Due to their high light absorption, size dependent bandgap and low material usage and low cost of fabrication, quantum
dots (QDs) are a close second to the conventionally used dyes for the dye-sensitised solar cells (DSCs). TiCl4 treatment
is one of the typical methods used to treat the anode or the working electrode of DSCs for performance improvement. In
this work, the effect of TiCl4 treatment on the performance of CdSe/CdS-sensitised solar cells was studied. The devices
made without TiCl4 treatment, perform with a moderate 1.83% efficiency under AM1.5, 1 sun illumination conditions. In
contrast, TiCl4 treated working electrodes helps to enhance the cell efficiency to 3.98%, mainly from a higher
photocurrent density (15.4 mAcm-2) and fill factor (0.51). Higher loading of the quantum dots in the working electrode
and passivation effect due to TiCl4 treatment are believed to be responsible performance improvement.
The strong light absorbing Cu2ZnSnS4 (CZTS) nanocrystals are interesting material in photovoltaic applications owing to the abundance and non-toxicity of the material. The optoelectronic property of CZTS light absorber depends on the size of nanocrystals which confines the electronic states within it. In the complex colloidal medium it is very difficult to predict the size of the particles by only theoretical calculations. However, suitable chemical approach is able to tune the size of the particles by adjusting the chemical potential of the medium for different sizes of CZTS nanocrystal formation. Here, we reported the size control of CZTS nanocrystals which were made by a hot-injection method using organic ligands based colloidal medium. The influence of solvent systems, within following five pure and mixing solvent systems: Oleylamine, 1-Octadecene + TOPO, mixture of Oleylamine:Oleicacid (1:1,v/v%), Oleicacid + TOPO and Oleylamine:Oleicacid (1:1,v/v%) + TOPO , and composition of metal precursors were studied. The final CZTS nanoparticles showed wurtzite crystal structures, and size of the particles can be tuned through different combination ratio of metal precursors. Our results indicate that metal precursor composition ratio has a pivotal role to tune the optoelectronic properties of CZTS nanocrystals for the photovoltaic applications.
The performance of dye-sensitized solar cells (DSC) based on the TiO2 film composed of 3 nm particles and mixtures of
3 nm and 400 nm or 25 nm particles synthesized by spray pyrolysis deposition has been investigated. An energy
conversion efficiency of 8.44% (under the illumination of 100 mW/cm2, AM 1.5) has been achieved with the DSC based
on the nanocrystalline TiO2 film consisting of 3 nm and 25 nm particles with a ratio of 3:4 by weight. The maximum
incident photo-to-current conversion efficiency (IPCE) of the cell is 0.91, which is much higher than the maximum IPCE
of the photoelectrode composed of either only 3 nm or the mixture of 3 nm and 400 nm particles (with the same ratio by
weight) over the visible spectrum. SEM images show the formation of clusters in the TiO2 film containing 25 nm
particles. It is proposed that the clusters are responsible for the high IPCE by increasing the light harvesting efficiency
through enhanced light scattering and facilitating the electron transport of the DSC.
Molecular-resolved real-space images of self-assembled structures of the conductive polymer regioregular poly(3-
hexylthiophene) (rrP3HT) on single-walled carbon nanotubes (SWNT) were obtained using scanning tunneling
microscopy (STM). The STM images revealed that the adsorbed polymer typically formed a 10 nm thick coating on
SWNT's. This is in agreement with transmission electron microscopy (TEM) results for drop-cast composite films that
provided strong evidence that SWNTs were isolated in a polymer matrix and coated with rrP3HT multilayers. A 10 nm
thick deposit corresponds to a coating of ~25 layers of polymer on SWNT, assuming that π-π interactions between
rrP3HT layers determine deposition and that the underlying SWNT directs the polymer self-assembly process. STM
measurements of adsorbed monolayers and multilayers of rrP3HT on SWNT surfaces were compared to rrP3HT
monolayer and multilayer deposition on highly ordered pyrolytic graphite (HOPG) surfaces. The average inter-lamellar
distances of adsorbed polymer was greater for both rrP3HT monolayer and multilayer films adsorbed onto the curved
surfaces of SWNTs than on the flat surfaces of HOPG samples. Analysis of STM images yielded the interchain spacings
of adsorbed macromolecules, dcc = 1.55 - 1.68 ± 0.02 nm. The polymer was observed to wrap around some SWNTs at an
angle with respect to the SWNT long-axis, which indicated that the rrP3HT self-assembly is hierarchical. The conductive
polymer's deposition appears to occur with epitaxy and is directed by the underlying SWNT chiral structure.
