Size dependent photodegradation of CdS particles deposited onto TiO2 mesoporous films by SILAR method

The properties of CdS nanoparticles incorporated onto mesoporous TiO2 films by a successive ionic layer adsorption and reaction (SILAR) method were investigated by Raman spectroscopy, UV-visible spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). High resolution TEM indicated that the synthesized CdS particles were hexagonal phase and the particle sizes were less than 5 nm when SILAR cycles were fewer than 9. Quantum size effect was found with the CdS sensitized TiO2 films prepared with up to 9 SILAR cycles. The band gap of CdS nanoparticles decreased from 2.65 eV to 2.37 eV with the increase of the SILAR cycles from 1 to 11. The investigation of the stability of the CdS/TiO2 films in air under illumination (440.6 µW/cm2) showed that the photodegradation rate was up to 85% per day for the sample prepared with 3 SILAR cycles. XPS analysis indicated that the photodegradation was due to the oxidation of CdS, leading to the transformation from sulphide to sulphate (CdSO4). Furthermore, the degradation rate was strongly dependent upon the particle size of CdS. Smaller particles showed faster degradation rate. The size-dependent photo-induced oxidization was rationalized with the variation of size-dependent distribution of surface atoms of CdS particles. Molecular Dynamics (MD) simulation has indicated that the surface sulphide anion of a large CdS particle such as CdS made with 11 cycles (CdS11, particle size = 5.6 nm) accounts for 9.6% of the material whereas this value is increased to 19.2% for (CdS3) based smaller particles (particle size: 2.7 nm). Nevertheless, CdS nanoparticles coated with ZnS material showed a significantly enhanced stability under illumination in air. A nearly 100% protection of CdS from photon induced oxidation with a ZnS coating layer prepared using four SILAR cycles, suggesting the formation of a nearly complete coating layer on the CdS nanoparticles.

Sol-gel synthesis and characterization of cubic bismuth zinc niobium oxide nanopowders

Bismuth zinc niobium oxide (BZN) was successfully synthesized by a diol-based sol-gel reaction utilizing metal acetate and alkoxide precursors. Thermal analysis of a liquid suspension of precursors suggests that the majority of organic precursors decompose at temperatures up to 150°C, and organic free powders form above 350°C. The experimental results indicate that a homogeneous gel is obtained at about 200°C and then converts to a mixture of intermediate oxides at 350–400°C. Finally, single-phased BZN powders are obtained between 500 and 900°C. The degree of chemical homogeneity as determined by X-ray diffraction and EDS mapping is consistent throughout the samples. Elemental analysis indicates that the atomic ratio of metals closely matches a Bi1.5ZnNb1.5O7 composition. Crystallite sizes of the BZN powders calculated from the Scherrer equation are about 33–98 nm for the samples prepared at 500–700°C, respectively. The particle and crystallite sizes increase with increased sintering temperature. The estimated band gap of the BZN nanopowders from optical analysis is about 2.60–2.75 eV at 500-600°C. The observed phase formations and measured results in this study were compared with those of previous reports.

Optical Characterization of the Hole Polaron in a Series of Diketopyrrolopyrrole Polymers Used for Organic Photovoltaics

Abstract: A strategy that is often used for designing low band gap polymers involves the incorporation of electron-rich (donor) and electron-deficient (acceptor) conjugated segments within the polymer backbone. In this paper we investigate such a series of Diketopyrrolopyrrole (DPP)-based co-polymers. The co-polymers consisted of a DPP unit attached to a phenylene, naphthalene, or anthracene unit. Additionally, polymers utilizing either the thiophene-flanked DPP or the furan-flanked DPP units paired with the naphthalene comonomer were compared. As these polymers have been used as donor materials and subsequent hole transporting materials in organic solar cells, we are specifically interested in characterizing the optical absorption of the hole polaron of these DPP based copolymers. We employ chemical doping, electrochemical doping, and photoinduced absorption (PIA) studies to probe the hole polaron absorption spectra. While some donor-acceptor polymers have shown an appreciable capacity to generate free charge carriers upon photoexcitation, no polaron signal was observed in the PIA spectrum of the polymers in this study. The relations between molecular structure and optical properties are discussed. Keywords: organic solar cell; organic photovoltaic; diketopyrrolopyrrole; chemical doping; spectroelectrochemistry; photoinduced absorption; hole polaron

