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Abstract: BiOCl and BiOBr nanodiscs (100–150 nm in diameter, 15–25 nm in thickness) are prepared via water-based nucleation and purified by a phase-transfer reaction, including oleylamine-induced transfer of the as-prepared nanodiscs from the polar water phase to the non-polar toluene phase. The oleylamine-capping is then removed by hydrazine treatment, and the BiOCl/BiOBr nanodiscs are redispersed in 2-propanol. The as-prepared nanodiscs are finally deposited as a porous, p-type semiconductor layer to obtain dye-sensitized solar cells (DSSCs). Herein, coumarin 343 is applied as sensitizer together with BiOCl as p-type semiconductor and a KI–I2 electrolyte. In addition, eosin Y is applied as sensitizer together with BiOBr as p-type semiconductor and a [C4MPyr]2[Br20] polybromide electrolyte (C4MPyr: N-butyl-N-methylpyrrolidinium). Such polybromide electrolyte is firstly applied in a DSSC and allows for a higher redox potential. Both here established p-DSSCs show the characteristic features and function of a solar cell (BiOCl/coumarin 343/KI–I2: V oc = 120 mV, J sc = 57 μA cm−2, FF = 40.6%, η = 0.003; BiOBr/eosin Y/[C4MPyr]2[Br20]: V oc = 78 mV, J sc = 3.1 μA cm−2, FF = 28.6%, η = 0.0005) as a result of this conceptual study. [Copyright &y& Elsevier]

Abstract: We demonstrate a small molecule solution processed hole interfacial layer approach to improve the dark current characteristics of polymer photodiodes. The two hole blocking materials under investigation 3-phenyl-4(1′-naphthyl)-5-phenyl-1,2,4-triazole (TAZ) and 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole (TPBi) are spincoated from ethanol as an orthogonal solvent on top of a P3HT:PCBM active layer. We reduce the dark current at a bias voltage of −1V by a factor of 17.2 by introducing a TAZ interfacial layer while keeping the responsivity unchanged. [Copyright &y& Elsevier]

Abstract: In this work we present regular and inverted organic tandem solar cells from poly[N-9′-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole): [6,6]-phenyl C70-butyric acid methyl ester (PCDTBT:PC71BM) with power conversion efficiencies of up to 4.5%. The recombination zone comprises an electron conducting, precursor based zinc oxide buffer layer that was applied from solution under ambient conditions and at moderate processing temperatures. Optimized active layer thicknesses in both subcells were derived from optical Transfer Matrix simulations. The short circuit current density of the tandem cell exceeds half the short circuit current density of the single absorber cells indicating a real gain in quantum yield when utilizing the tandem architecture. [Copyright &y& Elsevier]

Abstract: Cell populations often display heterogeneous behavior, including cell-to-cell variations in morphology, adhesion and spreading. However, better understanding the significance of such cell variations for the function of the population as a whole requires quantitative single-cell assays. To investigate adhesion variability in a CHO cell population in detail, we measured integrin-mediated adhesion to laminin and collagen, two ubiquitous ECM components, by AFM-based single-cell force spectroscopy (SCFS). CHO cells generally adhered more strongly to laminin than collagen but population adhesion force distributions to both ECM components were broad and partially overlapped. To determine the levels of laminin and collagen binding in individual cells directly, we alternatingly measured single cells on adjacent microstripes of collagen and laminin arrayed on the same adhesion substrate. In repeated measurements (≥60) individual cells showed a stable and ECM type-specific adhesion response. All tested cells bound laminin more strongly, but the scale of laminin over collagen binding varied between cells. Together, this demonstrates that adhesion levels to different ECM components are tightly yet differently set in each cell of the population. Adhesion variability to laminin was non-genetic and cell cycle-independent but scaled with the range of α6 integrin expression on the cell surface. Adhesive cell-to-cell variations due to varying receptor expression levels thus appear to be an inherent feature of cell populations and should to be considered when fully characterizing population adhesion. In this approach, SCFS performed on multifunctional adhesion substrates can provide quantitative single-cell information not obtainable from population-averaging measurements on homogeneous adhesion substrates. [Copyright &y& Elsevier]

Abstract: We present fully solution processable hybrid electrodes comprising highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) layers and hydrothermally grown zinc oxide nanorods. These electrodes exhibit conductivities of about 1400S/cm and a transmittance of more than 80%. By incorporating these electrodes into inverted polymer photovoltaic devices, power conversion efficiencies of 1.6% are achieved. Charge carrier lifetime measurements by means of impedance spectroscopy indicate an improved charge carrier extraction from the device upon the incorporation of the nanorod array. [Copyright &y& Elsevier]

