Enhancement of upconversion photoluminescence in phosphor nanoparticle thin films using metallic nanoantennas fabricated by colloidal lithography.

Lanthanide-doped upconversion nanoparticles (UCNPs), as multifunctional light sources, are finding utility in diverse applications ranging from biotechnology to light harvesting. However, the main challenge in realizing their full potential lies in achieving bright and efficient photon upconversion (UC). In this study, we present a novel approach to fabricate an array of gold nanoantennas arranged in a hexagonal lattice using a simple and inexpensive colloidal lithography technique, and demonstrate a significant enhancement of UC photoluminescence (UCPL) by up to 35-fold through plasmon-enhanced photoexcitation and emission. To elucidate the underlying physical mechanisms responsible for the observed UCPL enhancement, we provide a comprehensive theoretical and experimental characterization, including a detailed photophysical description and numerical simulations of the spatial electric field distribution. Our results shed light on the fundamental principles governing the enhanced UCNPs and pave the way for their potential applications in photonic devices.

Enhanced up-conversion photoluminescence in fluoride-oxyfluoride nanophosphor films by embedding gold nanoparticles.

Owing to their unique non-linear optical character, lanthanide-based up-converting materials are potentially interesting for a wide variety of fields ranging from biomedicine to light harvesting. However, their poor luminescent efficiency challenges the development of technological applications. In this context, localized surface plasmon resonances (LSPRs) have been demonstrated as a valuable strategy to improve light conversion. Herein, we utilize LSPR induced by gold nanoparticles (NPs) to enhance up-conversion photoluminescence (UCPL) in transparent, i.e. scattering-free, films made of nanophosphors formed by fluoride-oxyfluoride host matrix that feature high thermal stability. Transparency allows excitation by an external source without extinction losses caused by unwanted diffuse reflection. We provide a simple method to embed gold NPs in films made of YF/YOF:Yb3+,Er3+ UC nanophosphors, via preparation of a viscous paste composed of both UC nanophosphors and colloidal gold NPs, reducing complexity in sample fabrication. The dimensions of gold NPs are such that their associated LSPR matches spectrally with the green emission band of the Er3+ doped nanophosphors. In order to demonstrate the benefits of plasmonic nanoparticles for UCPL in nanophosphor films, we provide a careful analysis of the structural properties of the composite thin films along with precise characterization of the impact of the gold NPs on the photophysical properties of UC nanophosphors.

Highly Versatile Upconverting Oxyfluoride-Based Nanophosphor Films.

Fluoride-based compounds doped with rare-earth cations are the preferred choice of materials to achieve efficient upconversion, of interest for a plethora of applications ranging from bioimaging to energy harvesting. Herein, we demonstrate a simple route to fabricate bright upconverting films that are transparent, self-standing, flexible, and emit different colors. Starting from the solvothermal synthesis of uniform and colloidally stable yttrium fluoride nanoparticles doped with Yb3+ and Er3+, Ho3+, or Tm3+, we find the experimental conditions to process the nanophosphors as optical quality films of controlled thickness between few hundreds of nanometers and several micrometers. A thorough analysis of both structural and photophysical properties of films annealed at different temperatures reveals a tradeoff between the oxidation of the matrix, which transitions through an oxyfluoride crystal phase, and the efficiency of the upconversion photoluminescence process. It represents a significant step forward in the understanding of the fundamental properties of upconverting materials and can be leveraged for the optimization of upconversion systems in general. We prove bright multicolor upconversion photoluminescence in oxyfluoride-based phosphor transparent films upon excitation with a 980 nm laser for both rigid and flexible versions of the layers, being possible to use the latter to coat surfaces of arbitrary shape. Our results pave the way toward the development of upconverting coatings that can be conveniently integrated in applications that demand a large degree of versatility.

Interaction between Colloidal Quantum Dots and Halide Perovskites: Looking for Constructive Synergies.

