Solid-State Anion Exchange Enabled by Pluggable vdW Assembly for In Situ Halide Manipulation in Perovskite Monocrystalline Film.

The fabrication of perovskite single crystal-based optoelectronics with improved performance is largely hindered by limited processing techniques. Particularly, the local halide composition manipulation, which dominates the bandgap and thus the formation of heterostructures and emission of multiple-wavelength light, is realized via prevalent liquid- or gas-phase anion exchange with the utilization of lithography, while the monocrystalline nature is sacrificed due to polycrystalline transition in exchange with massive defects emerging, impeding carrier separation and transportation. Thus, a damage-free and lithography-free solid-state anion exchange strategy, aiming at in situ halide manipulation in perovskite monocrystalline film, is developed. Typically, CsPbCl3 working as medium to deliver halide is van der Waals (vdW) assembled to specific spots of CsPbBr3, followed by the removal of CsPbCl3 after anion exchange, with the halide composition in contact area modulated and monocrystalline nature of CsPbBr3 preserved. CsPbBr3-CsPbBrxCl3-x monocrystalline heterostructure has been achieved without lithography. Device based on the heterostructure shows apparent rectification behavior and improved photo-response rate. Heterostructure arrays can also be constructed with customized medium crystal. Furthermore, the halide composition can be accurately tuned to enable full coverage of visible spectra. The solid-state exchange enriches the toolbox for processing vulnerable perovskite and paves the way for the integration of monocrystalline perovskite optoelectronics.

Correlation-Induced Symmetry-Broken States in Large-Angle Twisted Bilayer Graphene on MoS2.

Strongly correlated states commonly emerge in twisted bilayer graphene (TBG) with "magic-angle" (1.1°), where the electron-electron (e-e) interaction U becomes prominent relative to the small bandwidth W of the nearly flat band. However, the stringent requirement of this magic angle makes the sample preparation and the further application facing great challenges. Here, using scanning tunneling microscopy (STM) and spectroscopy (STS), we demonstrate that the correlation-induced symmetry-broken states can also be achieved in a 3.45° TBG, via engineering this nonmagic-angle TBG into regimes of U/W > 1. We enhance the e-e interaction through controlling the microscopic dielectric environment by using a MoS2 substrate. Simultaneously, the width of the low-energy van Hove singularity (VHS) peak is reduced by enhancing the interlayer coupling via STM tip modulation. When partially filled, the VHS peak exhibits a giant splitting into two states flanked by the Fermi level and shows a symmetry-broken LDOS distribution with a stripy charge order, which confirms the existence of strong correlation effect in our 3.45° TBG. Our result demonstrates the feasibility of the study and application of the correlation physics in TBGs with a wider range of twist angle.

Microscopy aided detection of the self-intercalation mechanism and in situ electronic properties in chromium selenide.

Two-dimensional (2D) chromium-based self-intercalated materials Cr1+nX2 (0 ≤ n ≤ 1, X = S, Se, Te) have attracted much attention because of their tunable magnetism with good environmental stability. Intriguingly, the magnetic and electrical properties of the materials can be effectively tuned by altering the coverage and spatial arrangement of the intercalated Cr (ic-Cr) within the van der Waals gap, contributing to different stoichiometries. Several different Cr1+nX2 systems have been widely investigated recently; however, those with the same stoichiometric ratio (such as Cr1.25Te2) were reported to exhibit disparate magnetic properties, which still lacks explanation. Therefore, a systematic in situ study of the mechanisms with microscopy techniques is in high demand to look into the origin of these discrepancies. Herein, 2D self-intercalated Cr1+nSe2 nanoflakes were synthesized as a platform to conduct the characterization. Combining scanning transmission electron microscopy (STEM) and scanning tunneling microscopy (STM), we studied in depth the microscopic structure and local electronic properties of the Cr1+nSe2 nanoflakes. The self-intercalation mechanism of ic-Cr and local stoichiometric-ratio variation in a Cr1+nSe2 ultrathin nanoflake is clearly detected at the nanometer scale. Scanning tunneling spectroscopy (STS) measurements indicate that Cr1.5Se2/Cr2Se2 and Cr1.25Se2 exhibit conductive and semiconductive behaviors, respectively. The STM tip manipulation method is further applied to manipulate the microstructure of Cr1+nSe2, which successfully produces clean zigzag-type boundaries. Our systematic microscopy study paves the way for the in-depth study of the magnetic mechanism of 2D self-intercalated magnets at the nano/micro scale and the development of new magnetic and spintronic devices.

