Experimental investigation on the structural,dielectric, ferroelectric and piezoelectric properties of La doped ZnO nanoparticles and their application in dye-sensitized solar cells

Pure and lanthanum (La) doped ZnO nanorods were synthesized via co-precipitation method. The structure and morphology of as grown ZnO and La-ZnO nanoparticles were studied using transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) methods. The values of remnant polarization and coercive field were found to be 0.027 μC/cm² and 1.33 kV/cm, respectively, for as grown La-ZnO nanostructures. High Curie temperature (276 °C) for doped ZnO was observed in dielectric study. Piezoelectric coefficient at room temperature was found to be 101.30 pm/V. I-V characteristics were studied for both pure and doped ZnO nanoparticles. Photo-anodes of dye-sensitized solar cells (DSSCs) were made using ZnO and La-ZnO nanorods. The conversion efficiency and short circuit current density of La-ZnO nanorods based DSSC were 0.36% and 1.31 mA/cm², respectively, which were found to be largely enhanced when compared with that of pure ZnO based DSSC (0.20% and 0.94 mA/cm²).     

Organic compounds removal in soil in a seven-needle-to-net pulsed discharge plasma system

A pulsed discharge plasma (PDP) system (a seven-needle-to-net electrode geometry) was built to degrade pyrene and p-nitrophenol in soil. Pulse discharge time, contents of the pollutants in the soil, the initial pH value of the soil, Kaolin and Cr⁶⁺ addition on removal of pollutants was investigated. The obtained results show that 60 min was the better treatment time; removal of organic compounds decreased with the increase of the contents; removal of pyrene was higher at neutral pH condition, while p-nitrophenol has more oxidation in the basic soil; Kaolin and Cr⁶⁺ addition has positive effect on the organic compounds degradation.     

Franck–Hertz effect in cathodo- and photoluminescence of wide-gap materials

A brief overview of previously obtained and novel data on the manifestations of an analogue of Franck–Hertz effect in photo- and cathodoluminescence of wide-gap inorganic materials is presented. On the example of NaCl:Tl⁺ and MgO:Cr³⁺ single crystals, the excitation processes of the luminescence of 6s² Tl⁺ ions and 3d³ Cr³⁺ ions by 5–15 keV electrons or 5–20 eV photons at 6–420 K have been studied. The rapid processes of the direct energy transfer to Tl⁺ by hot conduction electrons or to Cr³⁺ centers by hot electrons and/or hot valence holes have been separated from rapid excitonic and more inertial electron–hole processes.     

Cr3+ doped Al2O3 nanoparticles: Effect of Cr3+ content in intensifying red emission

Cr³⁺-doped α-Al₂O₃ nanoparticles (Al_2−xCr_xO₃, 0.005 ≤ x ≤ 0.05) were synthesized by co-precipitation method. X-ray diffraction (XRD) patterns of Cr³⁺:Al₂O₃ nanoparticles revealed the crystallite size of ∼53 nm and electron microscopy (SEM & TEM) confirmed the spherical nanoparticle formation. Diffuse reflectance spectra (DRS) displayed peaks at 406 and 558 nm corresponding to the Cr³⁺ transitions which became prominent with the increase in Cr³⁺ concentration which was also evidenced by the gradually increasing pink coloration of the samples. Photoluminescence (PL) studies showed the sharp red emission at 694 nm (ruby line) which was observed for all samples. The Dq/B value for all samples was found to be greater than 2.3 confirming the presence of Cr³⁺ ions in the octahedral sites. Chromaticity diagrams displayed the maximum red appearance for the sample with x = 0.01 and a lifetime of 4 ms. The synthesized Cr³⁺:Al₂O₃ nanoparticles with smaller crystallite sizes and narrow near monochromatic emission can be used in various applications including sensing, lasing, and bioimaging applications.     

