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Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research.

Lead-free halide double perovskites have emerged as a nontoxic alternative to the heavily researched lead-based halide perovskites. However, their optical properties and the initial charge carrier relaxation processes are under debate. In this study, we apply time-resolved photoluminescence and differential transmission spectroscopy to investigate the photoexcited charge carrier dynamics within the indirect band structure of Cs 2 AgBiBr 6 nanocrystals. Interestingly, we observe a high energetic emission stemming from the direct band gap, besides the previously reported emission from the indirect band gap transition. We attribute this emission to the radiative recombination of direct bound excitons. This emission maximum redshifts nearly 1 eV within 10 ps due to electron intervalley scattering, which leads to a transfer of direct to indirect bound excitons. We conclude that these direct bound excitons possess a giant oscillator strength causing not only a pronounced absorption peak at the optical band gap energy but also luminescence to occur at the direct band gap transition in spite of the prevailing intervalley scattering process. These results expand the understanding of the optical properties and the charge carrier relaxation in double perovskites, thus, facilitating the further development of optoelectronic devices harnessing lead-free perovskites.

Colloidal InP-based quantum dots are a promising material for light-emitting applications as an environment friendly alternative to their Cd-containing counterparts. Especially for their use in optoelectronic devices, it is essential to understand how charge carriers relax to the emitting state after injection with excess energy and if all of them arrive at this desired state. Herein, we report time-resolved differential transmission measurements on colloidal InP/ZnS and InP/ZnSe core/shell quantum dots. By optically exciting and probing individual transitions, we are able to distinguish between electron and hole relaxation. This, in turn, allows us to determine how the initial excess energy of the charge carriers affects the relaxation processes. According to the electronic level scheme, one expects a strong phonon bottleneck for electrons, whereas holes should relax easier as their energy levels are more closely spaced. On the contrary, we find that electrons relax faster than holes. The fast electron relaxation occurs via an efficient Auger-like electron-hole scattering mechanism. On the other hand, a small wave function overlap between core and shell states slows the hole relaxation. Additionally, holes can be trapped at the core/shell interface, leading to either slow detrapping or nonradiative recombination. Overall, these results demonstrate that it is crucial to construct devices enabling the injection of charge carriers energetically close to their emitting states in order to maximize the radiative efficiency of the system.

We realized the synthesis of carbon nanorods-monodisperse colloidal particles with a length of 50 nm and a width of 20 nm-which can be considered an addition to the family of light-emitting carbon-based nanostructures. Their anisotropic shape is determined by the use of the surfactant aminopropylisobutyl polyhedral oligomeric silsesquioxane, and their optical properties originate from domains of polycyclic aromatic hydrocarbons incorporated within an inorganic framework. The nanorods show dual polarized emission with a quantum yield of 15-20% and emission anisotropy of ∼0.3, which changes from blue (460 nm) to yellow (565 nm) depending on the excitation wavelength. These carbon nanorods expand the range of light-emitting carbon nanomaterials available for optoelectronic and biolabeling applications.

Semiconductor nanorods (NRs) offer the useful property of linearly polarized light emission. While this would be an attractive functionality for strongly emitting perovskite nanoparticles, to date, there has been limited success in demonstrating a direct chemical synthesis of cesium lead halide perovskite NRs. In this work, we realized the direct synthesis of CsPbBr 3 NRs with an average width of around 5 nm and average lengths of 10.8 and 23.2 nm, respectively, in two samples, which show a high photoluminescence quantum yield of 60-76% and reasonably high emission anisotropy of about 0.2 for longer rods. Both CsPbCl 3 and CsPbI 3 NRs with similar dimensions have then been derived from the CsPbBr 3 NRs by anion-exchange reactions. Remarkably, the synthesis of the NRs has been achieved in polar alcohols, a class of solvents not usually found to be beneficial in classical perovskite nanoparticle synthesis. This work not only offers the possibility to control the shape of chemically synthesized perovskite nanocrystals but also constitutes the hitherto less common strategy of synthesizing perovskite nanoparticles in polar rather than nonpolar or only weakly polar solvents.

