Confinement of light inside an active medium cavity can amplify emission. Whispering gallery mode (WGM) is one of mechanisms that amplifies light effectively by confining it inside high-refractive-index microstructures, where light propagates along the circumference of a sphere via total internal reflection. Here we show that isolated single microspheres of 2–10 μm diameter, formed from self-assembly of π-conjugated alternating copolymers, display WGM photoemission induced by laser pumping. The wavelengths of the emission peaks depend sensitively on the sphere size, position of the excitation spot and refractive index of each polymer. The Q-factor increases with increasing sphere diameter and displays a linear correlation with the reciprocal radius, indicating that the small curvature increases the efficacy of the total internal reflection. WGM photoemission from π-conjugated polymer microspheres is unprecedented and may be of high technological impact since the microspheres fulfill the role of fluorophores, high-refractive-index media and resonators simultaneously, in addition to their simple fabrication process.

Color-tunable resonant photoluminescence (PL) was attained from polystyrene microspheres doped with a single polymorphic fluorescent dye, boron-dipyrrin (BODIPY) 1. The color of the resonant PL depends on the assembling morphology of 1 in the microspheres, which can be selectively controlled from green to red by the initial concentration of 1 in the preparation process of the microspheres. Studies on intersphere PL propagation with multicoupled microspheres, prepared by micromanipulation technique, revealed that multistep photon transfer takes place through the microspheres, accompanying energy transfer cascade with stepwise PL color change. The intersphere energy transfer cascade is direction selective, where energy donor-to-acceptor down conversion direction is only allowed. Such cavity-mediated long-distance and multistep energy transfer will be advantageous for polymer photonics device application.

Heterostructure n-GaAs/InGaP/p-GaAs core-multishell nanowire diodes are synthesized by metal-organic vapor-phase epitaxy. This structure allows a reproducible, selective wet etching of the individual shells and therefore a simplified contacting of single nanowire p-i-n junctions. Nanowire diodes show leakage currents in a low pA range and at a high rectification ratio of 3500 (at ±1V). Pronounced electroluminescence at 1.4 eV is measured at room temperature and gives evidence of the device quality. Photocurrent generation is demonstrated at the complete area of the nanowire p-i-n junction by scanning photocurrent microscopy. A solar-conversion efficiency of 4.7%, an open-circuit voltage of 0.5 V and a fill factor of 52% are obtained under AM 1.5G conditions. These results will guide the development of nanowire-based photonic and photovoltaic devices.

Besides its interesting physical properties, graphene as a two-dimensional lattice of carbon atoms promises to realize devices with exceptional electronic properties, where freely suspended graphene without contact to any substrate is the ultimate, truly two-dimensional system. The practical realization of nano-devices from suspended graphene, however, relies heavily on finding a structuring method which is minimally invasive. Here, we report on the first electron beam-induced nano-etching of suspended graphene and demonstrate high-resolution etching down to ~7 nm for line-cuts into the monolayer graphene. We investigate the structural quality of the etched graphene layer using two-dimensional (2D) Raman maps and demonstrate its high electronic quality in a nano-device: A 25 nm-wide suspended graphene nanoribbon (GNR) that shows a transport gap with a corresponding energy of ~60 meV. This is an important step towards fast and reliable patterning of suspended graphene for future ballistic transport, nano-electronic and nano-mechanical devices.

Highly luminescent π-conjugated polymeric microspheres were fabricated through self-assembly of energy-donating and energy-accepting polymers and their blends. To avoid macroscopic phase separation, the nucleation time and growth rate of each polymer in the solution were properly adjusted. Photoluminescence (PL) studies showed that efficient donor-to-acceptor energy transfer takes place inside the microspheres, revealing that two polymers are well-blended in the microspheres. Focused laser irradiation of a single microsphere excites whispering gallery modes (WGMs), where PL generated inside the sphere is confined and resonates. The wavelengths of the PL lines are finely tuned by changing the blending ratio, accompanying the systematic yellow-to-red color change. Furthermore, when several microspheres are coupled linearly, the confined PL propagates the microspheres through the contact point, and a cascade-like process converts the PL color while maintaining the WGM characteristics. The self-assembly strategy for the formation of polymeric nano- to microstructures with highly miscible polymer blends will be advantageous for optoelectronic and photonic device applications.

