Optical Membrane Control with Red Light Enabled by Red-Shifted Photolipids.

Photoswitchable phospholipids, or "photolipids", that harbor an azobenzene group in their lipid tails are versatile tools to manipulate and control lipid bilayer properties with light. So far, the limited ultraviolet-A/blue spectral range in which the photoisomerization of regular azobenzene operates has been a major obstacle for biophysical or photopharmaceutical applications. Here, we report on the synthesis of nano- and micrometer-sized liposomes from tetra-ortho-chloro azobenzene-substituted phosphatidylcholine (termed red-azo-PC) that undergoes photoisomerization on irradiation with tissue-penetrating red light (≥630 nm). Photoswitching strongly affects the fluidity and mechanical properties of lipid membranes, although small-angle X-ray scattering and dynamic light scattering measurements reveal only a minor influence on the overall bilayer thickness and area expansion. By controlling the photostationary state and the photoswitching efficiency of red-azo-PC for specific wavelengths, we demonstrate that shape transitions such as budding or pearling and the division of cell-sized vesicles can be achieved. These results emphasize the applicability of red-azo-PC as a nanophotonic tool in synthetic biology and for biomedical applications.

Mixed Mercaptocarboxylic Acid Shells Provide Stable Dispersions of InPZnS/ZnSe/ZnS Multishell Quantum Dots in Aqueous Media.

Highly luminescent indium phosphide zinc sulfide (InPZnS) quantum dots (QDs), with zinc selenide/zinc sulfide (ZnSe/ZnS) shells, were synthesized. The QDs were modified via a post-synthetic ligand exchange reaction with 3-mercaptopropionic acid (MPA) and 11-mercaptoundecanoic acid (MUA) in different MPA:MUA ratios, making this study the first investigation into the effects of mixed ligand shells on InPZnS QDs. Moreover, this article also describes an optimized method for the correlation of the QD size vs. optical absorption of the QDs. Upon ligand exchange, the QDs can be dispersed in water. Longer ligands (MUA) provide more stable dispersions than short-chain ligands. Thicker ZnSe/ZnS shells provide a better photoluminescence quantum yield (PLQY) and higher emission stability upon ligand exchange. Both the ligand exchange and the optical properties are highly reproducible between different QD batches. Before dialysis, QDs with a ZnS shell thickness of ~4.9 monolayers (ML), stabilized with a mixed MPA:MUA (mixing ratio of 1:10), showed the highest PLQY, at ~45%. After dialysis, QDs with a ZnS shell thickness of ~4.9 ML, stabilized with a mixed MPA:MUA and a ratio of 1:10 and 1:100, showed the highest PLQYs, of ~41%. The dispersions were stable up to 44 days at ambient conditions and in the dark. After 44 days, QDs with a ZnS shell thickness of ~4.9 ML, stabilized with only MUA, showed the highest PLQY, of ~34%.

Transfer of Direct to Indirect Bound Excitons by Electron Intervalley Scattering in Cs2AgBiBr6 Double Perovskite Nanocrystals.

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 Cs2AgBiBr6 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.

Manganese-Doping-Induced Quantum Confinement within Host Perovskite Nanocrystals through Ruddlesden-Popper Defects.

The concept of doping Mn2+ ions into II-VI semiconductor nanocrystals (NCs) was recently extended to perovskite NCs. To date, most studies on Mn2+ doped NCs focus on enhancing the emission related to the Mn2+ dopant via an energy transfer mechanism. Herein, we found that the doping of Mn2+ ions into CsPbCl3 NCs not only results in a Mn2+ -related orange emission, but also strongly influences the excitonic properties of the host NCs. We observe for the first time that Mn2+ doping leads to the formation of Ruddlesden-Popper (R.P.) defects and thus induces quantum confinement within the host NCs. We find that a slight doping with Mn2+ ions improves the size distribution of the NCs, which results in a prominent excitonic peak. However, with increasing the Mn2+ concentration, the number of R.P. planes increases leading to smaller single-crystal domains. The thus enhanced confinement and crystal inhomogeneity cause a gradual blue shift and broadening of the excitonic transition, respectively.

Fast Electron and Slow Hole Relaxation in InP-Based Colloidal Quantum Dots.

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.

A highly crystalline anthracene-based MOF-74 series featuring electrical conductivity and luminescence.

