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.

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.

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.

Quantum-Engineered Devices Based on 2D Materials for Next-Generation Information Processing and Storage.

As an approximation to the quantum state of solids, the band theory, developed nearly seven decades ago, fostered the advance of modern integrated solid-state electronics, one of the most successful technologies in the history of human civilization. Nonetheless, their rapidly growing energy consumption and accompanied environmental issues call for more energy-efficient electronics and optoelectronics, which necessitate the exploration of more advanced quantum mechanical effects, such as band-to-band tunneling, spin-orbit coupling, spin-valley locking, and quantum entanglement. The emerging 2D layered materials, featured by their exotic electrical, magnetic, optical, and structural properties, provide a revolutionary low-dimensional and manufacture-friendly platform (and many more opportunities) to implement these quantum-engineered devices, compared to the traditional electronic materials system. Here, the progress in quantum-engineered devices is reviewed and the opportunities/challenges of exploiting 2D materials are analyzed to highlight their unique quantum properties that enable novel energy-efficient devices, and useful insights to quantum device engineers and 2D-material scientists are provided.

Graphene-Transition Metal Dichalcogenide Heterojunctions for Scalable and Low-Power Complementary Integrated Circuits.

The most pressing barrier for the development of advanced electronics based on two-dimensional (2D) layered semiconductors stems from the lack of site-selective synthesis of complementary n- and p-channels with low contact resistance. Here, we report an in-plane epitaxial route for the growth of interlaced 2D semiconductor monolayers using chemical vapor deposition with a gas-confined scheme, in which patterned graphene (Gr) serves as a guiding template for site-selective growth of Gr-WS2-Gr and Gr-WSe2-Gr heterostructures. The Gr/2D semiconductor interface exhibits a transparent contact with a nearly ideal pinning factor of 0.95 for the n-channel WS2 and 0.92 for the p-channel WSe2. The effective depinning of the Fermi level gives an ultralow contact resistance of 0.75 and 1.20 kΩ·µm for WS2 and WSe2, respectively. Integrated logic circuits including inverter, NAND gate, static random access memory, and five-stage ring oscillator are constructed using the complementary Gr-WS2-Gr-WSe2-Gr heterojunctions as a fundamental building block, featuring the prominent performance metrics of high operation frequency (>0.2 GHz), low-power consumption, large noise margins, and high operational stability. The technology presented here provides a speculative look at the electronic circuitry built on atomic-scale semiconductors in the near future.

Gigahertz Field-Effect Transistors with CMOS-Compatible Transfer-Free Graphene.

High-quality graphene grown on metal-free substrates represents a vital milestone that provides an atomic clean interface and a complementary metal-oxide-semiconductor-compatible manufacturing process for electronic applications. We report a scalable approach to fabricate radio frequency field-effect transistors with a graphene channel grown directly on the sapphire substrate using the technique of remote-catalyzed chemical vapor deposition (CVD). A mushroom-shaped AlO x top gate is used to allow the self-aligned drain/source contacts, yielding remarkable increase of device transconductance and reduction of the associated parasitic resistance. The quality of thus-grown graphene is reflected in the high extrinsic cutoff frequency and maximum oscillation frequency of 10.1 and 5.6 GHz for the graphene channel of length 200 nm and width 80 µm, respectively, potentially comparable with those of transferred CVD graphene at the same channel length and holding promise for applications in high-speed wireless communications.

End-Bonded Metal Contacts on WSe2 Field-Effect Transistors.

