Dual plasmonic‐enhanced bulk‐heterojunction solar cell incorporating gold nanoparticles into solution‐processed anode buffer layer and active layer

A dual plasmonic resonance effect on the performance of poly(3‐hexylthiophene) (P3HT):phenyl C61‐butyricacid methyl ester (PC61BM) based polymer solar cells (PSCs) has been demonstrated by selectively incorporating 25 nm colloidal gold nanoparticles (Au NPs) in a solution‐processed molybdenum oxide (MoO₃) anode buffer layer and 5 nm colloidal Au NPs in the active P3HT:PCBM layer. The devices exhibit up to ～20% improvement in power conversion efficiency which is attributed to the dual effect of localized surface plasmon resonance (LSPR) of Au NPs with enhanced light absorption and exciton generation. Our report shows a guideline on the usage of dual LSPR effect for the solution‐processed polymer solar cells to achieve high efficiencies. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Broadband tunable plasmonic substrate using self-assembled gold–silver alloy nanoparticles

In the present work, a facile approach of Au–Ag alloy NPs fabrication is proposed for plasmonic inclusion applicative studies. These hybrid NPs were prepared by the sequential deposition of Ag, Au layers on a glass substrate via RF-sputtering followed by high-temperature annealing. Compositional and size controllability of the NPs was attained by changing the ratio of nominal thicknesses of the respective Au, and Ag layers during the deposition. LSPR red (blue) peak shift occurs with increasing layer thickness Au (Ag) signifying the peak sensitivity. The influence of geometrical, compositional, and background media for achieving LSPR-sensitivity is examined and validated by FDTD simulation studies. With the agreeable peak shift tendencies, the proposed study of broadband tunable LSPR-sensitivity is expected to provide a framework for a wide range of plasmonic applications.     

Plasmonic enhancement of the vanadium dioxide phase transition induced by low-power laser irradiation

Nanocomposites consisting of gold nanoparticle (NP) arrays and vanadium dioxide (VO₂) thin films are noteworthy for the tunability of both their thermal and optical properties. The localized surface plasmon resonance (LSPR) of the Au can be tuned when its dielectric environment is modulated by the semiconducting-to-metal phase transition (SMT) of the VO₂; the LSPR itself can be altered by changing the shape of the NPs and the pitch of the NP array. In principle, then it should be possible to choose a combination of VO₂ film and Au LSPR properties that maximizes the overall optical response of the nanocomposite. To demonstrate this effect, transient transmission measurements were conducted on lithographically fabricated arrays of Au NPs of diameter 140?nm, array spacing 350 nm, and covered with a 60?nm thick films of VO₂ via pulsed laser deposition. Both Au::VO₂ nanocomposites and bare VO₂ film were irradiated with a shuttered 785?nm pump laser, and their optical response was probed at 1550?nm by a fixed-frequency diode laser. The Au::VO₂ nanocomposite exhibited an increased effective absorption coefficient 1.5 times that of the plain film and required 37?% less laser power to induce the SMT. The time-dependent temperature rise in the film as a function of laser intensity was calculated from these measurements and compared with both analytic and finite-element models. Our results suggest that Au::VO₂ nanocomposites may be useful in applications such as thermal-management coatings for energy efficient ??smart?? windows.     

Enhanced spectroscopic properties and Judd–Ofelt parameters of Er-doped tellurite glass: Effect of gold nanoparticles

Glasses with composition 70TeO₂–20ZnO–10Na₂O–0.5Er₂O₃–(x)Au are synthesized by melt-quenching technique. Their spectroscopic and optical characterizations are made. The presence of gold nanoparticles (Au NPs) with average size ～9 nm is confirmed from TEM micrograph. The value of E_dir is found to lie between 3.082 and 3.073 eV, while E_indir lies within 2.765 to 2.724 eV. The observed visible up-conversion (UC) emission under 779 nm excitation wavelength exhibits two bands centered at 546 nm (green) and 637 nm (red) in all samples. The glass with 0.4 mol% Au NPs shows dominant enhancement in the UC emission intensity of the order of 3.5 times for the green band (⁴S_3/2 → ⁴I_15/2) and a weaker enhancement for the red (⁴F_9/2 → ⁴I_15/2) band. The optical properties of the system are affirmed to depend strongly on the Au concentration in the dielectric medium. The absorption spectra consist of six bands attributed to absorption from ground state (⁴I_15/2) to ⁴I_13/2, ⁴I_11/2, ⁴I_9/2, ⁴F_9/2, ²H_11/2, and ⁴F_7/2 excited states. The structural reveals that the types of bonding and difference in electro-negativity can be manipulated by the presence of metallic NPs in glass matrix. Judd–Ofelt analysis asserts the increase in Ω₂ and Ω₆ parameters with the addition of Au NPs and the enhancement of green and red emissions. The enhancement is mainly attributed to large plasmonic effect of Au NPs. The proposed glasses can be nominated as potential materials for solid state laser developments.     