The power conversion efficiency of Cu2ZnSn(S,Se)4 kesterite thin-film solar cells is mainly limited by a low open-circuit voltage VOC. In the literature, this low VOC has been amongst others attributed to electrostatic potential fluctuations leading to fluctuating band edges. This assignment was mainly based on the observation of a shift of the photoluminescence (PL) maximum to higher photon energies as a function of excitation power, which was interpreted in terms of a screening of the electrostatic potential fluctuations. However, in this paper, we show evidence that the observed shift of the PL maximum is dominantly caused by state filling rather than screening. Our assignment is based on the investigation of the full PL line shape (not only of the PL maximum) and the PL yield as a function of excitation power and temperature. Further support of our interpretation is given by the observation of additional band-tail emission showing up as a second high-energy PL band at the highest excitation powers. The spectral position of this additional band coincides with the absorption-tail deduced from photoluminescence excitation spectroscopy (PLE). [ABSTRACT FROM AUTHOR]

Rotationally symmetric micro-cavities with disk, ring or toroidal shape displaying whispering gallery modes (WGMs) play an essential role in modern-day photonics. Due to the reduced symmetry of such resonators compared to spheres, an exact analytical model yielding WGMs as solutions does not exist. The established WGM classification scheme based on approximated analytical solutions is generally useful but neglects a possible interaction between the different modes. In this paper, we assess the limitation of the validity of this established classification based on extensive finite element method (FEM) simulations. We investigate respective mode couplings as well as underlying selection rules based on avoided crossings of the modes' resonance wavelengths. We propose conserved mode properties solely based on true symmetries of the underlying refractive-index distribution and deduce a novel WGM classification scheme.

A method for the realization of low-loss integrated optical components is proposed and demonstrated. This approach is simple, fast, inexpensive, scalable for mass production, and compatible with both 2D and 3D geometries. The process is based on a novel dual-step soft nano imprint lithography process for producing devices with smooth surfaces, combined with fast sol-gel technology providing highly transparent materials. As a concrete example, this approach is demonstrated on a micro ring resonator made by direct laser writing (DLW) to achieve a quality factor improvement from one hundred thousand to more than 3 million. To the best of our knowledge this also sets a Q-factor record for UV-curable integrated micro-ring resonators. The process supports the integration of many types of materials such as light-emitting, electro-optic, piezo-electric, and can be readily applied to a wide variety of devices such as waveguides, lenses, diffractive elements and more.

We compare different excitation and collection configurations based on free-space optics and evanescently coupled tapered fibers for both lasing and fluorescence emission from dye-doped doped polymeric whispering gallery mode (WGM) micro-disk lasers. The focus of the comparison is on the lasing threshold and efficiency of light collection. With the aid of optical fibers, we localize the pump energy to the cavity-mode volume and reduce the necessary pump energy to achieve lasing by two orders of magnitude. When using fibers for detection, the collection efficiency is enhanced by four orders of magnitude compared to a free-space read-out perpendicular to the resonator plane. By enhancing the collection efficiency we are able to record a pronounced modulation of the dye fluorescence under continuous wave (cw) pumping conditions evoked by coupling to the WGMs. Alternatively to fibers as a collection tool, we present a read-out technique based on the detection of in-plane radiated light. We show that this method is especially beneficial in an aqueous environment as well as for size-reduced micro-lasers where radiation is strongly pronounced. Furthermore, we show that this technique allows for the assignment of transverse electric (TE) and transverse magnetic (TM) polarization to the observed fundamental modes in a water environment by performing polarization-dependent photoluminescence (PL) spectroscopy. We emphasize the importance of the polarization determination for sensing applications and verify expected differences in the bulk refractive index sensitivity for TE and TM WGMs experimentally.

We demonstrate the realization of 3D whispering-gallery-mode (WGM) microlasers by direct laser writing (DLW) and their replication by nanoimprint lithography using a soft mold technique ("soft NIL"). The combination of DLW as a method for rapid prototyping and soft NIL offers a fast track towards large scale fabrication of 3D passive and active optical components applicable to a wide variety of materials. A performance analysis shows that surface-scattering-limited Q-factors of replicated resonators as high as 1×10 5 at 635 nm can be achieved with this process combination. Lasing in the replicated WGM resonators is demonstrated by the incorporation of laser dyes in the target material. Low lasing thresholds in the order of 15  kW/cm 2 are obtained under ns-pulsed excitation.