Contact engineering has been the central issue in the context of high-performance field-effect transistors (FETs) made of atomic thin transition metal dichalcogenides (TMDs). Conventional metal contacts on TMDs have been made on top via a lithography process, forming a top-bonded contact scheme with an appreciable contact barrier. To provide a more efficient pathway for charge injection, an end-bonded contact scheme has been proposed, in which covalent bonds are formed between the contact metal and channel edges. Yet, little efforts have been made to realize this contact configuration. Here, we bridge this gap and demonstrate seeded growth of end-bonded contact with different TMDs by means of chemical vapor deposition (CVD). Monolayer WSe2 FETs with a CVD-grown channel and end contacts exhibit improved performance metrics, including an on-current density of 30 µA/µm, a hole mobility of 90 cm2/V·s, and a subthreshold swing of 94 mV/dec, an order of magnitude superior than those of top-contact FET counterparts that share the same channel material. A fundamental NOT logic gate constructed using top-gated and end-bonded WSe2 and MoS2 FETs is also demonstrated. Calculations using density functional theory indicate that the superior device performance stems mainly from the stronger metal-TMD hybridization and substantial gap states in the end-contact configuration.

Ultrafast Monolayer In/Gr-WS2-Gr Hybrid Photodetectors with High Gain.

One of the primary limitations of previously reported two-dimensional (2D) photodetectors is a low frequency response (≪ 1 Hz) for sensitive devices with gain. Yet, little efforts have been devoted to improve the temporal response of photodetectors while maintaining high gain and responsivity. Here, we demonstrate a gain of 6.3 × 103 electrons per photon and a responsivity of 2.6 × 103 A/W while simultaneously exhibiting an ultrafast response time of 40-65 µs in a hybrid photodetector that consists of graphene-WS2-graphene junctions covered with indium (In) adatoms atop. The resultant responsivity is 6 orders of magnitude higher than that of conventional photodetectors comprising solely of a Au-WS2-Au junction. The photogain is provided mainly by the adsorbed In adatoms, from which photogenerated electrons can be transferred to the WS2 channel, while holes remain trapped in In adatoms, leading to a photogating effect as electrons are recirculating during the residence of holes in In adatoms. At a gate voltage near the Dirac point of graphene, a detectivity of D* = 2.2 × 1012 Jones and an ON/OFF ratio of 104 are achieved. The enhanced performance of the device can be attributed partly to the transparent graphene/WS2 contact and partly to the strong capacitive coupling of the In adatoms with the WS2 channel, which enables ultrafast carrier dynamics.

Stable 1T Tungsten Disulfide Monolayer and Its Junctions: Growth and Atomic Structures.

Transition-metal dichalcogenides in the 1T phase have been a subject of increasing interest, which is partly due to their fascinating physical properties and partly to their potential applications in the next generation of electronic devices, including supercapacitors, electrocatalytic hydrogen evolution, and phase-transition memories. The primary method for obtaining 1T WS2 or MoS2 has been using ion intercalation in combination with solution-based exfoliation. The resulting flakes are small in size and tend to aggregate upon deposition, forming an intercalant-TMD complex with small 1T and 1T' patches embedded in the 2H matrix. Existing growth methods have, however, produced WS2 or MoS2 solely in the 2H phase. Here, we have refined the growth approach to obtain monolayer 1T WS2 up to 80 µm in size based on chemical vapor deposition. With the aid of synergistic catalysts (iron oxide and sodium chloride), 1T WS2 can nucleate in the infant stage of the growth, forming special butterfly-like single crystals with the 1T phase in one wing and the 2H phase in the other. Distinctive types of phase boundaries are discovered at the 1T-2H interface. The 1T structure thus grown is thermodynamically stable over time and even persists at a high temperature above 800 °C, allowing for a stepwise edge epitaxy of lateral 1T heterostructures. Atomic images show that the 1T WS2-MoS2 heterojunction features a coherent and defectless interface with a sharp atomic transition. The stable 1T phase represents a missing piece of the puzzle in the research of atomic thin van der Waals crystals, and our growth approach provides an accessible way of filling this gap.

Twisted bilayer graphene photoluminescence emission peaks at van Hove singularities.

We report on photoluminescence emission imaging by femtosecond laser excitation on twisted bilayer graphene samples. The emission images are obtained by tuning the excitation laser energies in the near infrared region. We demonstrate an increase of the photoluminescence emission at excitation energies that depends on the bilayer twist angle. The results show a peak for the light emission when the excitation is in resonance with transitions at the van Hove singularities in the electronic density of states. We measured the photoluminescence excitation peak position and width for samples with various twist angles showing resonances in the energy range of 1.2 to 1.7 eV.