Colloidal quantum dots (QDs) have received extensive attention during the last few decades because of their amazing properties emerging from quantum confinement. In parallel, halide perovskites have attracted attention because of the demonstration of very high performance, especially in solar cells, light-emitting diodes (LEDs), and other optoelectronic devices. Both families of materials can be prepared in a relatively simple way, facilitating their integration. There are several examples of their interaction enhancing the properties of the final nanocomposite. Perovskites can effectively passivate QDs or act as efficient charge transporters. QDs can be used to modify the selective contacts in perovskite devices or can be used as efficient light emitters or absorbers for enhanced LEDs and photodetectors, respectively. Moreover, QDs can seed the perovskite crystal growth, improving the morphology and ultimately the solar cell performance. In addition, new advanced devices can emerge as a result of the constructive synergy between both families of materials.

PbS quantum dots as additives in methylammonium halide perovskite solar cells: the effect of quantum dot capping.

Colloidal PbS quantum dots (QDs) have been successfully employed as additives in halide perovskite solar cells (PSCs) acting as nucleation centers in the perovskite crystallization process. For this strategy, the surface functionalization of the QDs, controlled via the use of different capping ligands, is likely of key importance. In this work, we examine the influence of the PbS QD capping on the photovoltaic performance of methylammonium lead iodide PSCs. We test PSCs fabricated with PbS QD additives with different capping ligands including methylammonium lead iodide (MAPI), cesium lead iodide (CsPI) and 4-aminobenzoic acid (ABA). Both the presence of PbS QDs and the specific capping used have a significant effect on the properties of the deposited perovskite layer, which affects, in turn, the photovoltaic performance. For all capping ligands used, the inclusion of PbS QDs leads to the formation of perovskite films with larger grain size, improving, in addition, the crystalline preferential orientation and the crystallinity. Yet, differences between the capping agents were observed. The use of QDs with ABA capping had a higher impact on the morphological properties while the employment of the CsPI ligand was more effective in improving the optical properties of the perovskite films. Taking advantage of the improved properties, PSCs based on the perovskite films with embedded PbS QDs exhibit an enhanced photovoltaic performance, showing the highest increase with ABA capping. Moreover, bulk recombination via trap states is reduced when the ABA ligand is used for capping of the PbS QD additives in the perovskite film. We demonstrate how surface chemistry engineering of PbS QD additives in solution-processed perovskite films opens a new approach towards the design of high quality materials, paving the way to improved optoelectronic properties and more efficient photovoltaic devices.

Enhancement of the Performance of Perovskite Solar Cells, LEDs, and Optical Amplifiers by Anti-Solvent Additive Deposition.

The efficiency of perovskite optoelectronic devices is increased by a novel method; its suitability for perovskite solar cells, light-emitting diodes, and optical amplifiers is demonstrated. The method is based on the introduction of organic additives during the anti-solvent step in the perovskite thin-film deposition process. Additives passivate grain boundaries reducing non-radiative recombination. The method can be easily extended to other additives.

Single step deposition of an interacting layer of a perovskite matrix with embedded quantum dots.

Hybrid lead halide perovskite (PS) derivatives have emerged as very promising materials for the development of optoelectronic devices in the last few years. At the same time, inorganic nanocrystals with quantum confinement (QDs) possess unique properties that make them suitable materials for the development of photovoltaics, imaging and lighting applications, among others. In this work, we report on a new methodology for the deposition of high quality, large grain size and pinhole free PS films (CH3NH3PbI3) with embedded PbS and PbS/CdS core/shell Quantum Dots (QDs). The strong interaction between both semiconductors is revealed by the formation of an exciplex state, which is monitored by photoluminescence and electroluminescence experiments. The radiative exciplex relaxation is centered in the near infrared region (NIR), ≈1200 nm, which corresponds to lower energies than the corresponding band gap of both perovskite (PS) and QDs. Our approach allows the fabrication of multi-wavelength light emitting diodes (LEDs) based on a PS matrix with embedded QDs, which show considerably low turn-on potentials. The presence of the exciplex state of PS and QDs opens up a broad range of possibilities with important implications in both LEDs and solar cells.