Composite films of tungsten oxide and CNCs are prepared through a sol–gel method and their electrochromic (EC) properties investigated. After mixing CNC gel into a tungsten oxide precursor solution, indium-tin-oxide-coated glass substrates are dipped into the composite solution and subsequently annealed at 170°C. The composite films consisted of CNCs dispersed in the tungsten oxide matrix. The resulting nanocomposite was found to be amorphous, exhibiting a high transmission modulation and very good cycling stability. After having tested a range of compositions, a film of WO3 with 10% CNC was found to be the most uniform and showed good EC performance. These results bode well for further work on CNC-EC composites for specific applications, especially when used on flexible substrates.
We report the theory and experiment of how an ultrathin (<80 nm) layer of vanadium dioxide (VO2) can be used to control and adjust the polarization state of light. The refractive index of vanadium dioxide undergoes large changes when the material makes a phase transition from semiconductor to metal at a temperature of 68 °C. In a thin film, this results in optical phase shifts that are different for s- and p-polarizations in reflection or transmission. We investigate the conditions under which the polarization state would changes between linear or circular or between linear polarizations oriented differently during the material’s phase transition. The effect is demonstrated from 600 nm to 1600 nm and optical devices are proposed based on experimental data on refractive indices with temperature.
The effect of the substrate to the absorption spectra of silver nanoparticles of sphere-like shapes is investigated. Silver nanoparticles of broken spherical symmetry are placed on substrates of different dielectric functions at various contact angles (α). The absorption efficiency of the supported nanoparticles is calculated by using the Discrete Dipole Approximation (DDA) method. Increasing the value of α and, hence the contact area of the supported nanoparticles,
results in an inhomogeneous distribution of the polarization charges over the nanoparticle-substrate system. This leads to the excitation of plasmonic bands of different characters (dipolar and quadrupole modes). The admixture of both dipolar and quadrupole modes is found to be more pronounced when a nanoparticle with highest contact area (α = 90o,
hemispherical shape) is considered. The band position of the Longitudinal Mode (LM) is red-shifted with α, while the resonance wavelength of the Transverse Mode (TM) is blue-shifted.
The strong optical absorption, scattering and local electric field enhancement associated with the longitudinal Surface Plasmon Resonance (SPR) of gold nanorods (AuNRs) have important applications in imaging, sensing, nonlinear optics, thermal therapy and data encoding. The longitudinal SPR mode can be optimally excited only in the NRs that are most aligned with the electric field of a linearly polarized incident light. Thus, in cast polymer based nanorod composite films, where the NRs orientation is random, only a fraction of the embedded NRs is actually usable to the maximal extent for the intended applications. To enhance the degree of alignment of the AuNRs by uniaxial stretching and increase the application efficiency, we have improved the polymer matrix with respect to plastic deformation and designed a suitable drawing device to reduce the fracture risks of the polymer. The resulting nanocomposite film was characterized by Scanning Electron Microscopy (SEM) and by spectroscopy using linearly polarized light in the UV-Visible range. The linear dichroic ratio of the stretched nanocomposite film was calculated based on the ratio of the peak absorbance of the incident light parallelly polarized, to that of the light polarized perpendicularly to the NRs long axes.
Different densities of gold nanorods (GNRs) were incorporated on the back electrode of bulk heterojunction organic
solar cell (OSC). GNRs layers (1, 3, and 5) were deposited on top of the poly(3-hexylthiophene) (P3HT) and phenyl-
C61-butyric acid methyl ester (PCBM) layer using spin-casting technique. According to the optical and structural
characterizations, the solar cell devices incorporated with one layer of gold nanorods showed an enhancement in both
power conversion efficiency and short-circuit current by up to 14% and 22% respectively as compared to the devices
without gold nanorods. This result suggests that GNRs in the back electrode of polymer solar cells act as backscattering
elements. They not only increase the optical path length in the active layer but also store energy in localized surface
plasmon resonance mode. Both mechanisms lead to enhancement of light absorption and in turn contribute to
photocurrent generation and the overall power conversion efficiency. On the other hand, the solar cells with high density
GNRs on the back electrode showed inferior performance compared to that of low density integrated ones. The decrease
in PCE would stem from enhanced charge recombination induced by high density GNRs. Furthermore, generation of
intense local electric fields named hotspots, would reduce the charge transportation and exciton dissociation probability.
