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Cadmium chalcogenide nanocrystals combined with co-catalyst nanoparticles hold promise for efficient solar to hydrogen conversion. Despite the progress, achieving high efficiency is hampered by high charge recombination rates and sample degradation. Here, we vary the decoration of platinum nanoparticles on CdS nanorods to demonstrate the important role of pathways for the photoelectrons to the co-catalyst. Contrary to expectations, the shortening of the path, by increasing the number of co-catalyst particles, increases the transfer rate but decreases the photocatalytic performance. This is because subsequent electron transfer to the acceptor is much slower; therefore, the recombination rate with the nearby holes increases. We show that with tip-decorated nanorods, the quantum yield of H2 production can reach and sustain nearly 90%, provided an efficient mechanism of mediated hole extraction is employed. The approach demonstrates that highly efficient photocatalysts may be prepared with only a minimal amou...

Coordination polymers show great potential for the tailored design of advanced photonic applications by employing crystal chemistry concepts. One challenge for achieving a rational design of nonlinear optically active MOF materials is deriving fundamental structure-property relations of the interplay between the photonic properties and the spatial arrangements of optically active chromophores within the network. We here investigate two-photon-absorption (TPA)-induced photoluminescence of two new MOFs based on a donor-acceptor tetraphenylphenylenediamine (tPPD) chromophore linker (H4TPBD) and Zn(II) and Cd(II) as metal centers. The TPA efficiencies are controlled by the network topologies, degree of interpenetration, packing densities, and the specific spatial arrangement of the chromophores. The effects can be rationalized within the framework of established excited-state theories of molecular crystals. The results presented here demonstrate the key effect of chromophore orientation on the nonlinear optical properties of crystalline network compounds and allow for establishing quantitative design principles for efficient TPA materials.

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.

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., Faster than fast: Shape‐controlled lead halide perovskite nanocrystals crystallize spontaneously at ambient conditions when precursor–ligand complexes are mixed directly in a nonpolar organic medium. Nanocubes and nanoplatelets have been obtained. This versatile synthetic process is generally applicable for a wide range of halide perovskite nanocrystals.

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. This work was supported by NPRP grant no. 8-878-1-172 from the Qatar National Research Fund (a member of the Qatar Foundation), the Research Grant Council of Hong Kong S.A.R. (CityU 11306619), the Ministry of Education and Science of the Russian Federation (grant 14.Y26.31.0028), by the RFBR Project No. 18-29-19122 mk, the National Natural Science Foundation of China (51702115), the Bavarian State Ministry of Science, Research, and Arts through the grant -Solar Technologies go Hybrid (SolTech), and the Alexander von Humboldt Foundation. Scopus

We report on trans-membrane interactions between blue-emitting carbon dots (CDs) and fluorescein. Hydrophobic CDs with a positive surface charge are embedded as-synthesized in the lipophilic sheet of the bilayer membrane of large synthetic phospholipid vesicles. The vesicles are prepared by mixing DOPC phospholipids and lipid molecules that contain anionic fluorescein attached to their hydrophilic head. Due to attractive electrostatic interactions, the CDs and fluorescein conjoin within the vesicle membrane, which leads to photoluminescence enhancement of fluorescein and facilitates trans-membrane energy transfer between the CDs and the dye., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas

Perovskite nanoplatelets (NPls) hold great promise for light-emitting applications, having achieved high photoluminescence quantum efficiencies (PLQEs) approaching unity in the blue wavelength range, where other metal-halide perovskites have typically been ineffective. However, the external quantum efficiency (EQE) of blue-emitting NPl light-emitting diodes (LEDs) have only reached 0.12%, with typical values well below 0.1%. In this work, we show that the performance of NPl LEDs is primarily hindered by a poor electronic interface between the emitter and hole-injector. Through Kelvin Probe and X-ray photoemission spectroscopy measurements, we reveal that the NPls have remarkably deep ionization potentials (>=6.5 eV), leading to large barriers for hole injection, as well as substantial non-radiative decay at the interface between the emitter and hole-injector. We find that an effective way to reduce these non-radiative losses is by using poly(triarylamine) interlayers. This results in an increase in the EQE of our blue LEDs emitting at 464 nm wavelength to 0.3%. We find that our results can be generalized to thicker sky-blue-emitting NPls, where we increase the EQE to 0.55% using the poly(triarylamine) interlayer. Our work also identifies the key challenges for further efficiency increases.

