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

Interpretation of the photoluminescence decay kinetics in metal halide perovskite nanocrystals and thin polycrystalline films

In this paper we present critical analysis of different points of view on interpretation of the photoluminescence (PL) decay kinetics in lead halide perovskites prepared in the form of well passivated nanocrystals (PNCs) or thin polycrystalline layers. In addition to the literature data, our own measurements are also considered. For PNCs, a strong dependence of the PL lifetimes on the type of passivating ligand was observed with a consistently high PL quantum yield. It is shown that such ligand effects, as well as a decrease in the PL lifetime with decreasing temperature, are well qualitatively explained by the phenomenological model of thermally activated delayed luminescence, in which the extension of the PL decay time with temperature occurs due to the participation of shallow non-quenching traps. In the case of thin perovskite layers, we conclude that the PL kinetics under sufficiently low excitation intensity is determined by the excitation quenching on the layer surfaces. We demonstrate that a large variety of possible PL decay kinetics for thin polycrystalline perovskite films can be modelled by means of one-dimensional diffusion equation with use of the diffusion coefficient D and surface recombination velocity S as parameters and conclude that long-lived PL kinetics are formed in case of low D and/or S values

Superradiance Emission and Its Thermal Decoherence in Lead Halide Perovskites Superlattices

Self-assembled nanocrystals (NCs) into superlattices (SLs) are alternative materials to polycrystalline films and single crystals, which can behave very differently from their constituents, especially when they interact coherently with each other. This work concentrates on the Superradiance (SR) emission observed in SLs formed by CsPbBr3 and CsPbBrI2 NCs. Micro-Photoluminescence spectra and transients in the temperature range 4–100 K are measured in SLs to extract information about the SR states and uncoupled domains of NCs. For CsPbBr3 SLs with mostly homogeneous SR lines (linewidth 1–5 meV), this work measures lifetimes as short as 160 ps, 10 times lower than the value measured in a thin film made with the same NCs, which is due to domains of near identical NCs formed by 1000 to 40 000 NCs coupled by dipole–dipole interaction. The thermal decoherence of the SR exciton state is evident above 25 K due to its coupling with an effective phonon energy of ≈8 meV. These findings are an important step toward understanding the SR emission enhancement factor and the thermal dephasing process in perovskite SLs.Financial support from the Spanish Ministry of Science (MICINN) through project no. PID2020- 120484RB-I00 is gratefully acknowledged. G.M.M. also thanks the support from the Spanish MICINN & AEI (project RTI2018-099015-J-I00). I.M.S. thanks the funding of MCIN/AEI/10.13039/501100011033 with the project STABLE PID2019-107314RB-I00. S.G. acknowledges her “Grisolia” grant from Generalitat Valenciana, and G.M.M. thanks the Ramon y Cajal programme (contract RYC2020-030099-I). Thanks are also due to Dr. Raúl Iván Sánchez Alarcón for his help with X-ray diffraction characterization of NC films and SLs

Homogeneous and inhomogeneous broadening in single perovskite nanocrystals investigated by micro-photoluminescence

Metal halides with perovskite crystalline structure have given rise to efficient optoelectronic and photonic devices. In the present work, we have studied the light emission properties of single CsPbBr3 and CsPbI3 semiconductor perovskite nanocrystals (PNCs), as the basis for a statistical analysis of micro-photoluminescence (micro-PL) spectra measured on tens of them. At room temperature, the linewidth extracted from PL spectra acquired in dense films of these nanocrystals is not very different from that of micro-PL measured in single nanocrystals. This means that the homogeneous linewidth due to exciton-phonon interaction is comparable or larger than the inhomogeneous effect associated to the micro-PL peak energy dispersion due to the nanocrystal size distribution defined by the chemical synthesis of the PNCs. Contrarily, we observe very narrow micro-PL lines in CsPbBr3 and CsPbI3 PNCs at 4 K, in the range of 1–5 meV and 0.1–0.5 meV, respectively, because they are limited by spectral diffusion. Aging of PNCs under ambient conditions has been also studied by micro-PL and a clear reduction of their nanocube edge size in the order of the nm/day is deduced

Van Der Waals Heteroepitaxy of GaSe and InSe, Quantum Wells and Superlattices

Bandgap engineering and quantum confinement in semiconductor heterostructures provide the means to fine-tune material response to electromagnetic fields and light in a wide range of the spectrum. Nonetheless, forming semiconductor heterostructures on lattice-mismatched substrates has been a challenge for several decades, leading to restrictions for device integration and the lack of efficient devices in important wavelength bands. Here, we show that the van der Waals epitaxy of two-dimensional (2D) GaSe and InSe heterostructures occur on substrates with substantially different lattice parameters, namely silicon and sapphire. The GaSe/InSe heterostructures were applied in the growth of quantum wells and superlattices presenting photoluminescence and absorption related to interband transitions. Moreover, we demonstrate a self-powered photodetector based on this heterostructure on Si that works in the visible-NIR wavelength range. Fabricated at wafer-scale, these results pave the way for an easy integration of optoelectronics based on these layered 2D materials in current Si technology.Comment: 16 Pages, 5 figures. Supplementary Information included in the end (+10 pages, +10 Figures, + 2 Tables). Partially presented at 21st ICMBE - September 202

Revealing giant exciton fine-structure splitting in 2D perovskites using van der Waals passivation

