Biosynthesis of zinc oxide nanoparticles from Azadirachta indica for antibacterial and photocatalytic applications

Green synthesis of nanoparticles is gaining importance and has been suggested as possible alternatives to chemical and physical methods. The present work reports low-cost, green synthesis of zinc oxide (ZnO) nanoparticles using 25% (w/v) of Azadirachta indica (Neem) leaf extract. The biosynthesized nanoparticles were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), UV–visible spectroscopy (UV–vis), X-ray diffraction (XRD) and fourier transform infrared spectroscopy (FTIR). The synthesized ZnO nanoparticles were pure, predominantly spherical in shape with size ranging from 9.6 to 25.5 nm. In the present work, the biosynthesized ZnO nanoparticles have been used for antibacterial and photocatalytic applications. The antibacterial activity of characterized samples was determined using different concentrations of biosynthesized ZnO nanoparticles (20 µg/mL, 40 µg/mL, 60 µg/mL, 80 µg/mL and 100 µg/mL) against Gram-positive and Gram-negative bacteria: Staphylococcus aureus, Streptococcus pyogenes and Escherichia coli using shake flask method. The obtained results revealed that the bacterial growth decreases with increase in concentration of biosynthesized ZnO nanoparticles. In Addition, Gram-positive bacteria seemed to be more sensitive to ZnO nanoparticles than Gram-negative bacteria. The biosynthesized ZnO nanoparticles showed photocatalytic activity under the UV light enhancing the degradation rate of methylene blue (MB), which is one of the main water-pollutant released by textile industries.     

Fabrication of Ag nanoparticle/ZnO thin films using dual-plasma-enhanced metal-organic chemical vapor deposition (DPEMOCVD) system incorporated with photoreduction method and its application

We report a novel method to grow silver nanoparticle/zinc oxide (Ag NP/ZnO) thin films using a dual-plasma-enhanced metal-organic chemical vapor deposition (DPEMOCVD) system incorporated with a photoreduction method. The crystalline quality, optical properties, and electrical characteristics of Ag NP/ZnO thin films depend on the AgNO₃ concentration or Ag content and annealing temperature. Optimal Ag NP/ZnO thin films have been grown with a AgNO₃ concentration of 0.12 M or 2.54 at%- Ag content and 500 °C- rapid thermal annealing (RTA); these films show orientation peaks of hexagonal-wurtzite-structured ZnO (002) and face-center-cubic-crystalline Ag (111), respectively. The transmittance and resistivity for optimal Ag NP/ZnO thin films are 85% and 6.9×10⁻⁴ Ω cm. Some Ag NP/ZnO transparent conducting oxide (TCO) films were applied to InGaN/GaN LEDs as transparent conductive layers. The InGaN/GaN LEDs with optimal Ag NP/ZnO TCO films showed electric and optical performance levels similar to those of devices fabricated with indium tin oxide.     

Photocatalytic degradation of methyl orange and gas-sensing performance of nanosized ZnO

ZnO nanoparticles were synthesized by calcining composites of zinc nitrate and poly(vinyl pyrrolidone) (PVP, molecular weight 30 000) at a mass ratio of 1:2 at 500 °C for 2 h. X-Ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques were used to characterize the as-synthesized ZnO nanoparticles. The particles ranged in size from 30 to 50 nm. Infrared spectra of PVP and the PVP+Zn(NO₃)₂·6H₂O composite revealed coordination between the carbonyl (C=O) of PVP and Zn²⁺ of zinc nitrate, which led to a uniform nanoparticle morphology. The gas-sensing properties and photocatalytic performance of the final product were systematically investigated. The results show that the ZnO nanoparticles exhibit both a high response for ethanol detection and excellent photocatalytic activity for degradation of methyl orange under UV irradiation for 30 min.     

Preparation,characterization and photocatalytic activity of porous zinc oxide superstructure

A porous ZnO “timber-like” superstructures comprising nanoparticles was synthesized through the thermal decomposition of zinc oxalate precursor, prepared from zinc sulfate and oxalic acid, without additive(s) in water. The resulting ZnO superstructure was systematically characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy and photoluminescence measurement. Using methyl orange as model, photocatalytic activity of ZnO superstructure was investigated. The heat treatment temperature and time was proved to have important influence for photocatalytic activity of ZnO superstructure. Longer heat treatment time at fixed heat treatment temperature and lower heat treatment temperature at fixed heat treatment time were favorable for the enhancement of photocatalytic activity. The optimum preparation condition for ZnO superstructure with higher photocatalytic activity was at 450 °C for 6 h.     