Devising strategies for the controlled injection of functional nanoparticles and reagents into living cells paves the way for novel applications in nanosurgery, sensing, and drug delivery. Here, we demonstrate the light-controlled guiding and injection of plasmonic Janus nanopens into living cells. The pens are made of a gold nanoparticle attached to a dielectric alumina shaft. Balancing optical and thermophoretic forces in an optical tweezer allows single Janus nanopens to be trapped and positioned on the surface of living cells. While the optical injection process involves strong heating of the plasmonic side, the temperature of the alumina stays significantly lower, thus allowing the functionalization with fluorescently labeled, single-stranded DNA and, hence, the spatially controlled injection of genetic material with an untethered nanocarrier. Fil: Maier, Christoph M.. Ludwig Maximilians Universitat; Alemania. Nanosystems Initiative Munich; Alemania Fil: Huergo, María Ana Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Milosevic, Sara. Ludwig Maximilians Universitat; Alemania Fil: Pernpeintner, Carla. Ludwig Maximilians Universitat; Alemania. Nanosystems Initiative Munich; Alemania Fil: Li, Miao. Ludwig Maximilians Universitat; Alemania Fil: Singh, Dhruv P.. Max Planck Institute for Intelligent Systems; Alemania Fil: Walker, Debora. Max Planck Institute for Intelligent Systems; Alemania Fil: Fischer, Peer. Max Planck Institute for Intelligent Systems; Alemania Fil: Feldmann, Jochen. Ludwig Maximilians Universitat; Alemania. Nanosystems Initiative Munich; Alemania Fil: Lohmüller, Theobald. Nanosystems Initiative Munich; Alemania. Ludwig Maximilians Universitat; Alemania

We describe the simple, scalable, single-step, and polar-solvent-free synthesis of high-quality colloidal CsPbX3 (X=Cl, Br, and I) perovskite nanocrystals (NCs) with tunable halide ion composition and thickness by direct ultrasonication of the corresponding precursor solutions in the presence of organic capping molecules. High angle annular dark field scanning transmission electron microscopy (HAADF-STEM) revealed the cubic crystal structure and surface termination of the NCs with atomic resolution. The NCs exhibit high photoluminescence quantum yields, narrow emission line widths, and considerable air stability. Furthermore, we investigated the quantum size effects in CsPbBr3 and CsPbI3 nanoplatelets by tuning their thickness down to only three to six monolayers. The high quality of the prepared NCs (CsPbBr3) was confirmed by amplified spontaneous emission with low thresholds. The versatility of this synthesis approach was demonstrated by synthesizing different perovskite NCs.

Wir berichten uber eine einfache, skalierbare, einstufige Synthese von kolloidalen Perowskit-Nanokristallen (NCs) aus CsPbX3 (X=Cl, Br und I) mit durchstimmbarer Halogenidionenzusammensetzung und Dicke mittels Ultraschalldispersion der entsprechenden Eduktlosungen im Gegenwart von organischen Liganden und ohne Verwendung von polaren Losungsmitteln. Die kubische Kristallstruktur sowie Oberflachenterminierung wurden mittels HAADF-STEM mit atomarer Prazision aufgelost. Die NCs weisen hohen Photoluminenszenzquantenausbeuten, schmale Emissionslinien und hohe Stabilitat gegenuber Luft auf. Zusatzlich untersuchen wir die Quanteneinschrankungseffekte in Nanoplattchen aus CsPbBr3 und CsPbI3 mit reduzierten Dicken von 3 bis 6 Monolagen. Die hohe optische Qualitat der NCs (CsPbBr3) wird durch verstarkter Spontanemission (ASE) mit extrem niedrigen Schwellen gezeigt. Weiterhin wird durch den Einsatz an verschiedenen Perowskiten die Flexibilitat der Synthesemethode demonstriert.

