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The luminescence and electroluminescence of an ethyne-linked zinc(ii) porphyrin pentamer have been investigated, by testing blends in two different conjugated polymer matrices, at a range of concentrations. The best results were obtained for blends with the conjugated polymer PIDT-2TPD, at a porphyrin loading of 1 wt%. This host matrix was selected because the excellent overlap between its emission spectrum and the low-energy region of the absorption spectrum of the porphyrin oligomer leads to efficient energy transfer. Thin films of this blend exhibit intense fluorescence in the near-infrared (NIR), with a peak emission wavelength of 886 nm and a photoluminescent quantum yield (PLQY) of 27% in the solid state. Light-emitting diodes (LEDs) fabricated with this blend as the emissive layer achieve average external quantum efficiencies (EQE) of 2.0% with peak emission at 830 nm and a turn-on voltage of 1.6 V. This performance is remarkable for a singlet NIR-emitter; 93% of the photons are emitted in the NIR (λ > 700 nm), indicating that conjugated porphyrin oligomers are promising emitters for non-toxic NIR OLEDs.

Loading of one-dimensional (1-D) porous silicon photonic crystals (PS-PhCs), known as rugate filters, with luminescent materials is generally limited by the potential for (undesired) “pore clogging,” in relation to the size of the nanoparticles (e.g. quantum dots) or molecular species, and so far mainly restricted to small molecular weight materials or small nanocrystals, or in situ polymerized dyes. Here we report the infiltration 1-D PS-PhCs with a green-emitting commercial luminescent polymer (F8BT, poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)]), with a molecular weight of approximately 46 kDa across their whole depth (approximately 7.5 μm), thereby showing that pore clogging is not a concern for these structures. We also characterize the modification of the photoluminescence (PL) and decay rates, and investigate the detailed inner morphology of the filters with the help of (scanning) transmission electron microscopy. We observe both suppression (in the stop-band) and enhancement (at the high-energy band-edge) of the PL. We also find that the photonic stop-band is red-shifted after polymer infiltration, due to the increased effective refractive index of the polymer-infiltrated nanostructured system. The presence of just one unbroadened peak in the reflectance spectra after infiltration confirms that infiltration extends for the whole depth of the rugate filters.

Supplemental Material, NM_NT_SI_rev for C-Si hybrid photonic structures by full infiltration of conjugated polymers into porous silicon rugate filters by Valentina Robbiano, Salvatore Surdo, Alessandro Minotto, Giancarlo Canazza, G Mattia Lazzerini, Shabbir M Mian, Davide Comoretto, Giuseppe Barillaro, and Franco Cacialli in Nanomaterials and Nanotechnology

We present recent progress on visible light communication systems using polymer light-emitting diodes as the transmitters and a commercial silicon photodetector as the receiver. In this paper, we use transmitters at red, green, and blue wavelengths to investigate the maximum on-off keying link performance of each device type as the first steps toward a wavelength-division multiplexed link. We show that a total transmission speed of 13 Mb/s is achievable when considering the raw bandwidth of each of the RGB PLEDs. Such a rate represents a 30% gain over previously demonstrated systems. Further capacity improvement can be achieved using high performance artificial neural network equalizer offering a realistic prospect for transmission speeds up to 54.9 Mb/s.

We have prepared a new borazine derivative that bears mesityl substituents at the boron centers and displays exceptional chemical stability. Detailed crystallographic and solid-state fluorescence characterizations revealed the existence of several polymorphs, each of which showed different emission profiles. In particular, a bathochromic shift is observed when going from the lower- to the higher-density crystal. Computational investigations of the conformational dynamics of borazine 1 in both the gas phase and in the solid state using molecular dynamics (MD) simulations showed that the conformation of the peripheral aryl groups significantly varies when going from an isolated molecule (in which the rings are able to flip over the 90 degrees barrier at RT) to the crystals (in which the rotation is locked by packing effects), thus generating specific nonsymmetric intermolecular interactions in the different polymorphs. To investigate the optoelectronic properties of these materials by fabrication and characterization of light-emitting diodes (LEDs) and light-emitting electrochemical cells (LECs), borazine 1 was incorporated as the active material in the emissive layer. The current and radiance versus voltage characteristics, as well as the electroluminescence spectra reported here for the first time are encouraging prospects for the engineering of future borazine-based devices.