A detailed study of poly(alkylthiophene) self-assembly and organization on single-walled carbon nanotubes (SWNTs) is presented. Experimental evidence for self-assembly and organization of regioregular poly(3-hexyl thiophene) (rrP3HT) on single-walled carbon nanotubes was obtained using scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). TEM images of drop-cast rrP3HT/SWNT composites displayed strong evidence that SWNTs were isolated from each other in a polymer matrix and coated with between 1-3 layers rrP3HT. STM measurements of adsorbed monolayers of rrP3HT on SWNT surfaces were compared to rrP3HT monolayer deposition on highly ordered pyrolytic graphite (HOPG) surfaces. The results show that average inter-lamellar distances of adsorbed polymer are greater for rrP3HT monolayers adsorbed onto the curved surfaces of SWNTs than on the flat surfaces of HOPG samples. Analysis of STM images yielded the chiral angles at which the thiophene polymer chains wrap around individual carbon nanotubes (41-48° with respect to nanotube axis) while the interchain spacings of adsorbed macromolecules was 1.68 ± 0.02 nm. Comparisons between the native polymer deposited on graphite and the composite structure confirmed that the presence of carbon nanotubes in rrP3HT produces a material with a high degree of order at the molecular level. This high level of order and close coupling of the two components of the composite are prerequisites for its use as the active layer of an organic photovoltaic.
We report a naturally grown stripe structure with a nanometer scale wavelength in REBa2Cu3O7-δ (RE = Sm and Eu) superconductors investigated with scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). Such a periodic array was unveiled owning to the 3 dimensionally spatial oscillation of RE and Ba around the stoichiometric ratio. The study displayed that novel nanostripes function as robust pinning sites and effectively enhance the peak effect and the irreversibility line at 77K. This illustrates an approach to fabricate high performance REBa2Cu3O7-δ superconductors for application in liquid nitrogen temperature.
This paper implements modification of tungsten oxide film using ion implantation and a physical characterization of the film. The film was implanted with nitrogen at energies between 10 keV and 40 keV and ion dose range 1014−1016 cm-2. The surface morphology of the film after implantation has been modified as observed using electron microscopy. The transmittance of the film was found to decrease with increasing implantation energy and ion dose as measured using conventional spectrophotometer. Depth profile of nitrogen was analyzed using Secondary Ion Mass Spectroscopy (SIMS) and found a peak of nitrogen across the depth of the implanted layer. The amount of nitrogen was found to increase with increasing ion dose and energy. From electron diffraction a broader diffraction rings were revealed from both the implanted and un-implanted layers, indicating that the crystalline properties of the tungsten oxide film after ion implantation remains the same.
Diamond-like carbon is a promising material for MEMS and opto-electronic systems applications. There is a notion that the hybridised sp3 (diamond-like) fraction controls the mechanical properties and the sp2 fraction (graphite-like) determines the electro-optical properties. We investigated amorphous hydrogenated diamond-like carbon (a-C:H) films synthesised using an inductively coupled hydrocarbon plasma reactor under varying bias. The films were characterised using UV Raman, X-ray C1s photoelectron, N-IR spectroscopy, scanning probe microscopy (SPM) and nano-indentation measurements. We found that all examined samples displayed essentially the same amount of the sp3 constituent, whereas the configuration of the sp2 fraction was different. The sp2 fraction of both aromatic rings and olefinic chains in examined films. We found that Tauc gap Et, was controlled by the perturbation of the π tail states of the sp2 fraction. The Tauc gap Et, was determined by N-IR and surface conduction band Eoi, measured by SPM changed inversely with an increase of bias. Results obtained using nanoindentation measurements show that mechanical properties such as hardness and Young's modulus increased with an increase of bias for all films studied. These results indicate that mechanical properties of a-C:H films (hardness and Young's modulus) not only controlled by the amount of the sp3 bonding but also are determined by the degree of the sp2 bonding arrangement.