SHINERS and plasmonic properties of Au Core SiO2 shell nanoparticles with optimal core size and shell thickness

Shell‐isolated nanoparticles (NPs)‐enhanced Raman spectroscopy (SHINERS) can be potentially applied to virtually any substrate type and morphology. How to take a step forward to prepare SHINERS NPs (SHINs) with superior performance is critical for the practical applications of surface‐enhanced Raman scattering (SERS) in the breadth and depth. Here, we present a method to obtain 120 nm diameter gold NPs coated with ultrathin silica shells (1–4 nm). The silica shell can be controlled growth through carefully tuning a series of parameters, such as amount of 3‐aminopropyl triethoxysilane used, pH, reaction time, and reaction temperature. We compare the enhancement factor of the obtained 120 nm Au with a 4 nm silica shell NPs to the 55 nm Au with a 4 nm silica shell NPs, and the activity of a 120 nm SHINs is nearly 24 times that the 55 nm SHIN from a single particle view. We also compare the enhancement factor of 1 nm silica shell Au@SiO₂ NPs with the bare Au NPs. The enhancement factor of 1 nm silica shell Au@SiO₂ NPs was found to be about twice that of the bare particles. For a deeper understanding of the source of the giant enhanced electrical field of the 1 nm silica shell Au@SiO₂ NPs, we study the plasmonic property of single 1 nm silica shell Au@SiO₂ NP on a gold film substrate through correlation of the structure of single NP using SEM with its SPR spectroscopy. We find that the multipolar interaction between the single Au@SiO₂ NP and gold film substrate is important for the SERS. Our studies on the performance of 120 nm SHINs and the plasmonic property of these particles can significantly expand the applications of SHINERS technique and improve the understanding of physical nature of SHINs. Copyright © 2013 John Wiley & Sons, Ltd.     

Silver,gold and the corresponding core shell nanoparticles: synthesis and characterization

Simple strategies for producing silver and gold nanoparticles (AgNP and AuNP) along with the corresponding core shell nanoparticles (Au–Ag and Ag–Au) by reduction of the metal salts AgBF₄ and HAuCl₄ by NaBH₄ in water will be presented. The morphologies of the obtained nanoparticles are determined by the order of addition of reactants. The obtained NPs, with sizes in the range 3–40 nm, are characterized by transmission electronic microscopy (TEM) and UV–Vis absorption spectroscopy, so as to evaluate their qualities. Moreover, a direct electrochemical detection protocol based on a cyclic voltammetry in water solution that involves the use of glassy carbon electrode is also applied to characterize the prepared NPs. The developed NPs and the related electroanalytical method seem to be with interest for future sensing and biosensing applications including DNA sensors and immunosensors.     

Laser generated Ag and Ag–Au composite nanoparticles for refractive index sensor

Localized surface plasmon resonance (LSPR) wavelength of metal nanoparticles (NPs) is highly sensitive to size, shape and the surrounding medium. Metal targets were laser ablated in liquid for preparation of spherical Ag and Ag@Au core–shell NP colloidal solution for refractive index sensing. The LSPR peak wavelength and broadening of the NPs were monitored in different refractive index liquid. Quasi-static Mie theory simulation results show that refractive index sensitivity of Ag, Ag–Au alloy and Ag@Au core–shell NPs increases nearly linearly with size and shell thickness. However, the increased broadening of the LSPR peak with size, alloy concentration and Au shell thickness restricts the sensing resolution of these NPs. Figure-of-merit (FOM) was calculated to optimize the size of Ag NPs, concentration of Ag–Au alloy NPs and Au shell thickness of Ag@Au core–shell NPs. The refractive index sensitivity (RIS) and FOM were optimum in the size range 20–40 nm for Ag NPs. Laser generated Ag@Au NPs of Au shell thickness in the range of 1–2 nm showed optimum FOM, where thin layer of Au coating can improve the stability of Ag NPs.     