Scanning force microscopy (SFM) is used to study the surface morphology of spin-coated thin films of the ion-transport polymer poly(ethylene oxide) (PEO) blended with either cyclodextrin (CD)-threaded conjugated polyrotaxanes based on poly(4,4′-diphenylene-vinylene) (PDV), β-CD-PDV, or their uninsulated PDV analogues. Both the polyrotaxanes and their blends with PEO are of interest as active materials in light-emitting devices. The SFM analysis of the blended films supported on mica and on indium tin oxide (ITO) reveals in both cases a morphology that reflects the substrate topography on the (sub-)micrometer scale and is characterized by an absence of the surface structure that is usually associated with phase segregation. This observation confirms a good miscibility of the two hydrophilic components, when deposited by using spin-coating, as suggested by the luminescence data on devices and thin films. Clear evidence of phase segregation is instead found when blending PEO with a new organic-soluble conjugated polymer such as a silylated poly(fluorene)-afr-poly(para-phenylene) based polyrotaxane (THS-β-CD-PF- PPP). The results obtained are relevant to the understanding of the factors influencing the interfacial and the intermolecular interactions with a view to optimizing the performance of light-emitting diodes, and light-emitting electrochemical cells based on supramolecularly engineered organic polymers. © 2007 WILEY-VCH Verlag GmbH and Co. KGaA.

A molecular wire consisting of a metal/molecule/metal junction can be regarded as the basic building block for future nanoelectronics applications. Alongside the great effort expended in the last ten years on the use of single molecules as electroactive components, there is also a growing interest centered on the use of supramolecular architectures as electroactive species to bridge metallic electrodes. The supramolecular approach can enhance the mechanical and electronic properties of the wire, which should improve the performance of electronic devices. One major challenge in the study of charge transfer across organic molecules is achieving reproducible attachment between metallic electrodes. Although different electrode pairs have been employed, including break junctions, lithographically tailored nanoelectrodes, and a solid substrate and a conductive tip of an atomic force microscope or a mercury drop, new, scalable routes to the controlled incorporation of nanometer-scale objects in the gap between nanoelectrodes are required. The manipulation and alignment of an anisotropic object using dielectrophoretic forces in an electric field has been successfully accomplished with a variety of different structures including metal and semiconducting nanoparticles and nanowires, DNA molecules, carbon nanotubes, block copolymers, ZnO–organic complexes, and dendron rod–coil ribbons. This has recently led, for example, to improved emission properties of single conjugated polymer molecules. The possibility of applying this technique to supramolecularly engineered nanostructures is thus of major interest in view of their reversible self-assembling properties under external stimuli such as temperature and chemical environment. We provide here the first direct quantitative determination of the electric-field-assisted alignment of single organic supramolecular fibers self-assembled at a surface. We have chosen a gel-forming functionalized 1,3,5-triamide cis,cis-cyclohexane derivative (cyclohexane trisamide gelator (CTG), Fig. 1a) that is known to self-assemble into supramolecular fibers in aqueous solution through the formation of hydrogen bonds. Due to its wider applicability for electronic applications, we present here attempts to form similar fibers in an organic solvent. Fibers were deposited from solution onto two gold electrodes arranged in a source–drain geometry with micrometer-scale separation. During deposition, a DC voltage was applied between the two electrodes and the system was cooled below its sol–gel transition temperature (Tsol–gel). In the gel, the three intermolecular hydrogen bonds among the amide moieties of CTGs are both parallel to one another and perpendicular to the plane of the cyclohexane ring (see Fig. 1a inset), endowing strong, self-complementary, and uniaxial intermolecular interactions that are necessary to enforce quasi-1D self-assembly. Since each hydrogen bond has a dipolar nature, the identical orientation of at least two of the three H-bonded networks provides the columnar architecture with a large dipole moment, making the CTG fibers excellent candidates to study the effect of applied electric fields. Micrometer-length CTG fibers were observed preferentially on the top of the negatively charged electrode and tended to align with the local electric field, which has been calculated for our system geometry using finite element analysis. Given C O M M U N IC A TI O N S

A series of polyfluorene-based polymers with a range of weight percentages (w/w) of a platinum(II)-containing porphyrin, 5,15-dimesityl-10,20-diphenylporphyrinato platinum(II) (MPP(Pt)), were synthesised and incorporated into organic light-emitting diodes. All polymers showed emission predominantly in the red/NIR region with only those polymers with porphyrin w/w of less than 2% showing residual tails at wavelengths lower than 600 nm, indicating increased emission from the porphyrin as w/w increases. The 2% loading of MPP(Pt) gave the highest efficiency LED (0.48%) and light output (2630 mW/m2).

A series of polyfluorene-based polymers with a range of weight percentages (w/w) of a platinum(II)-containing porphyrin, 5,15-dimesityl-10,20-diphenylporphyrinato platinum(II) (MPP(Pt)), were synthesised and incorporated into organic light-emitting diodes. All polymers showed emission predominantly in the red/NIR region with only those polymers with porphyrin w/w of less than 2% showing residual tails at wavelengths lower than 600 nm, indicating increased emission from the porphyrin as w/w increases. The 2% loading of MPP(Pt) gave the highest efficiency LED (0.48%) and light output (2630 mW/m2).

