Water-assisted synthesis of stable and multicolored CsPbX3@SiO2 core-shell nanoparticles as fluorescent probes for biosensing.

Colloidal lead halide perovskite nanocrystals are highly luminescent materials with great promise as fluorescent probes in biosensing as long as their intrinsic instability in aqueous media is effectively addressed. In this study, we successfully prepared stable and multicolored CsPbX3@SiO2 (X = Cl/Br, Br and I) core-shell nanoparticles through a simple method based on the water-induced transformation of Cs4PbX6 into CsPbX3, combined with sol-gel procedures. We observed that the concentration of the Cs4PbX6 precursor plays a crucial role in the formation of isolated nanospheres with uniform silica coating and in controlling the number of core-free particles. Furthermore, our research expands this approach to other halide compositions, resulting in multicolored core-shell nanoparticles with emission wavelengths ranging from 490 to 700 nm, average sizes below 30 nm, and photoluminescence quantum yields close to 60%. Unlike in previous reports, the silica coating boosts the photoluminescence quantum yields compared to uncoated counterparts and provides increased structural stability for more than four days. Moreover, a controlled thermal treatment confers water stability to the as-synthesized nanoparticles. To establish the feasibility of the developed materials as fluorescent probes, we successfully demonstrated their specific recognition of a humanized antibody (omalizumab) used in treating patients with severe allergic asthma. This work paves the way to develop in vitro tests using CsPbX3@SiO2 core-shell nanoparticles as fluorogenic probes.

Monodispersed CsPb2Br5@SiO2 Core-Shell Nanoparticles as Luminescent Labels for Biosensing.

Despite the rising advances in the field of metal halide perovskite nanocrystals (NCs), the exploitation of such nanoparticles as luminescent labels for ex vivo imaging and biosensing is still unclear and in the early stages of investigation. One of the major challenges toward the implementation of metal halide perovskite NCs in biosensing applications is to produce monodispersed nanoparticles with desired surface characteristics and compatible with aqueous environments. Here, we report the synthesis of monodispersed spherical CsPb2Br5@SiO2 core-shell nanoparticles by post-synthetic chemical transformation of 3D CsPbBr3 NCs in the presence of tetraethyl orthosilicate and a critical water/ammonia ratio. This method involves an ammonia-mediated and ammonia-induced "top-down" transformation of as-synthesized 3D CsPbBr3 NCs to smaller CsPb2Br5 nanoclusters (ca. 2-3 nm), which trigger a seed-mediated silica growth, yielding monodispersed spherical blue luminescent (λemission = 432 nm) CsPb2Br5@SiO2 perovskite nanoparticles. By adjusting the reaction conditions, core-shell nanoparticles of a 36.1 ± 4.5 nm diameter, which preserve their optical properties in water, were obtained. Besides that, the viability of the developed nanoparticles as a luminescent label for biosensing has been proven by specific biorecognition of the IgG protein in a direct immunoassay. Our work sheds light on the chemical processes and transformations involved in the silica nucleation mechanism in the presence of perovskite nanoparticles and opens the way for the future rational design of the next generation of semiconductor NC luminescent biological labels.

Efficient passivated phthalocyanine-quantum dot solar cells.

The power conversion efficiency of CdSe and CdS quantum dot sensitized solar cells is enhanced by passivation with asymmetrically substituted phthalocyanines. The introduction of the phthalocyanine dye increases the efficiency up to 45% for CdSe and 104% for CdS. The main mechanism causing this improvement is the quantum dot passivation. This study highlights the possibilities of a new generation of dyes designed to be directly linked to QDs instead of the TiO2 electrodes.

General working principles of CH3NH3PbX3 perovskite solar cells.

Organometal halide perovskite-based solar cells have recently realized large conversion efficiency over 15% showing great promise for a new large scale cost-competitive photovoltaic technology. Using impedance spectroscopy measurements we are able to separate the physical parameters of carrier transport and recombination in working devices of the two principal morphologies and compositions of perovskite solar cells, viz. compact thin films of CH3NH3PbI(3-x)Clx and CH3NH3PbI3 infiltrated on nanostructured TiO2. The results show nearly identical spectral characteristics indicating a unique photovoltaic operating mechanism that provides long diffusion lengths (1 µm). Carrier conductivity in both devices is closely matched, so that the most significant differences in performance are attributed to recombination rates. These results highlight the central role of the CH3NH3PbX3 semiconductor absorber in carrier collection and provide a new tool for improved optimization of perovskite solar cells. We report for the first time a measurement of the diffusion length in a nanostructured perovskite solar cell.