Tunable optical properties of nano-Au on vanadium dioxide

The optical properties of Au nanoparticles deposited on thermochromic thin films of VO₂ are investigated using spectroscopy. A localized modification on the transmittance spectrum of VO₂ film is formed due to the presence of Au nanoparticles which exhibit localized surface plasmon resonance (LSPR) in the visible-near IR region. The position of the modification wavelength region shows a strong dependence on the Au mass thickness and shifts toward the red as it increases. On the other hand, it was found that the LSPR of Au nanoparticles can be thermally tunable because of the thermochromism of the supporting material of VO₂. The LSPR wavelength, λ_SPR, shifts to the blue with increasing temperature, and shifts back to the red as temperature decreases. A fine tuning is achieved when the temperature is increased in a stepwise manner.     

Design of nanocomposite film-based plasmonic device for gas sensing

Surface plasmon resonance (SPR) is a very efficient tool for chemical and biological sensing in nanotechnology, nanobiotechnology, medicine and environmental monitoring. A theoretical simulation study incorporating the use of admittance loci design methodology in SPR-based sensing device using gold-tungsten trioxide (Au-WO_3?x ) nanocomposite film is reported in this paper. A simple Kretschmann–Raether-type prism-based plasmonic device consisting of a glass prism, Au-WO_3?x nanocomposite film and various gas samples is considered. Complex permittivity for both stoichiometric and non-stoichiometric Au-WO_3?x nanocomposite films has been used for the simulation of the admittance loci plots, resonance curves and sensitivity curves by considering angular interrogation at a fixed wavelength of 632.8 nm.     

Thermal behavior of surface plasmon resonance in dynamic suprastructure multilayer

Delicate thermodynamic control at confined space has been of importance in recent nano/micro-plasmonic sensing to be more accurate and to use lower quantity of specimens than conventional devices. In our study, experimental and computational study on thermal behavior of surface plasmon resonance (SPR) was carried out using various sizes of Au nanoparticles (NPs; 4, 18, and 57 nm) and thermo-reversible polymer, poly(N-isopropylacrylamide) (PNIPAm) on SPR chip. It was interesting that SPR angle shift on temperature was dependent on NP sizes, where the smaller size the better sensitive. It is probable that both plasmonic interaction and polymer dynamicity were collaboratively affected and presumably the latter dominated in the thermal monitoring of SPR signals. The simulations clearly indicated that the interaction between the Au NPs and polymers was strengthened by increasing temperature and NP sizes, resulting in decreasing sensitivity. These results are supportive to develop further accurate devices using plasmonics and polymer dynamics, such as plasmonic sensing devices, thermo-actuators, hybrid organic solar cell, and flexible display.     

Attachment and motion of hydrogen in hydrogen (deuterium) molybdenum bronzes,DxMoO3

Ambient temperature ²D NMR spectra are reported for powder samples of the single phase hydrogen (deuterium) molybdenum bronzes, D_xMoO₃, with x=0.36 (blue orthorhombic), x=0.90 (blue monoclinic), x=1.68 (red monoclinic) and x=2.0 (green monoclinic). Spectra over a range of temperatures are also reported for the red monoclinic and green monoclinic phases. Translation of H-atoms between magnetically inequivalent sites leads to narrowed spectra for all four phases. A consistent interpretation of results from a range of experimental techniques can be given in terms of H-atom sites corresponding to attachment to O-atoms as part of coordinated-OH (hydroxyl) and/or -OH₂ (water) groups.     

Fabrication of NIR‐Excitable SERS‐Active Composite Particles Composed of Densely Packed Au Nanoparticles on Polymer Microparticles

A simple fabrication method is demonstrated for surface‐enhanced Raman scattering (SERS)‐active plasmonic nanoballs, which consisted of Au nanoparticles (NPs) and core–shell polystyrene and amino‐terminated poly(butadiene) particles, by heterocoagulation and Au NP diffusion. The amount of Au NPs introduced into the core–shell particles increases with the concentration of Au NPs added to the aqueous dispersion of the core–shell particles. When the amount of Au NPs increases, closely packed, three‐dimensionally arranged and close‐packed Au NPs arrays are formed in the shells. Strong SERS signals from para‐mercaptophenol adsorbed onto composite particles with multilayered Au NPs arrays are obtained by near‐infrared (NIR) light illumination.     

