Metal halide perovskites represent a flourishing area of research, which is driven by both their potential application in photovoltaics and optoelectronics and by the fundamental science behind their ...unique optoelectronic properties. The emergence of new colloidal methods for the synthesis of halide perovskite nanocrystals, as well as the interesting characteristics of this new type of material, has attracted the attention of many researchers. This review aims to provide an up-to-date survey of this fast-moving field and will mainly focus on the different colloidal synthesis approaches that have been developed. We will examine the chemistry and the capability of different colloidal synthetic routes with regard to controlling the shape, size, and optical properties of the resulting nanocrystals. We will also provide an up-to-date overview of their postsynthesis transformations, and summarize the various solution processes that are aimed at fabricating halide perovskite-based nanocomposites. Furthermore, we will review the fundamental optical properties of halide perovskite nanocrystals by focusing on their linear optical properties, on the effects of quantum confinement, and on the current knowledge of their exciton binding energies. We will also discuss the emergence of nonlinear phenomena such as multiphoton absorption, biexcitons, and carrier multiplication. Finally, we will discuss open questions and possible future directions.
Metal halide perovskites have emerged as a promising new class of layered semiconductor material for light‐emitting and photovoltaic applications owing to their outstanding optical and optoelectronic ...properties. In nanocrystalline form, these layered perovskites exhibit extremely high photoluminescence quantum yields (PLQYs) and show quantum confinement effects analogous to conventional semiconductors when their dimensions are reduced to sizes comparable to their respective exciton Bohr radii. The reduction in size leads to strongly blueshifted photoluminescence and large exciton binding energies up to several hundreds of meV. This not only makes them interesting for optoelectronic devices, but also enables complex architectures based on cascaded energy transfer. Here, an overview of the current state‐of‐the‐art of quantum confinement effects in perovskite nanocrystals is provided, with a focus on synthetic strategies and resulting optical properties, characterization methods, and emerging applications.
Metal halide perovskites have emerged as a promising new class of material for light‐emitting and photovoltaic applications owing to their outstanding optical and optoelectronic properties. This research news provides an overview of the current state‐of‐the‐art of quantum‐confinement effects in perovskite nanocrystals, with a focus on synthetic strategies and resulting optical properties, characterization methods, and emerging applications.
Solar illumination of broadly absorbing metal or carbon nanoparticles dispersed in a liquid produces vapor without the requirement of heating the fluid volume. When particles are dispersed in water ...at ambient temperature, energy is directed primarily to vaporization of water into steam, with a much smaller fraction resulting in heating of the fluid. Sunlight-illuminated particles can also drive H2O–ethanol distillation, yielding fractions significantly richer in ethanol content than simple thermal distillation. These phenomena can also enable important compact solar applications such as sterilization of waste and surgical instruments in resource-poor locations.
Carbon dots (CDs) are a versatile nanomaterial with attractive photoluminescent and photocatalytic properties. Here we show that these two functionalities can be easily tuned through a simple ...synthetic means, using a microwave irradiation, with citric acid and varying concentrations of nitrogen-containing branched polyethyleneimine (BPEI) as precursors. The amount of BPEI determines the degree of nitrogen incorporation and the different inclusion modes within the CDs. At intermediate levels of BPEI, domains grow containing mainly graphitic nitrogen, producing a high photoluminescence yield. For very high (and very low) BPEI content, the nitrogen atoms are located primarily at the edge sites of the aromatic domains. Accordingly, they attract photogenerated electrons, enabling efficient charge separation and enhanced photocatalytic hydrogen generation from water. The ensuing ability to switch between emissive and photocatalytic behavior of CDs is expected to bring substantial improvements on their efficiency for on-demand light emission or energy conversion applications.
For high-speed optoelectronic applications relying on fast relaxation or energy-transfer mechanisms, understanding of carrier relaxation and recombination dynamics is critical. Here, we compare the ...differences in photoexcited carrier dynamics in two-dimensional (2D) and quasi-three-dimensional (quasi-3D) colloidal methylammonium lead iodide perovskite nanoplatelets via differential transmission spectroscopy. We find that the cooling of excited electron–hole pairs by phonon emission progresses much faster and is intensity-independent in the 2D case. This is due to the low dielectric surrounding of the thin perovskite layers, for which the Fröhlich interaction is screened less efficiently leading to higher and less density-dependent carrier-phonon scattering rates. In addition, rapid dissipation of heat into the surrounding occurs due to the high surface-to-volume ratio. Furthermore, we observe a subpicosecond dissociation of resonantly excited 1s excitons in the quasi-3D case, an effect which is suppressed in the 2D nanoplatelets due to their large exciton binding energies. The results highlight the importance of the surrounding environment of the inorganic nanoplatelets on their relaxation dynamics. Moreover, this 2D material with relaxation times in the subpicosecond regime shows great potential for realizing devices such as photodetectors or all-optical switches operating at THz frequencies.