In such cases, the power conversion efficiency of the device is observed to be less than that for one layer GNRs or even
the control device.
The optical aspects of plasmon coupling occurring through the near-field interactions among metallic spherical
nanoparticles assembled in close proximity to each other in two-dimensional and three-dimensional arrays have been
examined using the discrete dipole approximation (DDA). Calculations were performed for nano-sized close-packed
spheres of silver, gold or copper, hexagonally arranged in a planar monolayer target and extended gradually to three-dimensional
multilayer targets with a fastened interparticle spacing. Those targets were simulated under the incident ppolarized
light with an energy range of 1.5 - 4.5 eV by executing an open-source code of the DDA. The optical response
of three-dimensional targets was revealed in the absorption spectra calculated at various angles of the polarized incident
light, showing a blue shift of the plasmon resonance (PR) peak for both gold and copper targets. The splitting of the
surface plasmon resonance (SPR) observed in the response of the two-dimensional silver system eventually disappeared
into one well-defined resonance peak as the system grew in the third dimension. Moreover, to shed light on the nature of
the plasmon coupling among close-packed nanospheres of different metals, we simulated a target composed of mono-sized
nanospheres of the three metals placed spatially in three consecutive layers. A combined optical behaviour was
thus observed through the absorption spectrum, where the plasmon peaks attributed to the silver, gold and copper
interacting nanospheres emerged at the original energy values as if it was applied in isolated planar hexagonal arrays.
The effect of using an anodic layer with low density (~ 6x108 cm-2) of gold nanorods (GNR) in organic bulk
heterojunction poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) solar cells was studied.
GNRs were deposited using several techniques, which produced various densities of GNRs on the anode layer. The
anodic layers were characterized microscopically and spectroscopically. The power conversion efficiency and the short-circuit
current for experimental devices incorporating GNR anodic layer showed an enhancement of up to 18% as
compared to the control device. The results suggest that the electric field in the P3HT:PCBM active layer was increased
by the localized surface plasmon resonances in GNRs. The increase in the electric field enhanced the photo-generation of
excitons in the active layer near the plasmon peak, which improved the short-circuit current and the overall power
conversion efficiency. Interestingly, photovoltaic devices with a low density of GNRs in the anodic layer showed an
increase in the power conversion efficiency that was superior to that of devices with a higher density of GNRs in the
anodic layer. This suggests that although the anodic layer with a higher density of GNRs absorbed more light, part of this
light was confined in the anodic layer itself, and prevented from reaching the active layer of the bulk heterojunction
device. In such cases, the power conversion efficiency was even found to be decreased with respect to the value for the
control device.
Discrete Dipole Approximation (DDA) is a computational technique to simulate the optical properties of nanostructures
of different shapes, sizes, and compositions. The influence of the target size on the optical response of 5 nm-diameter
nanoparticles arranged in a monolayer hexagonal array is investigated by using DDA at various incident angles of the
incident light on the target considered for silver (Ag), gold (Au) and copper (Cu) nanoparticles. In our study, the target
size is controlled by the number of the spherical nanoparticles used to generate the two dimensional arrays. The
interparticle distance is kept constant in all the simulations. The anisotropic response of noble-metal nanoparticles is
generally characterized by the excitation of the high-energy (transverse) surface plasmon (SP) mode and the low-energy
(longitudinal) SP mode. Results of the simulations for the three chosen metals show an exponential dependency of the
absorption efficiency of the SP modes with respect to the target size. As the target size is increased, the energy of Ag-longitudinal
SP mode is red-shifted and it displays an exponential decay while the band position of the transverse mode
is blue-shifted. They however overlap when the smallest target size is considered. Although, the optical response of Au
and Cu nanoparticle arrays shows the same dependency on the target size as observed in the case of Ag, the positions of
their respective longitudinal and transverse modes are very close, making these almost indistinguishable. The
dependency of the absorption efficiency of SP modes on the incident angle is fitted linearly for Cu, Au and longitudinal-
Ag modes to the target size, while the transverse-Ag mode shows an exponential fitting. No change in the Ag-SP band
position is observed when the incident angle is changed, but the SP bands for both Au and Cu exhibit exponential
variation behavior.
