Ion induced controlled modifications in structural and optical properties of indium oxide thin films – studies with 25‐keV Co− and N+ beam implantations

Two sets of indium oxide thin films (~150 nm) grown on quartz substrates using thermal evaporation technique were processed separately with 25‐keV Co^? and N⁺ ions with several fluences ranging from 1.0 × 10¹⁵ to 1.0 × 10¹⁶ ions/cm². The pristine and the ion implanted films were characterized by Rutherford backscattering spectroscopy (RBS), X‐ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV–Vis spectrometry. The RBS spectra reveal signature of only cobalt and nitrogen in accordance to their fluences confirming absence of any contamination arising due to ion implantation. An increase in the average crystallite size (from 13.7 to 15.3 nm) of Co^? ions implanted films was confirmed by XRD. On the other hand, the films implanted with N⁺ ions showed a decrease in the average crystallite size from 20.1 to 13.7 nm. The XRD results were further verified by SEM micrographs. As seen in AFM images, the RMS surface roughness of the samples processed by both ion beams was found to decrease a bit (29.4 to 22.2 nm in Co^? implanted samples and 24.2 to 23.3 nm in N⁺ implanted samples) with increasing fluence. The Tauc's plot deduced from UV–visible spectroscopy showed that the band gap decreases from 3.54 to 3.27 eV in Co^? implanted films and increases from 3.38 to 3.58 eV for films implanted with N⁺ ions. The experimental results suggest that the modifications in structural and optical properties of indium oxide films can be controlled by optimizing the implantation conditions. Copyright © 2017 John Wiley & Sons, Ltd.     

Polystyrene nanoparticles doped with a luminescent europium complex

Polystyrene nanoparticles doped with a luminescent europium complex, Eu(tta)(3)phen, are prepared by miniemulsion polymerization. The influence of the complex on the miniemulsion polymerization is investigated by the systematic variation of the initial concentration of Eu(tta)(3)phen from 2 to 7 wt% relatively to styrene. A maximum doping level of about 2% by weight in the final particles can be achieved. At higher doping levels, destabilization of the miniemulsion leads to a loss of reproducibility with respect to both the degree of conversion and the final Eu content of the particles. Doped nanoparticles of varying diameter, ranging from 19 to 94 nm, are successfully prepared. Steady-state and time-resolved luminescence measurements indicate that the luminescence properties of Eu(tta)(3)phen in the doped latexes are unchanged from those found in THF solution. Aqueous dispersions of the doped particles exhibit characteristic red emission under UV light irradiation. The luminescence intensity increases linearly with Eu(tta)(3)phen content, indicating the absence of self-quenching despite the relatively high local concentrations within the particles.     

A comparison of modifications induced by Li<Superscript>3+</Superscript> and Ag<Superscript>8+</Superscript> ion beams irradiation in poly(lactide-<Emphasis Type="Italic">co</Emphasis>-glycolide) films

Poly(lactide-co-glycolide) (PLGA) films were irradiated by 180 MeV/amu Ag⁸⁺ ions and 50 MeV/amu Li³⁺ ions at different fluences of 5 × 10¹⁰, 5 × 10¹¹ and 1 × 10¹² ions/cm². Modifications of polymer films induced by the swift heavy ions (SHI) irradiation were studied by X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR) and UV–Vis spectroscopy. The dominant effect of the SHI beam irradiation is proposed to be chain scission which leads to breakage of polymer chains, followed by hydrogen abstraction. The results from FTIR spectroscopy showed that the intensity of all peaks of the irradiated samples decreased at high fluence of SHI, suggesting PLGA samples significantly degraded at high SHI fluence. The variation in optical band gap energy and Urbach energy with increasing fluence was calculated from UV–Vis spectroscopy and explained in terms of changes occurring in the polymer matrix. X-ray diffraction patterns also show appreciable changes in PLGA at high fluence. FESEM results revealed that the hydrophilicity of the PLGA surface increased with an increase in ion fluence. In this paper the optical, chemical and structural changes with different fluence rates are discussed.     

Microstructure,dielectric properties and optical band gap control on the photoluminescence behavior of Ba[Zr<Subscript>0.25</Subscript>Ti<Subscript>0.75</Subscript>]O<Subscript>3</Subscript> thin films

Ba[Zr_0.25Ti_0.75]O₃ (BZT) thin films were synthesized by the complex polymerization method and heat treated at 400 °C for different times and at 700 °C for 2 h. These thin films were analyzed by X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy, field emission gun-scanning electron microscopy (FEG-SEM) and atomic force microscopy (AFM), Ultraviolet–visible (UV–vis) absorption spectroscopy, electrical and photoluminescence (PL) measurements. FEG-SEM and AFM micrographs showed that the microstructure and thickness of BZT thin films can be influenced by the processing times. Dielectric constant and dielectric loss of BZT thin films heat treated at 700 °C were approximately 148 and 0.08 at 1 MHz, respectively. UV–vis absorption spectra suggested the presence of intermediary energy levels (shallow and deep holes) within the band gap of BZT thin films. PL behavior was explained through the optical band gap values associated to the visible light emission components.     

