Surface modification of all-inorganic lead halide perovskite nanocrystals

Abstract Newly emerged all-inorganic lead halide perovskite nanocrystals have shown unprecedented optical properties for a variety of display applications. Their superior optical properties over traditional semiconductor nanocrystals have opened a new paradigm in luminescent materials research. Because of their defect tolerance, the photoluminescent quantum yield of lead halide perovskite nanocrystals can reach near-unity. However, the ionic character of these nanocrystals causes extreme lability, which deteriorates its structural and optical properties. Moreover, the binding ability of surface ligands are quite weak and thus easily desorb during conventional purification techniques. Despit…

Nanotexturing To Enhance Photoluminescent Response of Atomically Thin Indium Selenide with Highly Tunable Band Gap.

Brotons-Gisbert, Mauro et al.

Photoconductivity and optical properties of silicon coated by thin TiO2 film in situ doped by Au nanoparticles

Light trapping enhancement by plasmonic-active metal nanoparticles (NPs) is believed to be a promising approach to increase silicon-based solar cell efficiency. Therefore, we investigated TiO2 films in situ doped by Au NPs (TiO2:AuNPs) deposited by spin coating on a silicon substrate. Photoconductivity and optical properties of the TiO2:AuNPs/Si structures were studied in comparison with those of TiO2/Si reference samples. We found that an introduction of the 40–50 nm diameter AuNPs into the antireflective TiO2 layer deteriorates the antireflection properties and decreases the external yield of photogeneration of charge carriers. This is due to an increase of the layer reflection in the red…

Solution-Processed Ni-Based Nanocomposite Electrocatalysts: An Approach to Highly Efficient Electrochemical Water Splitting

In this study, we report an up-scalable and low-cost solution-processed method to in situ synthesize an earth-abundant non-stoichiometric NiOx-based electrocatalytic film for water oxidation. The catalytic activity was found to be inversely proportional to the baking temperature, which varied from 50 to 500 °C. We found the formation of a hybrid nanocomposite thin film of NiOx nanocrystals (<2 nm size) inside an acetate-based organic matrix at low temperatures (<200 °C). The defective and short-range structural order of the NiOx-based nanocomposite electrocatalysts, compatible with lattice stress, low electrical conductivity, and high density of catalytically active surface species, and hig…

Laser-Ablation-Induced Synthesis of SiO2-Capped Noble Metal Nanoparticles in a Single Step

Here we describe a simple, powerful technique based on the laser ablation of a target immersed in a water solution of a metal salt. With this method, nanoparticles of different metals and alloys can be processed very quickly. Both the target and the salt solution can be chosen to produce metal nanoparticles of different sizes, surface-oxidized nanoparticles (silica-silver, for example), or even more complex structures to be defined by the researcher on one or more steps because the technique combines the advantages of both physical and chemical methods. We have applied this technique to the fabrication of inert silica-metal (silver, gold, and silver-gold) nanoparticles with a strong surface…

Au-ZnO Nanocomposite Films for Plasmonic Photocatalysis

Nanocomposites based on plasmonic nanoparticles and metal-oxide semiconductors are emerging as promising materials for conversion of solar energy into chemical energy. In this work, a Au–ZnO nanocomposite film with notably enhanced photocatalytic activity is successfully prepared by a single-step process. Both ZnO and Au nanoparticles are synthesized in situ during baking of the film spin-coated from a solution of Zn(CH3COO)2 and HAuCl4. Furthermore, it is shown that this precursor solution can be formulated as a nanoink for the generation of micropatterns by microplotter printing, opening the way for the miniaturization of devices with enhanced properties for photocatalysis, optoelectronic…

Molecularly Imprinted Silver Nanocomposites for Explosive Taggant Sensing

Laser ablation of a silicon target in chloroform: formation of multilayer graphite nanostructures

With the use of high-resolution transmission electron microscopy, selected area electron diffraction and x-ray photoelectron spectroscopy methods of analysis we show that the laser ablation of a Si target in chloroform (CHCl3) by nanosecond UV pulses (40 ns, 355 nm) results in the formation of about 50–80 nm core–shell nanoparticles with a polycrystalline core composed of small (5–10 nm) Si and SiC mono-crystallites, the core being coated by several layers of carbon with the structure of graphite (the shell). In addition, free carbon multilayer nanostructures (carbon nano-onions) are also found in the suspension. On the basis of a comparison with similar laser ablation experiments implement…

Enhancing the photocatalytic properties of PbS QD solids: the ligand exchange approach.