Advanced optical materials 10, (2021). doi:10.1002/adom.202101116, Published by Wiley-VCH, Weinheim

Funder: Royal Society; Id: http://dx.doi.org/10.13039/501100000288, Funder: Winton Programme for the Physics of Sustainability, Conjugated polymers are an important class of chromophores for optoelectronic devices. Understanding and controlling their excited state properties, in particular, radiative and non‐radiative recombination processes are among the greatest challenges that must be overcome. We report the synthesis and characterization of a molecularly encapsulated naphthalene diimide‐based polymer, one of the most successfully used motifs, and explore its structural and optical properties. The molecular encapsulation enables a detailed understanding of the effect of interpolymer interactions. We reveal that the non‐encapsulated analogue P(NDI‐2OD‐T) undergoes aggregation enhanced emission; an effect that is suppressed upon encapsulation due to an increasing π‐interchain stacking distance. This suggests that decreasing π‐stacking distances may be an attractive method to enhance the radiative properties of conjugated polymers in contrast to the current paradigm where it is viewed as a source of optical quenching.

We present the synthesis and characterization of a series of encapsulated diketopyrrolopyrrole red-emitting conjugated polymers. The novel materials display extremely high fluorescence quantum yields in both solution (>70%) and thin film (>20%). Both the absorption and emission spectra show clearer, more defined features compared to their naked counterparts demonstrating the suppression of inter and intramolecular aggregation. We find that the encapsulation results in decreased energetic disorder and a dramatic increase in backbone colinearity as evidenced by scanning tunnelling microscopy. This study paves the way for diketopyrrolopyrrole to be used in emissive solid state applications and demonstrates a novel method to reduce structural disorder in conjugated polymers.

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.A series of new near-infrared (NIR) emitting copolymers, based on a low band gap 6-(2-butyloctyl)-4,8-di(thiophen-2-yl)-[1,2,3]triazolo[4',5':4,5]benzo[1,2-c]-[1,2,5]thiadiazole (TBTTT) fluorophore copolymerized into a high band gap poly[3,3'-ditetradecyl-2,2'-bithiophene-5,5'-diyl-alt-5-(2-ethylhexyl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione-1,3-diyl] (P2TTPD) host backbone, for polymer light-emitting diode (PLED) applications is reported. PLEDs fabricated from the host polymer (P2TTPD-0) show external quantum efficiencies (EQEs) up to 0.49% at 690 nm, with turn-on voltage (Von) at only 2.4 V. By incorporating the TBTTT segments into the host polymer backbone, pure NIR emission peaking at ca. 900 nm is obtained with Von remaining below 5 V. This work demonstrates that such a low Von can be attributed to efficient intrachain energy and/or charge transfer to the TBTTT sites. When the NIR emitting copolymer (P2TTPD-10) is blended with P2TTPD-0, the TBTTT are confined to well-separated polymer chains. As a result, the EQE from the blend is lower and the Von higher than that obtained from the pure copolymer (P2TTPD-1.0) with equal content of TBTTT. An analogous copolymer (P4T-1.0), consisting of poly[3,3'-ditetradecyl-2,2':5',2'':5'',2'''-quaterthiophene-5,5'''-diyl] (P4T) as the host and 1% TBTTT as the NIR emitter, further demonstrates that pure NIR emission can be obtained only through optimized molecular orbital energy levels, as in P2TTPD-1.0, which minimizes chances for either charge trapping or exciton splitting.

We report the optical characterization of near-infrared (NIR) emitters for polymer light-emitting diode (PLEDs) applications based on the copolymerization of a phthalimide-thiophene host polymer with a low-gap emitter containing the bisthienyl(benzotriazolothiadiazole) unit. We investigate different loadings of the low-gap emitter (in the range 1-3% by weight) and the substitution of a sulphur atom with a selenium atom to further extend the emission in the NIR up to 1000 nm. PLEDs based on copolymers with 1% loading give the best efficiency (0.09%) and show an almost pure NIR EL (95% in the NIR) peaking at 895 nm. Refereed/Peer-reviewed

Near-infrared (NIR) polymer light-emitting diodes (PLEDs) based on a fluorene–dioctyloxyphenylene wide-gap host material copolymerized with a low-gap emitter are presented. Various loadings (1, 2.5, 10, 20 mol%) of the low-gap emitter are studied, with higher loadings leading to decreased efficiencies likely due to aggregation effects. While the 10 mol% loading resulted in almost pure NIR emission ( > 99.6%), the 1 mol% loading yielded optimum device performance, which is among the best reported to date for an unblended single-layer pure polymer emitter, with an external quantum efficiencies of 0.04% emitting at 909 nm. The high spectral purity of the PLEDs combined with their performance support the methodology of copolymerization as an effective strategy for developing NIR PLEDs. Refereed/Peer-reviewed

Nanoscale 12(9), 5444-5451 (2020). doi:10.1039/D0NR00724B, Published by RSC Publ., Cambridge