UV-degradation effect on optical and surface properties of polystyrene-TiO<Subscript>2</Subscript> nanocomposite film

Thin films of polystyrene and polystyrene-TiO₂ nanocomposite were prepared by spin coating from a polystyrene solution in which TiO₂ nanoparticles were dispersed by mechanical mixing. Thin films of polystyrene (PS) and polystyrene-TiO₂ nanocomposite were exposed to UV irradiation for varied time intervals. The effect of UV radiation on the optical properties, crystallinity, surface energy and degradation of PS-TiO₂ nano-composite has been studied. X-Ray diffraction analysis (XRD), UV-Vis and FTIR spectroscopy, Atomic Force Microscopy (AFM) and contact angle measurement were used to study the induced changes of the properties of the irradiated PS-TiO₂ nanocomposite. Optical band gaps and hydrophilicity in UV-irradiated samples were altered by destruction processes. The optical band gap values were found to reduce from 4.54 eV in pure PS to 4.45 eV for PS-TiO₂ nanocomposite prior to irradiation. This value is further reduced to 3.46 after UV irradiation for 45 h.     

Optical,thermal and microstructural studies of epoxy-CoSO4.7H2O hybrid material

Organic–inorganic polymer hybrid films of epoxy polymer were prepared, using Cobaltous sulfate heptahydrate (CoSO₄.7H₂O) as a filler component, by physical blending method. UV–Vis optical absorption spectra were analyzed to determine optical band gaps (E_g) of the hybrid material. FTIR studies revealed the interaction of inorganic component with molecules of the polymer matrix. Glass transition temperature (T_g) and degradation temperature were determined by DSC. TG analysis showed the improvement in thermal stability of prepared hybrid films. XRD patterns revealed the amorphous nature of the pure epoxy polymer. Additional sharp peaks were seen for higher filler levels (FLs), indicating self formed nanostructures in the material, which was also evident from SEM analysis.     

介孔氧化硅孔径尺寸对Eu(Ⅲ)配合物的影响

分别以十六烷基三甲基溴化铵(CTAB)和聚乙氧基-聚丙氧基-聚乙氧基三嵌段共聚物(P123)为模板剂、正硅酸乙酯(TEOS)为硅源，采用水热法合成了有序介孔分子筛MCM-41和SBA-15。选择Eu(DBM)₃phen为客体，有序介孔氧化硅MCM-41和SBA-15为载体，分别在氯仿中进行分子组装，制备出具有较强发光性能的介孔复合材料Eu(DBM)₃phen/APTES-MCM-41(EAM)和Eu(DBM)₃phen/APTES-SBA-15(EAS)。采用XRD、TEM、N₂吸附-脱附和荧光光谱等对产物的结构与性能进行了分析。结果表明，Eu(DBM)₃phen组装进有序介孔氧化硅的孔道中后，发光纯度提高。而且孔径越小，发光纯度越高。选用较大孔径的SBA-15为载体，在不显著影响发光纯度的同时，可以获得较高的发光强度。     

Photocatalytic Nanocomposite Films Fabricated by Layer‐by‐Layer Self‐assembly of TiO2 Nanoparticles and Lignosulfonates

Photocatalytic multilayer nanocomposite films composed of anatase TiO₂ nanoparticles and lignosulfonates (LS) were fabricated on quartz slides by the layer‐by‐layer (LBL) self‐assembly technique. X‐ray photoelectron spectroscopy (XPS), UV‐vis spectroscopy and atomic force microscopy (AFM) were used to characterize the TiO₂/LS multilayer nanocomposite films. Moreover, the photocatalytic properties (decomposition of methyl orange and bacteria) of multilayer nanocomposite films were investigated. XPS results indicated that the intensities of titanium and sulfur peaks increased with the LBL deposition process. A linear increase in absorbance at 280 nm was found by UV‐Vis spectroscopy, suggesting that stepwise multilayer growth occurs on the substrate and this deposition process is highly reproducible. AFM images showed that quartz slide was completely covered by TiO₂ nanoparticles when a 10‐bilayer multilayer film was formed. The decomposition efficiency of methyl orange by TiO₂/LS multilayer films under the same UV irradiation time increased linearly with the number of TiO₂ layers, and the results of decomposition of bacteria under UV irradiation showed that TiO₂/LS multilayer nanocomposite films exhibited excellent decomposition activity of bacteria (Escherichia coil).     

