Improving conversion efficiency of CdS quantum dots-sensitized TiO2 nanotube arrays by doping with Zn and decorating with ZnO nanoparticles

The Zn-doped TiO₂ nanotube arrays (TNTs) decorated with ZnO nanoparticles have been prepared via electrochemical anodization and immersing method. Furthermore, the CdS quantum dots (QDs) were deposited on the prepared Zn-doped TNTs-ZnO thin films by chemical bath deposition (CBD) method to fabricate the CdS QDs-sensitized Zn-doped TNTs-ZnO photoelectrodes. The nanostructure, morphology, optical properties and electrochemical properties of the CdS/Zn-doped TNTs-ZnO photoelectrode with comparison to those of the CdS/TNTs photoelectrodes were investigated. It has been found that the Zn-doped TNTs-ZnO photoelectrodes significantly increased the UV–vis light absorption of the CdS/Zn-doped TNTs-ZnO photoelectrodes and reduced the charge recombination at the surfaces of the CdS/Zn-doped TNTs-ZnO photoelectrodes. As a consequence, when the Zn-doped TNTs-ZnO film was adopted instead of the plain TNTs film, the light-chemical energy conversion efficiency of the CdS/Zn-doped TNTs-ZnO photoelectrode was much improved compared with the CdS/TNTs photoelectrode. A maximum energy conversion efficiency achieved for the CdS/Zn-doped TNTs-ZnO photoelectrode is 3.86%, which is a 17% improvement compared with the maximum energy conversion efficiency of 3.29% achieved for the CdS/TNTs photoelectrodes.     

Engineering of luminescence from Gd2O3:Eu nanophosphors by pulsed laser deposition

Nanostructured Gd₂O₃:Eu³⁺ thin films were prepared by pulsed laser ablation technique. The dependence of structural, morphological and optical properties of these films on photoluminescence was systematically studied by varying the annealing temperature, Eu³⁺ incorporation concentration and laser fluence. The intensity of the XRD peak from (2 2 2) crystal plane was found to increase with annealing temperature in the range 973–1173 K. Films annealed at 1173 K show a preferential growth along (2 2 2) crystal plane of the cubic Gd₂O₃ and enhanced photoluminescence at 612 nm. XRD and Micro-Raman spectra and lattice strain investigations suggest that Eu³⁺ incorporation introduce a strong lattice distortion in Gd₂O₃ matrix. Morphological investigations using atomic force microscopy indicate a strong influence of the annealing process on the surface roughness and particle size. This kind of transparent thin film phosphors may promise for applications in flat-panel displays and X-ray imaging systems.     

Energy transfer between lead sulfide quantum dots in the liquid phase

Förster resonant energy transfer (FRET) from smaller sized PbS Quantum Dots (QDs) to larger sized ones occurs in the liquid phase when adjacent QDs are brought in close proximity by the bridging action of the two SH groups in aromatic or aliphatic dithiols. Signatures of FRET were observed by the lowering of the fluorescence peak corresponding to the smaller particle group and intensification of the peak corresponding to the larger particle group in a mixture of the two in the liquid phase. The suspensions of the two QDs size distributions were mixed in a ratio such that total surface area of the smaller QDs was equal to that of the larger QDs. A 10–13% size deviation in each PbS QDs group also allows this phenomenon to be observed in these samples and is manifested by red-shift and broadening of the fluorescence peak. The ratio of the absorption peak intensity corresponding to the two groups of PbS QDs in the mixture remains the same.     