Luminescent vacuum ultraviolet spectroscopy of Cr3+ ions in nanostructured aluminum oxide

Impurity Cr³⁺ centers in submicron and nanostructured Al₂O₃ crystals of different phase compositions at temperatures of 300 and 7.5 K were studied by a luminescent vacuum ultraviolet (VUV) spectroscopy method. Photoluminescence (PL) spectra and the energies of ²E, ⁴T₂, and ⁴T₁ excited states of Cr³⁺ ion depend on the type of crystalline samples phase. The PL excitation spectrum of R-line in α-Al₂O₃ nanoscale crystals is formed by intracenter transitions (2.5–5.5 eV region), by charge transfer band (6.9 eV) and by effective formation of impurity-bound excitons (9.0 eV region). Such impurity-bound excitons correspond to O₂p→Al₃s electron transition in surroundings of an impurity Cr³⁺ center. The efficiency of impurity-bound excitons formation decreases with the increase of the grain size above 100 nm. The size dependence is noticeably shown in PL excitation spectra in VUV region. Excitons bound to impurity centers do not appear in nanostructured δ+θ-Al₂O₃ crystals. The effect of the electron excitation multiplication is observed distinctly in nanostrucured α-Al₂O₃ at an excitation energy above 19 eV (more than 2E_g).     

Synthesis of Cr2O3/TNTs nanocomposite and its photocatalytic hydrogen generation under visible light irradiation

A novel Cr₂O₃/TNTs nanocomposite was prepared by loaded suitable amount of amorphous Cr₂O₃ on titanate nanotubes (TNTs) via hydrothermal reaction and impregnation process. XRD, SEM and TEM results demonstrated that the amorphous Cr₂O₃ nanoparticles were homogeneously dispersed on the surface of TNTs. The diffuse reflectance UV–visible absorption spectra exhibited that the spectral response of TNTs was extended to visible light region by coupled with Cr₂O₃. The 2.5Cr₂O₃/TNTs nanocomposite showed the highest activity of hydrogen generation by photocatalytic water-splitting under visible light irradiation (λ > 400 nm). The high activity of H₂ evolution for Cr₂O₃/TNTs nanocomposites was associated with the donor level in the forbidden band of TNTs semiconductor provided by dopant Cr³⁺ and a probably photocatalytic mechanism was proposed.     

Structural, optical and magnetic properties of Cr doped ZnO microrods prepared by spray pyrolysis method

A series of Cr-doped ZnO micro-rod arrays were fabricated by a spray pyrolysis method. X-ray diffraction patterns of the samples showed that the undoped and Cr-doped ZnO microrods exhibit hexagonal crystal structure. Surface morphology analysis of the samples has revealed that pure ZnO sample has a hexagonal microrod morphology. From X-ray photoelectron spectroscopy studies, the Cr 2p3/2 binding energy is found to be 577.3 eV indicating that the electron binding energy of the Cr in ZnO is almost the same as the binding energy of Cr³⁺ states in Cr₂O₃. The optical band gap E_g decreases slightly from 3.26 to 3.15 eV with the increase of actual Cr molar fraction from x = 0.00 to 0.046 in ZnO. Photoluminescence studies at 10 K show that the incorporation of chromium leads to a relative increase of deep level band intensity. It was also observed that Cr doped samples clearly showed ferromagnetic behavior; however, 2.5 at.% Cr doped ZnO showed remnant magnetization higher than that of 1.1 at.% and 4.6 at.% Cr doped samples, while 4.6 at.% Cr doped ZnO samples had a coercive field higher than the other dopings.     

Synthesis of Cr-based mixed oxides by reactive ion beam mixing of Cr/X interfaces (X=Al or Si)

