Electrophoretic Deposition of Single Nanoparticles.

The controlled assembly of colloid particles on a solid substrate has always been a major challenge in colloid and surface science. Here we provide an overview of electrophoretic deposition (EPD) of single charge-stabilized nanoparticles. We demonstrate that surface templated EPD (STEPD) assembly, which combines EPD with top-down nanofabrication, allows a wide range of nanoparticles to be built up into arbitrary structures with high speed, scalability, and excellent fidelity. We will also discuss some of the current colloid chemical limitations and challenges in STEPD assembly for sub-10 nm nanoparticles and for the fabrication of densely packed single particle arrays.

Directed Gradients in the Excited-State Energy Landscape of Poly(3-hexylthiophene) Nanofibers.

Funneling excitation energy toward lower energy excited states is a key concept in photosynthesis, which is often realized with at most two chemically different types of pigment molecules. However, current synthetic approaches to establish energy funnels, or gradients, typically rely on Förster-type energy-transfer cascades along many chemically different molecules. Here, we demonstrate an elegant concept for a gradient in the excited-state energy landscape along micrometer-long supramolecular nanofibers based on the conjugated polymer poly(3-hexylthiophene), P3HT, as the single component. Precisely aligned P3HT nanofibers within a supramolecular superstructure are prepared by solution processing involving an efficient supramolecular nucleating agent. Employing hyperspectral imaging, we find that the lowest-energy exciton band edge continuously shifts to lower energies along the nanofibers' growth direction. We attribute this directed excited-state energy gradient to defect fractionation during nanofiber growth. Our concept provides guidelines for the design of supramolecular structures with an intrinsic energy gradient for nanophotonic applications.

The Preparation of a Challenging Superconductor Nb3Al by Exploiting Nano Effect.

The Nb3Al superconductor with excellent physical and working properties is one of the most promising materials in high-magnetic-field applications. However, it is difficult to prepare high-quality Nb3Al with a desired superconducting transition temperature (Tc) because of its narrow phase formation area at high temperatures (>1940 °C). This work reports a method to prepare stoichiometric Nb3Al powder samples at a relatively low temperature (1400 °C) by exploiting the nano effect of Nb particles with pretreatment of Nb powder under H2/Ar atmosphere. The obtained Nb3Al samples exhibit high Tc's of ~16.8K. Based on density functional theory (DFT) calculations and statistical mechanics analysis, the crucial role of quantum effect in leading to the success of the preparation method was studied. A new measure of surface energy (MSE) of a model particle is introduced to study its size and face dependence. A rapid convergence of the MSE with respect to the size indicates a quick approach to the solid limit, while the face dependence of MSE reveals a liquid-like behavior. The surface effect and quantum fluctuation of the Nbn clusters explain the success of the preparation method.

Emission modulation of fluorescent turn-on mode dibenzothienyl sulfonyl ethene photoswitches embedded in a polymer film.

For decades photochromic molecules have attracted attention for their potential in using light as an external stimulus to change their photophysical properties. Here we report the spectroscopic characterization of two emissive photochromic molecules that are intrinsically fluorescent and that undergo a photocyclization/cycloreversion reaction upon illumination with light in the UV and VIS spectral ranges. For appropriately adjusted illumination intensities the emission can be modulated between the high- and the low-level with a contrast ratio exceeding 80%. The data are in reasonable agreement with the predictions from a simple kinetic model.

Disorder in P3HT Nanoparticles Probed by Optical Spectroscopy on P3HT-b-PEG Micelles.

We employ photoluminescence (PL) spectroscopy on individual nanoscale aggregates of the conjugated polymer poly(3-hexylthiophene), P3HT, at room temperature (RT) and at low temperature (LT) (1.5 K), to unravel different levels of structural and electronic disorder within P3HT nanoparticles. The aggregates are prepared by self-assembly of the block copolymer P3HT-block-poly(ethylene glycol) (P3HT-b-PEG) into micelles, with the P3HT aggregates constituting the micelles' core. Irrespective of temperature, we find from the intensity ratio between the 0-1 and 0-0 peaks in the PL spectra that the P3HT aggregates are of H-type nature, as expected from π-stacked conjugated thiophene backbones. Moreover, the distributions of the PL peak ratios demonstrate a large variation of disorder between micelles (inter-aggregate disorder) and within individual aggregates (intra-aggregate disorder). Upon cooling from RT to LT, the PL spectra red-shift by 550 cm-1, and the energy of the (effective) carbon-bond stretch mode is reduced by 100 cm-1. These spectral changes indicate that the P3HT backbone in the P3HT-b-PEG copolymer does not fully planarize before aggregation at RT and that upon cooling, partial planarization occurs. This intra-chain torsional disorder is ultimately responsible for the intra- and inter-aggregate disorder. These findings are supported by temperature-dependent absorption spectra on thin P3HT films. The interplay between intra-chain, intra-aggregate, and inter-aggregate disorder is key for the bulk photophysical properties of nanoparticles based on conjugated polymers, for example, in hierarchical (super-) structures. Ultimately, these properties determine the usefulness of such structures in hybrid organic-inorganic materials, for example, in (bio-)sensing and optoelectronics applications.