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.

Hybrid organic-inorganic halide perovskites demonstrate high potential in several applications such as solar cells, field-effect transistors, light-emitting diodes and more. However, the main drawback which limits their use in such applications is their low stability in humid conditions. In this paper we implement one of Nature’s strategies found in bio-crystals in order to improve the stability of the hybrid perovskite methylammonium lead bromide (MAPbBr3) in water, as well as to tune its structure, optical and thermal properties. This was achieved, for the first time, by the incorporation of amino acids into the lattice of MAPbBr3. The amino acid lysine, which possesses two NH3+groups, is incorporated into the hybrid unit cell, by substituting two methylammonium ions and serves as a “molecular bridge”. This incorporation induces a decrease in the lattice parameter of the host, accompanied with an increase in the band gap and noticeable changes in its morphology. Furthermore, we observed an increase in thermal expansion coefficient and a shift of the phase transformation temperature of the hybrid crystal. The level of amino acid incorporation depends on the conditions of crystallization, which also influence the extent of MAPbBr3band gap changes. Notably, lysine incorporation strongly increases the perovskite stability in water. This study demonstrates the unique and promising approach to tune the properties and stability of hybrid perovskites via this novel bio-inspired route.

Full water splitting into hydrogen and oxygen on semiconductor nanocrystals is a challenging task; overpotentials must be overcome for both half-reactions and different catalytic sites are needed to facilitate them. Additionally, efficient charge separation and prevention of back reactions are necessary. Here, we report simultaneous H-2 and O-2 evolution by CdS nanorods decorated with nanoparticulate reduction and molecular oxidation co-catalysts. The process proceeds entirely without sacrificial agents and relies on the nanorod morphology of CdS to spatially separate the reduction and oxidation sites. Hydrogen is generated on Pt nanoparticles grown at the nanorod tips, while Ru(tpy)(bpy)Cl-2-based oxidation catalysts are anchored through dithiocarbamate bonds onto the sides of the nanorod. O-2 generation from water was verified by O-18 isotope labelling experiments, and time-resolved spectroscopic results confirmed efficient charge separation and ultrafast electron and hole transfer to the reaction sites. The system demonstrates that combining nanoparticulate and molecular catalysts on anisotropic nanocrystals provides an effective pathway for visible-light-driven photocatalytic water splitting.

Self-assembly of nanoscale building blocks into ordered nanoarchitectures has emerged as a simple and powerful approach for tailoring the nanoscale properties and the opportunities of using these properties for the development of novel optoelectronic nanodevices. Here, the one-pot synthesis of CsPbBr3 perovskite supercrystals (SCs) in a colloidal dispersion by ultrasonication is reported. The growth of the SCs occurs through the spontaneous self-assembly of individual nanocrystals (NCs), which form in highly concentrated solutions of precursor powders. The SCs retain the high photoluminescence (PL) efficiency of their NC subunits, however also exhibit a redshifted emission wavelength compared to that of the individual nanocubes due to interparticle electronic coupling. This redshift makes the SCs pure green emitters with PL maxima at approximate to 530-535 nm, while the individual nanocubes emit a cyan-green color (approximate to 512 nm). The SCs can be used as an emissive layer in the fabrication of pure green light-emitting devices on rigid or flexible substrates. Moreover, the PL emission color is tunable across the visible range by employing a well-established halide ion exchange reaction on the obtained CsPbBr3 SCs. These results highlight the promise of perovskite SCs for light emitting applications, while providing insight into their collective optical properties.

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.