Aqueous solutions containing light-absorbing nanoparticles have recently been shown to produce steam at high efficiencies upon solar illumination, even when the temperature of the bulk fluid volume ...remains far below its boiling point. Here we show that this phenomenon is due to a collective effect mediated by multiple light scattering from the dispersed nanoparticles. Randomly positioned nanoparticles that both scatter and absorb light are able to concentrate light energy into mesoscale volumes near the illuminated surface of the liquid. The resulting light absorption creates intense localized heating and efficient vaporization of the surrounding liquid. Light trapping-induced localized heating provides the mechanism for low-temperature light-induced steam generation and is consistent with classical heat transfer.
Strong coupling between resonantly matched localized surface plasmons and molecular excitons results in the formation of new hybridized energy states called plexcitons. Understanding the nature and ...tunability of these hybrid nanostructures is important for both fundamental studies and the development of new applications. We investigate the interactions between J-aggregate excitons and single plasmonic dimers and report for the first time a unique strong coupling regime in individual plexcitonic nanostructures. Dark-field scattering measurements and finite-difference time-domain simulations of the hybrid nanostructures show strong plexcitonic coupling mediated by the near-field inside each dimer gap, which can be actively controlled by rotating the polarization of the optical excitation. The plexciton dispersion curves, obtained from coupled harmonic oscillator models, show anticrossing behavior at the exciton transition energy and giant Rabi splitting ranging between 230 and 400 meV. These energies are, to the best of our knowledge, the largest obtained on individual hybrid nanostructures.
Carbon dots (CDs) are an intriguing fluorescent material; however, due to a plethora of synthesis techniques and precursor materials, there is still significant debate on their structure and the ...origin of their optical properties. The two most prevalent mechanisms to explain them are based on polycyclic aromatic hydrocarbon domains and small molecular fluorophores, for instance, citrazinic acid. Yet, how these form and whether they can exist simultaneously is still under study. To address this, we vary the hydrothermal synthesis time of CDs obtained from citric acid and ethylenediamine and show that in the initial phase molecular fluorophores, likely 2-pyridone derivatives, account for the blue luminescence of the dots. However, over time, while the overall size of the CDs does not change, aromatic domains form and grow, resulting in a second, faster decay channel at similar wavelengths and also creating additional lower energetic states. Electrophoresis provides further evidence that the ensemble of CDs consists of several subsets with different internal structure and surface charge. The understanding of the formation mechanism enables a control of the chemical origin of these emitters and the ensuing optical properties of the CDs through synthetic means.
Organometal halide perovskites have recently emerged displaying a huge potential for not only photovoltaic, but also light emitting applications. Exploiting the optical properties of specifically ...tailored perovskite nanocrystals could greatly enhance the efficiency and functionality of applications based on this material. In this study, we investigate the quantum size effect in colloidal organometal halide perovskite nanoplatelets. By tuning the ratio of the organic cations used, we can control the thickness and consequently the photoluminescence emission of the platelets. Quantum mechanical calculations match well with the experimental values. We find that not only do the properties of the perovskite, but also those of the organic ligands play an important role. Stacking of nanoplatelets leads to the formation of minibands, further shifting the bandgap energies. In addition, we find a large exciton binding energy of up to several hundreds of meV for nanoplatelets thinner than three unit cells, partially counteracting the blueshift induced by quantum confinement. Understanding of the quantum size effects in perovskite nanoplatelets and the ability to tune them provide an additional method with which to manipulate the optical properties of organometal halide perovskites.
The colloidal synthesis and assembly of semiconductor nanowires continues to attract a great deal of interest. Herein, we describe the single‐step ligand‐mediated synthesis of single‐crystalline ...CsPbBr3 perovskite nanowires (NWs) directly from the precursor powders. Studies of the reaction process and the morphological evolution revealed that the initially formed CsPbBr3 nanocubes are transformed into NWs through an oriented‐attachment mechanism. The optical properties of the NWs can be tuned across the entire visible range by varying the halide (Cl, Br, and I) composition through subsequent halide ion exchange. Single‐particle studies showed that these NWs exhibit strongly polarized emission with a polarization anisotropy of 0.36. More importantly, the NWs can self‐assemble in a quasi‐oriented fashion at an air/liquid interface. This process should also be easily applicable to perovskite nanocrystals of different morphologies for their integration into nanoscale optoelectronic devices.
Cubes, wires, and assemblies: Single‐crystalline perovskite nanowires were prepared directly from precursor powders in a single‐step ligand‐assisted process by ultrasonication. The nanowires likely resulted from the oriented attachment of nanocubes. Quasi‐oriented self‐assemblies of the perovskite nanowires were fabricated at air/liquid interfaces.
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