Surface engineering of nanomaterials is a promising tool towards the design of new materials for conversion of solar energy into chemical energy. In this work, we examine the influence of ligand exchange on the photocatalytic performance of solution-processed PbS films. We test different ligands such as oleylamine (OAm), 1,2-ethanedithiol (EDT), 3-mercaptopropionic acid (MPA) and tetrabutylammonium iodide (TBAI). The study demonstrates that PbS films capped with MPA and EDT exhibit 3.5-fold enhanced photocatalytic performance for the photodecomposition of methyl orange upon sunlight exposure. Both band energy alignment and charge carrier transport have a strong impact on the generation of r…

Recent advances in synthesis, surface chemistry of cesium lead-free halide perovskite nanocrystals and their potential applications

Abstract Cesium lead halide perovskite nanocrystals (NCs) have emerged as a key material for optoelectronic applications owing to their outstanding optical properties and easy synthesis in solution. Nowadays, the scientific community is facing a daring challenge toward the synthesis of lead-free perovskite NCs with high stability and excellent optical properties for the fabrication of optoelectronic devices with enhanced performance. In this sense, cesium lead-free halide perovskites (CsLFHPs) are demonstrated as extremely less susceptible toward oxygen and moisture and suitable candidates for long-term device applications. Thus, synthesis and identification of CsLFHP NCs essentially need u…

Numerical and experimental investigation of short Au nanorods

The plasmonic properties of Au nanorods (NRs) have been investigated theoretically and experimentally, a system that is of high current interest in relation to various nanophotonics applications. The non-aligned NRs arrays were formed by a seed-mediated growth method that relies on the reduction of metal salt by a weak reduction agent in the presence of preformed metallic seed nanoparticles. We applied the finite-element method to calculations of absorption spectra from gold NRs supported in an aqueous solution. Comparison to experimentally measured spectra is found in a good agreement.

Structural and chemical characterization of CdSe-ZnS core-shell quantum dots

Abstract The structural and compositional properties of CdSe-ZnS core-shell quantum dots (QDs) with a sub-nm shell thickness are analyzed at the atomic scale using electron microscopy. QDs with both wurtzite and zinc blende crystal structures, as well as intermixing of the two structures and stacking faults, are observed. High-angle annular dark-field scanning transmission electron microscopy suggests the presence of a lower atomic number epitaxial shell of irregular thickness around a CdSe core. The presence of a shell is confirmed using energy dispersive X-ray spectroscopy. Despite the thickness irregularities, the optical properties of the particles, such as photoluminescence and quantum…

Localized surface plasmon resonance sensor based on Ag-PVA nanocomposite thin films

In this work we demonstrate the use of nanocomposite thin films of poly(vinyl alcohol) with embedded silver NPs for chemosensing purposes. Silver NPs are in situ synthesized inside polyvinyl alcohol during the bake step of the formation of a nanocomposite thin film. The polymer in the nanocomposite provides an appropriate chemical and electromagnetic environment for metal NPs in order to interact with and hence detect the chemical species. A limit of detection below 20 nM is found when detecting 2-mercaptoethanol as the analyte, when measuring spectral changes (peak wavelength, linewidth and intensity) in the Localized Surface Plasmon Resonance. Potential qualitative and semi-quantitative s…

An advance Towards the Synthesis of Ag Nanorod Arrays with Controlled Surface Roughness for SERS Substrates

An innovative approach to produce silver nanorod (NRs) arrays with controlled morphological parameters and surface roughness is presented. The Ag NRs were obtained using a three-stage fabrication process based on the electron beam exposure of a metal-polymer nanocomposite resist on a transparent substrate and development, a post bake and then a series of non-electrochemical metallization steps. After each step the evolution of the Ag NRs was characterized by scanning electron microscopy (SEM) for morphology and optical transmittance (T) measurements for Localized Surface Plasmon Resonance (LSPR). The transmittance measurements were interpreted using models based on the Finite Element Method…

