Daniela Marongiu

Correlated electron–hole plasma in organometal perovskites

Organic-inorganic perovskites are a class of solution-processed semiconductors holding promise for the realization of low-cost efficient solar cells and on-chip lasers. Despite the recent attention they have attracted, fundamental aspects of the photophysics underlying device operation still remain elusive. Here we use photoluminescence and transmission spectroscopy to show that photoexcitations give rise to a conducting plasma of unbound but Coulomb-correlated electron-hole pairs at all excitations of interest for light-energy conversion and stimulated optical amplification. The conductive nature of the photoexcited plasma has crucial consequences for perovskite-based devices: in solar cells, it ensures efficient charge separation and ambipolar transport while, concerning lasing, it provides a low threshold for light amplification and justifies a favourable outlook for the demonstration of an electrically driven laser. We find a significant trap density, whose cross-section for carrier capture is however low, yielding a minor impact on device performance.

Absorption F-Sum Rule for the Exciton Binding Energy in Methylammonium Lead Halide Perovskites

Advances of optoelectronic devices based on methylammonium lead halide perovskites depend on understanding the role of excitons, whether it is marginal as in inorganic semiconductors, or crucial, like in organics. However, a consensus on the exciton binding energy and its temperature dependence is still lacking, even for widely studied methylammonium lead iodide and bromide materials (MAPbI3, MAPbBr3). Here we determine the exciton binding energy based on an f-sum rule for integrated UV-vis absorption spectra, circumventing the pitfalls of least-squares fitting procedures. In the temperature range 80-300 K, we find that the exciton binding energy in MAPbBr3 is EB = (60 ± 3) meV, independent of temperature; for MAPbI3, in the orthorhombic phase (below 140 K) EB = (34 ± 3) meV, while in the tetragonal phase the binding energy softens to 29 meV at 170 K and stays constant up to 300 K. Implications of binding energy values on solar cell and LED workings are discussed.

Shaping Mesoporous Films Using Dewetting on X-ray Pre-patterned Hydrophilic/Hydrophobic Layers and Pinning Effects at the Pattern Edge

Ordered mesoporous silica micrometer-sized structures have been fabricated via selective dewetting of the coating sol on a hydrophilic/hydrophobic fluorinated silica substrate, which had been pre-patterned using deep X-ray lithography with a synchrotron radiation source. We have observed that deposition of mesoporous films on the pre-patterned areas can be used as a design tool for obtaining regions of specific geometry and dimensions. The evaporation of the solution in constrained conditions because of pinning at the pattern edges gives layers with thicker edges. This edge effect appears dependent upon the dimension of the pre-patterned hydrophilic/hydrophobic layer; in smaller patterns, the evaporation is too fast and thickening of the edges is not observed. We have used infrared imaging, optical profilometry, and atomic force microscopy to characterize the patterned layers and the edge effect, produced by pinning at the border of the microstructures.

Optical determination of Shockley-Read-Hall and interface recombination currents in hybrid perovskites

Metal-halide perovskite solar cells rival the best inorganic solar cells in power conversion efficiency, providing the outlook for efficient, cheap devices. In order for the technology to mature and approach the ideal Shockley-Queissier efficiency, experimental tools are needed to diagnose what processes limit performances, beyond simply measuring electrical characteristics often affected by parasitic effects and difficult to interpret. Here we study the microscopic origin of recombination currents causing photoconversion losses with an all-optical technique, measuring the electron-hole free energy as a function of the exciting light intensity. Our method allows assessing the ideality factor and breaks down the electron-hole recombination current into bulk defect and interface contributions, providing an estimate of the limit photoconversion efficiency, without any real charge current flowing through the device. We identify Shockley-Read-Hall recombination as the main decay process in insulated perovskite layers and quantify the additional performance degradation due to interface recombination in heterojunctions.

Innovative Composite Films of Chitosan, Methylcellulose, and Nanoparticles

Plastic is readily available and inexpensive, so it is becoming the main material for packaging. Unfortunately plastics do not biodegrade and, if reduced in small pieces, contaminate soil and waterways. In the present work, natural films composed of chitosan, methylcellulose, and silica (SiO(2)) nanoparticles (NPs) were developed as new packaging materials. The effect of the incorporation of NPs into the polymeric film matrix was evaluated. An excellent improvement of the mechanical properties was obtained for nanostructured films with a composition of CH:MC 50:50 and NPs 1% w/v that make these materials able to replace plastics and derivatives, reducing environmental pollution.

