Metal Coordination Sphere Deformation Induced Highly Stokes-Shifted, Ultra Broadband Emission in 2D Hybrid Lead-Bromide Perovskites and Investigation of Its Origin.

Published studies of layered (2D) (100)-oriented hybrid lead-bromide perovskites evidence a correlation between increased inter-octahedral (Pb-Br-Pb) distortions and the appearance of broadband white light emission. However, the impact of distortions within their constituent [PbBr6 ]4- octahedra has yet to be assessed. Herein, we report two new (100)-oriented 2D Pb-Br perovskites, whose structures display unusually high intra-octahedral distortions, whilst retaining minimal inter-octahedral distortions. Using a combination of temperature-dependent, power-dependent and time-resolved photoluminescence spectroscopic measurements, we show that increased intra-octahedral distortion induces exciton localization processes and leads to formation of multiple photoinduced emissive colour centres. Ultimately, this leads to highly Stokes-shifted, ultrabroad white light emission at room temperature.

Monolithically Integrated Perovskite Semiconductor Lasers on Silicon Photonic Chips by Scalable Top-Down Fabrication.

Metal-halide perovskites are promising lasing materials for the realization of monolithically integrated laser sources, the key components of silicon photonic integrated circuits (PICs). Perovskites can be deposited from solution and require only low-temperature processing, leading to significant cost reduction and enabling new PIC architectures compared to state-of-the-art lasers realized through the costly and inefficient hybrid integration of III-V semiconductors. Until now, however, due to the chemical sensitivity of perovskites, no microfabrication process based on optical lithography (and, therefore, on existing semiconductor manufacturing infrastructure) has been established. Here, the first methylammonium lead iodide perovskite microdisc lasers monolithically integrated into silicon nitride PICs by such a top-down process are presented. The lasers show a record low lasing threshold of 4.7 µJcm-2 at room temperature for monolithically integrated lasers, which are complementary metal-oxide-semiconductor compatible and can be integrated in the back-end-of-line processes.

Large area porous 1D photonic crystals comprising silicon hierarchical nanostructures grown by plasma-assisted, nanoparticle jet deposition.

In this contribution, we describe a room-temperature, template-free, single-step approach for the growth of functional crystalline silicon nanostructures with tailored porosity and photonic properties. The method employs a plasma-assisted nanoparticle synthesis reactor in combination with a supersonic jet deposition stage, in what we call nanoparticle jet deposition or plasma-assisted, supersonic aerosol jet deposition. The relationship between plasma parameters, nanoparticle impaction conditions and the resulting silicon material structural characteristics is investigated. This understanding is successfully employed for the production of porous 1D photonic crystals obtained by periodically modulating the density of the hierarchical silicon nanostructures and hence their local refractive index. The open porosity of this device is then exploited in a proof of concept optical chemical sensor.

Broadband Emission in Two-Dimensional Hybrid Perovskites: The Role of Structural Deformation.

Only a selected group of two-dimensional (2D) lead-halide perovskites shows a peculiar broad-band photoluminescence. Here we show that the structural distortions of the perovskite lattice can determine the defectivity of the material by modulating the defect formation energies. By selecting and comparing two archetype systems, namely, (NBT)2PbI4 and (EDBE)PbI4 perovskites (NBT = n-butylammonium and EDBE = 2,2-(ethylenedioxy)bis(ethylammonium)), we find that only the latter, subject to larger deformation of the Pb-X bond length and X-Pb-X bond angles, sees the formation of VF color centers whose radiative decay ultimately leads to broadened PL. These findings highlight the importance of structural engineering to control the optoelectronic properties of this class of soft materials.

Integrated perovskite lasers on a silicon nitride waveguide platform by cost-effective high throughput fabrication.