Gold nanoparticles (GNPs) have been synthesized by a seed-mediated growth method. Hexadecyltrimethylammonium
bromide (CTAB) was used as a surfactant for both the seed formation and the anisotropic crystals growth. Anisotropic
GNPs of various sizes, shapes and aspect ratios were obtained by using different amounts of silver ions, temperatures
and durations of growth as parameters of the process. The SEM images and the Localized Surface Plasmon Resonance
(LSPR) bands in the UV-Vis of the anisotropic GNPs have been studied. Preliminary sensing experiments have been
carried out as well. This work has proved again the high sensitivity of the synthesis with respect to the conditions of
reaction.
The controllability of conductivity and the ease of manufacturing/coating of conducting polymers enable tailor- made dielectric loss components for radar absorbing materials (RAM). Different polypyrrole (PPy) based RAM, e.g. paint/rubber containing PPy powder and PPy coated structural phenolic foams with a gradient of impedance, have been examined. Reflection loss strongly depends on thickness and complex permittivity of the material. For a single layer material, the optimum values of the real part, (epsilon) ', and imaginary part, (epsilon) ", of the complex permittivity required to achieve a minimum reflectivity at a given sample thickness are found by theoretical calculations. The conductivity of the PPy powder is controlled to obtain RAM with lowest reflectivity according to the calculated optimum values of (epsilon) ' and (epsilon) ". A paint panel containing 2 wt% of the PPy powder with a thickness of 2.5 mm exhibits a reflectivity less than $minus 10 dB over 12 to 18 GHz. Blending and milling in the manufacturing process can destroy the original fibrous shape of PPy aggregates leading to low absorbing performances. PPy can be coated on rigid or flexible open cell foams to provide a lightweight broadband RAM. In particular, a coating technique on phenolic foams (12 - 15 mm thick) with a pore size of micrometer order has been developed to generate a gradient of conductivity across the foam thickness. The PPy coated foams are broadband RAM.
A brief historical background of ellipsometry is given, followed by a detailed assessment of its current status and future development. Spectroscopic ellipsometry in the near UV-VIS is now a well-established characterization technique, and its extension to the IR range is quickly reaching a mature state. Other important developments in both theory and instrumentation in the last decade are leading to better and faster in situ, real-time and imaging ellipsometry. Selected works from recent literature are presented to illustrate not only new development trends in the field but also other well-known applications of ellipsometry as a characterization technique.
Ellipsometric studies are generally carried out in reflection mode rather than in transmission mode, requiring invariably opaque substrates or substrates in which the back reflection is minimized or suppressed by different methods. In the present work, we have used a transmission and reflection photo-ellipsometry method to study electrochromic materials and their multilayer systems deposited on thick substrates. The role of the substrate is examined carefully and the contributions from multiple reflections in the substrate are taken into account in the theoretical treatment. This procedure not only allows the study of thin films deposited on quasi-transparent substrates but carried out in conjunction with reflection measurements improves greatly the accuracy in the determination of the optical constants. Optical measurements have been carried out on an automatic reflection-transmission spectrophoto- ellipsometer. Solid state ionics materials used in electrochromic systems such as indium-tin oxide, tungsten oxide, and their multilayer structures deposited on glass substrates are used as examples. A software based on the above theory, OPTIKAN, has been developed to model and analyze such systems. It is demonstrated that the photo-ellipsometry method proposed is especially suited to analyze in a non-destructive way electrochromic materials and transmitting devices.
