Ayan Sarkar

TiO2/ZnO core/shell nano-heterostructure arrays as photo-electrodes with enhanced visible light photoelectrochemical performance

The present article reports a facile method for preparing the vertically-aligned 1D arrays of a new type of type II n–n TiO2/ZnO core/shell nano-heterostructures by growing the nano-shell of ZnO on the electrochemically fabricated TiO2 nanotubes core for visible light driven photoelectrochemical applications. The strong interfacial interaction at the type II heterojunction leads to an effective interfacial charge separation and charge transport. The presence of various defects such as surface states, interface states and other defects in the nano-heterostructure enable it for improved visible light photoelectrochemical performance. The presence of such defects has also been confirmed by the UV-vis absorption, cathodoluminescence, and crystallographic studies. The TiO2/ZnO core/shell nano-heterostructures exhibit strong green luminescence due to the defect transitions. The TiO2/ZnO core/shell nano-heterostructures photo-electrode show significant enhancement of visible light absorption and it provides a photocurrent density of 0.7 mA cm−2 at 1 V vs. Ag/AgCl, which is almost 2.7 times that of the TiO2/ZnO core/shell nano-heterostructures under dark conditions. The electrochemical impedance spectroscopy results demonstrate that the substantially improved photoelectrochemical and photo-switching performance of the nano-heterostructures photoanode is because of the enhancement of interfacial charge transfer and the increase in the charge carrier density caused by the incorporation of the ZnO nano-shell on TiO2 nanotube core.

Multifunctional BiFeO3/TiO2 nano-heterostructure: Photo-ferroelectricity, rectifying transport, and nonvolatile resistive switching property

Multifunctional BiFeO3 nanostructure anchored TiO2 nanotubes are fabricated by coupling wet chemical and electrochemical routes. BiFeO3/TiO2 nano-heterostructure exhibits white-light-induced ferroelectricity at room temperature. Studies reveal that the photogenerated electrons trapped at the domain/grain boundaries tune the ferroelectric polarization in BiFeO3 nanostructures. The photon controlled saturation and remnant polarization opens up the possibility to design ferroelectric devices based on BiFeO3. The nano-heterostructure also exhibits substantial photovoltaic effect and rectifying characteristics. Photovoltaic property is found to be correlated with the ferroelectric polarization. Furthermore, the nonvolatile resistive switching in BiFeO3/TiO2 nano-heterostructure has been studied, which demonstrates that the observed resistive switching is most likely caused by the electric-field-induced carrier injection/migration and trapping/detrapping process at the hetero-interfaces. Therefore, BiFeO3/TiO2 ...

Defect engineered d0 ferromagnetism in tin-doped indium oxide nanostructures and nanocrystalline thin-films

Origin of unexpected defect engineered room-temperature ferromagnetism observed in tin-doped indium oxide (ITO) nanostructures (Nanowires, Nano-combs) and nanocrystalline thin films fabricated by pulsed laser deposition has been investigated. It is found that the ITO nanostructures prepared under argon environment exhibit strongest ferromagnetic signature as compared to that nanocrystalline thin films grown at oxygen. The evidence of singly ionized oxygen vacancy (V0+) defects, obtained from various spectroscopic measurements, suggests that such V0+ defects are mainly responsible for the intrinsic ferromagnetic ordering. The exchange interaction of the defects provides extensive opportunity to tune the room-temperature d0 ferromagnetism and optical properties of ITOs.

Surface functionalized H2Ti3O7 nanowires engineered for visible-light photoswitching, electrochemical water splitting, and photocatalysis

This article demonstrates comprehensive studies on different visible-light driven photoelectrochemical and photocatalytic aspects of a hydrothermally synthesized n-type H2Ti3O7 (HTO) nanowire mesh and its carbon and nitrogen functionalized counterparts, namely C-HTO and N-HTO. It was found that the presence of various defect states within the band gap of HTO, C-HTO and N-HTO nanowires, make them photoactive under visible-light. The photo-conversion efficiencies of HTO, C-HTO, and N-HTO nanowire electrodes are about 0.066, 0.129, and 0.076%, respectively, at around 1 V vs. Ag/AgCl. Carbon functionalization of HTO nanowires has been found to be most beneficial in increasing the charge carrier density, resulting in the highest current density, high photo conversion efficiency, remarkable photoelectrochemical water splitting performance and enhanced photocatalytic activity. The photocurrent density of the C-HTO NWs was found to be 0.0562 mA cm-2 at 1 V vs. Ag/AgCl, which is almost two times that of the pristine HTO NWs (0.029 mA cm-2). Although nitrogen functionalization increases the charge carrier density of the HTO nanowires, nitrogen incorporation produces lots of recombination centres in the nanowires, which are found to play a detrimental role in the photoelectrochemical and photocatalytic performance of N-HTO nanowires, limiting the expected performance. Therefore, the present study demonstrates a suitable surface engineering technique for nanostructures to maximize the utilization of green solar light.