Edge-by-Edge Lateral Heterostructure through Interfacial Sliding.

van der Waals heterostructures (vdWHs) based on two-dimensional (2D) semiconductors have attracted considerable attention. However, the reported vdWHs are largely based on vertical device structure with large overlapping area, while the realization of lateral heterostructures contacted through 2D edges remains challenging and is majorly limited by the difficulties of manipulating the lateral distance of 2D materials at nanometer scale (during transfer process). Here, we demonstrate a simple interfacial sliding approach for realizing an edge-by-edge lateral contact. By stretching a vertical vdWH, two 2D flakes could gradually slide apart or toward each other. Therefore, by applying proper strain, the initial vertical vdWH could be converted into a lateral heterojunction with intimately contacted 2D edges. The lateral contact structure is supported by both microscope characterization and in situ electrical measurements, exhibiting carrier tunneling behavior. Finally, this approach can be extended to 3D thin films, as demonstrated by the lateral 2D/3D and 3D/3D Schottky junction.

High-Density Vertical Transistors with Pitch Size Down to 20 nm.

Vertical field effect transistors (VFETs) have attracted considerable interest for developing ultra-scaled devices. In particular, individual VFET can be stacked on top of another and does not consume additional chip footprint beyond what is needed for a single device at the bottom, representing another dimension for high-density transistors. However, high-density VFETs with small pitch size are difficult to fabricate and is largely limited by the trade-offs between drain thickness and its conductivity. Here, a simple approach is reported to scale the drain to sub-10 nm. By combining 7 nm thick Au with monolayer graphene, the hybrid drain demonstrates metallic behavior with low sheet resistance of ≈100 Ω sq-1 . By van der Waals laminating the hybrid drain on top of 3 nm thick channel and scaling gate stack, the total VFET pitch size down to 20 nm and demonstrates a higher on-state current of 730 A cm-2 . Furthermore, three individual VFETs together are vertically stacked within a vertical distance of 59 nm, representing the record low pitch size for vertical transistors. The method pushes the scaling limit and pitch size limit of VFET, opening up a new pathway for high-density vertical transistors and integrated circuits.

Epitaxy of a Monocrystalline CsPbBr3 -SrTiO3 Halide-Oxide Perovskite p-n Heterojunction with High Stability for Photodetection.

Perovskite heterojunctions are essential components of perovskite optoelectronics, but their construction and investigation have been impeded by the instability and severe anion interdiffusion. This work epitaxially deposits p-type CsPbBr3 on n-type Nb:SrTiO3 (STO) to construct a functional perovskite heterojunction with high stability. The lattice match allows epitaxial growth of CsPbBr3 to occur over large scale, resulting in a monocrystalline thin film with excellent crystallinity and uniformity. The highly stable STO prevents the anion migration frequently happening in halide perovskites, forming a sharp interface of two perovskite with opposite conduction type, with which a diode is fabricated and a current rectification ratio of 374 is obtained. The diode is able to work as a photodetector with dark current of 2.01 × 10-12 A at -1 V and responsivity (R) of 8.26 A W-1 , rendering a detectivity (D*) of 2.98 × 1013 Jones. Owing to the all-inorganic architecture, effective photoresponse at temperature as high as 150 °C is guaranteed with D* of ≈1.52 × 1013 Jones. Combining the unique optoelectrical properties of halide perovskite and the rigidity of oxide perovskite, the epitaxy of CsPbBr3 on n-type STO opens up a new method to construct functional perovskite heterojunction for optoelectronics.

Wafer-scale and universal van der Waals metal semiconductor contact.

Van der Waals (vdW) metallic contacts have been demonstrated as a promising approach to reduce the contact resistance and minimize the Fermi level pinning at the interface of two-dimensional (2D) semiconductors. However, only a limited number of metals can be mechanically peeled and laminated to fabricate vdW contacts, and the required manual transfer process is not scalable. Here, we report a wafer-scale and universal vdW metal integration strategy readily applicable to a wide range of metals and semiconductors. By utilizing a thermally decomposable polymer as the buffer layer, different metals were directly deposited without damaging the underlying 2D semiconductor channels. The polymer buffer could be dry-removed through thermal annealing. With this technique, various metals could be vdW integrated as the contact of 2D transistors, including Ag, Al, Ti, Cr, Ni, Cu, Co, Au, Pd. Finally, we demonstrate that this vdW integration strategy can be extended to bulk semiconductors with reduced Fermi level pinning effect.

Strain Releasing of Flexible 2D Electronics through van der Waals Sliding Contact.

Two-dimensional (2D) materials have demonstrated promising potential for flexible electronics, owning to their atomic thin body thickness and dangling-bond-free surface. Here, we report a sliding contact device structure for efficient strain releasing. By fabricating a weakly coupled metal-2D junction with a van der Waals (vdW) gap in between, the applied strain could be effectively released through their interface sliding; hence minimized strain is transferred to the 2D lattice. Therefore, we observed stable device behavior with electrodes stretching over 110%, much higher than 2D devices using evaporated metal contacts. Furthermore, through multicycle straining-releasing measurements, we found the electrodes still form intimate contact with nearly constant contact resistance during sliding, confirming the optimization of device flexibility and electrical properties at the same time. Finally, we demonstrate this vdW sliding contact is a general device geometry and could be well-extended to various 2D or 3D bulk materials, leading to devices with much higher strain tolerance.