Interfacial electronic structure of molybdenum oxide on the fullerene layer,a potential hole-injecting layer in inverted top-emitting organic light-emitting diodes

The interfacial electronic structures of molybdenum oxide (MoO_x) deposited on fullerene (C₆₀) which could be used as a hole-injecting layer in inverted top-emitting organic light-emitting diodes (TE-OLEDs) were investigated by photoemission spectroscopy. The hole-injecting barrier height (Φ_B^h) at each interface investigated by an ultraviolet photoemission spectroscopy was reduced to from 1.4 to 0.1 eV as the thickness of MoO_x (Θ_MoOx) was increased from 0.1 to 5.0 nm on C₆₀. In these interface system, the sign of vacuum-level shift, highest occupied molecular orbital (HOMO)-level shift, and core-level shifts were all positive indicating that the interface mechanism is attributed to the work-function differences due to a band bending at these interfaces. Moreover, the near-edge X-ray absorption fine structure spectra at carbon K-edge did not show any structural modification as well as any chemical reaction at the MoO_x-on-C₆₀ interfaces when Θ_MoOx was changed on C₆₀. From these results, the inverted TE-OLED with C₆₀ (5.0 nm)/MoO_x (5.0 nm) showed the power efficiency of 1.7 lm/W at a luminance of about 1000 cd/m² and the maximum luminance of about 76.000 cd/m² at the bias voltage of 11.0 V. It exhibited the highest performance among the inverted TE-OLEDs fabricated as a function of MoO_x thickness from 0 to 5.0 nm.     

Fabrication of Rh based solid-solution bimetallic alloy nanoparticles with fully-tunable composition through femtosecond laser irradiation in aqueous solution

Many late transition binary alloy nanoparticles (NPs) have been fabricated through a wide variety of techniques. Various steps are involved in the fabrication of such NPs. Here, we used a simple and green route to fabricate solid-solution Rh–Pd and Rh–Pt bimetallic alloy NPs through femtosecond laser irradiation in a solution without any chemicals like reducing agents. X-ray diffraction (XRD) peaks of NPs obtained in the solutions with different ratios of Rh–Pd and Rh–Pt ions monotonically varied from the position of pure Rh to those of Pd and to Pt which respectively indicated that these NPs were alloy. Composition of fabricated NPs was fully tuned over the entire range of Rh_1?x –Pd _x , and Rh_1?x –Pt _x with varying the mixing ratio of metal ions in the solution. Studies of Rh–Pd and Rh–Pt solid-solution system suggest that the alloy formation occurs through the nucleation of Rh and then followed by the diffusion of Rh, Pd and Rh, Pt to form a homogeneous alloy. The variety of average size of the alloy NPs for different compositions could be attributed to different reduction rate and surface energies of metal ions. Our result implies that femtosecond laser irradiation in aqueous solution is one of the potential methodologies to form multimetallic solid-solution alloy NPs with fully tunable composition.     

Ultrasonic measurements on molybdenum bronze ceramic

Hydrogen molybdenum bronze, H_xMoO₃ (O<x⩽2), was produced for the first time as a ceramic in a low-temperature process. The elastic properties of the material were measured by ultrasound technique. For H_1.6MoO₃ ceramic an anomaly in the sound velocity was found near 200 K. This effect is connected with a significant thermal hysteresis. This behaviour and the correlation with positions and dynamics of the hydrogen in the lattice are discussed.     

Photoluminescence characterization of a novel red-emitting phosphor In2(MoO4)3:Eu3+ for white light emitting diodes

The red-emitting phosphor In₂(MoO₄)₃:Eu³⁺ with cubic crystal structure was synthesized by a conventional solid-state reaction technique and its photoluminescence properties were investigated. The prepared phosphor can be efficiently excited by ultraviolet (395 nm) and blue (466 nm) light. The emission spectra of the phosphor manifest intensive red-emitting lines at 612 nm due to the electric dipole ⁵D₀→⁷F₂ transitions of Eu³⁺. The chromaticity coordinates of x=0.63, y=0.35 (λ_ex=395 nm) and x=0.60, y=0.38 (λ_ex=466 nm) are close to the standard of National Television Standard Committee values (NTSC) values. The concentration quenching of In₂(MoO₄)₃:Eu³⁺ is 40 mol% and the concentration self-quenching mechanism under 466 nm excitation was the dd intereaction. As a result of the strong emission intensity and good excitation, the phosphor In₂(MoO₄)₃:Eu³⁺ is regarded as a promising red-emitting conversion material for white LEDs.     