We studied composites of single walled carbon nanotubes and poly(3hexylthiophene) by optical absorption, X-ray diffraction and transmission electron and scanning tunneling microscopy. Dispersing single walled carbon nanotubes in poly(3hexylthiophene) leads to sharpening of vibronic structure and enhanced optical absorbance near the band edge. We show that the enhanced order in the polymer is due to templating of the polymer chains by the surface of the carbon
nanotubes leading to increased electronic delocalization.
A new atmospheric pressure plasma electrolytic process has been developed for the deposition of TiO2 crystalline thin films on metal substrate. Contrary to the other deposition techniques, the process occurs in a liquid precursor, composed of titanium tetraisopropoxide and absolute ethanol. A plasma discharge is created and confined around the cathode in a superheated vapour sheath surrounded by the liquid phase, inducing the production of a thin TiO2 coating at the surface of the cathode. Because of the flexibility of the operating parameters, this technology allows the rapid deposition of thin films with a wide range of structural and physical properties. This process enables therefore the production of nanocrystalline titania films with adjustable morphology and structure (anatase, rutile) by adjusting the operating voltage, current intensity, the treatment time and calcination temperature. The analysis of the structure and composition of these TiO2 coatings have been carried out by Scanning Electron Microscopy, Transmission Electron Microscopy, Raman spectroscopy, X-ray Photoelectron Spectroscopy and X-Ray Diffraction. A thorough study has been performed to understand the influence of the operating parameters on the properties and structure of the coatings.
We report the influence of nitrogen implantation and annealing on the microstructures and photocatalytic properties of a nanostructured titania (TiO2) film. Titania samples were implanted at 40 keV and ion dose range of 1016/cm2 to 4×1016/cm2. From X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses it was found that the anatase phase of titania predominated with small amount of brookite, and the structure was stable at annealing temperatures up to 973 K. The samples showed narrower XRD peaks corresponding to larger mean-grain sizes comparing to the un-implanted titania samples. The SIMS (secondary ion mass spectroscopy) nitrogen depth profile showed a maximum nitrogen concentration at about 70 nm beneath the film surface. The absorption edge of the titania samples as measured using spectrophotometer was found to shift toward longer wavelengths with the increase of ion dose. The experiments of photodegradation of phenol were performed under a UV illumination for the N-implanted titania film which exhibited improved photocatalytic properties with the increase of annealing temperature.
Gallium nitride (GaN) thin films were grown by laser induced molecular beam epitaxy (LIMBE). Their microstructures were studied by transmission electron microscopy (TEM). Threading dislocations with Burgers vectors of 1/3<1120>, 1/3<1123> and [0001] were observed as common linear defects with predominantly the first type. Additionally, nano-structured planar defects as called domain boundaries were found. Convergent beam electron diffraction (CBED) technique coupled with chemical and cathodoluminescence measurements was employed to characterize the nano-structured domains, indicating that a domain is of Ga-polarity with respect to the adjacent matrix which is of N-polarity. It was found that experimental parameters such as N/Ga ratio were closely associated with the development of domains as well as the surface morphology. High-resolution transmission electron microscopy (HRTEM) results indicate that IDBs have Ga-N bonds between domains and the adjacent matrix without displacements along the c-axis in the basal planes. Upon the determination of the polar property of a thin GaN film and the optimization of experimental conditions, the nano-structured GaN films can be modified and controlled by changing substrate and pre-growing an AlGaN layer and a GaN buffer layer.
