Hysteresis-Free Contact Doping for High-Performance Two-Dimensional Electronics.

Contact doping is considered crucial for reducing the contact resistance of two-dimensional (2D) transistors. However, a process for achieving robust contact doping for 2D electronics is lacking. Here, we developed a two-step doping method for effectively doping 2D materials through a defect-repairing process. The method achieves strong and hysteresis-free doping and is suitable for use with the most widely used transition-metal dichalcogenides. Through our method, we achieved a record-high sheet conductance (0.16 mS·sq-1 without gating) of monolayer MoS2 and a high mobility and carrier concentration (4.1 × 1013 cm-2). We employed our robust method for the successful contact doping of a monolayer MoS2 Au-contact device, obtaining a contact resistance as low as 1.2 kΩ·µm. Our method represents an effective means of fabricating high-performance 2D transistors.

Internal Built-In Electric Fields at Organic-Inorganic Interfaces of Two-Dimensional Ruddlesden-Popper Perovskite Single Crystals.

Two-dimensional (2D) organic-inorganic hybrid Ruddlesden-Popper perovskites (OIRPPs), which consist of naturally formed "multiple quantum well (MQW)-like" structure, have received considerable interest in optoelectronic applications, owing to their outstanding optical properties and tailorable functionalities. While the quantum-confined electrons and holes at an MQW structure are under an applied electric field, the tilt of the energy bands may cause a significant influence on their optical properties. This work demonstrates the presence of internal built-in electric fields (BIEFs) at the as-synthesized 2D OIRPP single crystals. Spontaneous Franz-Keldysh oscillations, which usually act as the fingerprint to account for the presence of BIEFs in the MQW-like structures, are observed at 2D OIRPPs by the highly sensitive differential technique of modulated thermoreflectance spectroscopy. The strength of BIEFs at 2D OIRPP single crystals reduces with increased n values due to the increased width of the quantum well. The origin of the presence of BIEFs at 2D OIRPPs is further unveiled by atomically resolved scanning tunneling microscopy on their electronic band structures at organic-inorganic interfaces. Unlike the conventional III-V MQW semiconductors with the BIEFs, which are dominated by the spatial concentration gradients at heterointerfaces, the presence of BIEFs at the 2D OIRPP single crystals is attributed to the molecular dipoles within organic spacers pointing to the organic-inorganic interfaces. The discovery of internal BIEFs at the 2D OIRPPs may provide deep insight into understanding the fundamental optical properties for the future design of large-area and low-cost perovskite optoelectronic devices.

Atomically Resolved Quantum-Confined Electronic Structures at Organic-Inorganic Interfaces of Two-Dimensional Ruddlesden-Popper Halide Perovskites.

This work demonstrates the direct visualization of atomically resolved quantum-confined electronic structures at organic-inorganic heterointerfaces of two-dimensional (2D) organic-inorganic hybrid Ruddlesden-Popper perovskites (RPPs); this is accomplished with scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) by using solvent engineering to prepare perpendicularly oriented 2D RPPs. Atomically resolved band mapping images across the organic-inorganic interfaces of 2D RPPs yield typical quantum-well-like type-I heterojunction band alignment with band gaps depending on the thicknesses or n values of the inorganic perovskite slabs. The presence of edge states within the band gap due to organic cation vacancies is also observed. In addition, real-space visualization of atomic-scale structural phase transition behavior and changes in local electronic band structures are obtained simultaneously. Our results provide an unequivocal observation and explanation of the quantum-confined electronic structures formed at organic-inorganic interfaces of 2D RPPs.

Spatially Resolved Imaging on Photocarrier Generations and Band Alignments at Perovskite/PbI2 Heterointerfaces of Perovskite Solar Cells by Light-Modulated Scanning Tunneling Microscopy.

The presence of the PbI2 passivation layers at perovskite crystal grains has been found to considerably affect the charge carrier transport behaviors and device performance of perovskite solar cells. This work demonstrates the application of a novel light-modulated scanning tunneling microscopy (LM-STM) technique to reveal the interfacial electronic structures at the heterointerfaces between CH3NH3PbI3 perovskite crystals and PbI2 passivation layers of individual perovskite grains under light illumination. Most importantly, this technique enabled the first observation of spatially resolved mapping images of photoinduced interfacial band bending of valence bands and conduction bands and the photogenerated electron and hole carriers at the heterointerfaces of perovskite crystal grains. By systematically exploring the interfacial electronic structures of individual perovskite grains, enhanced charge separation and reduced back recombination were observed when an optimal design of interfacial PbI2 passivation layers consisting of a thickness less than 20 nm at perovskite crystal grains was applied.

Precisely Controlled Ultrastrong Photoinduced Doping at Graphene-Heterostructures Assisted by Trap-State-Mediated Charge Transfer.

Ultrastrong and precisely controllable n-type photoinduced doping at a graphene/TiOx heterostructure as a result of trap-state-mediated charge transfer is demonstrated, which is much higher than any other reported photodoping techniques. Based on the strong light-matter interactions at the graphene/TiOx heterostructure, precisely controlled photoinduced bandgap opening of a bilayer graphene device is demonstrated.

Atomic-scale mapping of electronic structures across heterointerfaces by cross-sectional scanning tunneling microscopy.

Interfacial science has received much attention recently based on the development of state-of-the-art analytical tools that can create and manipulate the charge, spin, orbital, and lattice degrees of freedom at interfaces. Motivated by the importance of nanoscale interfacial science that governs device operation, we present a technique to probe the electronic characteristics of heterointerfaces with atomic resolution. In this work, the interfacial characteristics of heteroepitaxial structures are investigated and the fundamental mechanisms that pertain in these systems are elucidated through cross-sectional scanning tunneling microscopy (XSTM). The XSTM technique is employed here to directly observe epitaxial interfacial structures and probe local electronic properties with atomic-level capability. Scanning tunneling microscopy and spectroscopy experiments with atomic precision provide insight into the origin and spatial distribution of electronic properties across heterointerfaces. The first part of this report provides a brief description of the cleavage technique and spectroscopy analysis in XSTM measurements. The second part addresses interfacial electronic structures of several model heterostructures in current condensed matter research using XSTM. Topics to be discussed include high-κ's/III-V's semiconductors, polymer heterojunctions, and complex oxide heterostructures, which are all material systems whose investigation using this technique is expected to benefit the research community. Finally, practical aspects and perspectives of using XSTM in interface science are presented.

Atomic-scale interfacial band mapping across vertically phased-separated polymer/fullerene hybrid solar cells.

Using cross-sectional scanning tunneling microscope (XSTM) with samples cleaved in situ in an ultrahigh vacuum chamber, this study demonstrates the direct visualization of high-resolution interfacial band mapping images across the film thickness in an optimized bulk heterojunction polymer solar cell consisting of nanoscale phase segregated blends of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM). We were able to achieve the direct observation of the interfacial band alignments at the donor (P3HT)-acceptor (PCBM) interfaces and at the interfaces between the photoactive P3HT:PCBM blends and the poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) anode modification layer with an atomic-scale spatial resolution. The unique advantage of using XSTM to characterize polymer/fullerene bulk heterojunction solar cells allows us to explore simultaneously the quantitative link between the vertical morphologies and their corresponding local electronic properties. This provides an atomic insight of interfacial band alignments between the two opposite electrodes, which will be crucial for improving the efficiencies of the charge generation, transport, and collection and the corresponding device performance of polymer solar cells.