Integration of optically active materials into whispering gallery mode (WGM) cavities enables low-threshold laser emission. In contrast to their passive counterparts, the WGMs of these microlasers can be pumped and read out easily via free-space optics. The WGMs interact with the cavity environment via their evanescent field, and thus lend themselves to label-free bio-sensing. The detection limit of such sensors, given as the ratio of the resolution of the whole measurement system to the sensitivity of the WGMs, is an important figure of merit. In this work we show that the detection limit of polymeric microdisk lasers can be improved by more than a factor of seven by optimizing their radius and thickness. We use the bulk refractive index sensitivity, the magnitude of the sensor reaction towards refractive index changes of the bulk environment, to quantify the sensing performance and show that it can be enhanced while the spectral resolution is maintained. Furthermore, we investigate the effect of the size of the cavity on the quality factor and the lasing threshold in an aqueous environment, hence allowing optimization of the cavity size for enhanced sensor performance. For all considered quantities, numerically computed expectations are verified by experimental results.

Optical micro-resonators have broad applications. They are used, for example, to enhance light-matter interactions in optical sensors or as model systems for investigating fundamental physical mechanisms in cavity quantum electrodynamics. Coupling two or more micro-cavities is particularly interesting as it enlarges the design freedom and the field of application. In this context, achieving tunability of the coupling strength and hence the inter-cavity gap is of utmost importance for adjusting the properties of the coupled micro-resonator system. In this paper, we report on a novel coupling approach that allows highly precise tuning of the coupling gap of polymeric micro-resonators that are fabricated side by side on a common substrate. We structure goblet-shaped whispering-gallery-mode resonators on an elastic silicone-based polymer substrate by direct laser writing. The silicone substrate is mechanically stretched in order to exploit the lateral shrinkage to reduce the coupling gap. Incorporating a laser dye into the micro-resonators transforms the cavities into micro-lasers that can be pumped optically. We have investigated the lasing emission by micro-photoluminescence spectroscopy, focusing on the spatial localization of the modes. Our results demonstrate the formation of photonic molecules consisting of two or even three resonators, for which the coupling strengths and hence the lasing performance can be precisely tuned. Flexibility and tunability are key elements in future photonics, making our approach interesting for various photonic applications. For instance, as our coupling approach can also be extended to larger cavity arrays, it might serve as a platform for tunable coupled-resonator optical waveguide devices., Competing Interests: The authors declare no conflict of interest.

Lasing from whispering-gallery mode (WGM) resonators occurs omnidirectional in azimuthal plane. Most applications of WGM resonators require spectral analysis with off-chip detectors, where in-plane emission and beam divergence hinder efficient detection. We demonstrate redirecting WGM laser emission from all azimuthal angles using a circular micromirror placed around the cavity. By collecting reflections off the micromirror via free-space optics, read-out intensity improved by one order of magnitude. Blocking vertically emitted spontaneous emission and recording reflections off the micromirror only, signal-to-noise ratio improved from 4.6 dB to 15 dB. Our read-out concept may be applied to arbitrary WGM cavity geometries without deteriorating the cavity's quality factor.

We report on a method for a highly flexible arrangement of polymeric high-Q whispering gallery mode resonators. Parallel on-chip fabricated goblet resonators are detached from the substrate by bonding a gold wire to the field-free center of their polymeric cavity. This enables the precise control of the resonator's spatial position. The modal spectrum of the detached resonator reveals preservation of its high optical quality. Manipulation of the resonators' position allows for designing coupled resonators geometries and tuning the coupling properties dynamically after batch fabrication. The properties of the modal spectrum evidence the successful optical coupling.

Bacteriochlorophylls (BChls) c, d, and e are the main light-harvesting pigments of green photosynthetic bacteria that self-assemble into nanostructures within the chlorosomes forming the most efficient antennas of photosynthetic organisms. All previous models of the chlorosomal antennae, which are quite controversially discussed because no single crystals could be grown so far from these organelles, involve a strong hydrogen-bonding interaction between the 3(1) hydroxyl group and the 13(1) carbonyl group. We have synthesized different self-assemblies of BChl c mimics having the same functional groups as the natural counterparts, that is, a hydroxyethyl substituent, a carbonyl group and a divalent metal atom ligated by a tetrapyrrole. These artificial BChl mimics have been shown by single crystal x-ray diffraction to form extended stacks that are packed by hydrophobic interactions and in the absence of hydrogen bonding. Time-resolved photoluminescence proves the ordered nature of the self-assembled stacks. FT-IR spectra show that on self-assembly the carbonyl frequency is shifted by approximately 30 cm(-1) to lower wavenumbers. From the FT-IR data we can infer the proximal interactions between the BChls in the chlorosomes consistent with a single crystal x-ray structure that shows a weak electrostatic interaction between carbonyl groups and the central zinc atom.