Long-range energy transport in single supramolecular nanofibres at room temperature.

Efficient transport of excitation energy over long distances is a key process in light-harvesting systems, as well as in molecular electronics. However, in synthetic disordered organic materials, the exciton diffusion length is typically only around 10 nanometres (refs 4, 5), or about 50 nanometres in exceptional cases, a distance that is largely determined by the probability laws of incoherent exciton hopping. Only for highly ordered organic systems has the transport of excitation energy over macroscopic distances been reported--for example, for triplet excitons in anthracene single crystals at room temperature, as well as along single polydiacetylene chains embedded in their monomer crystalline matrix at cryogenic temperatures (at 10 kelvin, or -263 degrees Celsius). For supramolecular nanostructures, uniaxial long-range transport has not been demonstrated at room temperature. Here we show that individual self-assembled nanofibres with molecular-scale diameter efficiently transport singlet excitons at ambient conditions over more than four micrometres, a distance that is limited only by the fibre length. Our data suggest that this remarkable long-range transport is predominantly coherent. Such coherent long-range transport is achieved by one-dimensional self-assembly of supramolecular building blocks, based on carbonyl-bridged triarylamines, into well defined H-type aggregates (in which individual monomers are aligned cofacially) with substantial electronic interactions. These findings may facilitate the development of organic nanophotonic devices and quantum information technology.

Long-term switching of single photochromic triads based on dithienylcyclopentene and fluorophores at cryogenic temperatures.

Photochromic molecules can be reversibly converted between two bistable forms by light. These systems have been intensively studied for applications as molecular memories, sensing devices, or super-resolution optical microscopy. Here, we study the long-term switching behavior of single photochromic triads under oxygen-free conditions at 10 K. The triads consist of a photochromic unit that is covalently linked to two strong fluorophores that were employed for monitoring the light-induced conversions of the switch via changes in the fluorescence intensity from the fluorophores. As dyes we use either perylene bisimide or boron-dipyrromethen, and as photochromic switch we use dithienylcyclopentene (DCP). Both types of triads showed high fatigue resistance allowing for up to 6000 switching cycles of a single triad corresponding to time durations in the order of 80 min without deterioration. Long-term analysis of the switching cycles reveals that the probability that an intensity change in the emission from the dyes can be assigned to an externally stimulated conversion of the DCP (rather than to stochastic blinking of the dye molecules) amounts to 0.7 ± 0.1 for both types of triads. This number is far too low for optical data storage using single triads and implications concerning the miniaturization of optical memories based on such systems will be discussed. Yet, together with the high fatigue resistance, this number is encouraging for applications in super-resolution optical microscopy on frozen biological samples.

Direct observation of backbone planarization via side-chain alignment in single bulky-substituted polythiophenes.

The backbone conformation of conjugated polymers affects, to a large extent, their optical and electronic properties. The usually flexible substituents provide solubility and influence the packing behavior of conjugated polymers in films or in bad solvents. However, the role of the side chains in determining and potentially controlling the backbone conformation, and thus the optical and electronic properties on the single polymer level, is currently under debate. Here, we investigate directly the impact of the side chains by studying the bulky-substituted poly(3-(2,5-dioctylphenyl)thiophene) (PDOPT) and the common poly(3-hexylthiophene) (P3HT), both with a defined molecular weight and high regioregularity, using low-temperature single-chain photoluminescence (PL) spectroscopy and quantum-classical simulations. Surprisingly, the optical transition energy of PDOPT is significantly (∼2,000 cm-1 or 0.25 eV) red-shifted relative to P3HT despite a higher static and dynamic disorder in the former. We ascribe this red shift to a side-chain induced backbone planarization in PDOPT, supported by temperature-dependent ensemble PL spectroscopy. Our atomistic simulations reveal that the bulkier 2,5-dioctylphenyl side chains of PDOPT adopt a clear secondary helical structural motif and thus protect conjugation, i.e., enforce backbone planarity, whereas, for P3HT, this is not the case. These different degrees of planarity in both thiophenes do not result in different conjugation lengths, which we found to be similar. It is rather the stronger electronic coupling between the repeating units in the more planar PDOPT which gives rise to the observed spectral red shift as well as to a reduced calculated electron-hole polarization.

