Liquid-Liquid Interface-Assisted Self-Assembly of Ag-Doped ZnO Nanosheets for Atomic Switch Application.

Developing facile and inexpensive methods for obtaining large-area two-dimensional semiconducting nanosheets is highly desirable for mass-scale device application. Here, we report a method for producing uniform and large-area films of a Ag-doped ZnO (AZO) nanosheet network via self-assembly at the hexane-water interface by controlling the solute/solvent ratio. The self-assembled film comprises of uniformly tiled nanosheets with size ∼1 µm and thicknesses∼60-100 nm. Using these films in a Pt/AZO/Ag structure, an atomic switch operation is realized. The switching mechanism is found to be governed by electrochemical metallization with nucleation as the rate-limiting step. Our results establish the protocol for large-scale device applications of AZO nanosheets for exploring advanced atomic switch-based neuromorphic systems.

Ag-Doped Free-Standing 2D TiO2 Sheets: Electronic, Optical, Magnetic, and Self-Healing Behaviour.

Beyond a critical doping level, Ag-2D TiO2 sheets (ATO) are deemed to be a flexible transparent conductor, useful for visible-range functional photonic/optoelectronic devices/sensors, sunlight-sensitive catalysis, and light-activated resistive switching. Due to the lack of control of surface energy which often leads to the formation of structural defects and even dimensionality crossover (2D to 0D) of materials during doping reaction, it is challenging to obtain ATO with a controlled doping level. Gauging the urgency, therefore we report the surface energy-controlled synthesis of ATO employing liquid phase exfoliation of TiO2 and subsequent hydrothermal Ag-doping in the presence of Hexamethylenetetramine (HMTA). Electron microscopy and atomic force microscopy reveal ATO sheets with large lateral dimensions. 6-fold, 4-fold, and strain-mediated crystallographic phases of 2D ATO have been revealed by high-resolution electron imaging. Successful tuning of the band gap down to ~2 eV with Ag doping up to ~10 % is obtained. Synthesized 2D ATO have been investigated for their electrical, optical, optoelectronic, photoluminescence, and ferromagnetic behaviour. Visible light-sensitive thermally/structurally robust semiconductor/conductor via tuneable doping will pave the way for their flexible as well as wearable device applications. Self-healing effect of AFM tip-generated mechanical stress has also been demonstrated.

Deciphering pressure-induced nanoarchitectonics in a monolayer of heterocoronene-based discotics at air-water and air-solid interfaces.

Understanding and control of molecular alignment at the nanoscale in self-assembled supramolecular structures is a prerequisite for the subsequent exploitation of molecules in functional devices. Here, we have clarified the surface-pressure induced molecular nanoarchitectures in a monolayer of a heterocoronene-based discotic liquid crystal (DLC) at air-water and air-solid interfaces using surface manometry, real-time Brewster angle microscopy, and real-space atomic force microscopy (AFM). Chloroform-spread DLCs at a concentration of ∼108 µM exhibit floating domains at the air-water interface comprising small aggregates of edge-on stacked molecules interacting via peripheral alkyl chains. Detailed analysis of surface manometry and relaxation measurements reveal that, upon compression, these domains coalesce to form a coherent monolayer which then undergoes irreversible structural transformations via mechanisms such as monolayer loss due to desorption and localized nucleation of defects. AFM images of the films transferred on a hydrophilic substrate reveal that with increasing surface-pressure, the nanoscale structure of the monolayer transforms from randomly oriented nanowires to tightly-packed nanowire domains, and finally to fragmented wire segments which diffuse locally above the film. These results provide a facile method for the preparation of compact, two-dimensional films of ambipolar DLC molecules with a tunable nanoarchitecture which will be crucial for their applications in nanoscale electronic devices.