Tuning optical/electrical properties of 2D/3D perovskite by the inclusion of aromatic cation.

The employment of bulky aliphatic cations in the manufacture of moisture-stable materials has triggered the development and application of 2D/3D perovskites as sensitizers in moisture-stable solar cells. Although it is true that the moisture stability increases, it is also true that the photovoltaic performance of 2D/3D PVK materials is severely limited owing to quantum and dielectric confinement effects. Accordingly, it is necessary the synthesis and deep optical characterization of materials with an adequate management of dielectric contrast between the layers. Here, we demonstrate the successful tuning of dielectric confinement by the inclusion of a conjugated molecule, as a bulky cation, in the fabrication of the 2D/3D PVK material (C6H5NH3)2(CH3NH3)n-1PbnI3n+1, where n = 3 or 5. The absence of excitonic states related to n ≥ 1 at room temperature, as well as the very low concentration of excitons after 1 ps of excitation of samples in which n ≥ 3, provide strong evidence of an excellent ability to dissociate excitons into free charge carriers. As consequence films with low n, presenting higher stability than standard 3D perovskites, improved significantly their performance, showing one of the highest short circuit current density (Jsc ≈ 13.8) obtained to date for perovskite materials within the 2D limit (n < 10).

MWP phase shifters integrated in PbS-SU8 waveguides.

We present new kind of microwave phase shifters (MPS) based on dispersion of PbS colloidal quantum dots (QDs) in commercially available photoresist SU8 after a ligand exchange process. Ridge PbS-SU8 waveguides are implemented by integration of the nanocomposite in a silicon platform. When these waveguides are pumped at wavelengths below the band-gap of the PbS QDs, a phase shift in an optically conveyed (at 1550 nm) microwave signal is produced. The strong light confinement produced in the ridge waveguides allows an improvement of the phase shift as compared to the case of planar structures. Moreover, a novel ridge bilayer waveguide composed by a PbS-SU8 nanocomposite and a SU8 passive layer is proposed to decrease the propagation losses of the pump beam and in consequence to improve the microwave phase shift up to 36.5° at 25 GHz. Experimental results are reproduced by a theoretical model based on the slow light effect produced in a semiconductor waveguide due to the coherent population oscillations. The resulting device shows potential benefits respect to the current MPS technologies since it allows a fast tunability of the phase shift and a high level of integration due to its small size.

Tailoring Single-Mode Random Lasing of Tin Halide Perovskites Integrated in a Vertical Cavity.

The development of random lasing (RL) with predictable and controlled properties is an important step to make these cheap optical sources stable and reliable. However, the design of tailored RL characteristics (emission energy, threshold, number of modes) is only obtained with complex photonic structures, while the simplest optical configurations able to tune the RL are still a challenge. This work demonstrates the tuning of the RL characteristics in spin-coated and inkjet-printed tin-based perovskites integrated into a vertical cavity with low quality factor. When the cavity mode is resonant with the photoluminescence (PL) peak energy, standard vertical lasing is observed. More importantly, single mode RL operation with the lowest threshold and a quality factor as high as 1 000 (twenty times the quality factor of the resonator) is obtained if the cavity mode lies above the PL peak energy due to higher gain. These results can have important technological implications toward the development of low-cost RL sources without chaotic behavior.

Unusual Spectrally Reproducible and High Q-Factor Random Lasing in Polycrystalline Tin Perovskite Films.

An unusual spectrally reproducible near-IR random lasing (RL) with no fluctuation of lasing peak wavelength is disclosed in polycrystalline films of formamidinium tin triiodide perovskite, which have been chemically stabilized against Sn2+ to Sn4+ oxidation. Remarkably, a quality Q-factor as high as ≈104 with an amplified spontaneous emission (ASE) threshold as low as 2 µJ cm-2 (both at 20 K) are achieved. The observed spectral reproducibility is unprecedented for semiconductor thin film RL systems and cannot be explained by the strong spatial localization of lasing modes. Instead, it is suggested that the spectral stability is a result of such an unique property of Sn-based perovskites as a large inhomogeneous broadening of the emitting centers, which is a consequence of an intrinsic structural inhomogeneity of the material. Due to this, lasing can occur simultaneously in modes that are spatially strongly overlapped, as long as the spectral separation between the modes is larger than the homogeneous linewidth of the emitting centers. The discovered mechanism of RL spectral stability in semiconductor materials, possessing inhomogeneous broadening, opens up prospects for their practical use as cheap sources of narrow laser lines.

