Morphology and Band Structure of Orthorhombic PbS Nanoplatelets: An Indirect Band Gap Material

PbS quantum dots and nanoplatelets (NPLs) are of enormous interest in the development of optoelectronic devices. However, some important aspects of their nature remain unclear. Recent studies have revealed that colloidal PbS NPLs may depart from the rock-salt crystal structure of bulk and form an orthorhombic (Pnma) modification instead. To gain insight into the implications of such a change over the optoelectronic properties, we have synthesized orthorhombic PbS NPLs and determined the lattice parameters by means of selected area electron diffraction measurements. We have then calculated the associated band structure using density functional theory with Perdew–Burke–Ernzerhof functional for solids and with the GW approximation, including spin–orbit interactions. An indirect band gap is found, which may explain the weak luminescence reported in experiments. We derive effective masses for conduction and valence bands and deduce that quantum confinement along the a crystallographic axis (short axis of the NPL) reinforces the indirect band gap but that along b and c axes favors a direct gap instead. Calculations for colloidal nanoplatelets of 1.8 nm thickness, carried out with k·p theory, show that excitonic effects are strong, with binding energies of about 150 meV

Preferred growth direction by PbS nanoplatelets preserves perovskite infrared light harvesting for stable, reproducible, and efficient solar cells

Formamidinium-based perovskite solar cells (PSCs) present the maximum theoretical efficiency of the lead perovskite family. However, formamidinium perovskite exhibits significant degradation in air. The surface chemistry of PbS has been used to improve the formamidinium black phase stability. Here, the use of PbS nanoplatelets with (100) preferential crystal orientation is reported, to potentiate the repercussion on the crystal growth of perovskite grains and to improve the stability of the material and consequently of the solar cells. As a result, a vertical growth of perovskite grains, a stable current density of 23 mA cm(-2), and a stable incident photon to current efficiency in the infrared region of the spectrum for 4 months is obtained, one of the best stability achievements for planar PSCs. Moreover, a better reproducibility than the control device, by optimizing the PbS concentration in the perovskite matrix, is achieved. These outcomes validate the synergistic use of PbS nanoplatelets to improve formamidinium long-term stability and performance reproducibility, and pave the way for using metastable perovskite active phases preserving their light harvesting capability

Chemi-Structural Stabilization of Formamidinium Lead Iodide Perovskite by Using Embedded Quantum Dots

The approaches to stabilize the perovskite structure of formamidinium lead iodide (FAPI) commonly result in a blue shift of the band gap, which limits the maximum photoconversion efficiency. Here, we report the use of PbS colloidal quantum dots (QDs) as a stabilizing agent, preserving the original low band gap of 1.5 eV. The surface chemistry of PbS plays a pivotal role by developing strong bonds with the black phase but weak ones with the yellow phase. As a result, a stable perovskite FAPI black phase can be formed at temperatures as low as 85 °C in just 10 min, setting a record of concomitantly fast and low-temperature formation for FAPI, with important consequences for industrialization. FAPI thin films obtained through this procedure reach an open-circuit potential (Voc) of 1.105 V, 91% of the maximum theoretical Voc, and preserve the efficiency for more than 700 h. These findings reveal the potential of strategies exploiting the chemi-structural properties of external additives to relax the tolerance factor and optimize the optoelectronic performance of perovskite materials