Limitations of Linear Dichroism Spectroscopy for Elucidating Structural Issues of Light-Harvesting Aggregates in Chlorosomes.

Linear dichroism (LD) spectroscopy is a widely used technique for studying the mutual orientation of the transition-dipole moments of the electronically excited states of molecular aggregates. Often the method is applied to aggregates where detailed information about the geometrical arrangement of the monomers is lacking. However, for complex molecular assemblies where the monomers are assembled hierarchically in tiers of supramolecular structural elements, the method cannot extract well-founded information about the monomer arrangement. Here we discuss this difficulty on the example of chlorosomes, which are the light-harvesting aggregates of photosynthetic green-(non) sulfur bacteria. Chlorosomes consist of hundreds of thousands of bacteriochlorophyll molecules that self-assemble into secondary structural elements of curved lamellar or cylindrical morphology. We exploit data from polarization-resolved fluorescence-excitation spectroscopy performed on single chlorosomes for reconstructing the corresponding LD spectra. This reveals that LD spectroscopy is not suited for benchmarking structural models in particular for complex hierarchically organized molecular supramolecular assemblies.

Enhancing Long-Range Energy Transport in Supramolecular Architectures by Tailoring Coherence Properties.

Efficient long-range energy transport along supramolecular architectures of functional organic molecules is a key step in nature for converting sunlight into a useful form of energy. Understanding and manipulating these transport processes on a molecular and supramolecular scale is a long-standing goal. However, the realization of a well-defined system that allows for tuning morphology and electronic properties as well as for resolution of transport in space and time is challenging. Here we show how the excited-state energy landscape and thus the coherence characteristics of electronic excitations can be modified by the hierarchical level of H-type supramolecular architectures. We visualize, at room temperature, long-range incoherent transport of delocalized singlet excitons on pico- to nanosecond time scales in single supramolecular nanofibers and bundles of nanofibers. Increasing the degree of coherence, i.e., exciton delocalization, via supramolecular architectures enhances exciton diffusivities up to 1 order of magnitude. In particular, we find that single supramolecular nanofibers exhibit the highest diffusivities reported for H-aggregates so far.

Identification of Multiple Kinetic Populations of DNA-Binding Proteins in Live Cells.

Understanding how multiprotein complexes function in cells requires detailed quantitative understanding of their association and dissociation kinetics. Analysis of the heterogeneity of binding lifetimes enables the interrogation of the various intermediate states formed during the reaction. Single-molecule fluorescence imaging permits the measurement of reaction kinetics inside living organisms with minimal perturbation. However, poor photophysical properties of fluorescent probes limit the dynamic range and accuracy of measurements of off rates in live cells. Time-lapse single-molecule fluorescence imaging can partially overcome the limits of photobleaching; however, limitations of this technique remain uncharacterized. Here, we present a structured analysis of which timescales are most accessible using the time-lapse imaging approach and explore uncertainties in determining kinetic subpopulations. We demonstrate the effect of shot noise on the precision of the measurements as well as the resolution and dynamic range limits that are inherent to the method. Our work provides a convenient implementation to determine theoretical errors from measurements and to support interpretation of experimental data.

Electronic Structure and Lithium Diffusion in LiAl2(OH)6Cl Studied by First Principle Calculations.

First-principles calculations based on the density functional theory (DFT) were carried out to study the atomic structure and electronic structure of LiAl2(OH)6Cl, the only material in the layered double hydroxide family in which delithiation was found to occur. Ab initio molecular dynamics (AIMD) simulations were used to explore the evolution of the structure of LiAl2(OH)6Cl during a thermally induced delithiation process. The simulations show that this process occurs due to the drastic dynamics of Li+ at temperatures higher than ~450 K, in which the [Al2(OH)6] host layers remain stable up to 1100 K. The calculated large value of the Li+ diffusion coefficient D, ~ 3.13 × 10 - 5 c m 2 / s , at 500 K and the high stability of the [Al2(OH)6] framework suggest a potential technical application of the partially-delithiated Li1-xAl2(OH)6Cl1-x (0 < x < 1) as a superionic conductor at high temperatures.