Copper(I)-based catalysts, such as Cu2S, are considered to be very promising materials for photocatalytic CO2 reduction. A common synthesis route for Cu2S via cation exchange from CdS nanocrystals requires Cu(I) precursors, organic solvents, and neutral atmosphere, but these conditions are not compatible with in situ applications in photocatalysis. Here we propose a novel cation exchange reaction that takes advantage of the reducing potential of photoexcited electrons in the conduction band of CdS and proceeds with Cu(II) precursors in an aqueous environment and under aerobic conditions. We show that the synthesized Cu2S photocatalyst can be efficiently used for the reduction of CO2 to carbon monoxide and methane, achieving formation rates of 3.02 and 0.13 μmol h(-1) g(-1), respectively, and suppressing competing water reduction. The process opens new pathways for the preparation of new efficient photocatalysts from readily available nanostructured templates.

Carbon dots (CDs) have attracted rapidly growing interest in recent years due to their unique and tunable optical properties, the low cost of fabrication, and their widespread uses. However, due to the complex structure of CDs, both the molecular ingredients and the intrinsic mechanisms governing photoluminescence of CDs are poorly understood. Among other features, a large Stokes shift of over 100 nm and a photoluminescence spectrally dependent on the excitation wavelength have so far not been adequately explained. In this Letter we investigate CDs and develop a model system to mimic their optical properties. This system comprised three types of polycyclic aromatic hydrocarbon (PAH) molecules with fine-tuned concentrations embedded in a polymer matrix. The model suggests that the Stokes shift in CDs is due to the self-trapping of an exciton in the PAH network. The width and the excitation dependence of the emission comes from a selective excitation of PAHs with slightly different energy gaps and from energy transfer between them. These insights will help to tailor the optical properties of CDs and help their implementation into applications, e.g., light-emitting devices and biomarkers. This could also lead to "artificial" tunable carbon dots by locally modifying the composition and consequently the optical properties of composite PAH films.

The controlled injection of nanoscopic objects into living cells with light offers promising prospects for the development of novel molecular delivery strategies or intracellular biosensor applications. Here, we show that single gold nanoparticles from solution can be patterned on the surface of living cells with a continuous wave laser beam. In a second step, we demonstrate how the same particles can then be injected into the cells through a combination of plasmonic heating and optical force. We find that short exposure times are sufficient to perforate the cell membrane and inject the particles into cells with a survival rate of >70%.

Multi-photon absorption and multiple exciton generation represent two separate strategies for enhancing the conversion efficiency of light into usable electric power. Targeting below-band-gap and above-band-gap energies, respectively, to date these processes have only been demonstrated independently. Here we report the combined interaction of both nonlinear processes in CsPbBr3 perovskite nanocrystals. We demonstrate nonlinear absorption over a wide range of below-band-gap excitation energies (0.5–0.8 Eg). Interestingly, we discover high-order absorption processes, deviating from the typical two-photon absorption, at specific energetic positions. These energies are associated with a strong enhancement of the photoluminescence intensity by up to 105. The analysis of the corresponding energy levels reveals that the observed phenomena can be ascribed to the resonant creation of multiple excitons via the absorption of multiple below-band-gap photons. This effect may open new pathways for the efficient conversion of optical energy, potentially also in other semiconducting materials., The effects of the combined interplay of below-band-gap multi-photon absorption and multiple exciton generation have not been investigated. Here, the authors show the combined interaction of these processes in perovskite nanocrystals, leading to an enhanced interband photoluminescence emission under resonant conditions.

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 CsPbBr

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., Carbon dots are an emergent class of nanomaterials that hold promise for innovations in imaging, sensing, and catalytic technologies. Here, Stolarczyk and colleagues control the nitrogen-atom content and location within carbon dots, reporting the resulting impact on emissivity and photocatalytic behaviour.