Recombination Study of Combined Halides (Cl, Br, I) Perovskite Solar Cells.

We report on the preparation of a series of solution-processed perovskite solar cells based on methylammonium (MA) lead halide derivatives, MAPbX3, which show tunable optical properties depending on the nature and ratio of the halides employed (X = Cl, Br, and I). Devices have been prepared with different cell architecture, thin film, and mesoporous scaffold (TiO2 and Al2O3). We have analyzed different sample sets focusing on the characterization of the charge recombination by means of impedance spectroscopy (IS). On the one hand, our study discloses that the insertion of both Cl and Br in the perovskite lattice reduces the charge recombination rates in the light absorber film, thus determining the open circuit voltage (Voc) of the device. The samples prepared on a mesoporous Al2O3 electrode present lower charge recombination rates than those devices prepared on mesoporous TiO2. Furthermore, the addition of Br in the perovskite structure was demonstrated to improve slightly the lifetime of the devices; in fact, the efficiencies of all devices tested remained at least at the 80% of the initial value 1 month after their preparation. These results highlight the crucial role of the charge-recombination processes on the performance of the perovskite solar cells and pave the way for further progress on this field.

Slow Dynamic Processes in Lead Halide Perovskite Solar Cells. Characteristic Times and Hysteresis.

Characteristic times of perovskite solar cells (PSCs) have been measured by different techniques: transient photovoltage decay, transient photoluminescence, and impedance spectroscopy. A slow dynamic process is detected that shows characteristic times in the seconds to milliseconds scale, with good quantitative agreement between transient photovoltage decay and impedance spectroscopy. Here, we show that this characteristic time is related with a novel slow dynamic process caused by the peculiar structural properties of lead halide perovskites and depending on perovskite crystal size and organic cation nature. This new process may lie at the basis of the current-voltage hysteresis reported for PSCs and could have important implications in PSC performance because it may give rise to distinct dynamical behavior with respect to other classes of photovoltaic devices. Furthermore, we show that low-frequency characteristic time, commonly associated with electronic carrier lifetime in other photovoltaic devices, cannot be attributed to a recombination process in the case of PSCs.

Mechanism of carrier accumulation in perovskite thin-absorber solar cells.

Photovoltaic conversion requires two successive steps: accumulation of a photogenerated charge and charge separation. Determination of how and where charge accumulation is attained and how this accumulation can be identified is mandatory for understanding the performance of a photovoltaic device and for its further optimization. Here we analyse the mechanism of carrier accumulation in lead halide perovskite, CH3NH3PbI3, thin-absorber solar cells by means of impedance spectroscopy. A fingerprint of the charge accumulation in high density of states of the perovskite absorber material has been observed at the capacitance of the samples. This is, as far as we know, the first observation of charge accumulation in light-absorbing material for nanostructured solar cells, indicating that it constitutes a new kind of photovoltaic device, differentiated from sensitized solar cells, which will require its own methods of study, characterization and optimization.

Selective contacts drive charge extraction in quantum dot solids via asymmetry in carrier transfer kinetics.

Colloidal quantum dot solar cells achieve spectrally selective optical absorption in a thin layer of solution-processed, size-effect tuned, nanoparticles. The best devices built to date have relied heavily on drift-based transport due to the action of an electric field in a depletion region that extends throughout the thickness of the quantum dot layer. Here we study for the first time the behaviour of the best-performing class of colloidal quantum dot films in the absence of an electric field, by screening using an electrolyte. We find that the action of selective contacts on photovoltage sign and amplitude can be retained, implying that the contacts operate by kinetic preferences of charge transfer for either electrons or holes. We develop a theoretical model to explain these experimental findings. The work is the first to present a switch in the photovoltage in colloidal quantum dot solar cells by purposefully formed selective contacts, opening the way to new strategies in the engineering of colloidal quantum dot solar cells.