Structural and electronic properties of layered arsenic and antimony arsenide

Layered materials exhibit intriguing electronic characteristics and the search for new types of two-dimensional (2D) structures is of importance for future device fabrication. Using state-of-art first principle calculations, we identify and characterize the structural and electronic properties of two 2D layered arsenic materials, namely, arsenic and its alloy AsSb. The stable 2D structural configuration of arsenic is confirmed to be the low-buckled two-dimensional hexagonal structure by phonon and binding energy calculations. The monolayer exhibits indirect semiconducting properties with gap around 1.5 eV (corrected to 2.2 eV by hybrid function), which can be modulated into a direct semiconductor within a small amount of tensile strain. These semiconducting properties are preserved when cutting into 1D nanoribbons, but the band gap is edge dependent. It is interesting to find that an indirect to direct gap transition can be achieved under strain modulation of the armchair ribbon. Essentially the same phenomena can be found in layered AsSb, except a weak Rashba induced band splitting is present in AsSb due to the nonsymmetric structure and spin orbit coupling. When an additional layer is added on the top, a semiconductor–metal transition will occur. The findings here broaden the family of 2D materials beyond graphene and transition metal dichalcogenides and provide useful information for experimental fabrication of new layered materials with possible application in optoelectronics.

One-step synthesis of high quality kesterite Cu2ZnSnS4nanocrystals: A hydrothermal approach

The present work demonstrates a systematic approach for the synthesis of pure kesterite-phase Cu2ZnSnS4 (CZTS) nanocrystals with a uniform size distribution by a one-step, thioglycolic acid (TGA)-assisted hydrothermal route. The formation mechanism and the role of TGA in the formation of CZTS compound were thoroughly studied. It has been found that TGA interacted with Cu2+ to form Cu+ at the initial reaction stage and controlled the crystal-growth of CZTS nanocrystals during the hydrothermal reaction. The consequence of the reduction of Cu2+ to Cu+ led to the formation Cu2−xS nuclei, which acted as the crystal framework for the formation of CZTS compound. CZTS was formed by the diffusion of Zn2+ and Sn4+ cations to the lattice of Cu2−xS during the hydrothermal reaction. The as-synthesized CZTS nanocrystals exhibited strong light absorption over the range of wavelength beyond 1000 nm. The band gap of the material was determined to be 1.51 eV, which is optimal for application in photoelectric energy conversion device.

Polyacrylic Acid Assisted Synthesis of Cu2ZnSnS4 by Hydrothermal Method

Pure phase Cu2ZnSnS4 (CZTS) nanoparticles were successfully synthesized via polyacrylic acid (PAA) assisted one-pot hydrothermal route. The morphology, crystal structure, composition and optical properties as well as the photoactivity of the as-synthesized CZTS nanoparticles were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectrometer, UV-visible absorption spectroscopy and photoelectrochemical measurement. The influence of various synthetic conditions, such as the reaction temperature, reaction duration and the amount of PAA in the precursor solution on the formation of CZTS compound was systematically investigated. The results have shown that the crystal phase, morphology and particle size of CZTS can be tailored by controlling the reaction conditions. The formation mechanism of CZTS in the hydrothermal reaction has been proposed based on the investigation of time-dependent phase evolution of CZTS which showed that metal sulfides (e.g., Cu2S, SnS2 and ZnS) were formed firstly during the hydrothermal reaction before forming CZTS compound through nucleation. The band gap of the as-synthesized CZTS nanoparticles is 1.49 eV. The thin film electrode based on the synthesized CZTS nanoparticles in a three-electrode photoelectrochemical cell generated pronounced photocurrent under illumination provided by a red light-emitting diode (LED, 627 nm), indicating the photoactivity of the semiconductor material.