Large Second Harmonic Generation (SHG) Effect and High Laser-Induced Damage Threshold (LIDT) Observed Coexisting in Gallium Selenide.

A big challenge for nonlinear optical (NLO) materials is the application in high power lasers, which needs the simultaneous occurrence of large second harmonic generation (SHG) and high laser induced damage threshold (LIDT). Herein we report the preparation of a new Ga2 Se3 phase, which shows the SHG intensities of around 2.3 times and the LIDT of around 16.7 times those of AgGaS2 (AGS), respectively. In addition, its IR transparent window ca. 0.59-25 µm is also significantly wider than that of AGS (ca. 0.48-≈11.4 µm). The occurrence of the strong SHG responses and good phase-matching indicate that the structure of the new Ga2 Se3 phase can only be non-centrosymmetric and have a lower symmetry than the cubic γ-phase. The observed excellent SHG and phase-matching properties are consistent with our diffraction experiments and can be well explained by using the orthorhombic models obtained through our high throughput simulations.

Interband Electron Pairing for Superconductivity from the Breakdown of the Born-Oppenheimer Approximation.

The origin of interband electron pairing, responsible for enhancing superconductivity, and the factors controlling its strength were examined. We show that interband electron pairing is a natural consequence of breaking down the Born-Oppenheimer approximation during electron-phonon interactions. Its strength is determined by the pair-state excitations around the Fermi surfaces that take place to form a superconducting state. Fermi surfaces favorable for the pairing were found, and the implications of this observation are discussed.

Non-invasive study of the three-dimensional structure of nanoporous triblock terpolymer membranes.

Nanoporous media are of great importance for drug delivery or filtration. Typically the pore structure of such media is characterized using high-resolution techniques such as electron microscopy or atomic force microscopy. However, these techniques are restricted to the surface of the material and/or are highly invasive. In a proof-of-concept experiment we have employed three-dimensional single-particle orbit tracking for testing the three-dimensional pore structure of a liquid filled nanoporous polystyrene-block-polyisoprene-block-poly(N-isopropylacrylamide) (PS-b-PI-b-PNiPAAm) triblock terpolymer membrane. Using fluorescent tracers with a diameter of about 10% of the relevant void structures, the tracking experiments yielded results that were comparable to those obtained from reference experiments using environmental scanning electron microscopy (eSEM). This testifies that single-particle orbit tracking can serve as a useful non-invasive alternative for characterising the structure of nanoporous materials.

Real-Time Observation of Iodide Ion Migration in Methylammonium Lead Halide Perovskites.

Organic-inorganic metal halide perovskites (e.g., CH3 NH3 PbI3-x Clx ) emerge as a promising optoelectronic material. However, the Shockley-Queisser limit for the power conversion efficiency (PCE) of perovskite-based photovoltaic devices is still not reached. Nonradiative recombination pathways may play a significant role and appear as photoluminescence (PL) inactive (or dark) areas on perovskite films. Although these observations are related to the presence of ions/defects, the underlying fundamental physics and detailed microscopic processes, concerning trap/defect status, ion migration, etc., still remain poorly understood. Here correlated wide-field PL microscopy and impedance spectroscopy are utilized on perovskite films to in situ investigate both the spatial and the temporal evolution of these PL inactive areas under external electric fields. The formation of PL inactive domains is attributed to the migration and accumulation of iodide ions under external fields. Hence, we are able to characterize the kinetic processes and determine the drift velocities of these ions. In addition, it is shown that I2 vapor directly affects the PL quenching of a perovskite film, which provides evidence that the migration/segregation of iodide ions plays an important role in the PL quenching and consequently limits the PCE of organometal halide-based perovskite photovoltaic devices.

Group of Quantum Bits Acting as a Bit Using a Single-Domain Ferromagnet of Uniaxial Magnetic Ions.

Read/write operations with individual quantum bits (i.e., qbits) are a challenging problem to solve in quantum computing. To alleviate this difficulty, we considered the possibility of using a group of qbits that act collectively as a bit (hereafter, a group bit or a gbit, in short). A promising candidate for a gbit is a single-domain ferromagnet (SDF) independent of its size, which can be prepared as a magnet of well-separated uniaxial magnetic ions (UMIs) at sites of no electric dipole moment with their uniaxial axes aligned along one common direction. When magnetized, the UMIs of such a magnet have a ferromagnetic (FM) arrangement and the resulting SDF becomes a gbit with its two opposite moment orientations representing the |0⟩ and |1⟩ states of a bit. We probed the requirements for such magnets and identified several 2H-perovskites as materials satisfying these requirements.