Enhanced photo-catalytic activity of TiO2 nanostructured thin films under solar light by Sn and Nb co-doping

In this study, preparation of Sn and Nb co-doped TiO₂ dip-coated thin films on glazed porcelain substrates via sol–gel process have been investigated. The effects of co-doping content on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction (XRD), field emission SEM (FE-SEM), high resolution transmission electron microscopy (HR-TEM), and UV–Vis absorption spectroscopy. Surface chemical state of thin films was examined by atomic X-ray photoelectron spectroscopy (XPS). XRD results suggest that adding impurities has a great effect on the crystallinity and particle size of TiO₂. Titania Rutile phase formation in thin film was promoted by Sn⁴⁺ addition but was inhibited by Nb⁵⁺ doping. The prepared co-doped TiO₂ photo-catalyst films showed optical absorption edge in the visible light area and exhibited excellent photo-catalytic ability for degradation of methylene blue (MB) solution under solar irradiation. Comparison with undoped and Sn or Nb-doped TiO₂, codoped TiO₂ shows an obviously higher catalytic activity under solar irradiation.     

微波辅助化学浴快速沉积Eu:YVO4薄膜

应用简单有效的微波辐射辅助化学浴技术快速沉积了Eu:YVO₄纳米颗粒膜. 所沉积的Eu:YVO₄薄膜均匀、密实、镜面. 产物用X射线衍射仪、原子力显微镜、紫外分光光度计和荧光分光光度计进行测试、表征和分析. 结果表明所得Eu:YVO₄薄膜由纳米颗粒组成, 具有高的(200)择优取向, 结晶性良好, 在紫外光激发下具有良好的荧光发射性能.     

High‐Performance Oxygen Sensors Based on EuIII Complex/Polystyrene Composite Nanofibrous Membranes Prepared by Electrospinning

An optical oxygen sensor based on an Eu^III complex/polystyrene (PS) composite nanofibrous membrane is prepared by electrospinning. The emission intensity of [Eu(TTA)₃(phencarz)] (TTA=2‐thenoyltrifluoroacetonate, phencarz=2‐(N‐ethylcarbazolyl‐4)imidazo[4,5‐f]1,10‐phenanthroline) decreases with increasing oxygen concentration, and thus the [Eu(TTA)₃ (phencarz)]/PS composite nanofibrous membranes can be used as an optical oxygen‐sensing material based on emission quenching caused by oxygen. Elemental analysis, UV/Vis absorption spectra, scanning electron microscopy (SEM), fluorescence microscopy, luminescence‐intensity quenching Stern–Volmer plots, and excited‐state decay analysis are used to characterize the obtained oxygen‐sensing materials. A high sensitivity (I_N2/I_O2) of 3.38 and short response and recovery times (t_↓=5.0, t_↑=8.0 s) are obtained. These results are the best values reported for oxygen sensors based on Eu^III complexes. The high surface area‐to‐volume ratio and porous structure of the electrospun nanofibrous membranes are taken to be responsible for the outstanding performance.     

Effect of synthesis parameters on the structural,morphological characteristics,and photocatalytic activity of La2O3 nanoparticles

This study investigates the influence of synthesis processes such as sonication, sol-gel, and microwave on the production of highly crystalline Lanthanum oxide nanoparticles (La₂O₃) employing Lanthanum nitrate and Ammonium hydroxide (NH₄OH) as precursors. X-ray diffraction (XRD), particle size analysis (DLS), Field emission scanning electron microscopy (FESEM), Fourier-transform infrared spectroscopy (FTIR), ultraviolet–visible absorption spectroscopy (UV–Vis), and electrochemical impedance spectroscopy (EIS) were used to examine the most effective processing method and its effects on the nanoparticle characteristics, such as structure, morphology, and optical and electrical behavior. Sonication produces La₂O₃ NPs with a smaller crystalline size, an agglomerated nanorod structure, a higher bandgap, and better electrical responsiveness than sol-gel and microwave techniques. Structural and optical characterization tests discovered this. The photocatalytic degradation activity of cationic Safranin and anionic Congo red dye exhibits degradation efficiency of around 90.13% and 89.66%, respectively.     