Plasmonic optical sensors printed from Ag–PVA nanoinks

In this paper we report on the use of a nanocomposite based on silver nanoparticles embedded in PVA as a plasmonic optical sensor to detect and quantify trace amounts of amines in gas and water, respectively. The transduction mechanism of the sensor is based on the changes of the LSPR band of Ag NPs when analyte molecules are chemisorbed on their surface. The Ag–PVA sensors are fabricated by means of a high-precision microplotter, a direct-write technology developed for printing materials from solution. The nanoink is formulated with a metal precursor (AgNO3) and a polymer (PVA) using an adequate mixture of solvents to meet the rheological requirements for the fluid dispensing process. The …

Photovoltaics: Photonic Crystal-Driven Spectral Concentration for Upconversion Photovoltaics (Advanced Optical Materials 4/2015)

Effect of alkali metal nitrate treatment on the optical properties of CsPbBr3 nanocrystal films

Abstract Colloidal cesium lead bromide (CsPbBr3) perovskite nanocrystals (NCs) are fabricated as densely packed thin films using doctor blade method through a layer-by-layer assembly approach. It is found that the optical properties of the CsPbBr3 NC films are significantly improved after a ligand exchange of oleic acid (OA) and oleylamine (OAm) by sodium and potassium nitrate in ethyl acetate. Ligand-induced surface defects are passivated by the sodium and potassium cations and nitrate, which leads to the improvement in photoluminescence (PL) and life-time properties. Compared with pristine OAm-OA capped CsPbBr3 NC film, Alkali-metal nitrate salts treated films are showing higher PL intens…

The effect of quantum size confinement on the optical properties of PbSe nanocrystals as a function of temperature and hydrostatic pressure

A study based on photoluminescence and absorption measurements as a function of temperature and pressure for PbSe nanocrystals with sizes in the range 3–13 nm reveals the influence of size quantum confinement on the observed variation. In the case of the temperature variation, the effective bandgap changes from showing a positive rate of change to showing a negative one (for a quantum dot 3 nm in diameter), which can be accounted for by incorporating a linear variation of the carrier effective masses into a simple calculation of the exciton ground state in the quantum dot. In the case of the pressure variation, we observe a clear inverse correlation between the absolute value of the pressur…

Au-PVA Nanocomposite Negative Resist for One-Step Three-Dimensional e-Beam Lithography

Au nanoparticles are synthesized in situ upon the electron beam exposure of a poly(vinyl alcohol) (PVA) thin film containing Au(III). The e-beam-irradiated areas are insoluble in water (negative-tone resist), and Au-PVA nanocomposite patterns with a variable profile along the structure can be thus generated (3D lithography) in a single step. A local characterization of the generated patterns is performed by high-resolution transmission electron microscopy and UV-vis localized surface plasmon resonance microspectroscopy. This characterization confirms the presence of crystalline nanoparticles and aggregates.

Homogeneous and inhomogeneous broadening in single perovskite nanocrystals investigated by micro-photoluminescence

Abstract Metal halides with perovskite crystalline structure have given rise to efficient optoelectronic and photonic devices. In the present work, we have studied the light emission properties of single CsPbBr3 and CsPbI3 semiconductor perovskite nanocrystals (PNCs), as the basis for a statistical analysis of micro-photoluminescence (micro-PL) spectra measured on tens of them. At room temperature, the linewidth extracted from PL spectra acquired in dense films of these nanocrystals is not very different from that of micro-PL measured in single nanocrystals. This means that the homogeneous linewidth due to exciton-phonon interaction is comparable or larger than the inhomogeneous effect asso…

Luminescent CdSe Quantum Dot Arrays for Rapid Sensing of Explosive Taggants

Chemical sensors based on fluorescent quantum dots have attracted intense interest because of their excellent optical and electronic properties compared to the routinely employed fluorescent organic dyes. This study reports a CdSe QD-polymer-based luminescent chemosensor, which is based on an array containing either green-emitting or red-emitting CdSe QDs embedded in polycaprolactone as a polymer host matrix. We evaluate the sensing capability of the nanocomposites by exposing both sensors to vapors of explosive taggants, explosive-like molecules, and some common solvents. Both nanocomposites exhibit a very fast response time of <30 s. The limit of detection of the sensors for 3-nitrotoluen…

