RESUMO
The synergistic combination of hybrid perovskites with graphene-related materials is leading to optoelectronic devices with enhanced performance and stability. Still, taking advantage of the solution processing of perovskite onto graphene is especially challenging. Here, MAPbBr3 perovskite is grown on single-layer graphene/graphene oxide (Gr/GO) patterns with 120 µm periodicity using a solution-processed method. MAPbBr3 rounded crystals are formed with sizes ranging from nanometers to microns, either forming continuous films or dispersed particles. A detailed morphological and structural study reveals a fully oriented perovskite and very different growth habits on the Gr/GO micro-patterns, which we relate to the substrate characteristics and the nucleation rate. A simple method for controlling the nucleation rate is proposed based on the concentration of the precursor solution and the number of deposited perovskite layers. The photoluminescence is analyzed in terms of the crystal size, strain, and structural changes observed. Notably, the growth on top of Gr/GO leads to a huge photostability of the MAPbBr3 compared with that on glass. Especially outstanding is that of the microcrystals, which endure light densities as high as 130 kW/cm2. These results allow for anticipating the design of integrated nanostructures and nanoengineered devices by growing high-stability perovskite directly on Gr/GO substrates.
RESUMO
The poor photostability under ambient conditions of hybrid halide perovskites has hindered their recently explored promising nonlinear optical properties. Here, we show how Bi3+ can partially substitute Pb2+ homogeneously in the commonly studied MAPbI3, improving both environmental stability and photostability under high laser irradiation. Bi content around 2 atom % produces thin films where the nonlinear refractive (n2) and absorptive coefficients (ß), which modify the refractive index (Δn) of the material with light fluence (I), increase up to factors of 4 and 3.5, respectively, compared to undoped MAPbI3. Higher doping inhibits the nonlinear parameters; however, the samples show higher fluence damage thresholds. Thus, these results provide a road map on how MAPbI3 can be engineered for practical cost-effective nonlinear applications by means of Bi doping, including optical limiting devices and multiple-harmonic generation into optoelectronics devices.
RESUMO
A deep comprehension of the local anodic oxidation process in 2D materials is achieved thanks to an extensive experimental and theoretical study of this phenomenon in graphene. This requires to arrange a novel instrumental device capable to generate separated regions of monolayer graphene oxide (GO) over graphene, with any desired size, from micrometers to unprecedented mm2 , in minutes, a milestone in GO monolayer production. GO regions are manufactured by overlapping lots of individual oxide spots of thousands µm2 area. The high reproducibility and circular size of the spots allows not only an exhaustive experimental characterization inside, but also establishing an original model for oxide expansion which, from classical first principles, overcomes the traditional paradigm of the water bridge, and is applicable to any 2D-material. This tool predicts the oxidation behavior with voltage and exposure time, as well as the expected electrical current along the process. The hitherto unreported transient current is measured during oxidation, gaining insight on its components, electrochemical and transport. Just combining electrical measurements and optical imaging estimating carrier mobility and degree of oxidation is possible. X-ray photoelectron spectroscopy reveals a graphene oxidation about 30%, somewhat lower to that obtained by Hummers' method.
RESUMO
We have developed a complete instrument to perform direct, dry, and cost-effective lithography on conductive materials, based on localized electrical discharges, which avoids using masks or chemicals typical of conventional photolithography. The technique is considered fully compatible with substrate transport based systems, like roll-to-roll technology. The prototype is based on two piezo nano-steppers coupled to three linear micro-stages to cover a large scale operation from micrometers to centimeters. The operation mode consists of a spring probe biased at low DC voltage with respect to a grounded conductive layer. The tip slides on the target layer keeping contact with the material in room conditions, allowing continuous electric monitoring of the process, and also real-time tilt correction via software. The sliding tip leaves an insulating path (limited by the tip diameter) along the material, enabling to draw electrically insulated tracks and pads. The physical principle of operation is based in the natural self-limitation of the discharge due to material removal or insulation. The so produced electrical discharges are very fast, in the range of µs, so features may be performed at speeds of few cm/s, enabling scalability to large areas. The instrument has been tested on different conducting materials as gold, indium tin oxide, and aluminum, allowing the fabrication of alphanumeric displays based on passive matrix of organic light emitting diodes without the use of masks or photoresists. We have verified that the highest potential is achieved on graphene, where no waste material is detected, producing excellent well defined edges. This allows manufacturing graphene micro-ribbons with a high aspect ratio up to 1200:1.