Size dependent electron transfer from CdTe quantum dots linked to TiO2 thin films in quantum dot sensitized solar cells

In this present study, we demonstrate the size dependent charge transfer from CdTe quantum dots (QDs) into TiO₂ substrate and relate this charge transfer to the actual behavior of a CdTe sensitized solar cell. CdTe QDs was synthesized using mercaptopropionic acid as the capping agent. The conduction band offset for TiO₂ and CdTe QDs indicates thermodynamically favorable band edge positions for smaller QDs for the electron-transfer at the QD–TiO₂ interface. Time-resolved emission studies were carried out for CdTe QD on glass and CdTe QD on TiO₂ substrates. Results on the quenching of QD luminescence, which relates to the transfer kinetics of electrons from the QD to the TiO₂ film, showed that at the smaller QD sizes the transfer kinetics are much more rapid than at the larger sizes. I–V characteristics of quantum dot sensitized solar cells (QDSSC) with different sized QDs were also investigated indicating higher current densities at smaller QD sizes consistent with the charge transfer results. The maximum injection rate constant and photocurrent were obtained for 2.5 nm CdTe QDs. We have been able to construct a solar cell with reasonable characteristics (V_oc = 0.8 V, J_sc = 1 mA cm⁻², FF = 60%, η = 0.5%).     

High luminescence quantum efficiency of green mesophase silicate thin film incorporated with rare earth complex

Mesophase silica thin film doped with in-situ formed binary terbium (Tb) complex was synthesized through a simple one-step evaporation-induced self-assembly method. In this process, the precursors of rare earth complex and surfactant were added into hydrolyzed tetramethoxy-silane (TMOS) together and the inorganic/organic mesophase thin film was formed after spin coating. The mesophase structure was characterized as a 2D-hexagonal structure by X-ray diffraction (XRD) analysis. The excitation spectra (λ_em = 544 nm) and emission spectra (λ_ex = 315 nm) indicated that the binary complex, Tb(SA)₃, formed in-situ during the formation of the film. Under the UV excitation, the mesophase silica thin film showed bright and consistent green luminescence. The luminescence quantum efficiency of the hybrid thin film was confirmed to be 35.2%.     

Effect of Al dopants on the structural,optical and gas sensing properties of spray-deposited ZnO thin films

Undoped and Al-doped ZnO thin films were deposited on glass substrates by the spray pyrolysis method. The structural, morphological and optical properties of these films were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV–Vis spectroscopy, photoluminescence (PL) and photoconductivity (PC) measurements, respectively. XRD analyses confirm that the films are polycrystalline zinc oxide with the hexagonal wurtzite structure, and the crystallite size has been found to be in the range 20–40 nm. SEM and AFM analyses reveal that the films have continuous surface without visible holes or faulty zones, and the surface roughness decreases on Al doping. The Al-doped films have been found to be highly transparent (>85%) and show normal dispersion behavior in the wavelength range 450–700 nm. The doped films show only ultraviolet emission and are found to be highly photosensitive. Among all the films examined, at 300 °C the 1.0 at% Al-doped film shows the selective high response (98.2%) to 100 ppm acetone concentration over to methanol, ethanol, propan-2-ol, formaldehyde and hydrogen.     

Influence of the film thickness on structural and optical properties of CdTe thin films electrodeposited on stainless steel substrates

CdTe thin films of different thicknesses were deposited by electrodeposition on stainless steel substrates (SS). The dependence of structural and optical properties on film thickness was evaluated for thicknesses in the range 0.17–1.5 μm. When the film is very thin the crystallites lack preferred orientation, however, thicker films showed preference for (111) plane. The results show that structural parameters such as crystallite size, lattice constant, dislocation density and strain show a noticeable dependence on film thickness, however, the variation is significant only when the film thickness is below 0.8 μm. The films were successfully transferred on to glass substrates for optical studies. Optical parameter such as absorption coefficient (α), band gap (E_g), refractive index (n), extinction coefficient (k_e), real (?_r) and imaginary (?_i) parts of the dielectric constant were studied. The results indicate that all the optical parameters strongly depend on film thickness.     