The 3 keV O₂⁺\mathrm{O}_{2}^{+} reactive ion beam mixing of Cr/X interfaces (X=Al or Si) has been used to synthesize Cr-based mixed oxide thin films. The kinetics of growth, composition, and electronic structure of those films has been studied using X-ray photoelectron spectroscopy, Auger electron spectroscopy, ultraviolet photoelectron spectroscopy, and factor analysis. Initially, for low ion doses, Cr₂O₃ species are formed. Later, with increasing the ion dose, Cr₂O₃ species are first transformed into Cr³⁺–O–X species, and subsequently, those Cr³⁺–O–X species are transformed into Cr⁶⁺–O–X species. This sequential transformation, Cr₂O₃→Cr³⁺–O–X→Cr⁶⁺–O–X, is accompanied by a slight increase of the oxygen concentration and a decrease of the Cr/X ratio in the films formed leading to the synthesis of custom designed Cr-based mixed oxides. The changes observed in the valence band and Auger parameters further support the formation of Cr–X mixed oxide species. Angle resolved X-ray photoelectron spectroscopy shows that for low ion doses, when only Cr₂O₃ and Cr³⁺–O–X species coexist, Cr³⁺–O–X species are located nearer the surface than Cr₂O₃ species, whereas for higher ion doses, when only Cr³⁺–O–X and Cr⁶⁺–O–X species coexist, the Cr⁶⁺–O–X species are those located nearer the surface.     

The optical properties and laser characteristics of Cr and Nd co-doped Y3Al5O12 ceramics

We have fabricated Cr³⁺ and Nd³⁺ co-doped YAG (Cr;Nd:YAG) ceramics, and investigated their optical properties and laser characteristics. The Cr;Nd:YAG has two broad absorption bands at around 440 nm (⁴A₂→⁴T₁) and 600 nm (⁴A₂→⁴T₂) respectively, caused by Cr³⁺ ions. In the case of pumping at 440 nm, the maximum effective lifetime of the Cr;Nd:YAG was 737 μs with a 0.1 at% Cr³⁺ and 1.0 at% Nd³⁺ co-doped YAG sample. Cr³⁺ ions take a role of an effective sensitizer to convert the UV light of flashlamp. For single-shot laser operation, a 10.4 J output energy at 1064 nm was obtained with 0.1 at% Cr³⁺ and 1.0 at% Nd³⁺ co-doped YAG ceramic rod with a laser efficiency of 4.9%. The laser efficiency was found to be more than twice that of a 1.0 at % Nd³⁺:YAG ceramic rod.     

Sonophotocatalytic inactivation of E. coli using ZnO nanofluids and its mechanism

The present study evaluated inactivation efficiency of a sonophotocatalytic process using ZnO nanofluids including ultrasonic parameters such as power density, frequency and time. The result showed that inactivation efficiency was increased by 20% when ultrasonic irradiation was combined with photocatalytic process in the presence of natural light. Comparison of inactivation efficiency in photocatalytic, ultrasonic and sonocatalytic processes using Escherichia coli as a model bacteria identified that inactivation efficiencies are shown in the following order: ultrasonic irradiation < sonocatalysis < photocatalysis < sonophotocatalysis. Furthermore, inactivation mechanism of sonophotocatalysis was proposed. Studies of reactive oxygen species (ROS) and zinc ions (Zn²⁺) release evaluation revealed that ROS play a key role in bacterial inactivation rather than Zn²⁺. Permeability of outer membrane (OM) and inner membrane (IM) of E. coli bacterial cells were studied and exhibited that sonophotocatalysis increased the permeability of OM and IM significantly. The enhanced bacterial inactivation effect in sonophotocatalytic process contributed to acoustic cavitation, sonocatalysis of ZnO and sonoporation phenomenon.     

Enhanced photoelectrochemical performance of ZnO photoanode with scattering hollow cavities

Abstract ZnO nanoparticles with average diameter of 12 nm were used to fabricate ZnO photoanodes by electrohydrodynamic (EHD) technique for dye-sensitized solar cells (DSSCs). To enhance the light scattering and conversion efficiency, the ZnO film with scattering hollow cavities (HCs) was realized by calcining polystyrene spheres (PSs) in the film. The films had strong light scattering ability and the overall light to electricity conversion efficiency (η) was improved and reached 5.5% under illumination of simulated solar light (AM-1.5, 100 mW/cm²).     

Controlled repeated chemical growth of ZnO films for dye-sensitized solar cells

The controlled growth of ZnO nanorods perpendicular to substrate surface i.e. c-axis by a repeated chemical deposition method for efficient dye-sensitized solar cell application is described. X-ray diffraction study shows the wurtzite structure of ZnO with high crystallinity. Intensity and newly evolved peaks of the ZnO are found to be thickness dependent. Dye loving flower-like globular architecture of ZnO is observed after 8 μm thickness. Dye-sensitized solar cell studies show the solar-to-electrical conversion efficiency of 2.21% for 11 μm ZnO electrode when illuminated with 80 mW/cm².     