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

[EN] 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 H-2 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).We acknowledge support by projects from Ministerio de Economia y Competitividad (MINECO) of Spain (Consolider HOPE CSD2007-00007, MAT2010-19827), Generalitat Valenciana (PROMETEO/2009/058 and Project ISIC/2012/008 "Institute of Nanotechnologies for Clean Energies"), and Fundacio Bancaixa (P1.1B2011-50). S.G. acknowledges support by MINECO of Spain under the Ramon y Cajal programme. The SCIC of the University Jaume I de Castello is also acknowledged for the gas analysis measurements. C.S. acknowledges the POSDRU/89/1.5/S/58852 Project "Postdoctoral programme for training scientific researchers", co-financed by the European Social Fund within the Sectorial Operational Program Human Resources Development 2007-2013. We want to acknowledge Prof. J. Bisquert for the fruitful discussions related to this manuscript.Trevisan, R.; Rodenas, P.; González-Pedro, V.; Sima, C.; Sánchez, RS.; Barea, EM.; Mora-Sero, I.... (2013). Harnessing Infrared Photons for Photoelectrochemical Hydrogen Generation. A PbS Quantum Dot Based "Quasi-Artificial Leaf". Journal of Physical Chemistry Letters. 4(1):141-146. https://doi.org/10.1021/jz301890mS1411464

Au Nanoparticles as Interfacial Layer for CdS Quantum Dot-sensitized Solar Cells

Quantum dot-sensitized solar cells based on fluorine-doped tin oxide (FTO)/Au/TiO2/CdS photoanode and polysulfide electrolyte are fabricated. Au nanoparticles (NPs) as interfacial layer between FTO and TiO2 layer are dip-coated on FTO surface. The structure, morphology and impedance of the photoanodes and the photovoltaic performance of the cells are investigated. A power conversion efficiency of 1.62% has been obtained for FTO/Au/TiO2/CdS cell, which is about 88% higher than that for FTO/TiO2/CdS cell (0.86%). The easier transport of excited electron and the suppression of charge recombination in the photoanode due to the introduction of Au NP layer should be responsible for the performance enhancement of the cell

Water oxidation at hematite photoelectrodes: the role of surface states

Hematite (α-Fe2O3) constitutes one of the most promising semiconductor materials for the conversion of sunlight into chemical fuels by water splitting. Its inherent drawbacks related to the long penetration depth of light and poor charge carrier conductivity are being progressively overcome by employing nanostructuring strategies and improved catalysts. However, the physical–chemical mechanisms responsible for the photoelectrochemical performance of this material (J(V) response) are still poorly understood. In the present study we prepared thin film hematite electrodes by atomic layer deposition to study the photoelectrochemical properties of this material under water-splitting conditions. We employed impedance spectroscopy to determine the main steps involved in photocurrent production at different conditions of voltage, light intensity, and electrolyte pH. A general physical model is proposed, which includes the existence of a surface state at the semiconductor/liquid interface where holes accumulate. The strong correlation between the charging of this state with the charge transfer resistance and the photocurrent onset provides new evidence of the accumulation of holes in surface states at the semiconductor/electrolyte interface, which are responsible for water oxidation. The charging of this surface state under illumination is also related to the shift of the measured flat-band potential. These findings demonstrate the utility of impedance spectroscopy in investigations of hematite electrodes to provide key parameters of photoelectrodes with a relatively simple measurement

Interpretation of diffusion coefficients in nanostructured materials from random walk numerical simulation

We make use of the numerical simulation random walk (RWNS) method to compute the ‘‘jump’’ diffusion coefficient of electrons in nanostructured materials via mean-square displacement. First, a summary of analytical results is given that relates the diffusion coefficient obtained from RWNS to those in the multiple-trapping (MT) and hopping models. Simulations are performed in a three-dimensional lattice of trap sites with energies distributed according to an exponential distribution and with a step-function distribution centered at the Fermi level. It is observed that once the stationary state is reached, the ensemble of particles follow Fermi–Dirac statistics with a well-defined Fermi level. In this stationary situation the diffusion coefficient obeys the theoretical predictions so that RWNS effectively reproduces the MT model. Mobilities can be also computed when an electrical bias is applied and they are observed to comply with the Einstein relation when compared with steady-state diffusion coefficients. The evolution of the system towards the stationary situation is also studied. When the diffusion coefficients are monitored along simulation time a transition from anomalous to trap-limited transport is observed. The nature of this transition is discussed in terms of the evolution of electron distribution and the Fermi level. All these results will facilitate the use of RW simulation and related methods to interpret steady-state as well as transient experimental technique