Thermal effects on the resonance fluorescence of doubly dressed artificial atoms

In this work, robustness of controlled density of optical states in doubly driven artificial atoms is studied under phonon dissipation. By using both perturbative and polaron approaches, we investigate the influence of carrier-phonon interactions on the emission properties of a two-level solid-state emitter, simultaneously coupled to two intense distinguishable lasers. Phonon decoherence effects on the emission spectra are found modest up to neon boiling temperatures ($\sim 30$ K), as compared with photon generation at the Fourier transform limit obtained in absence of lattice vibrations (zero temperature). These results show that optical switching and photonic modulation by means of double dressing, do not require ultra low temperatures for implementation, thus boosting its potential technological applications.Comment: Submitted versio

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

Engineering Sr-doping for enabling long-term stable FAPb1xSrxI3 quantum dots with 100% photoluminescence quantum yield

The Pb substitution in quantum dots (PQDs) with lesser toxic metals has been widely searched to be environmentally friendly, and be of comparable or improved performance compared to the lead-perovskite. However, the chemical nature of the lead substitute influences the incorporation mechanism into PQDs, which has not been explored in depth. In this work, we analyzed Sr-doping-induced changes in FAPbI3 perovskites by studying the optical, structural properties and chemical environment of FAPb1−xSrxI3 PQDs. The substitution of Pb by 7 at% Sr allows us to achieve FAPb1−xSrxI3 PQDs with 100% PLQY, high stability for 8 months under a relative humidity of 40–50%, and T80 = 6.5 months, one of the highest values reported for halide PQDs under air ambient conditions. FAPb0.93Sr0.07I3 PQDs also exhibit photobrightening under UV illumination for 12 h, recovering 100% PLQY at 15 days after synthesis. The suppression of structural defects mediated by Sr-doping decreases the non-radiative recombination mechanism. By attempting to increase the Sr content in PQDs, a mixture of 2D nanoplatelets/3D nanocubes has emerged, caused by a high Pb deficiency during the FAPb1−xSrxI3 synthesis. This contribution gives a novel insight to understand how the suitable/poor Pb substitution achieved through Sr-doping dictates the photophysical properties of PQDs that may be potentially applicable in optoelectronics

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

Biexcitons in CdSe nanoplatelets: geometry, binding energy and radiative rate

Biexciton properties in semiconductor nanostructures are highly sensitive to quantum confinement, relative electron–hole masses, dielectric environment and Coulomb correlations. Here we present a variational Quantum Monte Carlo model which, coupled to effective mass Hamiltonians, takes into account all of the above effects. The model is used to provide theoretical assessment on the biexciton ground state properties in colloidal CdSe nanoplatelets. A number of characteristic features is observed: (i) the finite thickness of these systems makes the biexciton geometry depart from the planar square expected in the two-dimensional (2D) limit, and form a distorted tetrahedron instead; (ii) the strong dielectric confinement enhances not only Coulomb attractions but also repulsions, which lowers the ratio of the biexciton-to-exciton binding energy down to EXXb/EXb = 0.07. (iii) EXXb is less sensitive than EXb to lateral confinement, and yet it can reach values above 30 meV, thus granting room temperature stability; (iv) the ratio of biexciton-to-exciton radiative rates, kradXX/kradX, decreases from 3.5 to ∼1 as the platelet area increases. These results pave the way for the rational design of biexciton properties in metal chalcogenide nanoplatelets

Comparison between Trion and Exciton Electronic Properties in CdSe and PbS Nanoplatelets

The optoelectronic properties of metal chalcogenide colloidal nanoplatelets are often interpreted in terms of excitonic states. However, recent spectroscopic experiments evidence the presence of trion states, enabled by the slow Auger recombination in these structures. We analyze how the presence of an additional charge in trions modifies the emission energy and oscillator strength as compared to neutral excitons. These properties are very sensitive to dielectric confinement and electronic correlations, which we describe accurately using the image-charge and variational Quantum Monte Carlo methods in effective mass Hamiltonians. We observe that the giant oscillator strength of neutral excitons is largely suppressed in trions. Both negative and positive trions are red-shifted with respect to the exciton, and their emission energy increases with increasing dielectric mismatch between the platelet and its surroundings, which is a consequence of the self-energy potential. Our results are consistent with experiments in the literature and assess the validity of previous theoretical approximations

Chemi-Structural Stabilization of Formamidinium Lead Iodide Perovskite by Using Embedded Quantum Dots for High-Performance Solar Cells

The extraordinary low non-radiative recombination and band gap versatility of halide perovskites have led to considerable development in optoelectronic devices. However, this versatility is limited by the stability of the perovskite phase, related to the relative size of the different cations and anions. The most emblematic case is that of formamidinium lead iodine (FAPI) black phase, which has the lowest band gap among all 3D lead halide perovskites, but quickly transforms into the non-perovskite yellow phase at room temperature. Efforts to optimize perovskite solar cells have largely focused on the stabilization of FAPI based perovskite structures, often introducing alternative anions and cations. However, these approaches commonly result in a blue-shift of the band gap, which limits the maximum photo-conversion efficiency. Here, we report the use of PbS colloidal quantum dots (QDs) as stabilizing agent for the FAPI perovskite black phase. 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, stable FAPI black phase can be formed at temperatures as low as 85°C in just 10 minutes, setting a record of concomitantly fast and low temperature formation for FAPI, with important consequences for industrialization. FAPI thin films obtained through this procedure preserve the original low band gap of 1.5 eV, reach a record open circuit potential (Voc) of 1.105 V -91% of the maximum theoretical Voc- and preserve high efficiency for more than 700 hours. 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.</b