Nano-engineering of p–n CuFeO2-ZnO heterojunction photoanode with improved light absorption and charge collection for photoelectrochemical water oxidation

The effective utilization of abundant visible solar light for photoelectrochemical water splitting is a green approach for energy harvesting, to reduce the enormous rise of carbon content in the atmosphere. Here, a novel efficient design strategy for p-n type nano-heterojunction photoanodes is demonstrated, with the goal of improving water splitting efficiency by growing low band gap p-CuFeO2 nanolayers on n-ZnO nanorods by an easy and scalable electrochemical route. The photoconversion efficiency of p-n CuFeO2/ZnO photoanodes is found to be ∼450% higher than that of pristine ZnO nanorod electrodes under visible solar light illumination (λ > 420 nm, intensity 10 mW cm-2). The p-n CuFeO2/ZnO nano-engineering not only boosts the visible light absorption but also resolves limitations regarding effective charge carrier separation and transportation due to interfacial band alignment. This photoanode also shows remarkably enhanced stability, where the formation of p-n nano-heterojunction enhances the easy migration of holes to the electrode/electrolyte interface, and of electrons to the counter electrode (Pt) for hydrogen generation. Therefore, this work demonstrates that p-n nano-engineering is a potential strategy to design light-harvesting electrodes for water splitting and clean energy generation.

Clustered vacancies in ZnO: chemical aspects and consequences on physical properties

Chemical nature of point defects, their segregation, cluster or complex formation in ZnO is an important area of investigation. In this report, 1.2 MeV Ar ion beam is used to incorporate defects in granular ZnO. Evolution of defective state with irradiation fluence 1 x 10^14 and 1 x 10^16 ions/cm2 has been monitored using XPS, PL and Raman spectroscopic study. XPS study shows presence of oxygen vacancies (VO) in the Ar ion irradiated ZnO. Zn(LMM) Auger spectra clearly identifies transition involving metallic zinc in the irradiated samples. Intense PL emission from IZn related shallow donor bound excitons (DBX) is visible in the 10 K spectra for all samples. Although overall PL is largely reduced with irradiation disorder, DBX intensity is increased for the highest fluence irradiated sample. Raman study indicates damage in both zinc and oxygen sub-lattice by energetic ion beam. Representative Raman modes from defect complexes involving VO, IZn and IO are visible after irradiation with intermediate fluence. Further increase of fluence shows, to some extent, a homogenization of disorder. Huge reduction of resistance is also noted for this sample. Certainly, high irradiation fluence induces a qualitative modification of the conventional (and highly resistive) grain boundary (GB) structure of granular ZnO. Low resistive path, involving IZn related shallow donors, across the GB can be presumed to explain resistance reduction. Open volumes (VZn and VO) agglomerate more and more with increasing irradiation fluence and finally get transformed to voids. Results as a whole have been elucidated with a model which emphasizes possible evolution of new defect microstructure that is distinctively different from the GB related disorder. Based on the model, qualitative explanations of commonly observed radiation hardness, colouration and ferromagnetism in disordered ZnO have been put forward.

Fabrication of One Dimensional MnO2‐TiO2 Nano‐Heterostructures for Enhanced Hole Mediated Oxidation of As(III) in Potable Water

The conversion of the toxic As(III) from drinking water is a challenging task and it becomes more difficult when As(III) is present in low concentrations (50–200 ppb). Considering this, the present article demonstrates an easy and cost effective wet chemical synthesis of MnO2−TiO2 nanoheterostructures (NHs) and its application as the electrode for the oxidation and subsequent conversion of the comparatively low concentration of As(III) from drinking water. The MnO2−TiO2 NHs have been employed as the anode to enhance the hole mediated fast and effective oxidation and subsequent conversion of As(III) from water under the applied bias of 1 V vs. Ag/AgCl at room temperature (30 °C) with the water pH ∼7 in a three‐electrode electrochemical cell. The nano‐interfacial electronic band engineering at MnO2‐TiO2 heterointerface is found to be very effective to boost the hole mediated oxidation of As(III). The same NHs also exhibit enhanced photo‐electrochemical oxidation of As(III) under the illumination of low‐intensity white light. The photo‐oxidation in assistance with the applied bias has considerably improved the overall conversion efficiency of As(III) to As(V) in water with a treatment time of just five minutes. The study shows that the material and the method described here is an easy and effective strategy for the enhanced preoxidation and subsequent elimination of As(III) from the drinking water with a low arsenic concentration in the typical weather of Indian subcontinent.