Reaction of Pertechnetate in Highly Alkaline Solution: Synthesis and Characterization of the Nitridotrioxotechnetate Ba[TcO3 N].

The preparation of novel technetium oxides, their characterization and the general investigation of technetium chemistry are of significant importance, since fundamental research has so far mainly focused on the group homologues. Whereas the structure chemistry of technetium in strongly oxidizing media is dominated by the Tc O 4 - ${{\left[{\rm { Tc}}{{\rm { O}}}_{{\rm { 4}}}\right]}^{-}}$ anion, our recent investigation yielded the new Tc O 3 N 2 - ${{\left[{\rm { Tc}}{{\rm { O}}}_{{\rm { 3}}}{\rm { N}}\right]}^{{\rm { 2}}-}}$ anion. Brown single crystals of Ba[TcO3 N] were obtained under hydrothermal conditions starting from Ba(OH)2 ⋅ 8H2 O and NH4 [TcO4 ] at 200 °C. Ba [ Tc O 3 N ] ${{\rm { Ba[Tc}}{{\rm { O}}}_{{\rm { 3}}}{\rm { N]}}}$ crystallizes in the monoclinic crystal system with the space group P21 /n (a=7.2159(4) Å, b=7.8536(5) Å, c=7.4931(4) Šand ß=104.279(2)°). The crystal structure of Ba [ Tc O 3 N ] ${{\rm { Ba[Tc}}{{\rm { O}}}_{{\rm { 3}}}{\rm { N]}}}$ consists of isolated Tc O 3 N 2 - ${{\left[{\rm { Tc}}{{\rm { O}}}_{{\rm { 3}}}{\rm { N}}\right]}^{{\rm { 2}}-}}$ tetrahedra, which are surrounded by Ba2+ cations. XANES measurements complement the oxidation state +VII for technetium and Raman spectroscopic experiments on Ba[TcO3 N] single crystals exhibit characteristic Tc-O and Tc-N vibrational modes.

Perovskite-organic tandem solar cells with indium oxide interconnect.

Multijunction solar cells can overcome the fundamental efficiency limits of single-junction devices. The bandgap tunability of metal halide perovskite solar cells renders them attractive for multijunction architectures1. Combinations with silicon and copper indium gallium selenide (CIGS), as well as all-perovskite tandem cells, have been reported2-5. Meanwhile, narrow-gap non-fullerene acceptors have unlocked skyrocketing efficiencies for organic solar cells6,7. Organic and perovskite semiconductors are an attractive combination, sharing similar processing technologies. Currently, perovskite-organic tandems show subpar efficiencies and are limited by the low open-circuit voltage (Voc) of wide-gap perovskite cells8 and losses introduced by the interconnect between the subcells9,10. Here we demonstrate perovskite-organic tandem cells with an efficiency of 24.0 per cent (certified 23.1 per cent) and a high Voc of 2.15 volts. Optimized charge extraction layers afford perovskite subcells with an outstanding combination of high Voc and fill factor. The organic subcells provide a high external quantum efficiency in the near-infrared and, in contrast to paradigmatic concerns about limited photostability of non-fullerene cells11, show an outstanding operational stability if excitons are predominantly generated on the non-fullerene acceptor, which is the case in our tandems. The subcells are connected by an ultrathin (approximately 1.5 nanometres) metal-like indium oxide layer with unprecedented low optical/electrical losses. This work sets a milestone for perovskite-organic tandems, which outperform the best p-i-n perovskite single junctions12 and are on a par with perovskite-CIGS and all-perovskite multijunctions13.

Making Graphene Nanoribbons Photoluminescent.

We demonstrate the alignment-preserving transfer of parallel graphene nanoribbons (GNRs) onto insulating substrates. The photophysics of such samples is characterized by polarized Raman and photoluminescence (PL) spectroscopies. The Raman scattered light and the PL are polarized along the GNR axis. The Raman cross section as a function of excitation energy has distinct excitonic peaks associated with transitions between the one-dimensional parabolic subbands. We find that the PL of GNRs is intrinsically low but can be strongly enhanced by blue laser irradiation in ambient conditions or hydrogenation in ultrahigh vacuum. These functionalization routes cause the formation of sp3 defects in GNRs. We demonstrate the laser writing of luminescent patterns in GNR films for maskless lithography by the controlled generation of defects. Our findings set the stage for further exploration of the optical properties of GNRs on insulating substrates and in device geometries.

Suppressed decomposition of organometal halide perovskites by impermeable electron-extraction layers in inverted solar cells.