Resumen del trabajo presentado a la 19th International Conference on Transparent Optical Networks (ICTON), celebrada en Girona (España) del 2 al 6 de julio de 2017., We report our recent results of investigation of the interactions between localized plasmons in gold nanorods and excitons in J-aggregates. We were able to track an anticrossing behavior of the hybridized modes both in the extinction and in the photoluminescence spectra of this hybrid system. We identified the nonlinear optical behavior of this system by transient absorption spectroscopy. Finally using magnetic circular dichroism spectroscopy, we show that nonmagnetic organic molecules exhibit magneto-optical response due to binding to a plasmonic nanoparticles. In our experiments, we also studied the effect of detuning as well as the effect of off- and on resonance excitation on the hybrid states.

Trabajo presentado a la 3rd International Conference on Applications of Optics and Photonics, celebrado en Faro (Portugal) del 8 al 12 de mayo de 2017., We investigated the interactions between localized plasmons in gold nanorods and excitons in J-aggregates and were able to track an anticrossing behavior of the hybridized modes both in the extinction and in the photoluminescence spectra of this hybrid system. We identified the nonlinear optical behavior of this system by transient absorption spectroscopy. Finally using magnetic circular dichroism spectroscopy we showed that nonmagnetic organic molecules exhibit magneto-optical response due to binding to a plasmonic nanoparticles. In our experiments we also studied the effect of detuning as well as the effect of off- and on resonance excitation on the hybrid states., We acknowledge financial support from Project Fis2016.80174-P (PLASMOQUANTA) from MINECO (Ministerio de Economía y Competitividad). L.L.-M. acknowledges funding from the European Research Council (ERC Advanced Grant 267867, Plasmaquo). This study was supported by the Ministry of Education and Science of the Russian Federation, grant no. 14.Y26.31.0011.

The primary amine groups on the heptazine-based polymer melon, also known as graphitic carbon nitride (g-C3N4), can be replaced by urea groups using a two-step postsynthetic functionalization. Under simulated sunlight and optimum Pt loading, this urea-functionalized carbon nitride has one of the highest activities among organic and polymeric photocatalysts for hydrogen evolution with methanol as sacrificial donor, reaching an apparent quantum efficiency of 18% and nearly 30 times the hydrogen evolution rate compared to the nonfunctionalized counterpart. In the absence of Pt, the urea-derivatized material evolves hydrogen at a rate over four times that of the nonfunctionalized one. Since “defects” are conventionally accepted to be the active sites in graphitic carbon nitride for photocatalysis, the work here is a demonstrated example of “defect engineering,” where the catalytically relevant defect is inserted rationally for improving the intrinsic, rather than extrinsic, photocatalytic performance. Furthermore, the work provides a retrodictive explanation for the general observation that g-C3N4 prepared from urea performs better than those prepared from dicyandiamide and melamine. In-depth analyses of the spent photocatalysts and computational modeling suggest that inserting the urea group causes a metal-support interaction with the Pt cocatalyst, thus facilitating interfacial charge transfer to the hydrogen evolving centers.

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. Fil: Perassi, Eduardo Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Hrelescu, Calin. Ludwig Maximilians Universitat; Alemania Fil: Wisnet, Andreas. Ludwig Maximilians Universitat; Alemania Fil: Doblinger, Markus. Ludwig Maximilians Universitat; Alemania Fil: Scheu, Christina. Ludwig Maximilians Universitat; Alemania Fil: Jäckel, Frank. Ludwig Maximilians Universitat; Alemania Fil: Coronado, Eduardo A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Feldmann, Jochen. Ludwig Maximilians Universitat; Alemania

The sensitization of dispersed P25 TiO2 nanoparticles (NPs) and macroporous TiO2 films with water-soluble and air-stable PbS quantum dots (QDs) capped with l-glutathione (GSH) ligands was investigated. Optimum sensitization was achieved by careful adjustment of the surface charges of TiO2 and PbS QDs by controlling the pH of the QD solution. Efficient electron transfer from photoexcited PbS QDs via the GSH ligands into the conduction band of TiO2 was demonstrated by photoluminescence (PL) spectroscopy of PbS-sensitized P25 nanoparticles. The PbS QD-sensitized porous TiO2 electrodes were used to prepare quantum-dot-sensitized solar cells (QDSSCs) utilizing a CuxSy counter electrode and aqueous polysulfide electrolyte. Cells with up to 64% injection efficiency, 1.1% AM 1.5 conversion efficiency, and short circuit current density of 7.4 mA cm–2 were obtained. The physical parameters of the cells were investigated using impedance spectroscopy.