High performance PbS Quantum Dot Sensitized Solar Cells exceeding 4% efficiency: the role of metal precursors in the electron injection and charge separation.

Here we report the preparation of high performance Quantum Dot Sensitized Solar Cells (QDSCs) based on PbS-CdS co-sensitized nanoporous TiO2 electrodes. QDs were directly grown on the TiO2 mesostructure by the Successive Ionic Layer Absorption and Reaction (SILAR) technique. This method is characterized by a fast deposition rate which involves random crystal growth and poor control of the defect states and lattice mismatch in the QDs limiting the quality of the electrodes for photovoltaic applications. In this work we demonstrate that the nature of the metallic precursor selected for SILAR has an active role in both the QD's deposition rate and the defect's distribution in the material, with important consequences for the final photovoltaic performance of the device. For this purpose, acetate and nitrate salts were selected as metallic precursors for the SILAR deposition and films with similar absorption properties and consequently with similar density of photogenerated carriers were studied. Under these conditions, ultrafast carrier dynamics and surface photovoltage spectroscopy reveal that the use of acetate precursors leads to higher injection efficiency and lower internal recombination due to contribution from defect states. This was corroborated in a complete cell configuration with films sensitized with acetate precursors, achieving unprecedented photocurrents of ~22 mA cm(-2) and high power conversion efficiency exceeding 4%, under full 1 sun illumination.

Effect of Organic and Inorganic Passivation in Quantum-Dot-Sensitized Solar Cells.

The effect of semiconductor passivation on quantum-dot-sensitized solar cells (QDSCs) has been systematically characterized for CdS and CdS/ZnS. We have found that passivation strongly depends on the passivation agent, obtaining an enhancement of the solar cell efficiency for compounds containing amine and thiol groups and, in contrast, a decrease in performance for passivating agents with acid groups. Passivation can induce a change in the position of TiO2 conduction band and also in the recombination rate and nature, reflected in a change in the ß parameter. Especially interesting is the finding that ß, and consequently the fill factor can be increased with the passivation treatment. Applying this strategy, record cells of 4.65% efficiency for PbS-based QDSCs have been produced.

Harnessing Infrared Photons for Photoelectrochemical Hydrogen Generation. A PbS Quantum Dot Based "Quasi-Artificial Leaf".

Hydrogen generation by using quantum dot (QD) based heterostructures has emerged as a promising strategy to develop artificial photosynthesis devices. In the present study, we sensitize mesoporous TiO2 electrodes with in-situ-deposited PbS/CdS QDs, aiming at harvesting light in both the visible and the near-infrared for hydrogen generation. This heterostructure exhibits a remarkable photocurrent of 6 mA·cm(-2), leading to 60 mL·cm(-2)·day(-1) hydrogen generation. Most importantly, confirmation of the contribution of infrared photons to H2 generation was provided by the incident-photon-to-current-efficiency (IPCE), and the integrated current was in excellent agreement with that obtained through cyclic voltammetry. The main electronic processes (accumulation, transport, and recombination) were identified by impedance spectroscopy, which appears as a simple and reliable methodology to evaluate the limiting factors of these photoelectrodes. On the basis of this TiO2/PbS/CdS heterostructrure, a "quasi-artificial leaf" has been developed, which has proven to produce hydrogen under simulated solar illumination at (4.30 ± 0.25) mL·cm(-2)·day(-1).

Photoanodes based on nanostructured WO3 for water splitting.

Anodically grown WO(3) photoelectrodes prepared in an N-methylformamide (NMF) electrolyte have been investigated with the aim of exploring the effects induced by anodization time and water concentration in the electrochemical bath on the properties of the resulting photoanodes. An n-type WO(3) semiconductor is one of the most promising photoanodes for hydrogen production from water splitting and the electrochemical anodization of tungsten allows very good photoelectrodes, which are characterized by a low charge-transfer resistance and an increased spectral response in the visible region, to be obtained. These photoanodes were investigated by a combination of steady state and transient photoelectrochemical techniques and a correlation between photocurrent produced, morphology, and charge transport has been evaluated.

A sulfide/polysulfide-based ionic liquid electrolyte for quantum dot-sensitized solar cells.