Enhanced Spontaneous Emission of CsPbI3 Perovskite Nanocrystals Using a Hyperbolic Metamaterial Modified by Dielectric Nanoantenna.

In this work, we demonstrate, theoretically and experimentally, a hybrid dielectric-plasmonic multifunctional structure able to provide full control of the emission properties of CsPbI3 perovskite nanocrystals (PNCs). The device consists of a hyperbolic metamaterial (HMM) composed of alternating thin metal (Ag) and dielectric (LiF) layers, covered by TiO2 spherical MIE nanoresonators (i.e., the nanoantenna). An optimum HMM leads to a certain Purcell effect, i.e., an increase in the exciton radiative rate, but the emission intensity is reduced due to the presence of metal in the HMM. The incorporation of TiO2 nanoresonators deposited on the top of the HMM is able to counteract such an undesirable intensity reduction by the coupling between the exciton and the MIE modes of the dielectric nanoantenna. More importantly, MIE nanoresonators result in a preferential light emission towards the normal direction to the HMM plane, increasing the collected signal by more than one order of magnitude together with a further increase in the Purcell factor. These results will be useful in quantum information applications involving single emitters based on PNCs together with a high exciton emission rate and intensity.

Birefringent porous silicon membranes for optical sensing.

In this work anisotropic porous silicon is investigated as a material for optical sensing. Birefringence and sensitivity of the anisotropic porous silicon membranes are thoroughly studied in the framework of Bruggeman model which is extended to incorporate the influence of environment effects, such as silicon oxidation. The membranes were also characterized optically demonstrating sensitivity as high as 1245 nm/RIU at 1500 nm. This experimental value only agrees with the theory when it takes into consideration the effect of silicon oxidation. Furthermore we demonstrate that oxidized porous silicon membranes have optical parameters with long term stability. Finally, we developed a new model to determine the contribution of the main depolarization sources to the overall depolarization process, and how it influences the measured spectra and the resolution of birefringence measurements.

Inhomogeneous Broadening of Photoluminescence Spectra and Kinetics of Nanometer-Thick (Phenethylammonium)2PbI4 Perovskite Thin Films: Implications for Optoelectronics.

An outstanding potentiality of layered two-dimensional (2D) organic-inorganic hybrid perovskites (2DHPs) is in the development of solar cells, photodetectors, and light-emitting diodes. In 2DHPs, an exciton is localized in an atomically thin lead(II) halide inorganic layer of sub-nanometer thickness as in a quantum well sandwiched between organic layers as energetic and dielectric barriers. In previous years, versatile optical characterization of 2DHPs has been carried out mainly for thin flakes of single crystals and ultrathin (of the order of 20 nm) polycrystalline films, whereas there is a lack of optical characterization of thick (hundreds of nanometers) polycrystalline films, fundamentals for fabrication of devices. Here, with the use of photoluminescence (PL) and absorption spectroscopies, we studied the exciton behavior in ∼200 nm polycrystalline thin films of 2D perovskite (PEA)2PbI4, where PEA is phenethylammonium. Contrary to the case of ultrathin films, we have found that peak energies and line width of the excitonic bands in our films demonstrate unusual extremely weak sensitivity to temperature in 20-300 K diapason. The excitonic PL band is characterized by a significant (∼30 meV) Stokes shift with respect to the corresponding absorption band as well as by a full absence of the exciton fine structure at cryogenic temperatures. We suggest that the observed effects are due to the large inhomogeneous broadening of the excitonic PL and absorption bands resulting from the (PEA)2PbI4 band gap energy dependence on the number of lead(II) halide layers of individual crystallites. The characteristic time of the exciton energy funneling from higher- to lower-energy crystallites within (PEA)2PbI4 polycrystalline thin films is about 100 ps.