Electronic structure of La1-xSrxCrO3

LaCrO3 is a wide-band-gap insulator which does not evolve to a metallic state even after hole doping. We report electronic structure of this compound and its Sr substituents investigated by photoemission and inverse photoemission spectroscopies in conjunction with various calculations. The results show that LaCrO 3 is close to the Mott-Hubbard insulating regime with a gap of about 2.8 eV. Analysis of Cr 2p core-level spectrum suggests that the intra-atomic Coulomb interaction strength and the charge-transfer energy to be 5.0 and 5.5 eV, respectively, We also estimate the intra-atomic exchange interaction strength and a crystal-field splitting of about 0.7 and 2.0 eV, respectively. Sr substitution leading to hole doping in this system decreases the charge-excitation gap, but never collapses it to give a metallic behavior. The changes in the occupied as well as unoccupied spectral features are discussed in terms of the formation of local Cr4+ configurations arising from strong electron-phonon interactions.

Electronic structure studies and photocatalytic properties of cubic Bi1.5ZnNb1.5O7

The photocatalytic ability of cubic Bi1.5ZnNb1.5O7 (BZN) pyrochlore for the decolorization of an acid orange 7 (AO7) azo dye in aqueous solution under ultraviolet (UV) irradiation has been investigated for the first time. BZN catalyst powders prepared using low temperature sol-gel and higher temperature solid-state methods have been evaluated and their reaction rates have been compared.The experimental band gap energy has been estimated from the optical absorption edge and has been used as reference for theoretical calculations. The electronic band structure of BZN has been investigated using first-principles density functional theory (DFT) calculations for random, completely and partially ordered solid solutions of Zn cations in both the A and B sites of the pyrochlore structure.The nature of the orbitals in the valence band (VB) and the conduction band (CB) has been identified and the theoretical band gap energy has been discussed in terms of the DFT model approximations.

Synthesis, characterization, and electronic structure studies of cubic Bi1.5ZnTa1.5O7 for photocatalytic applications

Bi1.5ZnTa1.5O7 (BZT) has been synthesized using an alkoxide based sol-gel reaction route. The evolution of the phases produced from the alkoxide precursors and their properties have been characterized as function of temperature using a combination of thermogravimetric analysis (TGA) coupled with mass spectrometry (MS), infrared emission spectrometry (IES), X-ray diffraction (XRD), ultraviolet and visible (UV-Vis) spectroscopy, Raman spectroscopy, and N2 adsorption/desorption isotherms. The lowest sintering temperature (600∘C) to obtain phase pure BZT powders with high surface area (14.5m2/g) has been determined from the thermal decomposition and phase analyses.The photocatalytic activity of the BZT powders has been tested for the decolorization of organic azo-dye and found to be photoactive under UV irradiation.The electronic band structure of the BZT has been investigated using density functional theory (DFT) calculations to determine the band gap energy (3.12 eV) and to compare it with experimental band gap (3.02 eV at 800∘C) from optical absorptionmeasurements. An excellent match is obtained for an assumption of Zn cation substitutions at specifically ordered sites in the BZT structure.

Quasi-static and dynamic strain sensing using carbon nanotube/epoxy nanocomposite thin films

Thin films are developed by dispersing carbon black nanoparticles and carbon nanotubes (CNTs) in an epoxy polymer. The films show a large variation in electrical resistance when subjected to quasi-static and dynamic mechanical loading. This phenomenon is attributed to the change in the band-gap of the CNTs due to the applied strain, and also to the change in the volume fraction of the constituent phases in the percolation network. Under quasi-static loading, the films show a nonlinear response. This nonlinearity in the response of the films is primarily attributed to the pre-yield softening of the epoxy polymer. The electrical resistance of the films is found to be strongly dependent on the magnitude and frequency of the applied dynamic strain, induced by a piezoelectric substrate. Interestingly, the resistance variation is found to be a linear function of frequency and dynamic strain. Samples with a small concentration of just 0.57% of CNT show a sensitivity as high as 2.5% MPa-1 for static mechanical loading. A mathematical model based on Bruggeman's effective medium theory is developed to better understand the experimental results. Dynamic mechanical loading experiments reveal a sensitivity as high as 0.007% Hz(-1) at a constant small-amplitude vibration and up to 0.13%/mu-strain at 0-500 Hz vibration. Potential applications of such thin films include highly sensitive strain sensors, accelerometers, artificial neural networks, artificial skin and polymer electronics.