Two-dimensional triphenylene-based metal-organic frameworks (TP-MOFs) attract significant scientific interest due to their long-range order combined with significant electrical conductivity. The deposition of these structures as oriented films is expected to promote their incorporation into diverse optoelectronic devices. However, to date, a controlled deposition strategy applicable for the different members of this MOF family has not been reported yet. Herein, we present the synthesis of highly oriented thin films of TP-MOFs by vapor-assisted conversion (VAC). We targeted the M-CAT-1 series comprising hexahydroxytriphenylene organic ligands and metal-ions such as Ni 2+ , Co 2+ , and Cu 2+ . These planar organic building blocks are connected in-plane to the metal-ions through a square planar node forming extended sheets which undergo self-organization into defined stacks. Highly oriented thin Ni- and Co-CAT-1 films grown on gold substrates feature a high surface coverage with a uniform film topography and thickness ranging from 180 to 200 nm. The inclusion of acid modulators in the synthesis enabled the growth of films with a preferred orientation on quartz and on conductive substrates such as indium-doped tin oxide (ITO). The van der Pauw measurements performed across the M-CAT-1 films revealed high electrical conductivity values of up to 10 -3 S cm -1 for both the Ni- and Co-CAT-1 films. Films grown on quartz allowed for a detailed photophysical characterization by means of UV-vis, photoluminescence, and transient absorption spectroscopy. The latter revealed the existence of excited states on a nanosecond time scale, sufficiently long to demonstrate a photoinduced charge generation and extraction in Ni-CAT-1 films. This was achieved by fabricating a basic photovoltaic device with an ITO/Ni-CAT-1/Al architecture, thus establishing this MOF as a photoactive material. Our results point to the intriguing capabilities of these conductive M-CAT-1 materials and an additional scope of applications as photoabsorbers enabled through VAC thin-film synthesis.

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.

We investigate the optical and morphological properties of gold nanoparticles grown by reducing a gold salt with Na2S. Lasers are tuned to the observed plasmon resonances, and the optical forces exerted on the nanoparticles are used to selectively print individual nanoparticles onto a substrate. This enables us to combine dark-field spectroscopy and scanning electron microscopy to compare the optical properties of single nanoparticles with their morphology. By arresting the synthesis at different times, we are able to investigate which type of nanoparticle is responsible for the respective resonances. We find that thin Au nanotriangles are the source of the observed near infrared (NIR) resonance. The initial lateral growth of these triangles causes the plasmon resonance to redshift into the NIR, whereas a subsequent thickening of the triangles and a concomitant truncation lead to a blueshift of the resonance. Furthermore, we find that the nanotriangles produced have extremely narrow line widths (187 ± 23 meV), show nearly isotropic scattering, and are stable for long periods of time. This shows their vast potential for applications such as in vivo imaging and bio(chemical) sensing. The method used here is generally applicable to other syntheses, and shows how complex nanostructures can be built up on substrates by selectively printing NPs of varying plasmonic resonances.

We report on a combined study of Rayleigh and Raman scattering spectroscopy, 3D electron tomography, and discrete dipole approximation (DDA) calculations of a single, complex-shaped gold nanoparticle (NP). Using the exact reconstructed 3D morphology of the NP as input for the DDA calculations, the experimental results can be reproduced with unprecedented precision and detail. We find that not only the exact NP morphology but also the surroundings including the points of contact with the substrate are of crucial importance for a correct prediction of the NP optical properties. The achieved accuracy of the calculations allows determining how many of the adsorbed molecules have a major contribution to the Raman signal, a fact that has important implications for analyzing experiments and designing sensing applications.

A mesoporous electron-donor covalent organic framework based on a benzodithiophene core, BDT-COF, was obtained through condensation of a benzodithiophene-containing diboronic acid and hexahydroxytriphenylene (HHTP). BDT-COF is a highly porous, crystalline, and thermally stable material, which can be handled in air. Highly porous, crystalline oriented thin BDT-COF films were synthesized from solution on different polycrystalline surfaces, indicating the generality of the synthetic strategy. The favorable orientation, crystallinity, porosity, and the growth mode of the thin BDT-COF films were studied by means of X-ray diffraction (XRD), 2D grazing incidence diffraction (GID), transmission and scanning electron microscopy (TEM, SEM), and krypton sorption. The highly porous thin BDT-COF films were infiltrated with soluble fullerene derivatives, such as [6,6]-phenyl C61 butyric acid methyl ester (PCBM), to obtain an interpenetrated electron-donor/acceptor host-guest system. Light-induced charge transfer from the BDT-framework to PCBM acceptor molecules was indicated by efficient photoluminescence quenching. Moreover, we monitored the dynamics of photogenerated hole-polarons via transient absorption spectroscopy. This work represents a combined study of the structural and optical properties of highly oriented mesoporous thin COF films serving as host for the generation of periodic interpenetrated electron-donor and electron-acceptor systems.

Noble-metal particles feature intriguing optical properties, which can be utilized to manipulate them by means of light. Light absorbed by gold nanoparticles, for example, is very efficiently converted into heat, and single particles can thus be used as a fine tool to apply heat to a nanoscopic area. At the same time, gold nanoparticles are subject to optical forces when they are irradiated with a focused laser beam, which renders it possible to print, manipulate, and optically trap them in two and three dimensions. Here, we demonstrate how these properties can be used to control the polymerization reaction and thermal curing of polydimethylsiloxane (PDMS) at the nanoscale and how these findings can be applied to synthesize polymer nanostructures such as particles and nanowires with subdiffraction limited resolution.