Strongly-coupled PbS QD solids by doctor blading for IR photodetection

Solution-processed QD solids are emerging as a novel concept for high-performance optoelectronic devices. In this work, doctor blading is proposed for the fabrication of strongly-coupled QD solids from a PbS nanoink for photodetection at telecom wavelengths. The key step of this procedure is the solid-state ligand exchange, which reduces the interparticle distance and increases the carrier mobility in the resulting strongly-coupled QD solid. This is accomplished by replacing the original long oleylamine molecules by shorter molecules like 3-mercaptopropionic acid, as confirmed by FTIR, TGA and XPS. Further, a detailed investigation with XPS confirms the air-stability of the QD solids and th…

Patterning of Conducting Polymers Using UV Lithography: The in-Situ Polymerization Approach

We report on the in-situ polymerization of 3T with Cu(ClO4)2 inside several host polymers such as Novolak-based negative-tone photoresist, polystyrene (PS), poly(4-vinylphenol) (P4VP), poly(methyl methacrylate) (PMMA), and poly(4-vinylphenol)-co-(methyl methacrylate) (P4VP-co-MMA) to form an interpenetrating polymer network (IPN). Conducting IPN films in the order of 10–4–150 S/cm are obtained depending on the specific IPN composition. Moreover, the convenience of this synthetic approach has been demonstrated using a commercially available negative-tone photoresist based on Novolak as a host polymer. Novolak photoresist was properly formulated with 3T and Cu(ClO4)2 to preserve as far as pos…

High-resolution electron-beam patternable nanocomposite containing metal nanoparticles for plasmonics

Polymer nanocomposites containing noble metal nanoparticles are promising materials for plasmonic applications. In this paper, we report on a high-resolution negative-tone nanocomposite resist based on poly(vinyl alcohol) where silver nanoparticles and nanopatterns are simultaneously generated by electron-beam lithography. Our results indicate nanostructures with a relatively high concentration of nanoparticles and, consequently, an electromagnetic coupling among the nanoparticles. Therefore, the patternable nanocomposite described in this work may be a suitable material for future plasmonic circuitry.

A novel method of nanocrystal fabrication based on laser ablation in liquid environment

Abstract Metal nanoparticles can be prepared by a novel technique that consists of the laser ablation of a solid target immersed in a water solution of a metal salt. Silicon was chosen as the most adequate target to synthesize silver and gold nanoparticles from a water solution of either AgNO3 or HAuCl4. The influence of both the silver nitrate concentrations and the irradiation time of the Si target on the optical properties of the Au and Ag nanoparticles have been investigated. The crystalline nature of the metal nanoparticles has been determined by X-ray diffraction (XRD). Average size and particle size distribution have been measured by means of TEM. The absorbance spectra show the char…

Photonic Crystal‐Driven Spectral Concentration for Upconversion Photovoltaics

The main challenge for applying upconversion (UC) to silicon photovoltaics is the limited amount of solar energy harvested directly via erbium-based upconverter materials (24.5 W m–2). This could be increased up to 87.7 W m–2 via spectral concentration. Due to the nonlinear behavior of UC, this could increase the best UC emission by a factor 13. In this paper, the combined use of quantum dots (QDs)—for luminescent down-shifting—and photonic crystals (PCs)—for reshaping the emission—to achieve spectral concentration is shown. This implies dealing with the coupling of colloidal QDs and PC at the high-density regime, where the modes are shifted and broadened. In the first fabricated all-optica…

Novel patternable and conducting metal-polymer nanocomposites: a step towards advanced mutlifunctional materials