Carbon nanodot decorated graphitic carbon nitride: New insights into the enhanced photocatalytic water splitting from ab initio studies

Interfacing carbon nanodots (C-dots) with graphitic carbon nitride (g-C3N4) produces a metal-free system that has recently demonstrated significant enhancement of photo-catalytic performance for water splitting into hydrogen [Science, 2015, 347, 970–974]. However, the underlying photo-catalytic mechanism is not fully established. Herein, we have carried out density functional theory (DFT) calculations to study the interactions between g-C3N4 and trigonal/hexagonal shaped C-dots. We find that hybrid C-dots/g-C3N4 can form a type-II van der Waals heterojunction, leading to significant reduction of band gap. The C-dot decorated g-C3N4 enhances the separation of photogenerated electron and hole pairs and the composite's visible light response. Interestingly, the band alignment of C-dots and g-C3N4 calculated by the hybrid functional method indicates that C-dots act as a spectral sensitizer in hybrid C-dots/g-C3N4 for water splitting. Our results offer new theoretical insights into this metal-free photocatalyst for water splitting.

Influence of non-stoichiometric defects on nonlinear absorption and refraction in Nd:Zn co-doped lithium niobate

Nonlinear absorption and refraction phenomena in stoichiometric lithium niobate (SLN) pure and co-doped with Zn and Nd, and congruent lithium niobate (CLN) were investigated using Z-scan technique. Femtosecond laser pulses from Ti:Sapphire laser (800 nm, 110 fs pulse width and 1 kHz repetition rate) were utilized for the experiment. The process responsible for nonlinear behavior of the samples was identified to be three photon absorption (3PA). This is in agreement with the band gap energies of the samples obtained from the linear absorption cut off and the slope of the plot of Ln(1 − TOA) vs. Ln(I0) using Sutherland’s theory (s = 2.1, for 3PA). The nonlinear refractive index (n2) of Zn doped samples was found to be lower than that of pure samples. Our experiments show that there exists a correlation between the nonlinear properties and the stoichiometry of the samples. The values of n2 fall into the same range as those obtained for the materials of similar band gap.

Novel ultrahigh resolution silverless photothermal imaging in obliquely deposited amorphous Se-Ge films

A new photothermal imaging process which utilizes no silver has been demonstrated in obliquely deposited Se-Ge films. Band-gap irradiation of Se-Ge films has been found to give rise to phases of the type SeOx, GeO, and Se as borne by x-ray initiated Auger electron spectroscopy and x-ray photoelectron spectroscopy. Annealing of SeOx leads to the formation of SeO2. The large (several orders of magnitude) difference in vapor pressures of SeO2 and Se-Ge films results in differential evaporation of the films when annealed around 200 °C, thereby leading to imaging. Such a large contrast in evaporation rates between the exposed and unexposed regions has great potential applications in high resolution image storage and phase holography. Applied Physics Letters is copyrighted by The American Institute of Physics.

A simple circuit to aid direct measurement of capture cross sections of deep level impurities

An inexpensive and simple circuit to aid the direct measurement of majority carrier capture cross sections of impurity levels in the band gap of a semiconductor by the variable width filling pulse technique is presented. With proper synchronisation, during the period of application of the pulse, the device is disconnected from the capacitance meter to avoid distortion of the pulse and is reconnected again to the meter to record the emission transient. Modes of operation include manual triggering for long emission transients, repetitive triggering for isothermal and DLTS measurements and the DLTS mode which is to be used with signal analysers that already provide a synchronising pulse for disconnection.

Effect of substrate temperature on the physical properties of dc magnetron sputtered CuAlO2 films

Copper aluminum oxide films were prepared by direct current (dc) reactive magnetron sputtering under various substrate temperatures in the range of 303–648 K and systematically studied their physical properties. The physical properties of the films were strongly affected by the substrate temperature. The films formed at substrate temperatures <373 K were amorphous while those deposited at higher substrate temperatures (≥373 K) were polycrystalline in nature. The electrical properties of the films enhanced with substrate temperature due to the improved crystallinity. The Hall mobility of 9.4 cm2/V s and carrier concentration of 3.5 × 1017 cm−3 were obtained at the substrate temperature of 573 K. The optical band gap of the films decreased from 3.87 to 3.46 eV with the increase of substrate temperature from 373 to 573 K.