Size- and shape-controlled synthesis of copper chalcogenide nanocrystals (NCs) is of paramount importance for a careful engineering and understanding of their optoelectronic properties and, thus, for their exploitation in energy- and plasmonic-related applications. From the copper chalcogenide family copper telluride NCs have remained fairly unexplored as a result of a poor size-, shape-, and monodispersity control that is achieved via one-step syntheses approaches. Here we show that copper telluride (namely Cu(2-x)Te) NCs with well-defined morphologies (spheres, rods, tetrapods) can be prepared via cation exchange of preformed CdTe NCs while retaining their original shape. The resulting copper telluride NCs are characterized by pronounced plasmon bands in the near-infrared (NIR), in analogy to other copper-deficient chalcogenides (Cu(2-x)S, Cu(2-x)Se). We demonstrate that the extinction spectra of the as-prepared NCs are in agreement with theoretical calculations based on the discrete dipole approximation and an empirical dielectric function for Cu(2-x)Te. Additionally we show that the Drude model does not appropriately describe the complete set of Cu(2-x)Te NCs with different shapes. In particular, the low-intensity longitudinal plasmon bands for nanorods and tetrapods are better described by a modified Drude model with an increased damping in the long-wavelength interval. Importantly, a Lorentz model of localized quantum oscillators describes reasonably well all three morphologies, suggesting that holes in the valence band of Cu(2-x)Te cannot be described as fully free particles and that the effects of localization of holes are important. A similar behavior for Cu2-xS and Cu(2-x)Se NCs suggests that the effect of localization of holes can be a common property for the whole class of copper chalcogenide NCs. Taken altogether, our results represent a simple route toward copper telluride nanocrystals with well-defined shapes and optical properties and extend the understanding on vacancy-doped copper chalcogenide NCs with NIR optical resonances.

Colloidal nanoparticles (NPs) have become versatile building blocks in a wide variety of fields. Here, we discuss the state-of-the-art, current hot topics, and future directions based on the following aspects: narrow size-distribution NPs can exhibit protein-like properties; monodispersity of NPs is not always required; assembled NPs can exhibit collective behavior; NPs can be assembled one by one; there is more to be connected with NPs; NPs can be designed to be smart; surface-modified NPs can directly reach the cytosols of living cells.

We propose and demonstrate a hybrid lithographic technique capable of nanopatterning surfaces by optothermal decomposition of a polymeric film induced by a single metal nanoparticle. A tightly focused laser beam exerting a strong optical force onto the nanoparticle is used to move it inside the polymer film. Due to efficient plasmonic absorption of the laser light, the nanoparticle is heated up to temperatures of several hundred degrees, causing melting or even thermal decomposition of the polymer film. By this method, grooves less than 100 nm wide and tens of micrometers long can be directly milled in a polymer layer., (© 2011 American Chemical Society)

We propose and demonstrate a new method of an all-optical, contactless, one-step injection of single gold nanoparticles through phospholipid membranes. The method is based on the combination of strong optical forces acting on and simultaneous optical heating of a gold nanoparticle exposed to laser light tuned to the plasmon resonance of the nanoparticle. A focused laser beam captures single nanoparticles from the colloidal suspension, guides them toward a phospholipid vesicle and propels them through the gel-phase membrane, resulting in the nanoparticle internalization into the vesicle. Efficient resonant optical heating of the gold nanoparticle causes a pore to form in the gel-phase membrane, a few-hundred nanometers in size, which remains open for several minutes.

Gold nanostars provide high sensitivity for single nanoparticle label-free biosensing. The nanostars present multiple plasmon resonances of which the lower energy ones, corresponding to the nanostar tips and core-tip interactions, are the most sensitive to environmental changes. Streptavidin molecules are detected upon binding to individual, biotin-modified gold nanostars by spectral shifts in the plasmon resonances. Concentrations as low as 0.1 nM produce a shift of the tip related plasmon resonances of about 2.3 nm (5.3 meV).

Electrostatic complexes of a water-soluble fluorescent conjugated polymer, poly[9,9-bis(3'-((N,N-dimethyl)-N-ethylammonium)propyl)-2,7-fluorene-alt-1,4-phenylene]dibromide (PDFD), and water-soluble CdTe quantum dots (QDs) are designed to provide a cascaded FRET for DNA hybridization detection. PDFD has two functions in the detection scheme: as a light-harvesting antenna, it enhances the emission of QDs by the first level FRET and inverts the sign of the surface charge of QDs, thus providing a positively charged surface to allow negatively charged dye-labeled DNA to interact with the resulting complex. This interaction causes the second level FRET to infrared-emitting dye labeled on the probe DNA, providing a reliable signal-on sensing platform discriminating between complementary and non-complementary DNA. A detailed spectroscopic study offers a clear description of photophysical processes in the designed polymer/QD/DNA complex, providing ample potential for further sensitivity and selectivity improvements.