High-Performance Organic Light-Emitting Diode with Substitutionally Boron-Doped Graphene Anode.

The hole-injection barrier between the anode and the hole-injection layer (HIL) is of critical importance to determine the device performance of organic light-emitting diodes (OLEDs). Here, we report on a record-high external quantum efficiency (EQE) (24.6% in green phosphorescence) of OLEDs fabricated on both rigid and flexible substrates, with the performance enhanced by the use of nearly defect-free and high-mobility boron-doped graphene as an effective anode and hexaazatriphenylene hexacarbonitrile as a new type of HIL. This new structure outperforms the existing graphene-based OLEDs, in which MoO3, AuCl3, or bis(trifluoromethanesulfonyl)amide are typically used as a doping source for the p-type graphene. The improvement of the OLED performance is attributed mainly to the appreciable increase of the hole conductivity in the nearly defect-free boron-doped monolayer graphene, along with the high work function achieved by the use of a newly developed hydrocarbon precursor containing boron in the graphene growth by chemical vapor deposition.

Scalable van der Waals Heterojunctions for High-Performance Photodetectors.

Atomically thin two-dimensional (2D) materials have attracted increasing attention for optoelectronic applications in view of their compact, ultrathin, flexible, and superior photosensing characteristics. Yet, scalable growth of 2D heterostructures and the fabrication of integrable optoelectronic devices remain unaddressed. Here, we show a scalable formation of 2D stacks and the fabrication of phototransistor arrays, with each photosensing element made of a graphene-WS2 vertical heterojunction and individually addressable by a local top gate. The constituent layers in the heterojunction are grown using chemical vapor deposition in combination with sulfurization, providing a clean junction interface and processing scalability. The aluminum top gate possesses a self-limiting oxide around the gate structure, allowing for a self-aligned deposition of drain/source contacts to reduce the access (ungated) channel regions and to boost the device performance. The generated photocurrent, inherently restricted by the limited optical absorption cross section of 2D materials, can be enhanced by 2 orders of magnitude by top gating. The resulting photoresponsivity can reach 4.0 A/W under an illumination power density of 0.5 mW/cm2, and the dark current can be minimized to few picoamperes, yielding a low noise-equivalent power of 2.5 × 10-16 W/Hz1/2. Tailoring 2D heterostacks as well as the device architecture moves the applications of 2D-based optoelectronic devices one big step forward.

Robust room temperature valley polarization in monolayer and bilayer WS2.

We report robust room temperature valley polarization in chemical-vapor-deposition (CVD) grown monolayer and bilayer WS2via polarization-resolved photoluminescence measurements using excitation below the bandgap. We show that excitation with energy slightly below the bandgap of the multi-valleyed transition metal chalcogenides can effectively suppress the random redistribution of excited electrons and, thereby, greatly enhance the efficiency of valley polarization at room temperature. Compared to mechanically exfoliated WS2, our CVD grown WS2 films also show enhancement in the coupling of spin, layer and valley degree of freedom and, therefore, provide improved valley polarization. At room temperature, using below-bandgap excitation and CVD grown monolayer and bilayer WS2, we have reached a record-high valley polarization of 35% and 80%, respectively, exceeding the previously reported values of 10% and 65% for mechanically exfoliated WS2 layers using resonant excitation. This observation provides a new direction to enhance valley control at room temperature.

High-performance and high-sensitivity applications of graphene transistors with self-assembled monolayers.