Defect-controlled growth of ZnO nanostructures using its different zinc precursors and their application for effective photodegradation

Various zinc precursors, such as zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride, have been used to control the formation of zinc oxide (ZnO) nanostructures onto aluminum substrate by chemical means. FESEM images of the ZnO nanostructures showed the formation of different morphologies, such as flakes, nanowalls, nanopetals, and nanodisks, when the nanostructures were synthesized using zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride precursors, respectively. The TEM image of disk-like ZnO nanostructures formed using zinc chloride as a precursor revealed hexagonally shaped particles with an average diameter of 0.5 μm. Room-temperature photoluminescence (PL) spectra revealed a large quantity of surface oxygen defects in ZnO nanodisks grown from zinc chloride compared with those using other precursors. Furthermore, the ZnO nanostructures were evaluated for photocatalytic activity under ultraviolet (UV) light illumination. Nanostructures having a disk-like shape exhibited the highest photocatalytic performance (k = 0.027 min⁻¹) for all the ZnO nanostructures studied. Improved photocatalytic activity of ZnO nanodisks was attributed to their large specific surface area (4.83 m² g⁻¹), surface oxygen defects, and super-hydrophilic nature of their surface, which is particularly suitable for dye adsorption.     

Photocatalytic degradation of methylene blue solution by diphenylanthrazoline compounds

The photocatalytic degradation of methylene blue solution by 8 photocatalytic diphenylanthrazoline compounds was investigated. All diphenylanthrazoline compounds exhibited a good photocatalytic activity towards the methylene blue solution. The removal rate for chemical oxygen demand (COD_Cr) in the methylene blue solution at 12 hours was ~54.1% to 96.3%. 2,8‐Bis(4‐triphenylamino)‐4,6‐diphenyl‐1,9‐anthrazoline ( TM‐2‐d ) was selected for further investigation because of its better photocatalytic activity. To study the optimal reaction conditions for the photocatalytic degradation of dye wastewater, photocatalyst was applied to degrade methylene blue solution. The decolorization rate for simulated dye solutions can exceed 99% in 10 hours, and the COD_Cr removal rate exceeded 91%. These organic semiconductor materials, diphenylanthrazoline compounds, displayed comparative photocatalytic properties to the inorganic semiconductor materials, which can be used in the photocatalytic degradation of organic pollutants.     

Characterization and photocatalytic activity of Zn–TiO2/AC composite photocatalyst

Activated carbon (AC) supported Zn²⁺–TiO₂ photocatalyst was prepared by sol–gel method. The prepared samples were characterized by X-ray diffraction, scanning electron micrograph, nitrogen absorption, diffuse reflectance UV/VIS and X-ray photoelectron spectroscopy. Using toluene as a pollution target, the photocatalytic activity of photocatalyst was evaluated. The results showed that prepared photocatalyst was obviously helpful for the removal of toluene in air. The photocatalytic degradation of toluene by Zn²⁺–TiO₂/AC reached 100% for 40 min and remained 75% after 160 min, while degradation by TiO₂ was only 30%. It indicated that the photocatalytic activity of prepared photocatalyst was enhanced. It is due to Zn²⁺-doping increased the oxidation and reduction of hole–electron pairs, which was the important factor in heterogeneous photocatalysis.     