Preparation and photocatalytic performance of Ag/ZnO nano-composites

Ag/ZnO nano-composites sized between 20 and 50 nm were prepared by the coordination homogeneous co-precipitation method. Thermogravimetry/differential thermal analysis (TG-DTA), Fourier transform infrared (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and ultraviolet–visible (UV–vis) were used to characterize the microstructure and morphology of the precursor and the products obtained at various temperatures. The research on the growth dynamics of product Ag/ZnO showed that the dynamic growth index was 1.32, indicating that the rate of the grain growth was quick at 300–600 °C. The results of the photocatalytic degradation of methyl orange (MO) in aqueous solution indicated that the Ag/ZnO photocatalyst prepared by the coordination homogeneous co-precipitation method exhibited better photocatalytic performance than that prepared by the photoreduction method, especially the photocatalyst calcined at 300 °C, and the photocatalytic performance decreased when the calcining temperature increased from 300 to 700 °C.     

Bio-fabrication of zinc oxide nanoparticles using leaf extract of curry leaf (Murraya koenigii) and its antimicrobial activities

The present study focused on the development of zinc oxide nanoparticles (ZnO NPs) from the leaf extract of Murraya koenigii where zinc nitrate acts as the precursor. The X-ray diffraction (XRD) analysis showed the crystalline structure, and atomic force microscopy (AFM) showed the morphology of the ZnO NPs to be spherical with an average size of 12 nm. Functional groups of the sample were identified by using Fourier transmission infrared (FT-IR) spectroscopy. Their shape, structure and composition were assessed by Field emission scanning electron microscopy (FE-SEM) and energy dispersive spectroscopy (EDS). The results depicted that synthesized ZnO NPs were moderately stable and hexagonal shape, spherical shape with maximum particle size less than 100 nm. The green-synthesized ZnO NPs had prominent activities against Staphylococcus aureus (14.0±0.50 mm) and followed by Bacillus subtilis (13.8±0.76 mm) at the concentration of 200 µg/mL.     

Effects of silver substrates on the visible light photocatalytic activities of copper-doped titanium dioxide thin films

Novel copper-doped titanium dioxide (Cu-doped TiO₂) thin films on silver (Ag) substrates with different thicknesses were prepared by sol–gel and magnetron sputtering methods. The influences of the Ag substrate thickness on the morphology and performance of the films were investigated by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, UV–visible spectroscopy, and photocatalytic degradation testing with methylene blue aqueous solution under visible light irradiation. The results indicated that Ag substrates with an optimal thickness of 30 nm not only maintained the tiny nanocrystals but also greatly improved dispersion of the nanoparticles on the surface of the nanofilms. Furthermore, during the calcination process, part of the Ag atoms diffused from the substrates into the Cu–TiO₂ films and substituted for the Cu ions to form Ag–TiO₂. A proper Ag substrate thickness (30 nm) greatly improved the photocatalytic properties of TiO₂ with photocatalytic efficiency, reaching approximately 86% in 300 minutes under visible light irradiation. However, an excess of Ag substrate not only led to the Cu ion separating out in the form of CuO but also resulted in the agglomeration of TiO₂ particles on the surface, which were detrimental to photocatalytic activities.     

Optical studies of nano-structured La-doped ZnO prepared by combustion method

Coral-shaped nano-structured zinc oxide (ZnO) was successfully synthesized and La-doped via a facile combustion process using glycine as a fuel. The auto-ignition (at ∼185 °C) of viscous reactants zinc nitrate and glycine resulted in ZnO powders. Hexagonal wurtzite structure of pure and doped ZnO powder was confirmed by X-ray powder diffraction analysis. The transmission electron micrograph shows that the nano-structured ZnO is coral-shaped and possess maximal pore (∼10–50 nm pore size) density in it and the grain size is approximately about 15 nm. Addition of dopants subsequently alters the structural and optical properties which were confirmed by UV–VIS studies.     

Top illuminated organic photodetectors with dielectric/metal/dielectric transparent anode

The top illuminated organic photodetectors (OPDs) with a Dielectric/Metal/Dielectric (DMD) transparent anode are fabricated. The transparent electrode is composed of molybdenum trioxide (MoO₃)/silver (Ag)/MoO₃ layers and zinc oxide (ZnO)/aluminum (Al) is used for bottom cathode. The optimized DMD electrode has an optical transmittance of 85.7% at the wavelength of 546 nm and sheet resistance of ∼6 Ω/sq. The fabricated OPDs exhibit a high detectivity and wide range linearity.     