Effect of Zr (IV) doping on the optical properties of sol–gel based nanostructured indium oxide films on glass

Zr (IV) doped indium oxide thin films (55 nm) were deposited onto pure silica glass by the sol–gel dip coating technique utilizing the precursors of 6 wt% equivalent oxide content. Three different Zr (IV) oxide (ZrO₂) dopant concentrations (5.0, 10.0 and 15.0 wt% w.r.t. total oxides) were chosen. XRD patterns suggested the films were of distinct cubic symmetry of In₂O₃. Nanostructured surface feature was revealed by FESEM images. Average cluster size decreased with increasing dopant concentration as evidenced from TEM study. Blue shift of band gap and UV cut off wavelength (lambda-50) occurred with increase in dopant concentration. The refractive index gradually increased with doping. Baking atmosphere plays an important role in tailoring the refractive index (RI) of the films and relatively high RI was obtained in the case of baking in pure oxygen. Presence of both free and bound excitons was detected by the photoluminescence (PL) study. The 5 wt% doped film exhibited relatively high PL intensity at 380 nm responsible for free exciton. The PL emissions gradually quenched with increase in dopant concentration. Similar behaviour was also observed when the film was baked in pure oxygen atmosphere.     

Electrochromic performance of mixed V2O5–MoO3 thin films synthesized by pulsed spray pyrolysis technique

Mixed V₂O₅–MoO₃ thin films were deposited onto the glass and fluorine doped tin oxide (FTO) coated glass substrates, at 400 °C by pulsed spray pyrolysis technique (PSPT). Equimolar vanadium chloride (VCl₃) and ammonium molybdate aqueous solutions were mixed together in volume proportions (5–15% molybdenum) and used as a precursor solution for the deposition of mixed V₂O₅–MoO₃ thin films. The structural, morphological, optical and electrochromic properties of the films deposited at different Mo concentrations were studied. With increase in the percentage of Mo the peaks belonging to tetragonal phase of V₂O₅ eventually disappear and the (1 0 1) orthorhombic V₂O₅ phase is observed. Scanning electron microscopy (SEM) shows micro thread like reticulated morphology. The optical band gap energy varied over 2.91–2.85 eV. All the films exhibited cathodic electrochromism in lithium containing electrolyte (0.5 M LiClO₄ + propylene carbonate (PC)). The highest coloration efficiency (CE) for the V₂O₅ film with 15% MoO₃ mixing was found 35.27 cm² C⁻¹.     

Chemosensory rhodamine-immobilized mesoporous silica material for extracting mercury ion in water with improved sensitivity

Mesoporous silica material, SBA-15, is an excellent support for constructing fluorescent surface sensor. In this paper, we reported a three-step surface reaction involved strategy to construct efficient fluorescent surface sensor for mercury ion by clicking rhodamine fluoroionophores onto APES-functionalized SBA-15, which is fully characterized by IR spectra, TGA analysis, elemental analysis, nitrogen adsorption experiment and TEM. Our experimental results indicated that such a strategy exhibits an obviously higher loading efficiency within SBA-15 than a previously reported strategy. The Hg²⁺ extracting efficiency for SBAIR was found to be enhanced (ca. 89%). In addition to the high selectivity, the current chemosensor shows improved sensitivity and can respond to Hg²⁺ as low as ppb level (1.0 × 10⁻⁸ M, 2 ppb) in water.     

Luminescent graphene quantum dots from oxidized multi-walled carbon nanotubes

Fluorescent nano-graphene quantum dots (GQD) were isolated from oxidized carbon nanotube suspension with the aid of cysteamine. The oxidized GQD were thiol functionalized with cysteamine in presence of dicyclohexylcarbodiimide as coupling agent. The GQD chemistry and morphology were characterized by means of X-ray photoelectron spectroscopy and atomic force microscopy. The thiolated graphene quantum dots exhibit an intense luminescence (quantum yield around 10%) in the visible range with an excitation wavelength-dependent fluorescence.     