Preparation and Properties of Transparent Ultrathin Lanthanide‐Complex Films

Highly transparent ultrathin films (UTFs) based on alternative layer‐by‐layer assembly of Eu‐ and Tb‐based lanthanide complexes (LCs) and Mg–Al‐layered double hydroxide (LDH) nanosheets are reported herein. UV–visible absorption and fluorescence spectroscopy showed an orderly growth of the two types of ultrathin films upon increasing the number of deposition cycles. AFM and SEM measurements indicate that the films feature periodic layered structures as well as uniform surface morphology. Luminescent investigations reveal that (LCs/LDH)_n UTFs can detect Fe³⁺ with relative selectivity and high sensitivity (Stern–Volmer constant K_SV=8.43×10³ L mol^?1); this suggests that (LCs/LDH)_n UTFs could be a promising luminescent probe for selectively sensing Fe³⁺ ion.     

Synthesis and Optical Properties of Europium‐Complex‐Doped Inorganic/Organic Hybrid Materials Built from Oxo–Hydroxo Organotin Nano Building Blocks

Hybrid materials doped with novel europium complexes were synthesized using PMMA‐co‐Sn₁₂Clusters (copolymers from oxohydroxo‐organotin dimethacrylate and methylmethacrylate) as the matrix material. Two types of hybrid materials were obtained: the physically doped product, PMMA‐co‐Sn₁₂Cluster/Eu(TTA)₃phen, and the grafted product, PMMA‐co‐Sn₁₂Cluster‐co‐[EuAA(TTA)₂phen] (TTA=2‐thenoyltrifluoroacetone, phen=phenanthroline and AA=acrylic acid). The hybrid materials exhibited characteristic luminescence of the Eu³⁺ ions, and also showed relative especial optical properties compared with samples just using PMMA as the matrix material. The PMMA‐co‐Sn₁₂Cluster matrix exhibited a high physical doping quantity of [Eu(TTA)₃phen], which can be attributed to the special structure of this kind of hybrid material. GPC (gel‐permeation chromatography), TGA (thermogravimetric analysis), SEM, ¹H NMR, ICP (inductively coupled plasma), ¹¹⁹Sn NMR, FTIR, and diffuse reflectance techniques were employed to characterize the structures and properties of these hybrid materials.     

Self‐Assembly of Azobenzene Derivatives into Organogels and Photoresponsive Liquid Crystals

A new class of coil–rod–coil molecules with an azobenzene core was synthesized. They were found to form robust organogels in several organic solvents. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), FTIR spectroscopy, UV/Vis absorption spectroscopy, ¹H NMR spectroscopy, and X‐ray diffraction (XRD) revealed that in these organogels, the molecules self‐assembled into a nanofiber network with an H‐type aggregation mode under the joint effect of π–π stacking, intermolecular hydrogen bonding, and van der Waals forces. Interestingly, the incorporation of the azobenzene mesogene into the rigid core led to photoisomerizable liquid crystal materials, which exhibited quick responsiveness to light and temperature, along with the trans–cis transition stimulated by UV light and heating.     

Cooperation among N,F and Fe in tri-doped TiO<Subscript>2</Subscript> photocatalyst

TiO₂ photocatalysts tri-doped with N, F and Fe were synthesized by a sol–gel method. The cooperation of N, F and Fe in tri-doped TiO₂ was verified by monitoring NH₃ decomposition, X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and ultraviolet–visible (UV–Vis) absorption spectroscopy, and by the simulation based on the density functional theory (DFT). The results from NH₃ decomposition revealed that the cooperation of N, F and Fe broadened the optical response of TiO₂ to the visible light range and also enhanced the photocatalytic activity of TiO₂ under UV light. The reusability of the tri-doped TiO₂ sample after three cycles under UV and visible light irradiation was very good. XRD patterns and SEM and HRTEM images indicated that the tri-doped sample was nanometric anatase with a small amount of rutile with an average particle size of 18 nm. Tri-doping with N, F and Fe suppressed the phase transition from anatase to rutile and also resulted in some more lattice defects. XPS analysis showed that the N, F and Fe atoms were doped into the TiO₂ lattice. UV–Vis absorption spectra of the tri-doped TiO₂ showed that its optical absorption edge was moved up to 640 nm and its UV absorption was also enhanced. The DFT results confirmed that the cooperation of Fe 3d and N 2p orbits narrowed the band gap of TiO₂ and the F 2p orbit broadened the upper valence bands. The synergistic electron density around N, F and Fe in tri-doped TiO₂ was capable of enhancing the photochemical stability and reusability of TiO₂.     