Two sets of WO3 thin films were prepared by rf sputtering from tungsten oxide and tungsten metal targets, respectively. Lithium insertion studies were carried out in these two types of films. It has been found that the films sputtered from the metal targets showed an irreversible uptake of lithium without any coloration. The aim of the present work is to study this specific behavior of such films in comparison to those deposited from tungsten oxide targets. These films have been studied by thermogravimetry, UV-Vis spectroscopy, electron probe, ellipsometry, and ATR-FTIR spectroscopy. The stoichiometry of both types of films is found to be identical. The ATR-FTIR spectra show a difference in the W-O stretching vibration pattern of the two types of films, clearly indicating structural differences in the as- deposited WO3 films. However, both types of films show the presence of little or no water in the as-deposited state. Upon the insertion of lithium it is found that the films deposited from the oxide target show the formation of 'bronze' right from the very early stage of insertion as indicated by the blue coloration. This formation is reflected in the ATR-FTIR spectra by the increasing slope of the absorption in the mid-infrared range. Contrary to this behavior, the films deposited from the metal target do not show any coloration in the initial stages of lithium insertion. The infrared spectra corresponding to this behavior show little change in the mid-infrared range. However, a widening of the W-O stretching band is observed in these spectra reflecting a structural reorganization in the films. With continued lithium insertion, however, the behavior in the two types of films becomes similar. Hence, in the initial stages of coloration the quantity of lithium participating in the electrochromic coloration of the films deposited from metal target seems to be lower than in the other types of film. The optical constants of these films have also been determined using reflection- transmission ellipsometry showing important differences in the films. Hence, the electrochromic behavior of sputtered tungsten oxide films depends strongly on the type of deposition.
In the present work we have studied in detail the lithiation behavior of reactively sputtered crystalline tungsten oxide (WO3) films. These films, depending on their thickness and other deposition conditions, exhibit a wide range of changes under lithium insertion from deep coloration to no coloration at all. This gives the possibility of using the WO3 films either as electrochromic (EC) layer or as counter electrode (CE) layer for lithium ion storage, respectively. From these results a quasi- symmetric electrochromic system encompassing a- WO3 as EC layer and c-WO3 as the CE layer is fabricated and studied for its electrochromic behavior.
Electrochromic systems with their reversible optical switching ability offer important and interesting application possibilities. Work was carried out in our laboratory towards the fabrication of an all-solid electrochromic system. Lithiation studies of two transition metal oxides (W03 and V205) were done for their use as base electrochromic layer and counter electrode layer in the solid system. Also a thermally evaporated layer of LiBO2 was studied for its application as ion conducting layer. The optimum results from these studies were used for the fabrication of an all-solid electrochromic prototype. The results on the electrochromic performance of this system are presented. Several hundred coloration and bleaching cycles of such systems have been carried out without any change in its performance. All results indicate the high suitability of such a system for "smart" window application.
Design considerations and fabrication method of an all-solid-state five layer electrochromic (EC) system are discussed. A dry method of lithiation of the system is proposed and characterized completely for its use in the fabrication of EC systems. Some preliminary data on the EC switching of the complete system are presented.
Solid state materials exhibiting ion conduction properties are usually referred to as "solid electrolytes", "fast ion conductors (FIC)", "superionic solids" or simply as "ion conductors", depending on the author's preference or the magnitude of electrical conductivity. Since the pioneering work by Yao and Kummer' in 1967 on sodium conduction in B-aluminas, a large number of studies have been made on alkali ion conduction in inorganic solids. Applications of these conductors can be found in various areas such as solid state batteries, fuel cells, electronic displays or memory devices. More recently, in the early 80's, suggestion of applying electrochromic (EC) materials to the fabrication of smart windows (SW) has prompted increased interest in ion conductor studies, especially those aiming at finding transparent ion conductors.
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