We focus on fabricating organic/inorganic halide perovskites with controlled dimensionality, size and composition and studying the optical and electrical properties of the resulting nanocrystals. By partially exchanging the most commonly used organic cation methylammonium for a cation with a larger chain we are able to fabricate two-dimensional nanoplatelets down to a single unit cell thickness.1 Through absorption and photoluminescence measurements we find that this leads to a strong-quantum size effect in the perovskites while additionally increasing the exciton bind energy to several hundreds of meV. We employ several fabrication techniques to increase the fluorescence quantum yield to be able to investigate single particles, and to study energy transport between individual nanocrystals by time-resolved spectroscopic methods. Our findings can lead to improvements in not only photovoltaic devices, but also for light-harvesting and light-emitting devices, such as LEDs and lasers. (1) Sichert, J. A.; Tong, Y.; Mutz, N.; Vollmer, M.; Fischer, S.; Milowska, K. Z.; Garcia Cortadella, R.; Nickel, B.; Cardenas-Daw, C.; Stolarczyk, J. K.; Urban, A. S.; Feldmann, J. Nano Letters 2015, 15, 6521.

Strong coupling of plasmons and excitons can form hybrid states, the so called “plexcitons”. Especially with molecular J-aggregated dye molecules strong interaction becomes observable even under ambient conditions. In our work we investigate the nature of plexcitonic states formed in gold nanorods coated with a cyanine dye by transient absorption spectroscopy. We demonstrate that plexcitons show tunable plasmonic and excitonic non-linear optical behaviour. Our experimental data can be explained on the basis of a simple Lorentz oscillator model. We find that both the quality factor and the coupling strength between plasmons and excitons can be optically manipulated on an ultrashort time scale. T. Simon, D. Melnikau, A. Sanchez-Iglesias, M. Grzelczak, L. Liz-Marzan, Y. Rakovich, J. Feldmann and A. Urban, Exploring the optical non-linearities of plasmon-exciton hybrid resonances in coupled colloidal nanostructures, submitted (2016)

Recently, layered hybrid perovskites have been attracting huge interest due to a wide range of possible chemical compositions and the resulting tunability of the materials’ properties. In this study, we investigate the effect of the chain length of the organic ligands on the optical properties of stacks of two-dimensional perovskite layers consisting of alkylammonium lead iodide (CnH2n+1NH3)2PbI4 with n = 4, …, 18. Photoluminescence and absorption spectroscopy reveal a blueshift with increasing chain length n including a jump of 110 meV between the n = 10 and n = 12 ligands due to a change in octahedral tilting. Using X-ray diffraction, we determine the crystal structure and find the octahedral tilting to be the main cause of this blueshift. However, for very short chain lengths, additional effects further reduce the transition energy. Results of effective mass approximation model calculations show good agreement between the expected reduction of transition energy and measured photoluminescence emission wavelength for these samples. This highlights how octahedral tilting plays a major role in determining the optical bandgap and suggests that miniband formation plays only a minor role in this material.

An optical printing technique is used to accurately position a 150 nm diameter gold nanoparticle onto a submicrometer linear three-hole defect of a photonic crystal nanocavity. It is shown (using both experiment and finite-difference time domain modelling), that there is an electromagnetic interaction between the nanoparticle and the cavity mode, with the electromagnetic field within the cavity being dissipated by driving the nanoparticle plasmon resonance. The use of a printing technique to selectively position nanoparticles onto a surface-accessible cavity potentially allows the hybridisation between electronic, excitonic, and optical states to be explored with high precision. Furthermore, through its scalable nature it also opens possibilities for the routine construction of new types of photonic devices and sensors.