Purcell Enhancement and Wavelength Shift of Emitted Light by CsPbI3 Perovskite Nanocrystals Coupled to Hyperbolic Metamaterials.

Manipulation of the exciton emission rate in nanocrystals of lead halide perovskites (LHPs) was demonstrated by means of coupling of excitons with a hyperbolic metamaterial (HMM) consisting of alternating thin metal (Ag) and dielectric (LiF) layers. Such a coupling is found to induce an increase of the exciton radiative recombination rate by more than a factor of three due to the Purcell effect when the distance between the quantum emitter and HMM is nominally as small as 10 nm, which coincides well with the results of our theoretical analysis. Besides, an effect of the coupling-induced long wavelength shift of the exciton emission spectrum is detected and modeled. These results can be of interest for quantum information applications of single emitters on the basis of perovskite nanocrystals with high photon emission rates.

Single-Exciton Amplified Spontaneous Emission in Thin Films of CsPbX3 (X = Br, I) Perovskite Nanocrystals.

CsPbX3 perovskite nanocrystals (PNCs) have emerged as an excellent material for stimulated emission purposes, with even more prospective applications than conventional colloidal quantum dots. However, a better understanding of the physical mechanisms responsible for amplified spontaneous emission (ASE) is required to achieve more ambitious targets (lasing under continuous wave optical or electrical excitation). Here, we establish the intrinsic mechanisms underlying ASE in PNCs of three different band gaps (CsPbBr3, CsPbBr1.5I1.5, and CsPbI3). Our characterization at cryogenic temperatures does not reveal any evidence of the biexciton mechanism in the formation of ASE. Instead, the measured shift toward long wavelengths of the ASE band is easily explained by the reabsorption in the PNC layer, which becomes stronger for thicker layers. In this way, the threshold of ASE is determined only by optical losses at a given geometry, which is the single-exciton mechanism responsible for ASE. Experimental results are properly reproduced by a physical model.

Optical Amplification in Hollow-Core Negative-Curvature Fibers Doped with Perovskite CsPbBr3 Nanocrystals.

We report a hollow-core negative-curvature fiber (HC-NCF) optical signal amplifier fabricated by the filling of the air microchannels of the fiber with all-inorganic CsPbBr3 perovskite nanocrystals (PNCs). The optimum fabrication conditions were found to enhance the optical gain, up to +3 dB in the best device. Experimental results were approximately reproduced by a gain assisted mechanism based on the nonlinear optical properties of the PNCs, indicating that signal regeneration can be achieved under low pump powers, much below the threshold of stimulated emission. The results can pave the road of new functionalities of the HC-NCF with PNCs, such as optical amplification, nonlinear frequency conversion and gas sensors.

Toward Metal Halide Perovskite Nonlinear Photonics.

The possibility of controlling light using the nonlinear optical properties of photonic devices opens new points of view in information and communications technology applications. In this Perspective, we review and analyze the potential role of metal halide perovskites in a framework different from their usual one in photovoltaic and light-emitting devices, namely, the one where they can play as nonlinear photonic materials. We contextualize this new role by comparing the few extant results on their nonlinear optical properties to those of other known nonlinear materials. As a result of this analysis, we provide a vision of future developments in photonics that can be expected from this new perspective on metal halide perovskites.

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 current and lower noise level as compared to ligand exchange with TBAI. In both cases, the mechanism responsible for photoconductivity is related to trap sensitization of the QD solid, in which traps are responsible of high photoconductive gain values, but slow response times under very low incident optical power (<1 pW). At medium⁻high incident optical powers (>100 pW), where traps are filled, both MPA- and TBAI-treated photodevices exhibit similar behavior, characterized by lower responsivity and faster response time, as limited by the mobility in the QD solid.