Metal-halide perovskites are a class of solution processed materials with remarkable optoelectronic properties such as high photoluminescence quantum yields and long carrier lifetimes, which makes them promising for a wide range of efficient photonic devices. In this work, we demonstrate the first successful integration of a perovskite laser onto a silicon nitride photonic chip. High throughput, low cost optical lithography is used, followed by indirect structuring of the perovskite waveguide. We embed methylammonium lead tri-iodide (MAPbI3) in a pre-patterned race-track microresonator and couple the emitted light to an integrated photonic waveguide. We clearly observe the build-up of spectrally narrow lasing modes at room temperature upon a pump threshold fluence of 19.6 µJcm-2. Our results evidence the possibility of on-chip lasers based on metal-halide perovskites with industry relevance on a commercially available dielectric photonic platform, which is a step forward towards low-cost integrated photonic devices.

Nonlinear Carrier Interactions in Lead Halide Perovskites and the Role of Defects.

The simple solution processability at room temperature exposes lead halide perovskite semiconductors to a non-negligible level of unintentional structural and chemical defects. Ascertained that their primary optoelectronic properties meet the requirement for high efficiency optoelectronic technologies, a lack of knowledge about the nature of defects and their role in the device operation currently is a major challenge for their market-scale application due to the issues with stability and reliability. Here, we use excitation correlation photoluminescence (ECPL) spectroscopy to investigate the recombination dynamics of the photogenerated carriers in lead bromide perovskites and quantitatively describe the carrier trapping dynamics within a generalization of the Shockley-Read-Hall formalism. The superior sensitivity of our spectroscopic tool to the many-body interactions enables us to identify the energetics of the defects. In fact, in the case of polycrystalline films, depending on the synthetic route, we demonstrate the presence of both deep and shallow carrier traps. The shallow defects, which are situated at about 20 meV below the conduction band, dope the semiconductor, leading to a substantial enhancement of the photoluminescence quantum yield despite carrier trapping. At excitation densities relevant for lasing, we observe breakdown of the rate-equation model, indicating a buildup of a highly correlated regime of the photocarrier population that suppresses the nonradiative Auger recombination. Furthermore, we demonstrate that colloidal nanocrystals represent virtually defect-free systems, suffering from nonradiative quenching only due to subpicosecond Auger-like interactions at high excitation density. By correlating the fabrication conditions to the nonradiative loss channels, this work provides guidelines for material engineering towards superior optoelectronic devices.

Fully Solution-Processed n-i-p-Like Perovskite Solar Cells with Planar Junction: How the Charge Extracting Layer Determines the Open-Circuit Voltage.

Fully solution-processed direct perovskite solar cells with a planar junction are realized by incorporating a cross-linked [6,6]-phenyl-C61-butyric styryl dendron ester layer as an electron extracting layer. Power conversion efficiencies close to 19% and an open-circuit voltage exceeding 1.1 V with negligible hysteresis are delivered. A perovskite film with superb optoelectronic qualities is grown, which reduces carrier recombination losses and hence increases V oc .

Charge trapping dynamics in PbS colloidal quantum dot photovoltaic devices.

The efficiency of solution-processed colloidal quantum dot (QD) based solar cells is limited by poor charge transport in the active layer of the device, which originates from multiple trapping sites provided by QD surface defects. We apply a recently developed ultrafast electro-optical technique, pump-push photocurrent spectroscopy, to elucidate the charge trapping dynamics in PbS colloidal-QD photovoltaic devices at working conditions. We show that IR photoinduced absorption of QD in the 0.2-0.5 eV region is partly associated with immobile charges, which can be optically detrapped in our experiment. Using this absorption as a probe, we observe that the early trapping dynamics strongly depend on the nature of the ligands used for QD passivation, while it depends only slightly on the nature of the electron-accepting layer. We find that weakly bound states, with a photon-activation energy of 0.2 eV, are populated instantaneously upon photoexcitation. This indicates that the photogenerated states show an intrinsically bound-state character, arguably similar to charge-transfer states formation in organic photovoltaic materials. Sequential population of deeper traps (activation energy 0.3-0.5 eV) is observed on the ~0.1-10 ns time scales, indicating that most of carrier trapping occurs only after substantial charge relaxation/transport. The reported study disentangles fundamentally different contributions to charge trapping dynamics in the nanocrystal-based optoelectronic devices and can serve as a useful tool for QD solar cell development.