Structural,optical and photocatalytic properties of ZnO nanoparticles modified with Cu

ZnO and ZnO modified with Cu nanoparticles have been prepared by a simple forced hydrolysis method. The concentration of Cu incorporated in ZnO ranged from 1% to 5% by atomic weight, and the influence of Cu concentration on the physical properties of ZnO and the relation to the photocatalytic performance has been investigated. The prepared ZnO and ZnO:Cu samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) spectroscopy and UV–vis transmittance spectroscopy. The results show that the ZnO nanomaterial was crystalline with the hexagonal wurtzite structure, with the preferential orientation of the grains along the (101) plane. The average grain size for samples with 1–5% Cu was in the range of 11–29 nm. The ZnO nanoparticles annealed at 420 °C showed an increased photocatalytic activity for the decomposition of methylene blue.     

Uniform 3D hydrothermally deposited zinc oxide nanorods with high haze ratio

We present low cost hydrothermally deposited uniform zinc oxide (ZnO) nanorods with high haze ratios for the a-Si thin film solar cells. The problem of low transmittance and conductivity of hydrothermally deposited ZnO nanorods was overcome by using RF magnetron sputtered aluminum doped zinc oxide (ZnO:Al ~300 nm) films as a seed layer. The length and diameters of the ZnO nanorods were controlled by varying growth times from 1 to 4 h. The length of the ZnO nanorods was varied from 1 to 1.5 µm, while the diameter was kept larger than 300 nm to obtain various aspect ratios. The uniform ZnO nanorods showed higher transmittance (~89.07%) and haze ratio in the visible wavelength region. We also observed that the large diameters (>300 nm) and average aspect ratio (3–4) of ZnO nanorods favored the light scattering in the longer wavelength region. Therefore, we proposed uniformly deposited ZnO nanorods with high haze ratio for the future low cost and large area amorphous silicon thin film solar cells.     

Enhanced photocatalytic activity of zinc oxide synthesized by calcination of zinc sulfide precursor

ZnO nanoparticles were synthesized by calcination of ZnS precursor in an air atmosphere, in which ZnS had been firstly synthesized through precipitation with sodium sulfide (Na₂S) as the precipitator. Detailed structure and morphology of the samples were characterized by X-ray diffraction, energy dispersive spectroscopy, scanning electron microscopy, and transmission electronic microscopy. Optical properties were examined by UV–vis absorption spectroscopy. Photocatalytic activities of the samples were evaluated by degradation of Reactive Blue 14 (KGL). The results indicate that ZnS precursor converted into pure ZnO stepwise via calcination at a temperature range of 400–800 °C, and pure ZnO can be achieved above 700 °C. ZnO obtained by calcination at 700 °C had an average crystalline size around 45 nm and exhibited the highest photocatalytic activity, degrading KGL by almost 97.1% after 60 min under ultraviolet irradiation, which was superior to that of the directly synthesized and commercial ZnO. The inherent correlation between different samples and their photocatalytic activities was discussed. The phase, crystalline size, specific surface area and oxygen vacancy defects of the samples were proposed to affect their photocatalytic activity.     

Synthesis of ZnO: Ge nanocomposite thin films by plasma gas condensation

In this work, we introduce a new method for the synthesis of Ge nanoparticles embedded ZnO thin films that are considered to be a potential candidate for photovoltaic applications. As opposed to current techniques, for the independent preparation of Ge nanoparticles, we propose using Cluster Deposition Source (CDS), which utilizes gas condensation of sputtered Ge atoms. For the synthesis of ZnO thin film host material conventional sputtering technique is employed. In the proposed technique independently synthesized Ge nanoparticles and ZnO thin films are combined into a composite structure on (100) oriented Si substrates. X-ray diffraction (XRD) patterns of the samples have revealed that Ge nanoparticles preferentially settle on (113) planes on top of the (002) oriented ZnO layer. It is realized that Ge nanoparticles with sizes ranging from 16 nm to 20 nm could be embedded into a well-defined ZnO matrix. In fact, transmission electron microscopy (TEM) studies performed on Ge nanoparticles captured on a Cu grids placed just above the substrate during deposition for about 60 s have manifested that Ge nanoparticles reach to ZnO matrix as clusters composed of particles with sizes of about 7–8 nm and then eventually grow larger due to substrate heating implemented during capping layer deposition. Optical absorption measurements have revealed that Ge nanoparticle inclusion lead to an additional absorption edge at about 2.75 eV along with 3.17 eV edge resulting from ZnO host.     

