RESUMEN
Molecular recognition underlies structure formation in supramolecular architectures either in materials or in living systems. Here, we used the nanoscale nontoxic Keplerate-type polyoxometalate (POM) {Mo72Fe30} as a template for the recognition of two different guest molecules [tetracycline (TC) and doxorubicin (DOX)] on the textured surface. By means of single crystal X-ray analysis and X-ray photoelectron spectroscopy (XPS), we revised the key features of the {Mo72Fe30} structure, showcasing the guest dimolybdenum units' {Mo2} location under the hexagonal pores and dynamic exchange of these units during dissolution in an aqueous medium. Based on the clarified POM structure, we demonstrated how the small differences between the TC and the DOX molecules can be recognized by the Keplerate surface, revealing the nature of the binding sitesâ{Mo6}/{FeO6} for TC and {FeO6} for DOX. Furthermore, using the Monte-Carlo method, we calculated the statistical distribution of the guest molecules in the stoichiometric compounds {Mo72Fe30}@TC12 and {Mo72Fe30}@DOX12, displaying the supramolecular ordering of the DOX species and randomization of the TC as a result of different coordinations to the POM surface. The produced {Mo72Fe30}@TC12 and {Mo72Fe30}@DOX12 associates were evaluated for bioactivity, showing how their interaction with POM can modulate the biological function of guest molecules.
RESUMEN
Ferroelectric materials attract much attention for applications in resistive memory devices due to the large current difference between insulating and conductive states and the ability of carefully controlling electronic transport via the polarization set-up. Bismuth ferrite films are of special interest due to the combination of high spontaneous polarization and antiferromagnetism, implying the possibility to provide multiple physical mechanisms for data storage and operations. Macroscopic conductivity measurements are often hampered to unambiguously characterize the electric transport, because of the strong influence of the diverse material microstructure. Here, we studied the electronic transport and resistive switching phenomena in polycrystalline bismuth ferrite using advanced conductive atomic force microscopy (CAFM) at different temperatures and electric fields. The new approach to the CAFM spectroscopy and corresponding data analysis are proposed, which allow deep insight into the material band structure at high lateral resolution. Contrary to many studies via macroscopic methods, postulating electromigration of the oxygen vacancies, we demonstrate resistive switching in bismuth ferrite to be caused by the pure electronic processes of trapping/releasing electrons and injection of the electrons by the scanning probe microscopy tip. The electronic transport was shown to be comprehensively described by the combination of the space charge limited current model, while a Schottky barrier at the interface is less important due to the presence of the built-in subsurface charge.
RESUMEN
The absorption of light in the near-infrared region of the electromagnetic spectrum by Au-hyperdoped Si has been observed. While silicon photodetectors in this range are currently being produced, their efficiency is low. Here, using the nanosecond and picosecond laser hyperdoping of thin amorphous Si films, their compositional (energy-dispersion X-ray spectroscopy), chemical (X-ray photoelectron spectroscopy), structural (Raman spectroscopy) and IR spectroscopic characterization, we comparatively demonstrated a few promising regimes of laser-based silicon hyperdoping with gold. Our results indicate that the optimal efficiency of impurity-hyperdoped Si materials has yet to be achieved, and we discuss these opportunities in light of our results.
RESUMEN
Monitoring the charged defect concentration at the nanoscale is of critical importance for both the fundamental science and applications of ferroelectrics. However, up-to-date, high-resolution study methods for the investigation of structural defects, such as transmission electron microscopy, X-ray tomography, etc., are expensive and demand complicated sample preparation. With an example of the lanthanum-doped bismuth ferrite ceramics, a novel method is proposed based on the switching spectroscopy piezoresponse force microscopy (SSPFM) that allows probing the electric potential from buried subsurface charged defects in the ferroelectric materials with a nanometer-scale spatial resolution. When compared with the composition-sensitive methods, such as neutron diffraction, X-ray photoelectron spectroscopy, and local time-of-flight secondary ion mass spectrometry, the SSPFM sensitivity to the variation of the electric potential from the charged defects is shown to be equivalent to less than 0.3 at% of the defect concentration. Additionally, the possibility to locally evaluate dynamics of the polarization screening caused by the charged defects is demonstrated, which is of significant interest for further understanding defect-mediated processes in ferroelectrics.