In this work, we present a novel patternable conducting nanocomposite containing gold nanoparticles. Here, the in-situ polymerization of 3T is carried out using HAuCl 4 as oxidizing agent inside PMMA as host matrix. During the bake step, the gold salt is also reduced from Au(III) to Au(0) generating Au nanoparticles in the interpenetrating polymer network (IPN) system. We found that this novel multifunctional resist shows electrical conductivity and plasmonic properties as well as potential patterning capability provided by the host matrix. The resulting nanocomposite has been investigated by TEM and UV-Vis spectroscopy. Electrical characterization was also conducted for different concentra…

Surface plasmon-polariton amplifiers

Propagation of surface plasmons at metal surfaces is receiving much interest nowadays because of its broad range of potential applications, like subwavelength photonics or biosensing. Although plasmonic devices achieve unique properties, surface plasmons suffer from high attenuation because of the absorption losses in the metal. This limitation can be overcome by providing the material adjacent to the metal with optical gain. Under these conditions, absorption losses are compensated and the propagation length of the plasmon is significantly increased. In this work, a review of plasmonic amplifiers is presented. To this end, the state of the art of such devices and the propagation characteri…

UV-patternable nanocomposite containing CdSe and PbS quantum dots as miniaturized luminescent chemo-sensors

In this study, a novel multifunctional hybrid polymer-based luminescent material, particularly formulated for photolithography, was developed, fabricated and tested as a miniaturized chemosensor. This nanocomposites were formulated with either luminescent CdSe (for the visible) or PbS (for the near-IR) colloidal QDs embedded in a polyisoprene-based photoresist (PIP). We checked the sensing capability of the nanocomposite by exposing 1 cm2 CdSe nanocomposite patterns to vapours of some analyte solutions such as 2-mercaptoethanol (MET) and ethylenediamine (EDA). The transduction mechanism of the sensor is based on changes of the QD photoluminescence (PL) when molecules are adsorbed on the QD …

Scalable heterogeneous synthesis of metallic nanoparticles and aggregates with polyvinyl alcohol

Here we report on a new route to synthesize colloidal silver and gold nanoparticles, potentially scalable for massive nanoparticle-production. This method is based on the microwave-assisted heterogeneous reduction of the metal salts with polyvinylalcohol. The reaction is carried out in alcohols, which are non-solvents for polyvinylalcohol. Nanoparticles can be very easily separated by filtration. The reaction kinetics are extremely fast. Size-controlled formation of nanoparticle agglomerates is accomplished with a seed-mediated synthesis of nanoparticles upon MW exposure.

Temperature Sensor Based on Colloidal Quantum Dots PMMA Nanocomposite Waveguides

In this paper, integrated temperature sensors based on active nanocomposite planar waveguides are presented. The nanocomposites consist of cadmium selenide (CdSe) and cadmium telluride (CdTe) quantum dots (QDs) embedded in a polymethylmethacrylate (PMMA) matrix. When the samples are heated in a temperature range from 25$^{circ}{rm C}$ to 50 $^{circ}{rm C}$, the waveguided photoluminescence of QDs suffers from a strong intensity decrease, which is approximately quadratic dependent on temperature. Moreover, the wavelength peak of the waveguided emission spectrum of CdTe-PMMA shows a blue shift of 0.25 ${rm nm}/^{circ}{rm C}$, whereas it remains constant in the case of CdSe-PMMA. A temperature…

Scientific and Technical Contributions from Research Projects

The main goal of this project is to demonstrate the advantages of sensor integration on a remotely controlled robotic platform for increasing operator safety and improving the classification of explosive targets. This is accomplished by combining the imaging provided by radars and an optoelectronic sensor, a time-of-flight (ToF) depth camera. An additional aim is to demonstrate the operability and practicality of the system in a field with landmine simulants having plastic cases.