A weak acid selective etching strategy was put forward to fabricate oxide-based hollow nanoparticles (HNPs) using core/shell nanostructures of active metal/oxide nanoparticles as sacrificial templates. ZnO-based HNPs, including pure ZnO, Au/ZnO, Pt/ZnO, and Au/Pt/ZnO HNPs with diameter below 50 nm and shell thickness below 6 nm has been first achieved at low temperature. The diameter, thickness, and even sizes of ZnO and noble metal ultrafine crystals of HNPs can be well adjusted by the etching process. Synchronous with the formation of HNPs, the internal metal-semiconductor interfaces can be controllably eliminated (Zn-ZnO) and reconstructed (noble metal-ZnO). Excitingly, such microstructure manipulation has endued them with giant improvements in related performances, including the very strong blue luminescence with enhancement over 3 orders of magnitude for the pure ZnO HNPs and the greatly improved photocatalytic activity for the noble metal/ZnO HNPs. These give them strong potentials in relevant applications, such as blue light emitting devices, environment remediation, drug delivery and release, energy storage and conversion, and sensors. The designed fabrication procedure is simple, feasible, and universal for a series of oxide and noble metal/oxide HNPs with controlled microstructure and improved performances.

The title dicyano compound was synthesized via cyanation and it self-assembles in nonpolar solvents giving red-shifted and broad absorption maxima just as the bacteriochlorophylls which are encountered in the light-harvesting organelles of early photosynthetic bacteria. In the crystal, stacks are formed through a hierarchic combination of pi-stacking and a CN-Zn electrostatic interaction. Push-pull 15-N,N-dialkylamino-5-cyano congeners could be obtained in high yields using a solvent- and catalyst-free direct amination of meso-bromoporphyrins. Importantly, the fluorescence of the self-assembled species due to the very orderly manner in which the chromophores are arranged is not entirely quenched and has a surprisingly long lifetime of over 1 ns. This lends hope of using the trapped energy in biomimetic hybrid solar cells.

A number of new porphyrins equipped with complementary triple hydrogen-bonding groups were synthesized in good yields. Self-assembly was investigated by NMR spectroscopy, dynamic light scattering (DLS), and atomic force microscopy (AFM). These artificial antenna systems were further characterized by stationary and time-resolved fluorescence techniques to investigate several yet unsolved questions on the mechanism of excitation energy transfer (EET) in supramolecular systems. For example, the photophysics of a simple D--U[triple chemical bond]P--A dyad was studied, in which donor D and acceptor A are ZnII- metalated and free-base porphyrins, respectively, and U (uracyl) and P (2,6-diacetamidopyridyl) are complementary hydrogen-bonding groups linked by flexible spacers. In this dyad, the EET occurs with about 20 % efficiency with a lifetime of 14 ps. Reversal of the nonsymmetric triple hydrogen-bonding groups to give a A--U[triple chemical bond]P--D construct results in an EET efficiency of about 25 % and a lifetime of 19 ps. Thus, there is a slight directionality of EET mediated by these asymmetric triple hydrogen-bonding units tethered to flexible spacers. In polymeric systems of the type P-D-P[triple chemical bond]U-A-U[triple chemical bond]P-D-P, or U-D-U[triple chemical bond]P-A-P[triple chemical bond]U-D-U, the EET efficiency doubles as each donor is flanked by two acceptors. Because doubling the probability of photon capture doubles the EET efficiency, there is no energy amplification, which is consistent with the "antenna effect". For these polymeric systems, AFM images and DLS data indicate large rodlike assemblies of a few hundred nanometers, whereas the components form much smaller aggregates under the same conditions. To understand the importance of the flexible hydrogen-bonding zipper, three different covalently bridged D-B-A molecules were synthesized in which the bridge B is a rigid steroidal system and the same ester chemistry was used to link the porphyrins to each end of the steroid. The geometry inferred from molecular modeling of D-B-A indicates geometric similarities between B and some conformations of the --P[triple chemical bond]U-- supramolecular bridge. Although the EET efficiency is a factor of two greater for the steroidal systems relative to the supramolecular dyads, the rate is 50-80 times slower, but still slightly faster than that predicted by Förster-type mechanisms. Circular dichrosim (CD) spectra provide a conformational sampling of the porphyrin groups appended on the steroidal skeleton, thus allowing an estimation of the orientation factor kappa for the transition dipole moments, which significantly affects the EET rate. We conclude that the flexible hydrogen-bonded linked systems are adaptive and have variable geometries with foldamers in which the D and A groups can approach well under 1 nm. In these folded conformations, a rapid EET process occurs, probably also involving a Dexter-type exchange mechanism, thus explaining the fast EET relative to the rigid steroidal compounds. This study predicts that it is indeed possible to build large supramolecular antennas and the component design and supramolecular dynamics are essential features that dictate EET rates and efficiencies.