Research Update: Photoelectrochemical water splitting and photocatalytic hydrogen production using ferrites (MFe2O4) under visible light irradiation

The utilization of solar light for the photoelectrochemical and photocatalytic production of molecular hydrogen from water is a scientific and technical challenge. Semiconductors with suitable properties to promote solar-driven water splitting are a desideratum. A hitherto rarely investigated group of semiconductors are ferrites with the empirical formula MFe2O4 and related compounds. This contribution summarizes the published results of the experimental investigations on the photoelectrochemical and photocatalytic properties of these compounds. It will be shown that the potential of this group of compounds in regard to the production of solar hydrogen has not been fully explored yet.

Sonochemical synthesis of CuO nanostructures and their morphology dependent optical and visible light driven photocatalytic properties

A controlled synthesis of CuO nanostructures with various morphologies were successfully achieved by presence/absence of low frequency (42 kHz) ultrasound with two different methods. The size, shape and morphology of the CuO nanostructures were tailored by altering the ultrasound, mode of addition and solvent medium. The crystalline structure and molecular vibrational modes of the prepared nanostructures were analysed through X-ray diffraction and FTIR measurement, respectively which confirmed that the nanostructures were phase pure high-quality CuO with monoclinic crystal structure. The morphological evaluation and elemental composition analysis were done using TEM and EDS attached with SEM, respectively. Furthermore, we demonstrated that the prepared CuO nanostructures could be served as an effective photocatalyst towards the degradation of methyl orange (MO) under visible light irradiation. Among the various nanostructures, the spherical shape CuO nanostructures were found to have the better catalytic activities towards MO dye degradation. The catalytic degradation performance of MO in the presence of CuO nanostructures showed the following order: spherical\nanorod \layered oval \nanoleaf \triangular \shuttles structures. The influence of loading and reusability of catalyst revealed that the efficiency of visible light assisted degradation of MO was effectively enhanced and more than 95 % of degradation was achieved after 3 cycles

Low temperature and rapid deposition of ZnO nanorods on Si(100) substrate with tunable optical emissions

This research article describes the large scale fabrication of ZnO nanorods of various shapes on Si(100) substrate, by using metalorganic precursor of Zn in solutions with microwave as the source of energy. This is a low temperature, environmental friendly and rapid thin film deposition process, where ZnO nanorods (1-3 mu m length) were grown only in 1-5 min of microwave irradiation. All as-synthesized nanorods are of single crystalline grown along the < 0001 > crystallographic direction. The coated nanorods were found to be highly dense having a thickness of similar to 1-3 mu m over the entire area 20 mm x 20 mm of the substrate. The ZnO thin film comprising of nanorods exhibits good adhesion with the substrate. A possible mechanism for the initial nucleation and growth of ZnO is discussed. A cross over from a strong visible light emission to an enhanced UV emission is observed, when the nature of the surfactants are varied from polymeric to ionic and nonionic. The position of the chromaticity coordinates in yellow region of the color space gives an impression of white light generation from these coatings by exciting with a blue laser.

Photoluminescence of undoped and B-doped ZnO in silicate glasses

Photoluminescence of undoped and B-doped ZnO in silicate glasses was investigated by varying the concentration of ZnO (3550 mol%) and B dopant (0-10 mol%) in the glass matrices. The broad and intense near band edge emissions were observed while the visible light emission was very weak. UV luminescence in all samples was red-shifted relative to the exciton transition in bulk ZnO and enhanced by decreased ZnO concentration due to higher degree of structural integrity and the lower aggregation degree of ZnO. Donor B dopant played the double roles of filling conduction bands to broaden band gap when its concentration was lower than 5 mol%, and emerging with conduction bands to narrow the gap when B dopant exceeded this value. (c) 2007 Elsevier B.V. All rights reserved.