Structure,luminescence and photocatalytic activity of Mg-doped ZnO nanoparticles prepared by auto combustion method

A series of Zn_1−xMg_xO nanoparticles with x=0 to 0.15 were prepared by auto combustion method using citric acid as the fuel and chelating agent. Structure, luminescence and photocatalytic properties were systematically investigated by means of X-ray diffraction, scanning electron microscopy, photoluminescence spectra, ultraviolet–visible absorbance measurement and photochemical reactions etc. The samples retained hexagonal wurtzite structure of ZnO and single phase below x=0.13, and the sizes of the nanoparticles were 60–70 nm. The photoluminescence spectroscopy demonstrated blue shift of ultraviolet emission with increasing Mg doping concentration. Both optical measurements of the as grown and Mg doped ZnO nanoparticles showed that the optical band gap could be modified from ~3.28 eV to 3.56 eV as the Mg content x increased from 0 to 0.13. The photocatalytic activities of the samples were evaluated by photocatalytic degradation of methyl orange, and the results showed that the doping of Mg into ZnO nanoparticles could enhance photocatalytic activity compared to the undoped ZnO nanoparticles, which was attributed to increased band gap and superior textural properties. In addition, according to the PL and photocatalytic studies, the critical doping content of effective Mg in ZnO is up to 0.09.     

ZnO nanonails: Organometallic synthesis,self-assembly and enhanced hydrogen gas production

We report the rational synthesis and characterizations of defect-rich zinc oxide (ZnO) nanonails that were prepared by organometallic approach and their implementation as an efficient photocatalyst for hydrogen (H₂) generation. The ZnO nanonails were prepared from zinc stearate in n-octadecene that serves as non-coordinating solvent without the presence of any capping agent. Transmission electron microscopy (TEM) studies reveal that the individual triangular prismatic nanonail has an average edge length of 50–70 nm and it appears to have preferred growth orientation along [0001] crystal axis. Intriguingly, this nanonails show oriented-attachment along the flat-basal edge and self-assembled into twinned structure. Such structure is interconnected via a narrow-gap to form symmetrical twinned-like nanonails with truncated tips at both ends. In comparison to ZnO commercial nanopowder, ZnO nanonails show significant enhancement in photocatalytic H₂ gas generation rate of 53.33% under UV light for 5 h. These results demonstrate ZnO nanonails to be a substantial potential photocatalyst for efficient photocatalytic applications.     

Solution-processed annealing-free ZnO nanoparticles for stable inverted organic solar cells

We report the development and application of high-quality zinc oxide nanoparticles (ZnO NPs) processed in air for stable inverted bulk heterojunction solar cells as an electron extraction layer (EEL). The ZnO NPs (average size ∼11 nm) were dispersed in chloroform and stabilized by propylamine (PA). We demonstrated that the ZnO NP dispersion with 4 vol.% of PA as stabilizer can be used in air directly and remains clear up to one month after preparation. Our inverted solar cells consisted of a blade-coated poly(N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole (PCDTBT) and [6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM) (1: 4 by weight) active layer sandwiched between a ZnO electron extraction layer and a MoO₃/Ag anode. All solar cells with ZnO films fabricated in air using PA-stabilized ZnO dispersions prepared within a time window of one month exhibited power conversion efficiencies (PCE) above 4%. In contrast, if the ZnO film was prepared in air using regular un-stabilized ZnO NP dispersion, the PCE would drop to 0.2% due to poor film quality. More interestingly, X-ray photoelectron spectroscopy and nuclear magnetic resonance measurements indicated that the PA ligands were not covalently bonded to ZnO NPs and did not exist in the deposited ZnO films. The spin-cast ZnO thin films (without any thermal treatment) are insoluble in organic solvents and can be directly used as an EEL in solar cells. This feature is beneficial for fabricating organic solar cells on flexible polymer substrates. More importantly, our non-encapsulated inverted solar cells are highly stable with their PCEs remaining unchanged after being stored in air for 50 days.     

Electrical switching and conduction mechanisms of nonvolatile write-once-read-many-times memory devices with ZnO nanoparticles embedded in polyvinylpyrrolidone

We reported on the influence of zinc oxide nanoparticles (ZnO NPs) on the electrical bistable behavior of nonvolatile write-once-read-many-times (WORM) memory devices based on an indium-tin oxide/polyvinylpyrrolidone (PVP):ZnO NPs/aluminum (ITO/PVP:ZnO/Al) structure. The maximum ON/OFF current ratio of the nonvolatile WORM memory devices was approximately 3 × 10³ and the devices remained in the ON state even after the applied voltage was turned off. In addition, reliability studies for response time and once write/continuous read operations of the optimal ZnO NPs concentration are presented. The response times of both rise-time and fall-time were about 3 and 6 μs respectively. The conduction mechanisms of all voltage regions of the device were analyzed by theoretical models and electron trapping in the ZnO NPs of the electron tunneling among a PVP matrix was discussed.     

