel comprising vertically stacked monolayer WSe2 nanodots on monolayer WS2. The band offset modulation leads to electron doping from WSe2 nanodots into the WS2 channel without any external driving electric field. As a result, the tested device outperformed with a memory window as high as 34 V and a negligible charge loss of 7% in a retention period of 10 years while maintaining a high extinction ratio of 106. The doping technique presented in this work provides a feasible route to modulate the electrical properties of 2D channel materials without hampering charge transport, paving the way for high-performance 2D memory devices.

Patterning and doping of transition metals in tungsten dichalcogenides.

Substitutional transition metal doping in two-dimensional (2D) layered dichalcogenides is of fundamental importance in manipulating their electrical, excitonic, magnetic, and catalytic properties through the variation of the d-electron population. Yet, most doping strategies are spatially global, with dopants embedded concurrently during the synthesis. Here, we report an area-selective doping scheme for W-based dichalcogenide single layers, in which pre-patterned graphene is used as a reaction mask in the high-temperature substitution of the W sublattice. The chemical inertness of the thin graphene layer can effectively differentiate the spatial doping reaction, allowing for local manipulation of the host 2D materials. Using graphene as a mask is also beneficial in the sense that it also acts as an insertion layer between the contact metal and the doped channel, capable of depinning the Fermi level for low contact resistivity. Tracing doping by means of chalcogen labelling, deliberate Cr embedment is found to become energetically favorable in the presence of chalcogen deficiency, assisting the substitution of the W sublattice in the devised chemical vapor doping scheme. Atomic characterization using scanning transmission electron microscopy (STEM) shows that the dopant concentration is controllable and varies linearly with the reaction time in the current doping approach. Using the same method, other transition metal atoms such as Mo, V, and Fe can also be doped in the patterned area.