ZnO : Zn phosphor thin films prepared by face-to-face annealing

ZnO:Zn phosphor thin films were prepared by face-to-face annealing at 450 degrees C in air. The effects of the face-to-face annealing on the structural and optical properties of the ZnO films were investigated by X-ray diffraction (XRD), photoluminescence (PL), optical transmittance and absorption measurements. Measurement results showed that the crystal quality of ZnO films was improved by face-to-face annealing. Both UV light emission and visible light emission were enhanced compared to those of open annealing films. The UV emission peak was observed to have a blueshift towards higher energy. The optical band-gap edge of as-annealed films shifted towards longer wavelength. (c) 2005 Elsevier B.V.. All rights reserved.

Getting high-efficiency photoluminescence from Si nanocrystals in SiO2 matrix

Silicon nanocrystals in SiO2 matrix are fabricated by plasma enhanced chemical vapor deposition followed by thermal annealing. The structure and photoluminescence (PL) of the resulting films is investigated as a function of deposition temperature. Drastic improvement of PL efficiency up to 12% is achieved when the deposition temperature is reduced from 250 degreesC to room temperature. Low-temperature deposition is found to result in a high quality final structure of the films in which the silicon nanocrystals are nearly strain-free, and the Si/SiO2 interface sharp. The demonstration of the superior structural and optical properties of the films represents an important step towards the development of silicon-based light emitters. (C) 2002 American Institute of Physics.

Photoluminescence and Raman scattering of silicon nanocrystals prepared by silicon ion implantion into SiO2 films

Photoluminescence (PL) and Raman spectra of silicon nanocrystals prepared by Si ion implantion into SiO2 layers on Si substrate have been measured at room temperature. Their dependence on annealing temperature was investigated in detail. The PL peaks observed in the as-implanted sample originate from the defects in SiO2 layers caused by ion implantation. They actually disappear after thermal annealing at 800 degrees C. The PL peak from silicon nanocrystals was observed when thermal annealing temperatures are higher than 900 degrees C. The PL peak is redshifted to 1.7 eV and the intensity reaches maximum at the thermal annealing temperature of 1100 degrees C. The characterized Raman scattering peak of silicon nanocrystals was observed by using a right angle scattering configuration. The Raman signal related to the silicon nanocrystals appears only in the samples annealed at temperature above 900 degrees C. It further proves the formation of silicon nanocrystals in these samples. (C) 2000 American Institute of Physics. [S0021-8979(00)00215-2].

Optical properties of nanometer silicon prepared by silicon ion implanted into SiO2 layers

The samples of silicon nanocrystals (nc-Si) were prepared by Si ion implanted into SiO2 layers. Photoluminescence spectra were measured at room temperature and their dependence on thermal annealing was investigated. The experimental results show that PL peaks originate from the defects in SiO2 layers caused by ion implantation when the thermal annealing temperature is lower than 800 C. The PL peak from nc-Si was observed when the thermal annealing temperature was higher than 900 C, and PL intensity reached its maximum at the thermal annealing temperature of 1100 C. As the annealing temperature increases the red shift of PL peak from nc-Si shows the quantum size effect. The characterized Raman scattering peak of nc-Si was observed at the right angle scattering configuration for the first time. It provides further support for the PL measurements.

Fabrication of luminescent Ge nanocrystals started from unlayered hydrogenated amorphous SiGe films or hydrogenated amorphous Si hydrogenated amorphous Ge multilayers

Nanocrystalline Ge embedded in SiOx matrix is fabricated by oxidizing hydrogenated amorphous Sice alloys or hydrogenated amorphous Si/hydrogenated amorphous Ge multilayers. The structures before and after oxidation are systematically investigated. Visible light emission was observed from both samples. The luminescence peak is located at 2.2 eV which is independent of the starting materials. Compared to the luminescence from unlayered samples, the photoluminescence spectrum from multilayered samples has a narrower band width, which can be attributed to the uniform size distribution. The light emission origin is also discussed briefly and a mechanism different from the quantum size effect is suggested.

