Crystal Size Effect on Carrier Transport of Microscale Perovskite Junctions via Soft Contact.

To reduce the size of optoelectronic devices, it is essential to understand the crystal size effect on the carrier transport through microscale materials. Here, we show a soft contact method to probe the properties of irregularly shaped microscale perovskite crystals by employing a movable liquid metal electrode to form a self-adaptative deformable electrode-perovskite-electrode junction. Accordingly, we demonstrate that (1) the photocurrents of perovskite quantum dot films and microplatelets show profound differences regarding both the on/off ratio and the response time upon light illumination; and (2) small-size perovskite (<50 µm) junctions may show negative differential resistance (NDR) behavior, whereas the NDR phenomenon is absent in large-size perovskite junctions within the same bias regime. Our studies provide a method for studying arbitrary-shaped crystals without mechanical damage, assisting the understanding of the photogenerated carriers transport through microscale crystals.

Shaping the Atomic-Scale Geometries of Electrodes to Control Optical and Electrical Performance of Molecular Devices.

A straightforward method to generate both atomic-scale sharp and atomic-scale planar electrodes is reported. The atomic-scale sharp electrodes are generated by precisely stretching a suspended nanowire, while the atomic-scale planar electrodes are obtained via mechanically controllable interelectrodes compression followed by a thermal-driven atom migration process. Notably, the gap size between the electrodes can be precisely controlled at subangstrom accuracy with this method. These two types of electrodes are subsequently employed to investigate the properties of single molecular junctions. It is found, for the first time, that the conductance of the amine-linked molecular junctions can be enhanced ≈50% as the atomic-scale sharp electrodes are used. However, the atomic-scale planar electrodes show great advantages to enhance the sensitivity of Raman scattering upon the variation of nanogap size. The underlying mechanisms for these two interesting observations are clarified with the help of density functional theory calculation and finite-element method simulation. These findings not only provide a strategy to control the electron transport through the molecule junction, but also pave a way to modulate the optical response as well as to improve the stability of single molecular devices via the rational design of electrodes geometries.

In situ photoconductivity measurements of imidazole in optical fiber break-junctions.

We developed a method based on the mechanically controllable break junction technique to investigate the electron transport properties of single molecular junctions upon fiber waveguided light. In our strategy, a metal-coated tapered optical fiber is fixed on a flexible substrate, and this tapered fiber serves as both the optical waveguide and metal electrodes after it breaks. For an imidazole bridged single-molecule junction, two probable conductance values below 1G0 are observed. The higher value shows an approximately 40% enhancement under illumination, while the lower one does not show distinguishable difference under illumination. Theoretical calculations reveal these two conductance values resulting from the imidazole monomer junction and the imidazole dimer junction linked via a hydrogen bond, respectively. In imidazole monomer junctions, the absorption of a single photon strongly shifts the transmission function resulting in optical-induced conductance enhancement. In contrast, the transmission function of imidazole dimer junctions remains at the same level in the bias window despite the light illumination. This work provides a robust experimental framework for studying the underlying mechanisms of photoconductivity in single-molecule junctions and offers tools for tuning the optoelectronic performance of single-molecule devices in situ.

Reversible Rectification of Microscale Ferroelectric Junctions Employing Liquid Metal Electrodes.

Both ferroelectric crystals and liquid metal electrodes have attracted extensive attention for potential applications in next-generation devices and circuits. However, the interface information between ferroelectric crystals and liquid metal electrodes has so far been lacking. To better understand the optoelectronic properties of microscale ferroelectric crystals (potassium tantalate niobate, KTN) and its potential integration with liquid metal electrodes (a "printing ink" for flexible electric circuit production), microscale KTN crystals sandwiched by eutectic gallium indium (EGaIn, a liquid metal) with varied contact geometries were studied. Unlike the bulk KTN crystal junctions, the microscale KTN junctions show electrical rectifying characteristics upon light illumination, and the directionality of the rectification can be reversed by increasing the ambient temperature to a few degrees. Furthermore, a strong suppression of the current upon increasing voltage, that is, the quasi-negative differential resistance, is observed when the microscale KTN is half-enclosed by the EGaIn electrode. Our results show that trapping/detrapping of carriers affected by the crystal size and the ambient temperature is the dominant physical mechanism for these observations. These results not only facilitate a better understanding of charge transport through the microscale ferroelectric crystals but also advance the design of miniaturized hybrid devices.

Atomic switches of metallic point contacts by plasmonic heating.

Electronic switches with nanoscale dimensions satisfy an urgent demand for further device miniaturization. A recent heavily investigated approach for nanoswitches is the use of molecular junctions that employ photochromic molecules that toggle between two distinct isoforms. In contrast to the reports on this approach, we demonstrate that the conductance switch behavior can be realized with only a bare metallic contact without any molecules under light illumination. We demonstrate that the conductance of bare metallic quantum contacts can be reversibly switched over eight orders of magnitude, which substantially exceeds the performance of molecular switches. After the switch process, the gap size between two electrodes can be precisely adjusted with subangstrom accuracy by controlling the light intensity or polarization. Supported by simulations, we reveal a more general and straightforward mechanism for nanoswitching behavior, i.e., atomic switches can be realized by the expansion of nanoelectrodes due to plasmonic heating.

Molecular Orbital Gating Surface-Enhanced Raman Scattering.

One of the promising approaches to meet the urgent demand for further device miniaturization is to create functional devices using single molecules. Although various single-molecule electronic devices have been demonstrated recently, single-molecule optical devices which use external stimulations to control the optical response of a single molecule have rarely been reported. Here, we propose and demonstrate a field-effect Raman scattering (FERS) device with a single molecule, an optical counterpart to field-effect transistors (a key component of modern electronics). With our devices, the gap size between electrodes can be precisely adjusted at subangstrom accuracy to form single molecular junctions as well as to reach the maximum performance of Raman scattering via plasmonic enhancement. Based on this maximum performance, we demonstrated that the intensity of Raman scattering can be further enhanced by an additional ∼40% if the orbitals of the molecules bridged two electrodes were shifted by a gating voltage. This finding not only provides a method to increase the sensitivity of Raman scattering beyond the limit of plasmonic enhancement, but also makes it feasible to realize addressable functional FERS devices with a gate electrode array.