Structural characterization of bulk and nanoparticle lead halide perovskite thin films by (S)TEM techniques.

Lead halide (APbX3) perovskites, in polycrystalline thin films but also perovskite nanoparticles (NPs) has demonstrated excellent performance to implement a new generation of photovoltaic and photonic devices. The structural characterization of APbX3 thin films using (scanning) transmission electron microscopy ((S)TEM) techniques can provide valuable information that can be used to understand and model their optoelectronic performance and device properties. However, since APbX3 perovskites are soft materials, their characterization using (S)TEM is challenging. Here, we study and compare the structural properties of two different metal halide APbX3 perovskite thin films: bulk CH3NH3PbI3 prepared by spin-coating of the precursors in solution and CsPbBr3 colloidal NPs synthetized and deposited by doctor blading. Both specimen preparation methods and working conditions for analysis by (S)TEM are properly optimized. We show that CH3NH3PbI3 thin films grown by a one-step method are composed of independent grains with random orientations. The growth method results in the formation of tetragonal perovskite thin films with good adherence to an underlying TiO2 layer, which is characterized by a photoluminescence (PL) emission band centered at 775 nm. The perovskite thin films based on CsPbBr3 colloidal NPs, which are used as the building blocks of the film, are preserved by the deposition process, even if small gaps are observed between adjacent NPs. The crystal structure of CsPbBr3 NPs is cubic, which is beneficial for optical properties due to its optimal band gap. The absorption and PL spectra measured in both the thin film and the colloidal solution of CsPbBr3 NPs are very similar, indicating a good homogeneity of the thin films and the absence of aggregation of NPs. However, a particular care was required to avoid long electron irradiation times during our structural studies, even at a low voltage of 80 kV, as the material was observed to decompose through Pb segregation.

Optical contrast of 2D InSe on SiO2/Si and transparent substrates using bandpass filters.

The particular optical and electronic properties recently reported for 2D InSe depict this 2D material as being very versatile for future electronic and optoelectronic devices with tunable and optimized functionalities. For its fundamental study and the development of practical applications, rapid and accurate identification methods of atomically thin InSe are essential. Here, we demonstrate an enhancement of the optical contrast between InSe nanosheets and the underlying SiO2/Si substrate by illuminating with a 40 nm wide bandpass filter centered at 500 nm. Moreover, we study the optical contrast of 2D InSe on transparent substrates. Our results suggest that a good optical contrast is achieved for transparent substrates with low real refractive indices such as LiF or a viscoelastic polydimethylsiloxane stamp. In this case, an optimum optical contrast would be achieved by using a bandpass filter centered at 450 nm. These results can be very useful for speeding up the continuously growing research on 2D InSe and its applications.

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.

Plasmonic layers based on Au-nanoparticle-doped TiO2 for optoelectronics: structural and optical properties.

The anti-reflective effect of dielectric coatings used in silicon solar cells has traditionally been the subject of intensive studies and practical applications. In recent years the interest has permanently grown in plasmonic layers based on metal nanoparticles, which are shown to increase light trapping in the underlying silicon. In the present work we have combined these two concepts by means of in situ synthesis of Au nanoparticles in a dielectric matrix (TiO2), which is commonly used as an anti-reflective coating in silicon solar cells, and added the third element: a 10-20% porosity in the matrix. The porosity is formed by means of a controllable wet etching by low concentration HF. As a consequence, the experimentally measured reflectance of silicon coated by such a plasmonic layer decreases to practically zero in a broad wavelength region around the localized surface plasmon resonance. Furthermore, we demonstrate that extinction and reflectance spectra of silicon coated by the plasmonic films can be successfully accounted for by means of Fresnel formulae, in which a double refractive index of the metal-dielectric material is used. This double refractive index cannot be explained by effective medium theory (Maxwell-Garnett, for example) and appears when the contribution of Au nanoparticles located at the TiO2/Si interface is high enough to result in formation of interface surface plasmon modes.

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.

Spatial carrier distribution in InP/GaAs type II quantum dots and quantum posts.

We performed a detailed investigation of the structural and optical properties of multi-layers of InP/GaAs quantum dots, which present a type II interface arrangement. Transmission electronic microscopy analysis has revealed relatively large dots that coalesce forming so-called quantum posts when the GaAs layer between the InP layers is thin. We observed that the structural properties and morphology affect the resulting radiative lifetime of the carriers in our systems. The carrier lifetimes are relatively long, as expected for type II systems, as compared to those observed for single layer InP/GaAs quantum dots. The interface intermixing effect has been pointed out as a limiting factor for obtaining an effective spatial separation of electrons and holes in the case of single layer InP/GaAs quantum-dot samples. In the present case this effect seems to be less critical due to the particular carrier wavefunction distribution along the structures.

Enhanced Nonlinear Optical Coefficients of MAPbI3 Thin Films by Bismuth Doping.

The poor photostability under ambient conditions of hybrid halide perovskites has hindered their recently explored promising nonlinear optical properties. Here, we show how Bi3+ can partially substitute Pb2+ homogeneously in the commonly studied MAPbI3, improving both environmental stability and photostability under high laser irradiation. Bi content around 2 atom % produces thin films where the nonlinear refractive (n2) and absorptive coefficients (ß), which modify the refractive index (Δn) of the material with light fluence (I), increase up to factors of 4 and 3.5, respectively, compared to undoped MAPbI3. Higher doping inhibits the nonlinear parameters; however, the samples show higher fluence damage thresholds. Thus, these results provide a road map on how MAPbI3 can be engineered for practical cost-effective nonlinear applications by means of Bi doping, including optical limiting devices and multiple-harmonic generation into optoelectronics devices.

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.