Microstructure and photoluminescence of a-SiOx : H

Two strong photoluminescence (PL) bands in the spectral range of 550-900 nm have been observed at room temperature from a series of a-SiOx:H films fabricated by plasma-enhanced chemical vapor deposition (PECVD) technique. One is composed of a main band in the red-light region and a shoulder; the other is located at about 850 nm, only found after 1170 degrees C annealing in N-2 atmosphere. In conjunction with infrared (IR) and micro-Raman spectra, it is thought that the two PL bands are associated with a-Si clusters in the SiOx network and nanocrystalline silicon in SiO2, respectively.

Annealing behaviors of photoluminescence from SiOx : H

The strong photoluminescence (PL) of SiOx:H prepared by plasma enhanced chemical vapor deposition has been systematically studied in conjunction with infrared and micro-Raman spectra. We have found that each PL spectrum is comprised of two Gaussian components, a main band and a shoulder. The main band might originate from amorphous silicon clusters embedded in die SiOx network, and its redshift with annealing temperature is due to expansion of the silicon clusters. The shoulder remains at about 835 nm in spite of the annealing temperature and possibly comes from luminescent defect centers. The enhanced PL spectra after 1170 degrees C annealing are attributed to the quantum confinement effects of nanocrystalline silicon embedded in the SiO2 matrix. (C) 1998 American Institute of Physics.

Photoluminescence from surface-oxidized Ge nanoclusters

Photoluminescence from gas-evaporated Ge nanoclusters consisting of a crystalline core encased in an oxide shell are presented. An as-grown sample shows room temperature luminescence with separate peaks around 357 and 580 nm. Prolonged air exposure of the clusters reduces the Ge core dimensions, and the emission initially at 580 nm shifts to 420 nm; however, the violet luminescence at 357 nm displays no difference. These results indicate that there are two mechanisms involved with light emission from Ge nanoclusters, visible light emission associated with the quantum confinement effect, and violet light emission correlated to luminescent centers. (C) 1998 Elsevier Science B.V.

A study of strong photoluminescence of SiOx : H films

We have examined photoluminescence (PL), IR absorption and Raman spectra of a series of hydrogenated amorphous silicon oxide (a-SiOx:H, (0 < x < 2)) films fabricated by plasma enhanced chemical vapor deposition (PECVD). Two strong luminescence bands were observed at room temperature, one is a broad envelope comprising a main peak around 670 nm and a shoulder at 835 nm, and the other, peaked around 850 nm; is found only after being annealed up to 1170 degrees C in N-2 environment. In conjunction with IR and Raman spectra, the origins of the two luminescent bands and their annealing behaviors are discussed on the basis of quantum confinement effects.

Quantum confinement effect in thin quantum wires

The electronic states and optical transition properties of three semiconductor wires Si? GaAs, and ZnSe are studied by the empirical pseudopotential homojunction model. The energy levels, wave functions, optical transition matrix elements, and lifetimes are obtained for wires of square cross section with width from 2 to 5 (root 2a/2), where a is the lattice constant. It is found that these three kinds of wires have different quantum confinement properties. For Si wires, the energy gap is pseudodirect, and the wave function of the electronic ground state consists mainly of four bulk Delta states. The optical transition matrix elements are much smaller than that of a direct transition, and increase with decreasing wire width. Where the width of wire is 7.7 Angstrom, the Si wire changes from an indirect energy gap to a direct energy gap due to mixing of the bulk Gamma(15) state. For GaAs wires. the energy gap is also pseudodirect in the width range considered, but the optical transition matrix elements are larger than those of Si wires by two orders of magnitude for the same width. However, there is no transfer to a direct energy gap as the wire width decreases. For ZnSe wires, the energy gap is always direct, and the optical transition matrix elements are comparable to those of the direct energy gap bulk semiconductors. They decrease with decreasing wire width due to mixing of the bulk Gamma(1) state with other states. All quantum confinement properties are discussed and explained by our theoretical model and the semiconductor energy band structures derived. The calculated lifetimes of the Si wire, and the positions of photoluminescence peaks, are in good agreement with experimental results.

Microstructure, dielectric properties and optical band gap control on the photoluminescence behavior of Ba[Zr0.25Ti0.75]O-3 thin films

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