Recently, a small group of metal-organic frameworks (MOFs) has been discovered featuring substantial charge transport properties and electrical conductivity, hence promising to broaden the scope of potential MOF applications in fields such as batteries, fuel cells and supercapacitors. In combination with light emission, electroactive MOFs are intriguing candidates for chemical sensing and optoelectronic applications. Here, we incorporated anthracene-based building blocks into the MOF-74 topology with five different divalent metal ions, that is, Zn2+, Mg2+, Ni2+, Co2+ and Mn2+, resulting in a series of highly crystalline MOFs, coined ANMOF-74(M). This series of MOFs features substantial photoluminescence, with ANMOF-74(Zn) emitting across the whole visible spectrum. The materials moreover combine this photoluminescence with high surface areas and electrical conductivity. Compared to the original MOF-74 materials constructed from 2,5-dihydroxy terephthalic acid and the same metal ions Zn2+, Mg2+, Ni2+, Co2+ and Mn2+, we observed a conductivity enhancement of up to six orders of magnitude. Our results point towards the importance of building block design and the careful choice of the embedded MOF topology for obtaining materials with desired properties such as photoluminescence and electrical conductivity.

Chemically Synthesized Carbon Nanorods with Dual Polarized Emission.

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.

Spontaneous Crystallization of Perovskite Nanocrystals in Nonpolar Organic Solvents: A Versatile Approach for their Shape-Controlled Synthesis.

The growing demand for perovskite nanocrystals (NCs) for various applications has stimulated the development of facile synthetic methods. Perovskite NCs have often been synthesized by either ligand-assisted reprecipitation (LARP) at room temperature or by hot-injection at high temperatures and inert atmosphere. However, the use of polar solvents in LARP affects their stability. Herein, we report on the spontaneous crystallization of perovskite NCs in nonpolar organic media at ambient conditions by simple mixing of precursor-ligand complexes without application of any external stimuli. The shape of the NCs can be controlled from nanocubes to nanoplatelets by varying the ratio of monovalent (e.g. formamidinium+ (FA+ ) and Cs+ ) to divalent (Pb2+ ) cation-ligand complexes. The precursor-ligand complexes are stable for months, and thus perovskite NCs can be readily prepared prior to use. Moreover, we show that this versatile synthetic process is scalable and generally applicable for perovskite NCs of different compositions.

Using Polar Alcohols for the Direct Synthesis of Cesium Lead Halide Perovskite Nanorods with Anisotropic Emission.

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 CsPbBr3 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 CsPbCl3 and CsPbI3 NRs with similar dimensions have then been derived from the CsPbBr3 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.

Facile Synthesis of FAPbI3 Nanorods.

Metal halide perovskites are promising materials for a range of applications. The synthesis of light-emitting perovskite nanorods has become popular recently. Thus far, the facile synthesis of perovskite nanorods remains elusive. In this work, we have developed a facile synthesis to fabricate FAPbI3 nanorods for the first time, demonstrating a high photoluminescence quantum yield of 35-42%. The fabrication of the nanorods has been made possible by carefully tuning the concentration of formamidine-oleate as well as the amount of oleic acid with pre-dissolved PbI2 in toluene with oleic acid/oleylamine.

Chemical Cutting of Perovskite Nanowires into Single-Photon Emissive Low-Aspect-Ratio CsPbX3 (X=Cl, Br, I) Nanorods.

Post-synthetic shape-transformation processes provide access to colloidal nanocrystal morphologies that are unattainable by direct synthetic routes. Herein, we report our finding about the ligand-induced fragmentation of CsPbBr3 perovskite nanowires (NWs) into low aspect-ratio CsPbX3 (X=Cl, Br and I) nanorods (NRs) during halide ion exchange reaction with PbX2 -ligand solution. The shape transformation of NWs-to-NRs resulted in an increase of photoluminescence efficiency owing to a decrease of nonradiative decay rates. Importantly, we found that the perovskite NRs exhibit single photon emission as revealed by photon antibunching measurements, while it is not detected in parent NWs. This work not only reports on the quantum light emission of low aspect ratio perovskite NRs, but also expands our current understanding of shape-dependent optical properties of perovskite nanocrystals.

Tuning the Optical Properties of Perovskite Nanoplatelets through Composition and Thickness by Ligand-Assisted Exfoliation.

High-quality hybrid halide perovskite nanocrystals are fabricated through a simple, versatile, and efficient two-step process involving a dry step followed by a ligand-assisted liquid-phase exfoliation step. The emission wavelength of the resulting nanocrystals can be tuned either through composition by varying the halide content or by reducing their thickness.