Further development of quantum dot-sensitized solar cells (QDSCs) will require long-term stability in addition to the continuous increase of photovoltaic (PV) conversion efficiency achieved in the last years. We report a robust S(2-)/S(n)(2-) electrolyte that has been specifically designed for compatibility with CdSe quantum dots in sensitized solar cells. The new pyrrolidinium ionic liquid reaches 1.86% efficiency and a short-circuit current close to 14 mA·cm(-2) under air-mass 1.5 global illumination and improves the device lifetime with good photoanode stability over 240 h. PV characterization showed that the solar cell limitations relate to poor catalysis of regeneration at the counter electrode and high recombination. Further improvement of these factors in the robust electrolyte configuration may thus have a significant impact for advancing the state-of-the-art in QDSCs.

Modeling high-efficiency quantum dot sensitized solar cells.

With energy conversion efficiencies in continuous growth, quantum dot sensitized solar cells (QDSCs) are currently under an increasing interest, but there is an absence of a complete model for these devices. Here, we compile the latest developments in this kind of cells in order to attain high efficiency QDSCs, modeling the performance. CdSe QDs have been grown directly on a TiO(2) surface by successive ionic layer adsorption and reaction to ensure high QD loading. ZnS coating and previous growth of CdS were analyzed. Polysulfide electrolyte and Cu(2)S counterelectrodes were used to provide higher photocurrents and fill factors, FF. Incident photon-to-current efficiency peaks as high as 82%, under full 1 sun illumination, were obtained, which practically overcomes the photocurrent limitation commonly observed in QDSCs. High power conversion efficiency of up to 3.84% under full 1 sun illumination (V(oc) = 0.538 V, j(sc) = 13.9 mA/cm(2), FF = 0.51) and the characterization and modeling carried out indicate that recombination has to be overcome for further improvement of QDSC.

Selective chemical modification of silicon nitride/silicon oxide nanostructures to develop label-free biosensors.

The selective introduction of functional groups on the surface of silicon nitride/silicon oxide nanostructures was studied. Chemical strategies based on organosilane, Si-H and N-H reactivities were assayed. Among these strategies, the use of glutaraldehyde to selectively immobilize biomolecules only on the silicon nitride part of the chip surface was the most effective for the covalent attachment of proteins, maintaining also their bioavailability. The biomolecule surface coverage results up to 80% and the modification is selective versus silicon oxide; the biomolecule attaching only to silicon nitride and leaving the silicon oxide area of the device unmodified. The effectiveness of our novel selective surface modification procedure is also supported by comparing experimental and numerical calculations of the optical performance of a label-free optical ring resonator based on Si(3)N(4)/SiO(2) slot-waveguides.

Label-free optical biosensing with slot-waveguides.

We demonstrate label-free molecule detection by using an integrated biosensor based on a Si(3)N(4)/SiO(2) slot-waveguide microring resonator. Bovine serum albumin (BSA) and anti-BSA molecular binding events on the sensor surface are monitored through the measurement of resonant wavelength shifts with varying biomolecule concentrations. The biosensor exhibited sensitivities of 1.8 and 3.2 nm/(ng/mm(2)) for the detection of anti-BSA and BSA, respectively. The estimated detection limits are 28 and 16 pg/mm(2) for anti-BSA and BSA, respectively, limited by wavelength resolution.

PMMA isocyanate-modified digital discs as a support for oligonucleotide-based assays.

A mild chemical procedure for the derivatization of PMMA as the isocyanate on rigid supports is described. The proposal is based on spin-coating the support with a hydroxy-modified PMMA polymer, followed by treatment with (3-isocyanatopropyl)triethoxysilane, developing an isocyanate-ended PMMA. Oligonucleotide hybridization assays performed on this surface demonstrate that the process is simple and highly effective and agree with the results of other modified materials, including aminated PMMA, gold, and glass. As a demonstration, it has been applied to covalently attached aminated oligonucleotides on a modified audio-video compact disc (CD) surface to perform DNA probe hybridization assays. Measurements were carried out with a CD player, by detecting the solid microspots precipitated from an enzymatic reaction (HRP-TMB). This new approach, being a competitive technique, opens a broad horizon of applications for point of care or in situ needs.