We report on the tuning of specific binding of DNA attached to gold nanoparticles at the individual particle pair (dimer) level in an optical trap by means of plasmonic heating. DNA hybridization events are detected optically by the change in the plasmon resonance frequency due to plasmonic coupling of the nanoparticles. We find that at larger trapping powers (i.e., larger temperatures and stiffer traps) the hybridization rates decrease by more than an order of magnitude. This result is explained by higher temperatures preventing the formation of dimers with lower binding energies. Our results demonstrate that plasmonic heating can be used to fine tune the kinetics of biomolecular binding events.

We study electronic and optical properties of the low-bandgap co-polymer PCPDT-BT (poly-cyclopentadithiophene-co-benzothiadiazole) and compare it with the corresponding homo-polymer PCPDT (poly-cyclopentadithiophene). We investigate the linear absorptivity in these systems for neutral molecules and for their singly charged ions based on quantum-chemical calculations and experiments. One of our main findings is that the ions of the homo-polymer show a polaron absorption that is symmetric between anion and cation, whereas for polaron excitations in the co-polymer this symmetry is strongly lifted. We demonstrate that this asymmetry can be attributed to the absence of symmetry between the high-lying occupied and low-lying unoccupied molecular orbitals in the co-polymer with type-II orbital alignment between the moieties constituting the chain. This notion is of importance for the qualitative and quantitative interpretation of spectroscopic polaron data and is not specific t o the system studied here but similarly applies to other co-polymers.

We report a two-step approach for the fabrication of quasi-hexagonal ordered arrays of star-shaped gold nanoparticles (gold nanostars) as reliable, large-scale homogeneous substrates for surface-enhanced Raman scattering (SERS) spectroscopy by a combination of block-copolymer micelle nanolithography and electroless deposition. The applicability of this platform for SERS imaging is demonstrated by pH-sensitive Raman measurements of 4-mercaptobenzoic acid adsorbed to the nanostars in the array. A homogeneous enhancement factor of ∼105 was observed on the nanostar monolayer over an area of several hundreds of square micrometers.

We investigate the role of excess excitation energy on the nature of photoexcitations in donor-acceptor π-conjugated materials. We compare the polymer poly(2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[1,2-b;3,4-b']dithiophene)-4,7-benzo[2,1,3]thiadiazole) (PCPDTBT) and a short oligomer with identical constituents at different excitation wavelengths, from the near-infrared up to the ultraviolet spectral region. Ultrafast spectroscopic measurements clearly show an increased polaron pair yield for higher excess energies directly after photoexcitation when compared to the exciton population. This effect, already observable in the polymer, is even more pronounced for the shorter oligomer. Supported by quantum chemical simulations, we show that excitation in high-energy states generates electron and hole wave functions with reduced overlap, which likely act as precursors for the polaron pairs. Interestingly, in the oligomer we observe a lifetime of polaron pairs which is one order of magnitude longer. We suggest that this behavior results from the intermolecular nature of polaron pairs in oligomers. The study excludes the presence of carrier multiplication in these materials and highlights new aspects in the photophysics of donor-acceptor small molecules when compared to polymers. The former are identified as promising materials for efficient organic photovoltaics.

The self-assembly of nanoscale elements into three-dimensional structures with precise shapes and sizes is important in fields such as nanophotonics, metamaterials and biotechnology. Short molecular linkers have previously been used to create assemblies of nanoparticles, but the approach is limited to small interparticle distances, typically less than 10 nm. Alternatively, DNA origami can precisely organize nanoscale objects over much larger length scales. Here we show that rigid DNA origami scaffolds can be used to assemble metal nanoparticles, quantum dots and organic dyes into hierarchical nanoclusters that have a planet-satellite-type structure. The nanoclusters have a tunable stoichiometry, defined distances of 5-200 nm between components, and controllable overall sizes of up to 500 nm. We also show that the nanoscale components can be positioned along the radial DNA spacers of the nanostructures, which allows short- and long-range interactions between nanoparticles and dyes to be studied in solution. The approach could, in the future, be used to construct efficient energy funnels, complex plasmonic architectures, and porous, nanoengineered scaffolds for catalysis.