The area of thin-film photovoltaics has been overwhelmed by organometal halide perovskites. Unfortunately, serious stability concerns arise with perovskite solar cells. For example, methyl-ammonium lead iodide is known to decompose in the presence of water and, more severely, even under inert conditions at elevated temperatures. Here, we demonstrate inverted perovskite solar cells, in which the decomposition of the perovskite is significantly mitigated even at elevated temperatures. Specifically, we introduce a bilayered electron-extraction interlayer consisting of aluminium-doped zinc oxide and tin oxide. We evidence tin oxide grown by atomic layer deposition does form an outstandingly dense gas permeation barrier that effectively hinders the ingress of moisture towards the perovskite and-more importantly-it prevents the egress of decomposition products of the perovskite. Thereby, the overall decomposition of the perovskite is significantly suppressed, leading to an outstanding device stability.

Non-steady-state photoelectromotive force effect under linear and periodical phase modulation: application to detection of Doppler frequency shift.

Non-steady-state photoelectromotive force effect in the presence of periodical and linear phase shift was investigated both theoretically and experimentally. It was shown that superposition of oscillating and linear movements of the interference pattern leads to the appearance of the sharp peak in the frequency dependence of the photoelectromotive force output current when the frequency of periodical modulation matches the frequency of the linear phase shift. We demonstrated experimentally that this effect can be used for determination of a Doppler frequency shift between signal and reference beam.

Electric field assisted charge carrier photogeneration in poly(spirobifluorene-co-benzothiadiazole).

The dynamics of charge carrier generation in poly(spirobifluorene-co-benzothiadiazole) was investigated by electric field-induced fluorescence quenching and differential absorption measurements. Three different time domains of carrier generation have been identified: an ultrafast phase, a subnanosecond phase, and an entire lifetime phase. The charge generation efficiencies during the first and second phases were found to be almost independent of temperature, being about 25% and 10%, respectively, at an applied electric field of 1.3×10(6) V/cm, while the generation efficiency during the third phase increases from 2% at 80 K to 10% at room temperature. The results of transient spectroscopy measurements and quantum chemical calculations suggest an intramolecular charge transfer for about 1 ps from the alkoxy-substituted fluorene side group to the benzothiadiazole subunit of the main chain. The formation and evolution of the resulting charge transfer states determine the way of charge carrier generation.

Ultrafast dynamics of carrier mobility in a conjugated polymer probed at molecular and microscopic length scales.

We used time-resolved electric-field-induced second-harmonic generation to probe the charge-carrier-mobility dynamics in amorphous organic materials on an ultrafast time scale. We were able to show that the mobility in poly-spiro-bifluorene-co-benzothiadiazol decreases from 0.1 cm 2/V s at 1 ps to 10-6 cm2/V s within 1 mus. We attribute this dramatic decrease to the relaxation of the charge carriers within the density of states, clearly demonstrating the impact of disorder on the nanoscale charge transport in amorphous semiconductors.

Three-dimensional holographic imaging of living tissue using a highly sensitive photorefractive polymer device.

Photorefractive materials are dynamic holographic storage media that are highly sensitive to coherent light fields and relatively insensitive to a uniform light background. This can be exploited to effectively separate ballistic light from multiply-scattered light when imaging through turbid media. We developed a highly sensitive photorefractive polymer composite and incorporated it into a holographic optical coherence imaging system. This approach combines the advantages of coherence-domain imaging with the benefits of holography to form a high-speed wide-field imaging technique. By using coherence-gated holography, image-bearing ballistic light can be captured in real-time without computed tomography. We analyzed the implications of Fourier-domain and image-domain holography on the field of view and image resolution for a transmission recording geometry, and demonstrate holographic depth-resolved imaging of tumor spheroids with 12 microm axial and 10 microm lateral resolution, achieving a data acquisition speed of 8 x 10(5) voxels/s.

Triplet-polaron quenching in conjugated polymers.

We studied the triplet-polaron quenching in a platinum(II) porphyrin- (PtOEP-) doped polyspirobifluorene (PSF-TAD) copolymer. The copolymer contains a hole-transporting phenylenediamine unit (TAD) as a comonomer. Triplet-polaron quenching was probed by the change in PtOEP phosphorescence lifetime under an applied voltage in a unipolar device. The charge-induced reduction of the optically excited lifetime of PtOEP is one-third for the highest applied bias. The charge density can be obtained from current-voltage characteristics in the space-charge-limited (SCL) regime. The obtained hole mobility under SCL conditions is (7 +/- 2) x 10(-5) cm(2)/(V s). This result is in accord with recent mobility measurements of the time-of-flight mobility in our polymer. The triplet-polaron recombination constant was evaluated to be (4 +/- 1) x 10(-13) cm(3)/s, implying a triplet-polaron interaction radius of 2 x 10(-10) m. The results show that triplet-polaron annihilation cannot be neglected in device models for phosphorescent light-emitting diodes.

ATOP dyes. optimization of a multifunctional merocyanine chromophore for high refractive index modulation in photorefractive materials.