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 lower current-potential hysteresis indicating that NP incorporation also affects the ion accumulation at the perovskite interface, providing an additional beneficial effect. The results stress the importance of the appropriated management of the optical properties on further optimization of perovskite solar cell technology.

Enhancement of the Performance of Perovskite Solar Cells, LEDs, and Optical Amplifiers by Anti-Solvent Additive Deposition.

The efficiency of perovskite optoelectronic devices is increased by a novel method; its suitability for perovskite solar cells, light-emitting diodes, and optical amplifiers is demonstrated. The method is based on the introduction of organic additives during the anti-solvent step in the perovskite thin-film deposition process. Additives passivate grain boundaries reducing non-radiative recombination. The method can be easily extended to other additives.

Single step deposition of an interacting layer of a perovskite matrix with embedded quantum dots.

Hybrid lead halide perovskite (PS) derivatives have emerged as very promising materials for the development of optoelectronic devices in the last few years. At the same time, inorganic nanocrystals with quantum confinement (QDs) possess unique properties that make them suitable materials for the development of photovoltaics, imaging and lighting applications, among others. In this work, we report on a new methodology for the deposition of high quality, large grain size and pinhole free PS films (CH3NH3PbI3) with embedded PbS and PbS/CdS core/shell Quantum Dots (QDs). The strong interaction between both semiconductors is revealed by the formation of an exciplex state, which is monitored by photoluminescence and electroluminescence experiments. The radiative exciplex relaxation is centered in the near infrared region (NIR), ≈1200 nm, which corresponds to lower energies than the corresponding band gap of both perovskite (PS) and QDs. Our approach allows the fabrication of multi-wavelength light emitting diodes (LEDs) based on a PS matrix with embedded QDs, which show considerably low turn-on potentials. The presence of the exciplex state of PS and QDs opens up a broad range of possibilities with important implications in both LEDs and solar cells.

Tunable light emission by exciplex state formation between hybrid halide perovskite and core/shell quantum dots: Implications in advanced LEDs and photovoltaics.

We report the first observation of exciplex state electroluminescence due to carrier injection between the hybrid lead halide perovskite (MAPbI3-xClx) and quantum dots (core/shell PbS/CdS). Single layers of perovskite (PS) and quantum dots (QDs) have been produced by solution processing methods, and their photoluminescent properties are compared to those of bilayer samples in both PS/QD and QD/PS configurations. Exciplex emission at lower energies than the band gap of both PS and QD has been detected. The exciplex emission wavelength of this mixed system can be simply tuned by controlling the QD size. Light-emitting diodes (LEDs) have been fabricated using those configurations, which provide light emission with considerably low turn-on potential. The "color" of the LED can also be tuned by controlling the applied bias. The presence of the exciplex state PS and QDs opens up a broad range of possibilities with important implications not only in tunable LEDs but also in the preparation of intermediate band gap photovoltaic devices with the potentiality of surpassing the Shockley-Queisser limit.

Polymer/Perovskite Amplifying Waveguides for Active Hybrid Silicon Photonics.

The emission properties of hybrid halide perovskites are exploited to implement a stable and very low power operation waveguide optical amplifier integrated in a silicon platform. By optimizing its design with a poly(methyl methacrylate) (PMMA) encapsulation, this novel photonic device presents a net gain of around 10 dB cm(-1) and 3-4 nm linewidth with an energy threshold as low as 2 nJ pulse(-1) and exhibiting no degradation after one year.

[Biovolume of some centric diatoms from the northeastern continental shelf of Venezuela]. / Biovolumen de algunas diatomeas céntricas de la plataforma nororiental de Venezuela.