Temperature dependence of the conversion efficiency of photochromic perylene bisimide dithienylcyclopentene triads embedded in a polymer.

Photochromic molecules that are covalently linked to a strong fluorophore combine the requirements of external control and strong fluorescence, which will become increasingly important for super-resolution microscopy techniques based on single molecules. However, given the bulky structure of such constructs, steric hindrance might affect their photoconversion efficiencies upon immobilising them for imaging purposes. In this study the efficiencies of the photochromic conversion processes of molecular triads that are embedded in a polymer have been studied as a function of temperature. The triads consist of two perylene bisimide dye molecules that are connected via a dithienylcyclopentene photochromic bridge that undergoes a cyclization/cycloreversion reaction upon appropriate illumination. It is found that photochromic switching remains active, even at 5 K, yet with reduced but finite efficiency for the cycloreversion reaction. This might even be an advantage for the achievement of high labelling densities in super-resolution microscopy.

Influence of the Conjugation Length on the Optical Spectra of Single Ladder-Type (p-Phenylene) Dimers and Polymers.

We employ low-temperature single-molecule photoluminescence spectroscopy on a π-conjugated ladder-type (p-phenylene) dimer and the corresponding polymer methyl-substituted ladder-type poly(p-phenylene), MeLPPP, to study the impact of the conjugation length (π-electron delocalization) on their optical properties on a molecular scale. Our data show that the linear electron-phonon coupling to intramolecular vibrational modes is very sensitive to the conjugation length, a well-known behavior of organic (macro-) molecules. In particular, the photoluminescence spectra of single dimers feature a rather strong low-energy (150 cm(-1)) skeletal mode of the backbone, which does not appear in the spectra of individual chromophores on single MeLPPP chains. We attribute this finding to a strongly reduced electron-phonon coupling strength and/or vibrational energy of this mode for MeLPPP with its more delocalized π-electron system as compared to the dimer. In contrast, the line widths of the purely electronic zero-phonon lines (ZPL) in single-molecule spectra do not show differences between the dimer and MeLPPP; for both systems the ZPLs are apparently broadened by fast unresolved spectral diffusion. Finally, we demonstrate that the low-temperature ensemble photoluminescence spectrum of the dimer cannot be reproduced by the distribution of spectral positions of the ZPLs. The dimer's bulk spectrum is rather apparently broadened by electron-phonon coupling to the low-energy skeletal mode, whereas for MeLPPP the inhomogeneous bulk line shape resembles the distribution of spectral positions of the ZPLs of single chromophores.

Spin orientations of the spin-half Ir(4+) ions in Sr3NiIrO6, Sr2IrO4, and Na2IrO3: Density functional, perturbation theory, and Madelung potential analyses.

The spins of the low-spin Ir(4+) (S = 1/2, d(5)) ions at the octahedral sites of the oxides Sr3NiIrO6, Sr2IrO4, and Na2IrO3 exhibit preferred orientations with respect to their IrO6 octahedra. We evaluated the magnetic anisotropies of these S = 1/2 ions on the basis of density functional theory (DFT) calculations including spin-orbit coupling (SOC), and probed their origin by performing perturbation theory analyses with SOC as perturbation within the LS coupling scheme. The observed spin orientations of Sr3NiIrO6 and Sr2IrO4 are correctly predicted by DFT calculations, and are accounted for by the perturbation theory analysis. As for the spin orientation of Na2IrO3, both experimental studies and DFT calculations have not been unequivocal. Our analysis reveals that the Ir(4+) spin orientation of Na2IrO3 should have nonzero components along the c- and a-axis directions. The spin orientations determined by DFT calculations are sensitive to the accuracy of the crystal structures employed, which is explained by perturbation theory analyses when interactions between adjacent Ir(4+) ions are taken into consideration. There are indications implying that the 5d electrons of Na2IrO3 are less strongly localized compared with those of Sr3NiIrO6 and Sr2IrO4. This implication was confirmed by showing that the Madelung potentials of the Ir(4+) ions are less negative in Na2IrO3 than in Sr3NiIrO6 and Sr2IrO4. Most transition-metal S = 1/2 ions do have magnetic anisotropies because the SOC induces interactions among their crystal-field split d-states, and the associated mixing of the states modifies only the orbital parts of the states. This finding cannot be mimicked by a spin Hamiltonian because this model Hamiltonian lacks the orbital degree of freedom, thereby leading to the spin-half syndrome. The spin-orbital entanglement for the 5d spin-half ions Ir(4+) is not as strong as has been assumed.