This paper reports synthesis, characterization and structural optimization of amino-thienyl-dioxocyano-pyridine (ATOP) chromophores toward a multifunctional amorphous material with unprecedented photorefractive performance. The structural (dynamic NMR, XRD) and electronic (UV/vis, electrooptical absorption, Kerr effect measurements) characterization of the ATOP chromophore revealed a cyanine-type pi-conjugated system with an intense and narrow absorption band (epsilon(max) = 140 000 L mol(-)(1) cm(-)(1)), high polarizability anisotropy (deltaalpha(0) = 55 x 10(-)(40) C V(-)(1) m(2)), and a large dipole moment (13 D). This combination of molecular electronic properties is a prerequisite for strong electrooptical response in photorefractive materials with low glass-transition temperature (T(g)). Other important materials-related properties such as compatibility with the photoconducting poly(N-vinylcarbazole) (PVK) host matrix, low melting point, low T(g), and film-forming capabilities were optimized by variation of four different alkyl substituents attached to the ATOP core. A morphologically stable PVK-based composite containing 40 wt % of ATOP-3 showed an excellent photorefractive response characterized by a refractive index modulation of Deltan approximately 0.007 and a gain coefficient of Gamma approximately 180 cm(-)(1) at a moderate electrical field strength of E = 35 V microm(-)(1). Even larger effects were observed with thin amorphous films consisting of the pure glass-forming dye ATOP-4 (T(g) = 16 degrees C) and 1 wt % of the photosensitizer 2,4,7-trinitro-9-fluorenylidene-malononitrile (TNFM). This material showed complete internal diffraction at a field strength of only E = 10 V microm(-)(1) and Deltan reached 0.01 at only E = 22 V microm(-)(1) without addition of any specific photoconductor.

A straightforward modular approach to NLO-active beta-amino vinyl nitrothiophenes

Secondary amines add very efficiently to 2-ethynyl-5-nitrothiophene to give beta-amino vinyl nitrothiophenes, a novel class of push-pull chromophores. According to first HRS measurements these highly solvochromic compounds with relatively short dipole axes display remarkably high static first hyperpolarizabilities = 29-31 x 10(-)(30) esu.

Improving the performance of doped pi-conjugated polymers for use in organic light-emitting diodes

Organic light-emitting diodes (OLEDs) represent a promising technology for large, flexible, lightweight, flat-panel displays. Such devices consist of one or several semiconducting organic layer(s) sandwiched between two electrodes. When an electric field is applied, electrons are injected by the cathode into the lowest unoccupied molecular orbital of the adjacent molecules (simultaneously, holes are injected by the anode into the highest occupied molecular orbital). The two types of carriers migrate towards each other and a fraction of them recombine to form excitons, some of which decay radiatively to the ground state by spontaneous emission. Doped pi-conjugated polymer layers improve the injection of holes in OLED devices; this is thought to result from the more favourable work function of these injection layers compared with the more commonly used layer material (indium tin oxide). Here we demonstrate that by increasing the doping level of such polymers, the barrier to hole injection can be continuously reduced. The use of combinatorial devices allows us to quickly screen for the optimum doping level. We apply this concept in OLED devices with hole-limited electroluminescence (such as polyfluorene-based systems), finding that it is possible to significantly reduce the operating voltage while improving the light output and efficiency.

Efficient blue organic light-emitting diodes with graded hole-transport layers.

Using a derivative of the blue-emitting polyfluorene (see the graph for the output spectrum and the inset picture for the color), efficient devices exhibiting a power efficiency close to 2.7 cd A(-1) at 100 cd m(-2) light output were realized.

Influence of the Glass-Transition Temperature and the Chromophore Content on the Grating Buildup Dynamics of poly(N-vinylcarbazole)-based Photorefractive Polymers.

The influence of the glass-transition temperature T(g) and the electro-optical chromophore content on the grating buildup dynamics in photorefractive polymer composites is investigated. The response times were found to be strongly dependent on both parameters. In the low-T(g) regime, composites of different chromophore content respond similarly quickly (200-500 ms), whereas significant differences occur for T(g) above the measurement (room) temperature. The composites with the highest chromophore content give the best steady-state performance; however, their response is much slower than that for those containing less chromophore.

Non-Bragg orders in dynamic self-diffraction on thick phase gratings in a photorefractive polymer.

We demonstrate that recording thick holographic phase gratings in photorefractive polymers can lead not only to very efficient Bragg diffraction but also to rather strong diffraction into non-Bragg orders. We show that this effect has features drastically different from those of Raman-Nath diffraction on thin gratings. We compare the experimental results with a model based on the theory of dynamic self-diffraction in a photorefractive medium. Applications of this effect in devices for optical image processing are proposed.