Charge impurities and polar molecules on the surface of dielectric substrates has long been a critical obstacle to using graphene for its niche applications that involve graphene's high mobility and high sensitivity nature. Self-assembled monolayers (SAMs) have been found to effectively reduce the impact of long-range scatterings induced by the external charges. Yet, demonstrations of scalable device applications using the SAMs technique remains missing due to the difficulties in the device fabrication arising from the strong surface tension of the modified dielectric environment. Here, we use patterned SAM arrays to build graphene electronic devices with transport channels confined on the modified areas. For high-mobility applications, both rigid and flexible radio-frequency graphene field-effect transistors (G-FETs) were demonstrated, with extrinsic cutoff frequency and maximum oscillation frequency enhanced by a factor of ~2 on SiO2/Si substrates. For high sensitivity applications, G-FETs were functionalized by monoclonal antibodies specific to cancer biomarker chondroitin sulfate proteoglycan 4, enabling its detection at a concentration of 0.01 fM, five orders of magnitude lower than that detectable by a conventional colorimetric assay. These devices can be very useful in the early diagnosis and monitoring of a malignant disease.

Single-Layer ReS2: Two-Dimensional Semiconductor with Tunable In-Plane Anisotropy.

Rhenium disulfide (ReS2) and diselenide (ReSe2), the group 7 transition metal dichalcogenides (TMDs), are known to have a layered atomic structure showing an in-plane motif of diamond-shaped-chains (DS-chains) arranged in parallel. Using a combination of transmission electron microscopy and transport measurements, we demonstrate here the direct correlation of electron transport anisotropy in single-layered ReS2 with the atomic orientation of the DS-chains, as also supported by our density functional theory calculations. We further show that the direction of conducting channels in ReS2 and ReSe2 can be controlled by electron beam irradiation at elevated temperatures and follows the strain induced to the sample. Furthermore, high chalcogen deficiency can induce a structural transformation to a nonstoichiometric phase, which is again strongly direction-dependent. This tunable in-plane transport behavior opens up great avenues for creating nanoelectronic circuits in 2D materials.

Three-fold rotational defects in two-dimensional transition metal dichalcogenides.

As defects frequently govern the properties of crystalline solids, the precise microscopic knowledge of defect atomic structure is of fundamental importance. We report a new class of point defects in single-layer transition metal dichalcogenides that can be created through 60° rotations of metal-chalcogen bonds in the trigonal prismatic lattice, with the simplest among them being a three-fold symmetric trefoil-like defect. The defects, which are inherently related to the crystal symmetry of transition metal dichalcogenides, can expand through sequential bond rotations, as evident from in situ scanning transmission electron microscopy experiments, and eventually form larger linear defects consisting of aligned 8-5-5-8 membered rings. First-principles calculations provide insights into the evolution of rotational defects and show that they give rise to p-type doping and local magnetic moments, but weakly affect mechanical characteristics of transition metal dichalcogenides. Thus, controllable introduction of rotational defects can be used to engineer the properties of these materials.

In Situ Tuning of Switching Window in a Gate-Controlled Bilayer Graphene-Electrode Resistive Memory Device.

A resistive random access memory (RRAM) device with a tunable switching window is demonstrated for the first time. The SET voltage can be continuously tuned from 0.27 to 4.5 V by electrical gating from -10 to +35 V. The gate-controlled bilayer graphene-electrode RRAM can function as 1D1R and potentially increase the RRAM density.

Layer-dependent optical conductivity in atomic thin WS2 by reflection contrast spectroscopy.

Optical conductivity, which originates from the interband transition due to electron-phonon interaction, is one of the powerful tools used for studying the electronic states in layered transition metal dichalcogenides (TMDCs). Here, we report for the first time the optical conductivity of WS2, one of the emerging classes of TMDCs, prepared directly on SiO2/Si substrate using reflection contrast spectroscopy. The measured optical conductivity at direct excitonic transition point K of the Brillouin zone for monolayer WS2 shows a value of 0.37 e(2)/πℏ in the visible range of the energy spectrum. Our results reveal that the optical conductivity of WS2 layers is frequency-dependent and show additional features in the conductivity spectra for bilayer to bulk counterparts, signifying a transition from direct band gap to indirect band gap with the evolution of layer numbers as predicted by our calculations.