Combustion synthesis and characterization of NiO nanoparticles

Nickel oxide nanoparticles (NiO NPs) have been prepared by gel-combustion technique using 1:0.5 (N 105) and 1:1 (N 11) weight ratios of oxidizer, nickel nitrate hexahydrate and fuel, cassava starch, respectively. The X-ray diffraction pattern of the samples revealed cubic phase of nickel oxide and the average crystallite size of 28 and 38 nm for N 105 and N 11, respectively, were noted. In comparison to particle size measured using TEM (35 and 60 nm), the average particle size obtained from DLS (250 and 350 nm) was larger for N 105 and N 11, respectively. NiO NPs were found to have indirect band gap (2.98 and 2.3 eV) as revealed by optical spectroscopy. They were tested for energy storage, antimicrobial activity and photocatalytic applications. Electrochemical studies showed NiO NPs had a reversible capacity of 940 and 785 mA h/g for N 105 and N 11, respectively and they retained a capacity of 59% and 47% upto 50 cycles. The antimicrobial activity was tested against two bacterial strains and a fungal strain. The photocatalytic activity was measured for degradation of methylene blue in ultra-violet as well as sunlight. NiO, obtained by using 1:1 oxidizer to fuel ratio, (N 11) exhibited 94% degradation efficiency in sunlight because of a visible light-active band gap (2.3 eV).     

Preparation,characterization and photocatalytic properties of polythiophene-sensitized zinc oxide hybrid nanocomposites

The composites of polythiophene (PT)/zinc oxide (ZnO) nanoparticles with different PT wt%, (2%, 4%, 6%, 10% and 20%), were synthesized by an in situ chemical oxidative polymerization method. Zinc oxide nanoparticles, prepared by polymer pyrolysis method, with average particle size of 30 nm were used as inorganic phase of these composites. The particle size of ZnO powder was measured by transmission electron microscopy (TEM). FTIR measurements and X-ray diffraction analyses showed that PT/ZnO composites were successfully synthesized. Optical properties of the prepared composites were investigated by diffuse reflectance spectroscopy (DRS) that showed a broad peak in the visible region. The morphologies of the obtained composites were studied by scanning electron microscopy (SEM). Also Barrett–Emmett–Teller (BET) technique was used to measure the specific surface area of the samples. The photocatalytic activities of the composites were evaluated by degradation of methyl orange (MO) aqueous solution under visible light (9 W LED lamp) and sunlight irradiation.     

Effect of pH on the properties of electrochemically prepared ZnO thin films

Zinc Oxide (ZnO) thin films have been electrochemically deposited on fluorine doped tin oxide (FTO) coated glass substrates from an aqueous electrolyte. Deposition potential −0.96 V was optimized by cyclic voltammetry experiment for slow scan rate 5 mV/s with moderate agitation of electrolyte. The effect of pH on the electrodeposition of ZnO is studied by cyclic voltammetry, X-ray diffraction (XRD), scanning electron microscopy (SEM), optical spectroscopy and photoelectrochemical I-t transient characteristics. It is revealed that the pH of the electrolyte has significant influence on the surface morphology and structural properties. Highly crystalline ZnO layers with hexagonal crystal structure deposited for all pH of the solutions. A systematic shift observed in the reflections (002) and (101) is correlated with an effective tensile strain developed in the crystal lattice. A remarkable improvement in the crystallinity was noticed in the as-deposited ZnO samples with increasing pH and upon heat treatment. Optical direct band gap ~ 3.26–3.33 eV and transmittance ~70 −80% was measured by optical spectroscopy. PL measurement showed the band edge emission at 375–382 nm and a visible light emission at 410–550 nm. The intensities of emission peaks are found to be affected by the pH of bath. The compact, densely packed and well adherent thin films of ZnO electrodeposited in zinc nitrate bath for pH 2.0, 3.5 and 6.0. The surface morphology has been changed from granular to disc shaped and finally a large hexagonal sheets were obtained with an increase in the pH of bath. Nearly stoichiometric ZnO thin films are electrodeposited at −0.96 V versus Ag/AgCl reference electrode for pH 6.0. The photoelectrochemical (PEC) measurement (I-t transient curve) shows the enhancement in photocurrent with increasing the pH of zinc nitrate solution. After heat treatment the photocurrent is increased by 54%, 98% and 130% in the samples deposited from 2.0, 3.5 and 6.0 pH of the bath. I-V measurements were further confirmed the current enhancement in all samples after heat treatment.