Au–NiOx nanocomposite for hot electron-assisted plasmonic photocatalysis

Nanocomposites of metal–oxide semiconductors containing Au nanoparticles are emerging multifunctional materials for sunlight-driven highly efficient photocatalysis. Here we report a solution-processed nanocomposite synthesis of Au–NiOx nanocomposite films by slot-die coating and plotter printing in a straightforward in situ synthesis approach. Our study demonstrated a significantly enhanced photocatalytic decomposition reaction of MO upon exposure of Au–NiOx films to a sunlight simulator. The excellent photocatalytic activity is ascribed to the generation of hot carriers after LSPR excitation in Au NPs. Suitable band alignment between the valence band of NiOx and the Fermi level of Au NPs l…

Understanding Acid Reaction and Diffusion in Chemically Amplified Photoresists: An Approach at the Molecular Level

Acid diffusion in chemically amplified resist might limit the ultimate minimum half-pitch that can be achieved with high sensitivity resists unless diffusion length is reduced until new methods of sensitizing resists are found. Precise knowledge of molecular dynamics of resist materials and advanced techniques need to be developed actively for this issue. In this sense, computer simulations have become a valuable tool in terms of reducing time and costs. However, simulations are generally based on continuum or mesoscale models, which are unable to accurately predict variations at the molecular level. Deeper understanding and investigation of the coupled reaction-diffusion kinetics at the mo…

High spatial resolution mapping of individual and collective localized surface plasmon resonance modes of silver nanoparticle aggregates: correlation to optical measurements

Non-isolated nanoparticles show a plasmonic response that is governed by the localized surface plasmon resonance (LSPR) collective modes created by the nanoparticle aggregates. The individual and collective LSPR modes of silver nanoparticle aggregated by covalent binding by means of bifunctional molecular linkers are described in this study. Individual contributions to the collective modes are investigated at nanometer scale by means of energy-filtering transmission electron microscopy and compared to ultraviolet–visible spectroscopy. It is found that the aspect ratio and the shape of the clusters are the two main contributors to the low-energy collective modes.

Optical Optimization of the TiO2 Mesoporous Layer in Perovskite Solar Cells by the Addition of SiO2 Nanoparticles

In this work, SiO2 nanoparticles (NPs) were integrated into the mesoporous TiO2 layer of a perovskite solar cell to investigate their effect on cell performance. Different concentrations of SiO2/ethanol have been combined in TiO2/ethanol to prepare pastes for the fabrication of the mesoporous layer with which perovskite solar cells have been fabricated. Addition of SiO2 NPs of 50 and 100 nm sizes produces an enhancement of cell performance mainly because of an improvement of the photocurrent. This increment is in good agreement with the theoretical predictions based on light scattering induced by dielectric SiO2 NPs. The samples using modified scaffolds with NPs also present a significant l…

Color Tuning and White Light by Dispersing CdSe, CdTe, and CdS in PMMA Nanocomposite Waveguides

In this paper, active nanocomposite waveguides based on the dispersion of CdS, CdTe, and CdSe colloidal quantum dots (QDs) in PMMA are proposed. Their propagation properties are studied as a function of the concentration of nanoparticles in the polymer using the variable length stripe method. When the three nanostructures are dispersed in the same film, the structure is able to waveguide the three basic colors: red (CdSe), green (CdTe), and blue (CdS), it being possible to engineer any waveguided color by an appropriate choice of the filling factor of each QD in the PMMA matrix. For this purpose, it is important to take into account reabsorption effects and the F&#x00F6;rster energy transfe…

Novel Method of Preparation of Gold-Nanoparticle-Doped TiO2 and SiO2 Plasmonic Thin Films: Optical Characterization and Comparison with Maxwell-Garnett Modeling

SiO2 and TiO2 thin films with gold nanoparticles (NPs) are of particular interest as photovoltaic materials. A novel method for the preparation of spin-coated SiO2–Au and TiO2–Au nanocomposites is presented. This fast and inexpensive method, which includes three separate stages, is based on the in situ synthesis of both the metal-oxide matrix and the Au NPs during a baking process at relatively low temperature. It allows the formation of nanocomposite thin films with a higher concentration of Au NPs than other methods. High-resolution transmission electron microscopy studies revealed a homogeneous distribution of NPs over the film volume along with their narrow size distribution. The optica…

Efficient excitation of photoluminescence in a two-dimensional waveguide consisting of a quantum dot-polymer sandwich-type structure

International audience; In this Letter, we study a new kind of organic polymer waveguide numerically and experimentally by combining an ultrathin (10–50 nm) layer of compactly packed CdSe/ZnS core/shell colloidal quantum dots (QDs) sandwiched between two cladding poly(methyl methacrylate) (PMMA) layers. When a pumping laser beam is coupled into the waveguide edge, light is mostly confined around the QD layer, improving the efficiency of excitation. Moreover, the absence of losses in the claddings allows the propagation of the pumping laser beam along the entire waveguide length; hence, a high-intensity photoluminescence (PL) is produced. Furthermore, a novel fabrication technology is develo…

In Situ Synthesis of Conducting Polymers: A Novel Approach toward Polymer Thermoelectrics

The efficient conversion of thermal energy into electricity by means of durable and scalable solid-state thermoelectric devices has been a well stablished aim. Electrically conducting polymers have...

