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.

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

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…

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 …

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…

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…

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 …

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…

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 Förster energy transfe…

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…

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…

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…

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…

Propagation length enhancement of surface plasmon polaritons in gold nano-/micro-waveguides by the interference with photonic modes in the surrounding active dielectrics

Abstract In this work, the unique optical properties of surface plasmon polaritons (SPPs), i.e. subwavelength confinement or strong electric field concentration, are exploited to demonstrate the propagation of light signal at 600 nm along distances in the range from 17 to 150 μm for Au nanostripes 500 nm down to 100 nm wide (30 nm of height), respectively, both theoretically and experimentally. A low power laser is coupled into an optical fiber tip that is used to locally excite the photoluminescence of colloidal quantum dots (QDs) dispersed in their surroundings. Emitted light from these QDs is generating the SPPs that propagate along the metal waveguides. Then, the above-referred propagat…

Metasurfaces for colour printing

We present a theoretical analysis and experimental evidences of metasurfaces based on particle resonators that achieve bright-field colour prints. We created pixels that support individual colours, miniaturized and juxtaposed at the optical diffraction limit. Different strategies are followed to offer the flexibility of using both transmitting and epi (reflective) white light sources. We discuss their potential applications in large-volume colour printing via nanoimprint lithography.

Dielectric and plasmonic waveguides based on quantum dots embedded in polymers

espanolEn este trabajo se propone una revision de la implementacion de guias de onda activas basadas en la dispersion de puntos cuanticos coloidales (QDs) en polimeros. Para ello, guias de onda planas fueron fabricadas embebiendo distintos tipos de nanoestructuras semiconductoras con emision en el visible e infrarrojo (CdS, CdTe, CdSe, PbS) en PMMA, encontrandose las condiciones optimas para el guiado de su fotoluminiscencia y sus propiedades de ganancia y atenuacion. Si varios tipos de puntos son dispersados en la misma capa se propagan varios colores, siendo posible obtener luz blanca con las proporciones adecuadas de rojo, verde y azul. Asimismo, el guiado puede ser mejorado si una cubie…

In-situ synthesis of thiophene-based multifunctional polymeric networks with tunable conductivity and high photolithographic performance

Abstract Design of novel multifunctional polymeric materials combining electrically conducting properties with patterning capability is a significant challenge in materials science. Herein, we report on the synthesis of multifunctional interpenetrating polymer networks (IPN) by the in-situ oxidative polymerization of thiophene-based monomers with Cu(ClO 4 ) 2 inside a novolac-based photoresist. The resulting IPNs show conductivities up to 20 S/cm depending on the monomer properties. Among them, 3,3‴-Dihexyl-2,2’:5′,2’’:5″,2‴-quaterthiophene (DH4T) is chosen because it has the largest conjugation length and excellent solubility in organic solvents. Moreover, it renders a low percolation thre…

Ligand-Length Modification in CsPbBr3 Perovskite Nanocrystals and Bilayers with PbS Quantum Dots for Improved Photodetection Performance

Nanocrystals surface chemistry engineering offers a direct approach to tune charge carrier dynamics in nanocrystals-based photodetectors. For this purpose, we have investigated the effects of altering the surface chemistry of thin films of CsPbBr3 perovskite nanocrystals produced by the doctor blading technique, via solid state ligand-exchange using 3-mercaptopropionic acid (MPA). The electrical and electro-optical properties of photovoltaic and photoconductor devices were improved after the MPA ligand exchange, mainly because of a mobility increase up to 5 &times