Voltage-time curves, concentration profiles and surface concentration of lithium for the electrochromic process at WO3 electrodes have been calculated using a model based on constant current charge injection into electrochromic WO3. The simulated data agree well with the experimental data for both sol-gel and sputter deposited WO3 films. Parameters such as diffusion coefficient, series resistance and ion mobility can be estimated from theoretical fitting to the experimental data. The results are comparable to those obtained by the AC impedance measurements. The model predicts a higher concentration of Li+ ions in the region near the electrolyte/WO3 interface than in the region far from the interface. For higher diffusion coefficients, a more homogeneous lithium distribution is established in the film at the conclusion of the coloration part of the cycle. This result has significant implications for the long term testing of electrochromic devices, as testing to reflect real device conditions should ensure that bleaching starts when the charge distribution in the device is the same as in a window which has been colored for several hours. It is well known that LixWO3 is not reversible for x greater than 0.4. The contours of diffusion coefficient in charge density-current density plane obtained from the model show that for a given current density a lower diffusion coefficient corresponds to a smaller allowable amount of charge injection for a reversible cycle, while for a given diffusion coefficient a smaller current density allows a larger amount of charge injection. This gives a quantitative way to determine appropriate operational limits for electrochromic devices.
The manufacturing and operation of window size (30 cm by 90 cm) electrochromic devices is described. Both the electrochromic electrode (WO3) and the counter electrode (V2O5) were deposited by sol-gel method. Electrochromic measurements were performed on both electrodes and the complete device to correlate device performance to fabrication conditions. The paper describes the affects of temperature on the switching characteristics of electrochromic window. The devices were tested in the temperature range between 10 degrees Celsius and 50 degrees Celsius. The switching algorithm described in this paper ensures identical optical performance of electrochromic device in the wide range of temperatures. The algorithm is based on the charge control and does not require monitoring of device transmittance.
The dispersion relation of optical constants of sol-gel deposited hydrated tungsten oxide films have been measured using spectroscopic ellipsometry. The films were deposited on glass substrates from a tungsten butoxide precursor solution using a dip-coating technique and fired a t three different temperatures, 200 degree(s)C, 300 degree(s)C, and 400 degree(s)C. Ellipsometric measurements at 7 different angles of incidence and over the range 1.5-5 eV have been made for each of the films. The amorphous semiconductor dispersion relation proposed by Forouhi and Bloomer was used to model the tungsten oxide optical constants and to fit the measured ellipsometric angles to determine the parameters in the model. the refractive index and extinction coefficient have been found using this procedure. Computer simulations of transmittance of the films, based on the optical constants obtained from the ellipsometric measurements and the fitting procedure, have been compared to the measured spectra. This comparison confirms that the optical constants found from ellipsometry describe the system accurately. The effect of increasing the annealing temperature of the films on the optical parameters is also discussed. In particular, changes are observed in the optical energy gap and film thickness. The reasons for these variations is discussed in terms of the microstructure of the films.
Electrochromism is sol-gel deposited TiO2 films and films containing TiO2 and WO3 has been observed. The films are deposited by dip-coating from a precursor containing titanium isopropoxide in ethanol or titanium propoxide in ethanol, and after deposition the films are heat treated to between 250 degree(s)C and 300 degree(s)C. The films do not show any signs of crystallinity. However substantial coloration is observed using Li+ ions in a non-aqueous electrolyte, both in pure TiO2 films and in mixed metal oxide films (WO3:TiO2), although the voltage required to produce coloration is different in the two cases. Results will be presented detailing the optical switching and charge transport properties of the films during cyclic voltammetry. These results will be used to compare the performance of the TiO2 films with other electrochromics. The TiO2 and mixed metal films all color cathodically, and the colored state is a neutral greyish color for TiO2, while the bleached state is transparent and colorless, Results on coloration efficiency and the stability under repeated electrochemical cycling will also be presented. The neutral color of the TiO2 films and mixed-metal films means that electrochromic windows based on TiO2 may have significant advantages over WO3-based windows. A detailed analysis of the optical properties of the colored state of the films will be presented. The dynamics of coloration for these films is also under investigation, and preliminary results will be presented.