Biovolume variation of twelve centric diatom species from eight natural habitats of the northeastem continental shelf of Venezuela were analyzed. Also, the morphometric variable that exerts the greatest influence on the biovolume was determined. Samples were collected with a net (mesh 36 microns), or with a Niskin bottle (5 l) and fixed with neutralized formaldehyde (4%). Water temperature and salinity were measured. The species studied were: Detonula sp., Skeletonema costatum, Lauderia annulata, Pseudoguinardia recta, Cerataulina pelagica, Helicotheca tamesis, Rhizosolenia styliformis, Proboscia alata, Guinardia flaccida, G. striata, Dactyliosolen fragilissimus y Leptocylindrus danicus. Forty individuals of each species from each locality were isolated and measured with a Leitz Wetzlar binocular microscope with an ocular micrometer, magnified 400X. A one-way ANOVA showed the existence of highly significant differences (p < 0.001) in the biovolume of the species regarded with its locality. These differences could be due to: (a) temporal differences in sample collection: (b) the existence of populations in different phases of their vital cycles; (c) genetic differences; (d) and differences in the physical-chemical environment at each locality. The diameter was the morphometric variable exhibiting the largest positive correlation (r > or = 0.77, p < 0.001) with biovolume for all species, except for H. tamesis. In the latter, the apical axis (or side) exhibited the best correlation with biovolume (r = 0.94, p < 0.001). The high correlation between the diameter and/or the apical axis with the biovolumen suggests that the latter could be predicted from these morphometric variables with great reliability in these species.

[Diatoms from Unare and Píritu Lagoons, Anzoátegui state, Venezuela. Subclass Bacillariophycidae D. G. Mann ]. / Diatomeas de las lagunas de Unare y Piritu, estado Anzoategui, Venezuela. Subclase Bacillariophycidae D.G. Mann.

The diatom flora of Unare and Píritu Lagoons, Venezuela, comprises freshwater, estuarine and marine organisms. In this paper, 15 species of diatoms belonging to the subclass Bacillariophyceae D.G. Mann are described. Water samples from Unare and Píritu lagoons (Venezuela) were collected from November 1988 to July 1989. Samples were fixed with neutral formaldehyde (10%) and were examined under phase contrast microscopy. Species under study were Dictyoneis marginata (Lewis) Cleve, Cymbella affinis (Kützing) Cleve, Cymbella sp., Achnanthes brevipes var. intermedia (Kützing) Cleve, Lyrella irroratoides (Hustedt) Mann, Navicula carinifera (Grunow) Peragallo, Navicula liber (W. Smith) Peragallo, Navicula vacillans (Schmidt) Peragallo, Navicula sp, Amphora crassa var. campechiana Grunow, Amphora decussata Grunow, Caloneis powelli (Lewis) Cholnoky, Tryblionella acuta (Cleve) Mann in Round et al., Tryblionella apiculata Gregory, Surirella febigerii Lewis.

Diatomeas de las lagunas de Unare y Píritu, estado Anzoategui Venezuela: subclases thalassiosirophycidae y coscinodiscophycidae round & crawford / Diatoms from unare and piritu lagoons, Anzoayegui state Venezuela: subclasses thalassiosirophycidae and coscinodiscophycidae round & crawford

Se describen 9 especies de diatomeas (Bacillariophyta) pertenecientes a las Subclase Thalassiosirophycidae y Coscinodiscophycidae. Las muestras de agua de las lagunas de Unare y Píritu (Venezuela) fueron colectadas entre Noviembre 1988 y Julio 1989. Los especimenes fijados con formol neutralizado y montados con Bálsamo de Canadá, se examinaron mediante microscopia de contraste de fase. Las especies estudiadas fueron: Thalassiosira eccentrica (Ehrenberg) Lange et al., T. leptopus (Grun) Hasle & Fryxell, Cyclotella menenghianiana (Kützing) Wood, C. striata (Kützing) Grunow in Cleve et Grunow, Coscinodiscus asteromphallus (Ehrenberg) Makarova, C. janischi (Schmidt) Wood, C. marginatus (Ehrenberg) Navarro, C. subtilis (Ehrenberg) var. normanii (Gregory) Van Heurck, Actinocyclus octonarius (Ehrenberg) Navarro.