Boosting, probing and switching-off visible light-induced photocurrents in eumelanin-porous silicon hybrids

A relatively intense photocurrent density up to 3.8 mA cm−2 was induced by visible light in n+-doped porous silicon (n-PSi) coated with a eumelanin thin film produced by ammonia-induced solid state polymerization (AISSP) of 5,6-dihydroxyindole (DHI). The photocurrent was not affected by acetic acid vapors but was irreversibly abated by gaseous ammonia. No detectable photocurrent was observed using p+-PSi as the inorganic substrate. These results point to eumelanin as a powerful enhancer of PSi photoresponse to visible light via hole-type electrical conduction.

Optical Sensitivity Gain in Silica-Coated Plasmonic Nanostructures.

Ultrathin films of silica realized by sol-gel synthesis and dip-coating techniques were successfully applied to predefined metal/polymer plasmonic nanostructures to spectrally tune their resonance modes and to increase their sensitivity to local refractive index changes. Plasmon resonance spectral shifts up to 100 nm with slope efficiencies of ∼8 nm/nm for increasing layer thickness were attained. In the ultrathin layer regime (<10 nm), which could be reached by suitable dilution of the silica precursors and optimization of the deposition speed, the sensitivity of the main plasmonic resonance to refractive index changes in aqueous solution could be increased by over 50% with respect to the bare plasmonic chip. Numerical simulations supported experimental data and unveiled the mechanism responsible for the optical sensitivity gain, proving an effective tool in the design of high-performance plasmonic sensors.

Colloidal synthesis and characterization of Bi2S3 nanoparticles for photovoltaic applications

Bismuth sulfide is a promising n-type semiconductor for solar energy conversion. We have explored the colloidal synthesis of Bi2S3 nanocrystals, with the aim of employing them in the fabrication of solution-processable solar cells and to replace toxic heavy metals chalcogenides like PbS or CdS, that are currently employed in such devices. We compare different methods to obtain Bi2S3 colloidal quantum dots, including the use of environmentally benign reactants, through organometallic synthesis. Different sizes and shapes were obtained according to the synthesis parameters and the growth process has been rationalized by comparing the predicted morphology with systematic physical-chemistry characterization of nanocrystals by X-ray diffraction, FT-IR spectroscopy, Transmission Electron Microscopy (TEM).

Synergic combination of the sol-gel method with dip coating for plasmonic devices

Summary Biosensing technologies based on plasmonic nanostructures have recently attracted significant attention due to their small dimensions, low-cost and high sensitivity but are often limited in terms of affinity, selectivity and stability. Consequently, several methods have been employed to functionalize plasmonic surfaces used for detection in order to increase their stability. Herein, a plasmonic surface was modified through a controlled, silica platform, which enables the improvement of the plasmonic-based sensor functionality. The key processing parameters that allow for the fine-tuning of the silica layer thickness on the plasmonic structure were studied. Control of the silica coating thickness was achieved through a combined approach involving sol–gel and dip-coating techniques. The silica films were characterized using spectroscopic ellipsometry, contact angle measurements, atomic force microscopy and dispersive spectroscopy. The effect of the use of silica layers on the optical properties of the plasmonic structures was evaluated. The obtained results show that the silica coating enables surface protection of the plasmonic structures, preserving their stability for an extended time and inducing a suitable reduction of the regeneration time of the chip.

Novel Physical Vapor Deposition Approach to Hybrid Perovskites: Growth of MAPbI3 Thin Films by RF-Magnetron Sputtering

Solution-based methods represent the most widespread approach used to deposit hybrid organic-inorganic perovskite films for low-cost but efficient solar cells. However, solution-process techniques offer limited control over film morphology and crystallinity, and most importantly do not allow sequential film deposition to produce perovskite-perovskite heterostructures. Here the successful deposition of CH3NH3PbI3 (MAPI) thin films by RF-magnetron sputtering is reported, an industry-tested method to grow large area devices with precisely controlled stoichiometry. MAPI films are grown starting from a single-target made of CH3NH3I (MAI) and PbI2. Films are single-phase, with a barely detectable content of unreacted PbI2, full surface coverage and thickness ranging from less than 200 nm to more than 3 μm. Light absorption and emission properties of the deposited films are comparable to as-grown solution-processed MAPI films. The development of vapor-phase deposition methods is of interest to advance perovskite photovoltaic devices with the possibility of fabricating perovskite multijunction solar cells or multicolor bright light-emitting devices in the whole visible spectrum.