Cu2O nanorod thin films prepared by CBD method with CTAB: Substrate effect,deposition mechanism and photoelectrochemical properties

Cuprous oxide (Cu₂O) films with different nanostructures are deposited on different substrates of fluorine-doped SnO₂ (FTO) glass, Cu and Ti foil respectively by using chemical bath deposition (CBD) technique with the presence of cetyltrimethylammonium bromide (CTAB). The samples are characterized by X-ray diffractmeter, scanning electron microscopy and UV–vis diffuse reflectance spectroscopy. The results show that the prepared Cu₂O films are composed of nanorod arrays when there is CTAB in reaction system. Without CTAB, Cu₂O films with nanospheres are formed. The concentration of CTAB is crucial for the controllable synthesis of nanorod structured Cu₂O films with different length to diameter ratio and nanorod array density is dependent on both substrates and CTAB. A possible mechanism for the formation of Cu₂O nanorods is discussed. Additionally, the UV–vis absorption property for Cu₂O nanorods is much better than that for nanospheres. The photovoltage produced under visible light for Cu₂O nanorod films is higher than that for the nanospheres. Although Cu₂O nanorods on Ti foil can absorb the most visible light, those on Cu foil demonstrate better and more stable photoelectrochemical property than those on any other substrates. This study may be extremely useful for Cu₂O based device with nanostructures.     

Film morphology modification in ion-assisted glancing angle deposition

Porous structured films grown with the glancing angle deposition technique have been widely studied for thin film optical device applications. We report the use of ion assistance to modify the structural and optical properties of porous silicon dioxide and titanium dioxide columnar thin films grown at deposition angles of 70° and 85°. Optical characterization studies show that tilted columnar structures will undergo an increase in tilt angle and film density with increasing ion dose. These two trends contrast with unassisted films where film density and column tilt angle are primarily controlled by the deposition angle. Thus, a regime of film structures simultaneously exhibiting high film density and large column tilt angle is enabled by incorporating an ion-assisted process. The phisweep substrate motion algorithm for minimizing columnar anisotropy used in conjunction with ion-assisted deposition provides additional control over film morphology and expands the utility of this modified fabrication process.     

White-emitting phosphors Ca6La2Na2(PO4)6F2:Dy and luminescence enhancement through Ce → Dy energy transfer

Ce³⁺ and Dy³⁺ activated fluoro-apatite Ca₆La₂Na₂(PO₄)₆F₂ with chemical formulas Ca₆La_2−xLn_xNa₂(PO₄)₆F₂ (Ln = Ce³⁺, Dy³⁺) were prepared by a solid state reaction technique at high temperature. The vacuum-ultraviolet (VUV) and ultraviolet (UV) spectroscopic properties are investigated. The results indicate that Ce³⁺ ions show the lowest 5d excitation band at ∼305 nm and a broad emission band centered at ∼345 nm. Dy³⁺ ions exhibit intense absorption at VUV and UV range. White-emitting under 172 nm excitation is obtained based on two dominant emissions from Dy³⁺ ions centered at 480 and 577 nm. In addition, the energy transfer from Ce³⁺ to Dy³⁺ in the co-doped samples are observed and discussed.     

Cyclopentadithiophene–naphthalenediimide polymers; synthesis,characterisation, and n-type semiconducting properties in field-effect transistors and photovoltaic devices

The synthesis, characterisation, and device performance of a series of cyclopentadithiophene (CPDT)-naphthalenediimide (NDI) donor-acceptor-donor (D-A-D) polymers is reported. The monomers with various alkyl chains are synthesised via direct arylation using palladium complex catalyst. The monomers are then polymerised by oxidative polymerisation using FeCl₃ to provide high molecular weight polymers (M_n = 21,800–76,000). The polymer films show deep-red absorption including near-infrared region up to 1100 nm to give optical bandgap of approximately 1.16 eV. The polymers exhibit only n-type semiconducting properties giving the highest electron mobility of 9 × 10^-3 cm² V⁻¹ s⁻¹ in organic field-effect transistors (OFETs). Organic photovoltaic (OPV) devices are fabricated from solutions of the polymers as acceptors and poly(3-hexylthiophene) (P3HT) as a donor.     