Preparation of highly efficient Al-doped ZnO photocatalyst by combustion synthesis

Novel Al-doped ZnO (AZO) photocatalysts with different Al concentrations (0.5–6.0 mol%) were prepared through a facile combustion method and followed by calcination at 500 °C for 3 h. The obtained nanopowders were characterized by powder X-ray diffraction (XRD), scanning electron microscope (SEM) combined with EDX, transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FTIR), UV–vis spectroscopy and photoluminescence spectroscopy. The XRD patterns of AZO nanopowders were assigned to wurtzite structure of ZnO with the smallest crystallite size about 11 nm consistent with the results from TEM. The doping of Al in ZnO crystal structure successfully suppressed the growth of ZnO nanoparticles confirmed by XRD patterns. The absorption spectra analysis showed that the optical band gap energy (E_g) for the AZO nanopowders were in the range of 3.12–3.21 eV and decreased with increasing of Al dopant. The photocatalytic activities of the samples were evaluated by photocatalytic degradation of methyl orange under visible light (λ ≥ 420 nm) and sunlight irradiation. The results showed that the AZO photocatalyst doped with 4.0 mol% Al exhibited five times enhanced photocatalytic activity compared to pure ZnO. The enhanced photocatalytic activity could be attributed to extended visible light absorption, inhibition of the electron–hole pair's recombination and enhanced adsorptivity of MO dye molecule on the surface of AZO nanopowders.     

Structural Properties of Cr<Superscript>3+</Superscript>-Doped Cadmium Oxide Nanopowders

The Cr³⁺-doped cadmium oxide nanopowder is prepared at room temperature by a mild and simple solution method. The prepared powder is characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), optical, electron paramagnetic resonance (EPR) and Fourier transform infrared (FT-IR) techniques. The XRD powder pattern reveals the lattice structure and cell parameters are evaluated. The SEM image shows the stone-like morphology of the nanopowder. The optical absorption spectrum indicates the distorted octahedral site symmetry of Cr³⁺ ions. The crystal field Dq and interelectronic repulsion parameters B and C are evaluated. The EPR spectrum gives a resonance signal at g = 1.973 for Cr³⁺ ions. The FT-IR spectrum reveals the characteristic vibrations of cadmium oxide.     

Using the Mössbauer spectroscopy of <Superscript>121</Superscript>Sb nuclei to differentiate the effects of Cr and Sb co-dopants on the photocatalytic activity of anatase-type polycrystalline TiO<Subscript>2</Subscript> powders

The rates of the photocatalytic decolorization of methyl orange solutions in the presence of anatase powders modified by Cr³⁺ and Sb⁵⁺ co-dopants are compared with allowance for data on the actual valence state of antimony in the catalyst, obtained using ¹²¹Sb Mössbauer spectroscopy. The reported results point to the catalytic activity of the Cr⁶⁺ ions formed to compensate for the Cr³⁺ charge deficit in antimony-free samples.     

Improved efficiencies of hybrid organic light‐emitting diodes using efficient electron injection layer

Hybrid organic‐inorganic light‐emitting diodes were developed with pristine ZnO (2.0 wt%) and Cu‐doped ZnO (2.0 wt%) as electron injection layer and iridium(III)‐bis‐2‐(4‐fluorophenyl)‐1‐(naphthalen‐1‐yl)‐1H‐phenanthro[9,10‐d]imidazole (acetylacetonate) [Ir(fpnpi)₂ (acac)] as green emissive layer (521 nm). The pristine ZnO and Cu‐doped ZnO are deposited at indium tin oxide cathode and emissive layer interface. The electroluminescent performances increased by electron injection layer–Cu‐doped ZnO compared with ZnO‐based device because Cu‐doped ZnO injects electron efficiently result in balanced h⁺ ? e^? recombination in emissive layer than ZnO‐based device. The Cu‐doped ZnO (2.0 %) device shows luminance (L) of 10 982 cd/m² at 23.0 V (ZnO, 1450 cd/m² at 23.0 V).     

Phase analysis in Zn1− x Cr x O through charge density

Cr-doped zinc oxide Zn_{1? x} Cr _x O powder samples are synthesized by a standard high-temperature solid-state reaction technique with x?=?0.00, 0.04, and 0.08. The powders are analyzed for the electron densities using X-ray diffraction. The electron densities of observed wurtzite phase ZnO as well as the spinel phase ZnCr₂O₄ are mapped and analyzed for Cr doping concentration. The charge density study reveals that the Cr atom is added in the lattice as Cr³⁺ rather than Cr²⁺.