Unprecedented Charge‐Transfer Complex of Fused Diporphyrin as Near‐Infrared Absorption‐Induced High‐Aspect‐Ratio Nanorods

Charge‐transfer (CT) complexes of near‐infrared absorbing systems have been unknown until now. Consequently, structural similarities between donor and acceptor are rather important to achieve this phenomenon. Herein, we report electron donors such as non‐fused diporphyrin‐anthracene (DP), zinc diporphyrin‐anthracene (ZnDP) and fused zinc diporphyrin‐anthracene (FZnDP) in which FZnDP absorbs in NIR region and permits a CT complex with the electron acceptor, perylene diimide (PDI ) in CHCl₃ exclusively. UV/Vis‐NIR absorption, ¹H NMR, NOESY and powder X‐ray diffraction analysis demonstrated that the CT complex formation occurs by π–π stacking between perylene units in FZnDP and PDI upon mixing together in a 1:1 molar concentration in CHCl₃, unlike non‐fused ZnDP and DP. TEM and AFM images revealed that the CT complex initially forms nanospheres leading to nanorods by diffusion of CH₃OH vapors into the CHCl₃ solution of FZnDP/PDI (1:1 molar ratio). Therefore, these CT nanorods could lead to significant advances in optical, biological and ferroelectric applications.     

Tunable Emissive Lanthanidomesogen Derived from a Room‐Temperature Liquid‐Crystalline Schiff‐Base Ligand

A novel photoluminescent room‐temperature liquid‐crystalline salicylaldimine Schiff base with a short alkoxy substituent and a series of lanthanide(III) complexes of the type [Ln(LH)₃(NO₃)₃] (Ln=La, Pr, Sm, Gd, Tb, Dy; LH=(E)‐5‐(hexyloxy)‐2‐ [{2‐(2‐hydroxyethylamino)ethylimino]methyl}phenol) have been synthesized and characterized by FTIR, ¹H and ¹³C NMR, UV/Vis, and FAB‐MS analyses. The ligand coordinates to the metal ions in its zwitterionic form. The thermal behavior of the compounds was investigated by polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). The ligand exhibits an enantiotropic hexagonal columnar (Col_h) mesophase at room temperature and the complexes show an enantiotropic lamellar columnar (Col_L) phase at around 120 °C with high thermal stability. Based on XRD results, different space‐filling models have been proposed for the ligand and complexes to account for the columnar mesomorphism. The ligand exhibits intense blue emission both in solution and in the condensed state. The most intense emissions were observed for the samarium and terbium complexes, with the samarium complex glowing with a bright‐orange light (ca. 560–644 nm) and the terbium complex emitting green light (ca. 490–622 nm) upon UV irradiation. DFT calculations performed by using the DMol3 program at the BLYP/DNP level of theory revealed a nine‐coordinate structure for the lanthanide complexes.     

Fabrication of Self‐Assembled Tris(1,10‐phenanthroline) ruthenium/12‐Molybdophosphoric Acid Films with Bifunctional Electrocatalytic and Photoluminescent Properties

The thin films containing transition metal complex tris(1,10‐phenanthroline) ruthenium(II) Ru(phen)₃Cl₂ (abbr Ru(phen)₃, phen=1,10‐phenanthroline), and 12‐molybdophosphoric acid [PMo₁₂O₄₀]_3? (abbr PMo₁₂) were fabricated on quartz, silicon and ITO substrates by layer‐by‐layer (LBL) method. The LBL films were characterized by the UV‐vis spectroscopy, X‐ray photoelectron spectroscopy, atomic force microscopy and cyclic voltammetry. The films can catalyze both the reduction of ClO , BrO , IO , and the oxidation of C₂O due to the presence of bifunctional composite, and the redox potentials depend on pH as a result of protonation. The photoluminescence of films were also investigated. The films exhibited photoluminescence arising from π*–t_2g ligand‐to‐metal transition of Ru(phen)₃.     

Ag@Bi2WO6Composites with High Visible‐Light‐Driven Photocatalytic Activities Prepared in UV Light Irradiation

Bi₂WO₆ microstructures were synthesized through hydrothermal process and Ag@Bi₂WO₆ composites were synthesized by simple UV light irradiation for 5 min using Bi₂WO₆ and AgNO₃ as raw materials. Ag@Bi₂WO₆ composites were characterized by X‐ray powder diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), and UV‐Vis absorption spectrum (UV‐Vis). Few Ag deposited on the Bi₂WO₆ leads to an increase in photocatalytic activity, which clearly indicates that the recombination of photogenerated charge carrier between the hybrid orbital of Bi6s and O2p (valence band) to the empty W5d orbital is inhibited greatly in the Ag@Bi₂WO₆ composite. In addition, a few H₂O₂ will greatly enhance photocatalytic activity of Ag@Bi₂WO₆, and the proper reason is discussed.