The study of two-dimensional (2D) van der Waals materials has been an active field of research in the development of new optoelectronics and photonic applications over the last decade. Organic-inorganic layered perovskites are currently some of the most promising 2D van der Waals materials, due to their exceptional optical brightness and enhanced excitonic effects. However, low crystal quality and spectral diffusion usually broaden the exciton linewidth, obscuring the fine structure of the exciton in conventional photoluminescence experiments. Here, we propose a mechanical approach for reducing the effect of spectral diffusion by means of hBN-capping on layered perovskites with different thicknesses, revealing the exciton fine structure. We used a stochastic model to link the reduction of the spectral linewidth with the population of active charge fluctuation centres present in the organic spacer taking part in the dynamical Stark shift. Active fluctuation centres are reduced by a factor of 3.7 to 7.1 when we include hBN-capping according to our direct spectral measurements. This rate is in good agreement with the analysis of the overlap between the squared perovskite lattice and the hexagonal hBN lattice. Van der Waals forces between both lattices cause the partial clamping of the perovskite organic spacer molecules, and hence, the amplitude of the dynamical Stark shift characteristic of the spectral diffusion effect is reduced. Our work provides an easy and low-cost solution to the problem of accessing important fine-structure excitonic state information, along with an explanation of the important carrier dynamics present in the organic spacer that affect the quality of the optical emission

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

Manipulation of emitted light by structured lead halide perovskite nanocrystals for photonics applications

Historically, active materials in photonic integrated circuits (PICs) have been implemented using III-V semiconductors, glasses, and ferroelectrics doped with rare-earth ions. However, there is a low-cost alternative based on (nano)materials synthesized using colloidal chemistry techniques. Their use in colloidal suspensions allows for the easy integration into any optical architecture via coating or printing techniques. The structure of perovskite nanocrystals (PNCs) are compounds with general formula ABX3, being A an inorganic or organic bulky cation, B a metal cation such as Pb2+ or Sn2+ and X the halide anion. In this context, all inorganic CsPbX3 (with X = Cl, Br, I) PNCs have recently emerged as an outstanding material with fascinating optical properties, such as a high absorption efficiency, a quantum yield of emission exceeding 90% at room temperature, a tunable band gap depending on chemical composition or size and shape tuning, and high nonlinear optical coefficients. A remarkable point of the CsPbX3 PNCs is the tuning of their band gap, and consequently of their light emission spectrum, by modifying the composition of the halide anion (X): their peak wavelength is observed at around 400 nm (near UV), 510 nm (green) and 680 nm (deep red) for X = Cl, Br and I, respectively, in addition to the ClxBryI1-x-y combinations with 0≤x, y≤1. Moreover, light emission of these PNCs is characterized by high color purity, with PL Full Width at Half Maximum (FWHM) as low as 20 nm for CsPbBr3(green emission) and less than 15 nm for those of CsPbCl3 (emission in blue-violet). In light of these considerations, the goal of this Ph.D. thesis is to fully reveal the significance of PNCs as an active material for photonics and quantum technologies, from both a fundamental and an application standpoint. For the first research objective within that goal, it is mandatory to examine all physical mechanisms responsible for spontaneous emission in PNCs. In the first step, single PNC samples are analyzed as basic building blocks from which more sophisticated architectures can be built. Controlling emitted light in single PNCs and fully characterizing its dependence on excitation fluence, temperature, and ambient conditions, as well as its dynamics, is a major step forward. Once the optimal conditions for PNCs are established, the PNCs can be used to grow super-crystals (SCs) to study super-fluorescence (SF) coherent light and cavity modes within SCs in the second step. The thermal decoherence of this SF will be the next step to be studied, because it is necessary to get coherent light from low to room temperature (RT) for use in photonics and quantum devices. All these results provide novel knowledge on the possible use of cesium lead halide PNCs as an active material and can pave the road for new quantum photonic devices based on PNCs. A second objective is focused on the applications of these PNCs in photonics. Particularly, Hyperbolic metamaterials (HMMs) have recently grasped much attention because they possess the ability for broadband manipulation of the photon density of states and sub-wavelength light confinement. These exceptional properties arise due to the excitation of electromagnetic states with high momentum (high-k modes). Accordingly, HMMs are properly designed, simulated, and fabricated as a fantastic photonic structure able to control the spontaneous emission rate (to achieve Purcell enhancement) of lead halide PNCs deposited on the top. Finally, in order to overcome the PL intensity reduction of the emitters deposited on top of the HMM structures caused by the coupling of perovskite emitters to the HMM modes, due to preferential emission of light into the high-k HMM modes, these HMM structures were modified by light scattering centers. The modifying strategy is easily implemented by dispersing spherical dielectric Mie scatterers onto the HMM/PMMA substrate at the same time. In light of the above-written results, this Ph.D. thesis suggests that colloidal PNCs are promising candidates for opening the way for a new generation of quantum and photonic applications and devices

Revealing giant exciton fine-structure splitting in two-dimensional perovskites using van der Waals passivation

Organic–inorganic layered perovskites are currently some of the most promising 2D van der Waals materials. Low crystal quality usually broadens the exciton line width, obscuring the fine structure of the exciton in conventional photoluminescence experiments. Here, we propose a mechanical approach to reducing the effect of spectral diffusion by means of hBN capping on layered perovskites, revealing the exciton fine structure. We used a stochastic model to link the reduction of the spectral line width with the population of charge fluctuation centers present in the organic spacer. van der Waals forces between both lattices cause the partial clamping of the perovskite organic spacer molecules, and hence the amplitude of the overall spectral diffusion effect is reduced. Our work provides a low-cost solution to the problem of accessing important fine-structure excitonic state information, along with an explanation of the important carrier dynamics present in the organic spacer that affect the quality of the optical emission