Spray-driven halide exchange in solid-state CsPbX3 nanocrystal films.

CsPbI3 perovskite nanocrystals (NCs) are promising building blocks for photovoltaics and optoelectronics. However, they exhibit an essential drawback in the form of phase stability: α-phase, with a ∼1.80 eV bandgap, can easily experience a phase transition to a non-radiative orthorhombic δ-phase in an ambient environment. This leads to the need to carry out the CsPbI3-based device fabrication in an inert atmosphere, which is technologically inconvenient and expensive. One of the most successful approaches proposed to overcome this problem is synthesizing mixed halide CsPbBr3-xIx NCs to improve the stability of the α-phase perovskite structure. However, the formation of high-quality thin films of CsPbBr3-xIx NCs with high PLQY is challenging owing to the degradation of their optical properties after deposition on a substrate. This work presents spray coating to carry out a solid-state anion exchange in CsPbBr3 NCs thin films at ambient conditions with low-demanding reaction conditions. This constitutes a novel open-air and annealing-free technology to manufacture CsPbBr3-xIx NC thin films with high optical quality and record high photoluminescence quantum yields (PLQY) based on spray-driven halide (Br- to I-) anion exchange in a solid-state phase. Besides, tunable emission wavelengths between 520 and 670 nm can be obtained from CsPbBr3-xIx NC films using accurate tuning volumes of HI solution sprayed over the initial surface of CsPbBr3 film to provide the halide exchange. The optical quality of the halide-exchanged PNCs films remains practically identical to that of initial Br-containing layers, with a remarkable PLQY enhancement after anion exchange, from ∼61% for CsPbBr3 thin films emitting at 520 nm to ∼84% for mixed halide CsPbBr3-xIx film emitting at 640 nm. The huge potential of the system is confirmed by demonstrating a low-threshold amplified spontaneous emission.

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 section at a desired wavelength. Then the nanocomposite is patterned inside a PMMA waveguide to exploit its scattering properties to couple and guide a normal incident laser light beam along the polymer. In this way, light coupling is experimentally demonstrated in a broad wavelength range (404-780 nm). Due to the elliptical shape of the MNPs the nanocomposite demonstrates a birefringence, which enhances the coupling to the TE mode up to efficiencies of around 1%.

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

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 developed to pattern the PMMA into ridge structures by UV lithography in order to provide additional light confinement. The sandwich-type waveguide is analyzed in comparison to a similar one formed by a PMMA film homogeneously doped by the same QDs. A 100-fold enhancement in the waveguided PL is found for the sandwich-type case due to the higher concentration of QDs inside the waveguide.

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 fluorescent and immunohistochemistry studies indicated that in segments injected at ≥10 ml s(-1), good and wide gene expression was present in the liver sections and the molecular analysis reinforced the histological observation in a quantitative manner (index of apparent gene delivery: 10(2)-10(4) eGFP DNA copy per 100 pg of total DNA; transcription index: 10(5)-2 × 10(6) eGFP RNA copy per 100 ng of total RNA). In addition, injected gold nanoparticles (15 nm diameter) suggested that DNA delivery to hepatocytes must involve a facilitated permeation process without membrane disruption. In summary, we show that retrograde venous injection of watertight human liver segment is an anadromous procedure that results in wide liver gene delivery and good gene expression. However, additional studies will be necessary to clarify the influence of the prolonged ischemia injury to hepatocytes in our model.

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 found for waveguiding.

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 to form an interpenetrating polymer network (IPN) which could combine their properties. Novolak was used as the host polymer and terthiophene (3T) as the monomer to polymerize. Cu(ClO(4))(2) initiates simultaneously the oxidative polymerization of the 3T and its subsequent doping inside Novolak during the bake step in a one-step reaction. Solvent-resistant and homogeneous conducting films with smooth surfaces were achieved. The conductivity was of the order of 10(-2) S cm(-1). Patterning of the top resist was carried out without disturbing its lithographic performance.

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.