Polymer waveguide couplers based on metal nanoparticle–polymer nanocomposites

In this work Au nanoparticles (AuNPs) are incorporated into poly(methyl methacrylate) (PMMA) waveguides to develop optical couplers that are compatible with planar organic polymer photonics. A method for growing AuNPs (of 10 to 100 nm in size) inside the commercially available Novolak resist is proposed with the intention of tuning the plasmon resonance and the absorption/scattering efficiencies inside the patterned structures. The refractive index of the MNP-Novolak nanocomposite (MNPs: noble metal nanoparticles) is carefully analysed both experimentally and numerically in order to find the appropriate fabrication conditions (filling factor and growth time) to optimize the scattering cross…

MWP true time delay implemented in PbS-SU8 waveguides

Es presenta un nou tipus de dispositiu de retard en temps real de microones (TTD) basat en la dispersió de punts quàntics col·loïdals PbS (QD) en el fotoresist SU8 disponible comercialment. Amb aquest propòsit, els nanocompostos PbS-SU8 s’integren en una plataforma de silici en forma de guies d’ones de cresta. Quan aquestes estructures es bomben a longituds d’ona per sota de l’interval de banda dels PbS QD, es realitza un desplaçament de fase en un senyal de microones transmès òpticament (a 1550 nm) i, per tant, es produeix un retard temporal. A més, es milloren els resultats mitjançant la implementació d’una nova guia d’ones de doble capa de cresta composta per un nanocompost PbS-SU8 i una…

Charge Transport in Trap-Sensitized Infrared PbS Quantum-Dot-Based Photoconductors: Pros and Cons

Control of quantum-dot (QD) surface chemistry offers a direct approach for the tuning of charge-carrier dynamics in photoconductors based on strongly coupled QD solids. We investigate the effects of altering the surface chemistry of PbS QDs in such QD solids via ligand exchange using 3-mercaptopropionic acid (MPA) and tetrabutylammonium iodide (TBAI). The roll-to-roll compatible doctor-blade technique was used for the fabrication of the QD solid films as the photoactive component in photoconductors and field-effect phototransistors. The ligand exchange of the QD solid film with MPA yields superior device performance with higher photosensitivity and detectivity, which is due to less dark cur…

Charge dissipation in e-beam lithography with Novolak-based conducting polymer films

Charging of common resist materials during electron beam (e-beam) writing leads to deflection of the electron beam path, which can result in significant pattern displacement. Here we report a new conducting polymer to eliminate charging. A common approach is to place the conducting layer underneath the e-beam resist layer. Conductivity equal or greater than 10(-4) S cm(-1) has been reported to prevent pattern displacement. Some other properties such as a flat surface layer, chemical inertness and insolubility in both the top resist solvent and the developer are also necessary. The way to achieve all these properties consisted in synthesizing a conducting polymer inside an insulating polymer…

Molecular-mediated assembly of silver nanoparticles with controlled interparticle spacing and chain length

In the present work, we report on a one-pot method for the assembly of noble metal nanoparticles with tunable optical properties, assembly length and interparticle spacing. The synthetic colloidal route is based on the covalent binding among OH-terminated silver nanoparticles by means of dicarboxylic acids with a defined molecular length. As a result, the initially symmetric plasmon band of silver nanoparticles splits into two plasmonic modes when nanoparticles are assembled due to the strong near-field plasmon coupling. We noticed a very good correlation between the plasmon wavelength shift and the interparticle spacing that is represented by the universal scaling law of the surface plasmo…

Preparation and processing of nanocomposites of all-inorganic lead halide perovskite nanocrystals