Lipid membranes are almost impermeable for charged molecules and ions that can pass the membrane barrier only with the help of specialized transport proteins. Here, we report how temperature manipulation at the nanoscale can be employed to reversibly control the electrical resistance and the amount of current that flows through a bilayer membrane with pA resolution. For this experiment, heating is achieved by irradiating gold nanoparticles that are attached to the bilayer membrane with laser light at their plasmon resonance frequency. We found that controlling the temperature on the nanoscale renders it possible to reproducibly regulate the current across a phospholipid membrane and the membrane of living cells in absence of any ion channels.

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., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas

Strong coupling of plasmons and excitons can form hybrid states, the so-called “plexcitons”. Although plasmons have a low quality factor, the exceptionally high coupling strength with molecular aggregates, in particular J-aggregates, allows the realization of strong interaction. Despite several studies in recent years showing the formation of plexcitonic states, their nature, especially at very short times, is still insufficiently investigated. In this article, we identify the nonlinear optical behavior of plexcitons formed on gold nanorods coated with J-aggregated cyanine molecules at short times by transient absorption spectroscopy and a simple Lorentz oscillator model. We control the spectral overlap of the two resonances and analyze the effect of detuning as well as the effect of off- and on resonance excitation on the hybrid states. We demonstrate that at ultrashort time scales plexcitons show tunable plasmonic and excitonic nonlinear performance according to the hybridization model. In a first approach, we discover a way to optically manipulate the quality factor and study the effects on the coupled hybrid states. As a second approach, we find that the coupling strength can also be influenced on an ultrashort time scale in the strong coupling regime when plexcitons are excited., This work has been financially supported by the ERC Advanced Grant HYMEM and the Bavarian State Ministry of Science, Research, and Arts through “Solar Technologies Go Hybrid” (SolTech) as well as through Projects FIS2013-41184-P and MAT2013-46101-R of the Spanish Ministry of Economy and Competitiveness (MINECO).

In transient absorption (TA) spectra, the bleach features originating from state filling are overlapped by their energy-shifted derivatives, arising from excited state energy level shifts. This makes the direct extraction of carrier dynamics from a single-wavelength time-trace misleading. Fitting TA spectra in time, as Gaussian functions and their derivative-like shifted Gaussians, allows to individually extract the real dynamics of both photobleached transitions, and their energy shifts. In CdTe nanorods (NRs) we found a delayed heating of holes due to the release of the large excess energy in the electron relaxation process. The slow hole-trapping process is consistent with a high number of surface trap states in these model NRs. Our results show that only a correct disentanglement of bleaching and energy shift contributions provides a reliable framework to extract the underlying carrier relaxation dynamics, including trapping, non-radiative recombination, and eventually carrier multiplication.

We introduce size-selected subnanometer cluster catalysts deposited on thin films of colloidal semiconductor nanocrystals as a novel platform to obtain atomic scale insight into photocatalytic generation of solar fuels. Using Pt-cluster-decorated CdS nanorod films for photocatalytic hydrogen generation as an example, we determine the minimum amount of catalyst necessary to obtain maximum quantum efficiency of hydrogen generation. Further, we provide evidence for tuning photocatalytic activities by precisely controlling the cluster catalyst size.

Surface-chemistry of individual, optically trapped plasmonic nanoparticles is modified and accelerated by plasmonic overheating. Depending on the optical trapping power, gold nanorods can exhibit red-shifts of their plasmon resonance (i.e. increasing aspect ratio) under oxidative conditions. In contrast, in bulk exclusively blue shifts (decreasing aspect ratios) are observed. Supported by calculations, we explain this finding by local temperatures in the trap exceeding the boiling point of the solvent which can not be achieved in bulk.