The time-resolved photoluminescence (PL) characteristics of single CdSe/ZnS nanoparticles, embedded in a PMMA layer is studied at room temperature. We observe a strong spectral jitter of up to 55 meV, which is correlated with a change in the observed linewidth. We evaluate this correlation effect using a simple model, based on the quantum confined Stark effect induced by a diffusing charge in the vicinity of the nanoparticle. This allows us to derive a mean distance between the center of the particle and the diffusing charge of approximately 3.3 nm on average, as well as a mean charge carrier displacement within the integration time. The distances are larger than the combined radius of particle core and shell of about 3 nm, but smaller than the overall radius of 5 nm including ligands. These results are reproducible, even for particles which exhibit strong blueing, with shifts of up to 150 meV. Both the statistics and its independence of core-shell alterations lead us to conclude that the charge causing the spectral jitter is situated in the ligands.

Self-assembly of highly fluorescent isolated conjugated polymers (ICPs), comprising alternating phenylene moieties with an insulating cyclic side chain and different arylene moieties, was comprehensively studied. Two out of nine ICPs were identified to form well-defined spheres of 1−6 μm diameter. The degree of twisting of the main chains was found to be an important structural factor enabling formation of spheres, for which dihedral angles >50°between the neighboring arylene moieties were required. A single microsphere with high sphericity exhibited whispering gallery mode (WGM) photoemission upon excitation with a focused laser. In this emission, sharp and periodic emission lines were superimposed on a broad photoemission spectrum. The WGM spectral profiles were very sensitive to the integrity of the spherical geometries and surface smoothness, which depends on the self-assembling condition as well as the structure of the polymer backbone. Microspherical optical resonators consisting of such highly fluorescent conjugated polymers are novel. They also present advantages in that (i) there is no need for a light waveguide and fluorescent-dye doping, (ii) its high refractive index is beneficial for light confinement, and (iii) the fabrication process is simple, not requiring sophisticated, costly microfabrication technology. ■ INTRODUCTIONπ-Conjugated polymers possess charge transport, photoemission, and redox properties, which are useful for applications in electronic and optoelectronic devices such as light-emitting diodes, transistors, solar cells, and electrochromic devices. 1−6 Recently, spherical colloids formed from π-conjugated polymers have attracted attention for additional optical and biomedical applications involving fluorescence imaging, drug and gene delivery, and colloidal photonic crystals. 7−9 However, in general, π-conjugated polymers are hard to form into well-defined spheres because of their rigid and planar backbones. Thus, there have been few examples of π-conjugated polymer spheres reported so far. 8,10−16 Moreover, most of these were prepared using miniemulsion polymerization and dispersion polymerization methods.In this context, we have recently reported several π-conjugated alternating copolymers that form well-defined microspheres quantitatively via self-assembly in a thermodynamic solution process. 17,18 The slow diffusion of a polar nonsolvent vapor into a solution of a low-crystallinity polymer results in the formation of spheres with diameters in the submicrometer to several micrometers range. Interestingly, upon laser excitation of a single sphere, clear whispering gallery modes (WGM) were observed in photoemission. 19 Because the refractive indices (η) of these polymers are in the range of 1.6− 1.8, which is high enough in comparison with the refractive index of air (η air ∼ 1.0), fluorescence generated inside the microspheres is efficiently confined via total internal reflection at the polymer/air interface. As a result, sharp and periodic emission lines appear in their photolumine...

We investigate the whispering gallery modes (WGMs) of self-assembled single microspheres. They consist of a recently developed highly fluorescent π-conjugated copolymer and exhibit excellent optical properties with Q-factors up to 104. Under continuous laser irradiation, we observe a splitting of the highly degenerate spherical WGMs into a multiplet of lines. Comparison with the calculated spectral response of a weakly distorted sphere shows that the optical excitation induces a change of the optical path length in the microcavity so that it resembles a prolate spheroid. The separation of the lines is given by the ellipticity and the azimuthal mode number. Measurements in various gaseous environments suggest that the distortion is caused by light induced oxidation of the polymer. Our findings show that photooxidation can be a beneficial mechanism for in-situ tuning of optically active polymer structures.