Abstract Solution processed all-inorganic trihalide perovskite nanocrystals are potential materials for the fabrication of future generation optoelectronic devices. However, the surface of the perovskite nanocrystals should be encapsulated to prevent degradation. Because of their stability under ambient conditions, nanocomposites of perovskite nanocrystals have been intensively researched for display applications. Perovskite nanocrystals dispersion or growth in a polymer matrix imparts structural stability and influences the optical properties, preventing effects such as halide migration. Developing flexible, high-performance lighting devices through perovskite nanocomposites will need to b…

Photoluminescence waveguiding in CdSe and CdTe QDs–PMMA nanocomposite films

In this paper, active planar waveguides based on the incorporation of CdSe and CdTe nanocrystal quantum dots in a polymer matrix are demonstrated. In the case of doping the polymer with both types of quantum dots, the nanocomposite film guides both emitted colors, green (550 nm, CdTe) and orange (600 nm, CdSe). The optical pumping laser can be coupled not only with a standard end-fire coupling system, but also directing the beam to the surface of the sample, indicating a good absorption cross-section and waveguide properties. To achieve these results, a study of the nanocomposite optical properties as a function of the nanocrystal concentration is presented and the optimum conditions are fo…

In Situ Synthesis of Polythiophene and Silver Nanoparticles within a PMMA Matrix: A Nanocomposite Approach to Thermoelectrics

The processability of organic thermoelectric materials plays a crucial role due to their clear advantages of applicability in large-scale areas compared to traditional inorganic counterparts. A promising way to process thermoelectric materials based on conductive polymers is through in situ polymerization in an insulating polymer matrix. This work shows an interpenetrating polymeric network based on polythiophene, silver nanoparticles (Ag NPs), and poly(methyl methacrylate) (PMMA) produced by the oxidative polymerization of terthiophene by an oxidizing silver salt in a PMMA matrix. Ag NPs are in situ synthesized simultaneously as a byproduct. The reaction occurs very fast in the solid state…

Spray-driven Solid-State Halide Exchange in CsPbX3 Nanocrystal Films

Metal-polymer nanocomposite resist: a step towards in-situ nanopatterns metallization

In this work we propose an alternative method for the fabrication of metal micro/nanostructures from metal-polymer nanocomposite resists and their subsequent electroless metallization. The process consists of three simple steps: 1. Fabrication of micro or nanopatterns by lithography or any other direct printing technologies (inkjet or microplotter printing...), 2. In-situ synthesis of metal nanoparticle during a post-bake step and 3. Non-electrochemical metallization of nanocomposite patterns. The novelty of our approach is that both Ag and Au nanoparticles are embedded into the polymer pattern and act as seeds for the reduction of Ag(I) when immersed into a solution of the corresponding pr…

DNA delivery to 'ex vivo' human liver segments.

Hydrodynamic injection is an efficient procedure for liver gene therapy in rodents but with limited efficacy in large animals, using an 'in vivo' adapted regional hydrodynamic gene delivery system. We study the ability of this procedure to mediate gene delivery in human liver segments obtained by surgical resection. Watertight liver segments were retrogradely injected from hepatic vein with a saline solution containing a plasmid bearing the enhanced green fluorescent protein (eGFP) gene, under different conditions of flow rate (1, 10 and 20 ml s(-1)) and final perfused volume. Samples were cultured for 1 to 2 days and used for microscopy and molecular analysis of gene expression. The fluore…

Solution-processed Nickel Oxide electrocatalyst for Electrochemical Water Splitting

Resist-based silver nanocomposites synthesized by lithographic methods

In this work, the formation of silver metal nanoparticles inside a negative-tone resist based on poly(vinyl alcohol) is achieved by electron beam lithography. The chemistry of this sensitive resist allows the production of nanoparticles as well as the polymer crosslinking by the electron radiation. Due to the presence of the silver nanoparticles, the final composite exhibits a plasmonic behavior, which was characterized by measuring the absorbance. The lithographic properties of the resist have been characterized. The technique has also been exported to UV lithography, where silver nanoparticles are obtained inside the polymeric patterns after optical lithography.