Characteristics of n-Cd0.9 Zn0.1S/p-CdTe heterojunctions

CdTe thin films were prepared by thermal evaporation under a vacuum of 10⁻⁶ Torr and with a deposition rate of about 60 nm/min. X-ray diffraction studies of the as-deposited films revealed polycrystalline films with cubic structure. The effect of heat treatment with or without CdCl₂ enhances the grain size and improves the crystallinity of the films. Moreover, the activation energy decreases upon heat treatment with or without CdCl₂ for CdTe thin films. The optical spectra of CdTe films show interference oscillations indicating the good optical quality of these films. The calculated energy gap decreases with or without CdCl₂ treatments. The current-voltage and capacitance-voltage characteristics for dark and illuminated three junction cells are measured. By analysing these measurements the different junction parameters are obtained and the effect of CdCl₂ treatment on the performance of the heterojunctions is investigated.     

Temperature dependence of the band gap, refractive index and single-oscillator parameters of amorphous indium selenide thin films

InSe thin films are obtained by evaporating InSe crystal onto ultrasonically cleaned glass substrates under pressure of 10⁻⁵ Torr. The structural and compositional analysis revealed that these films are of amorphous nature and are atomically composed of 51% In and 49% Se. The reflectance and transmittance of the films are measured at various temperatures (300–450 K) in the incident photon energy range of 1.1–2.1 eV. The direct allowed transitions band gap – calculated at various temperatures – show a linear dependence on temperature. The absolute zero value band gap and the rate of change of the band gap with temperature are found to be (1.62 ± 0.01) eV and −(4.27 ± 0.02) × 10⁻⁴ eV/K, respectively. The room temperature refractive index is estimated from the transmittance spectrum. The later analysis allowed the identification of the static refractive index, static dielectric constant, oscillator strength and oscillator energy.     

Structural and optical properties of CdS thin films grown by chemical bath deposition

Cubic cadmium sulphide (CdS) thin films with (111) preferential orientation were prepared by chemical bath deposition (CBD) technique, using the reaction between NH₄OH, CdSO₄ and CS(NH₂)₂. The films properties have been investigated as a function of bath temperature and deposition time. Structural properties of the obtained films were studied by X-ray diffraction analysis. The structural parameters such as crystallite size have been evaluated. The transmission spectra, recorded in the UV visible range reveal a relatively high transmission coefficient (70%) in the obtained films. The transmittance data analysis indicates that the optical band gap is closely related to the deposition conditions, a direct band gap ranging from 2.0 eV to 2.34 eV was deduced. The electrical characterization shows that CdS films' dark conductivities can be controlled either by the deposition time or the bath temperature.     

Sensitized monomer fluorescence and excitation energy transfer in perylene-doped phenanthrene in crystalline and in polymer matrix

Sensitized monomer fluorescence and excitation energy transfer in crystalline and spin cast polymer films was investigated at room temperature. The fluorescence spectra of perylene doped phenanthrene reveals the characteristic monomeric emission of perylene and partial quenching of phenanthrene emission. The excimer formation of perylene is not observed in mixed crystalline luminophors and in spin cast films of the phenanthrene luminophors. The observed quenching of phenanthrene emission indicates the excitation energy transfer from phenanthrene to perylene in crystalline as well as in polymer matrix. Energy transfer is not observed in the experiments when phenanthrene and perylene were physically mixed where the components exist separately. The overlap between the excitation spectrum of perylene and emission spectrum of the phenanthrene supports the fact that the perylene molecules accept the excitation energy from phenanthrene. The energy transfer was found to depend upon the perylene concentration.     

Controlled self-assembly of PbS nanoparticles into macrostar-like hierarchical structures

The synthesis of macrostar-like PbS hierarchical structures by a simple hydrothermal method at 180 °C for 24 h is proven successful with the assistance of a new surfactant called tetrabutylammonium bromide (TBAB). The as-obtained product is characterized by means of X-ray powder diffraction, field emission scanning electron microscopy, energy dispersive spectrometry, high resolution transmission electron microscopy, and selected area electron diffraction. The presence of TBAB and NaF plays an important role in the formation of PbS macrostructures. Ostwald-ripening-assisted oriented attachment is believed to play a key role in the growth behavior of novel 3D structures. As such, a possible self-assembly mechanism is proposed to explain the formation of the said structures. The present study aims to introduce new insights into understanding the formation process of such unique hierarchical superstructures.