Enhanced blue photoluminescence and new crystallinity of Ag/organic rubrene core-shell nanoparticles through hydrothermal treatment

Light-emitting organic semiconductors have attracted considerable attention for the nanoscale fabrication of organic-based displays and their potential application in optoelectronics, plasmonics, and photonics. In this study, core-shell hybrid nanostructures of organic rubrene coated on Ag nanoparticles (NPs) have been synthesized using a chemical reduction method. The thickness of the rubrene shell was 2.6–6.0 nm and the diameter of the Ag core was 30–70 nm. The optical and structural properties of the Ag/rubrene core-shell NPs were tuned by hydrothermal (HT) treatment at 190 °C. The Ag/rubrene core-shell NPs were characterized by high-resolution transmission electron microscopy and energy-dispersive X-ray (EDX) spectroscopy before and after the HT treatment, and their structural properties were confirmed through X-ray diffraction (XRD) analysis. XRD peaks related to an orthorhombic phase were observed along with the original triclinic crystal structure of the rubrene shell, and the triclinic crystal domain size increased from 28.2 nm to 30.8 nm owing to the HT treatment. Interestingly, the green light emission (λ_em = 550 nm) of the Ag/rubrene core-shell NPs changed to blue light emission (λ_em = 425 nm), increasing in intensity through the HT treatment. This is caused by the crystal change with H-type aggregation and enhanced energy transfer from a surface plasmon resonance.     

Effect of NaF on optical and structural properties of CdxZn1−xS nano crystalline films

This work investigates the effect of NaF on optical and structural properties of nano crystalline Cd_xZn_1?xS films. The Cd_xZn_1?xS films are prepared through chemical bath deposition (CBD) technique in aqueous alkaline bath and their subsequent condensation on substrates. The as-obtained samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV–VIS absorption spectroscopy. Micro structural features, obtained from XRD analysis confirm the formation of cubic phase of undoped as well as NaF doped Cd_xZn_1?xS nano particles while SEM observations depict non-uniform distribution of grains. These results show the average grain size of pure as well as NaF doped samples to range from 50 to 90 nm. Tauc's plots, extracted from absorption spectra exhibit absorption to be dominating mainly in blue-green region of visible spectrum. The room-temperature photoluminescence (PL) spectra of Cd_xZn_1?xS samples show a peak around 425 nm, which gets blue shifted for doped sample indicating improvement in PL properties on its addition.     

Plasmonics: Absorption and scattering of light of non-straight ordered array of Au rings

In this paper, Au nanorings in a SiO₂ substrate have been utilized to design a plasmonic waveguide with lower losses and perfect energy coupling. Our recommended structure consists of a chain of dozen Au nanorings with a given intercenter space between them going on resonance, if a beam with specific wavelength is launched in the input area of the waveguide. Nanoring has an extra degree of freedom in its geometry and have a preferable tunability in comparison to other shapes of nanoparticles (e.g. nanospheres). It is shown that a modified plasmon waveguide structure can be utilized at optical communication band (λ = 1550 nm), in optical integrated devices. Red-shifted of localized surface plasmon resonance (LSPR) has been considered as a fundamental condition to have a maximum of optical response at λ = 1550 nm. Cross-sectional depictions of field propagation through the structure are displayed in order to show the absorption and scattering of light by particles. Ultimately, transmitted power ratio is computed for the structure to clear-cutting its characteristics.     

Tuning the contact resistance in organic thin-film transistors with an organic-inorganic hybrid interlayer

We demonstrated the tunable contact resistance in pentacene thin film transistor (TFT) by inserting an organic-inorganic hybrid interlayer between Au electrode and pentacene layer. The contact resistance of pentacene-TFT varies with concentration of pentacene-TFT varies with concentration of MoO_x in organic-inorganic hybrid interlayer. MoO_x in organic-inorganic hybrid interlayer. The contact resistance of the device with 55 wt% MoO_x doped pentacene interlayer is about 7.8 times smaller than that of device without interlayer at the gate voltage of −20 V. Comparing the properties of pentacene-TFT without interlayer, the performance of the pentacene-TFT with 55 wt% MoO_x doped pentacene was significantly improved: saturation mobility increased from 0.39 to 0.87 cm²/V s, threshold voltage reduced from −21.3 to −7.2 V, and threshold swing varied from 3.75 to 1.39 V/dec. Our results indicated that the organic-inorganic hybrid interlayer is an effective way to improve the performance of p-channel OTFTs.