We discuss the preparation and performance of various electrochromic devices based on sol- gel deposited thin films. The films are deposited by dip-coating from alcohol-based sol-gel precursor solutions and the process is well suited to scaling up to large areas for window production. The coloration and bleaching performance of the devices is compared with the performance of individual films colored in liquid electrolytes, as well as with devices deposited using sputtered and evaporated films. Devices are based on sol-gel deposited tungsten oxide thin films which forms the active electrode. A range of counter-electrode materials have been tested, including sol-gel deposited vanadium pentoxide and titania films. Various ion conductors have been tested with these films, including simple, doped PEO and hartolyte, as well as a range of other polymers and inorganic ion conductors. Results will be presented showing the optical switching performance of the devices and comparing the performance of the devices with other device configurations. Initial results show that the sol- gel-based devices exhibit good switching performance, but the devices are sensitive to the details of the precursor solution used. Long term switching performance is an important issue in window applications, and the behavior of the sol-gel deposited films under repeated cycling will also be discussed, in particular a significant difference between the performance in liquid electrolytes and solid-state devices.
Tungsten oxide thin films prepared by a dip-coating process show great promise as the electrochromic layer in optically switchable windows. Current models describe the electrochemical response of electrochromic evaporated or anodized WO3 thin films, using conventional chronoamperometric theory applied to a two-dimensional electrode. Here, we place emphasis on electrochemical ion diffusion in and through a non-two-dimensional thin- film electrode using a liquid electrolyte, in order to characterize the current-time (i-t) and current-voltage response. In particular, these characteristics can be related to the thickness, surface roughness and microstructure of the film using fractal theory. Complimentary microstructural analyses of these films are carried out using electron and atomic force microscopic techniques, with particular attention focussed on the effects of ion intercalation on the microstructure of sol-gel deposited thin films.
Thin films produced by dip-coating from tungsten alkoxide solutions are of interest for large area electrochromic (switchable) window coatings. The window systems consist, in part, of a layer of tungsten oxide (WO3) on a layer of indium tin oxide (ITO) on glass substrate. Sol-gel processing has several advantages over other preparation techniques. However, there is the possibility of hydrocarbon residue within the films. Such carbon may restrict the electrochromic performance of the films. Rutherford backscattering spectroscopy (RBS) has been used for determining elemental composition and depth profiles in these film structures. The spectra confirm that sol-gel samples contain a substantial level of a light element, such as carbon. Auger electron spectroscopy supports the estimate obtained for the carbon content. The residual carbon can, however, be burnt out by firing at > 500 degree(s)C. Under certain conditions, a sub-layering is seen in the depth profiles.
Electrochromic tungsten oxide thin films produced by dip-coating from a sol-gel solution are of interest for large area electrochromic window applications. The influence of the sol-gel formulation and the subsequent processing of the film required to produce uniform WO3 films are discussed together with the effects of the dipping and processing parameters on the structure, optical properties, and electrochemical behavior of the films. The electrochemical behavior of the films has been studied using cyclic voltammetry. Electrolyte solutions, with different cations for insertion into the WO3 layers, have been used in this work, and the resultant coloration of the films studied using spectrophotometry. Both colored and uncolored films have been studied using Rutherford backscattering spectrometry (RBS) and scanning electron microscopy (SEM). The sol-gel processing steps are shown to have a significant influence on the film microstructure and therefore the electrochemical coloration behavior of the films, as well as the lifetime of the film under repeated cycling. Results are shown illustrating the coloration behavior of the films, and the transmittance of the films over the visible and near-infrared spectra. WO3 films approximately 0.15 micrometers thick are highly transparent and color quite uniformly, although the process is not completely reversible. There is evidence from the auger electron spectroscopy (AES) and RBS data that there is residual carbon in the films after conventional processing. Some progress has been made toward examination of the effect of this carbon on both coloration efficiency and long-term switching life of prototype devices.
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