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We report the synthesis of a new conjugated polymer bearing crown ether moieties, poly[(

Organic electrochemical transistors (ECTs) are an important building block for bioelectronics. To promote the required ion transport through the active layer, state-of-the-art semiconducting polymers feature hydrophilic ethylene glycol side chains that increase the volumetric capacitance and transconductance of the devices. Here, we apply this concept to polymer-wrapped single-walled carbon nanotubes (SWCNTs) as a high-mobility semiconducting material. We replace the polyfluorene copolymer (PFO-BPy), which is used for selectively dispersing semiconducting (6,5) SWCNTs and contains octyl side chains, by an equivalent polymer with tetraethylene glycol side chains. Aerosol-jet printed networks of these SWCNTs are applied as the active layer in water-gated ECTs. These show high hole mobilities (3-15 cm

Diblock copolymer electrolytes based on a π-conjugated polyfluorene (PF) backbone were synthesized comprising nanodomains of a polymerized ionic liquid (PIL) and of a solid polymer electrolyte (SPE...

Poly(4,4-dialkyl-cyclopenta[2,1

Conjugated polymers exhibit strong interactions with single-walled carbon nanotubes (SWNTs). These enable the selective dispersion of specific semiconducting SWNTs in organic solvents and polymer-m...

Funding: This research was funded by European commission under FP7 LAMP project “Laser Induced Synthesis of Polymeric Nanocomposite Materials and Development of Micro-patterned Hybrid Light Emitting Diodes (LED) and Transistors (LET)” (Grant No. 247928) Many displays involve the use of color conversion layers. QDs are attractive candidates as color converters because of their easy processability, tuneable optical properties, high photoluminescence quantum yield, and good stability. Here, we show that emissive QDs with narrow emission range can be made in-situ in a polymer matrix, with properties useful for color conversion. This was achieved by blending the blue-emitting pyridine based polymer with a cadmium selenide precursor and baking their films at different temperatures. To achieve efficient color conversion, blend ratio and baking temperature/time were varied. We found that thermal decomposition of the precursor leads to highly emissive QDs whose final size and emission can be controlled using baking temperature/time. The formation of the QDs inside the polymer matrix was confirmed through morphological studies using atomic force microscopy (AFM) and transmission electron microscopy (TEM). Hence, our approach provides a cost-effective route to making highly emissive color converters for multi-color displays. Publisher PDF

Polarity control in semiconducting single-walled carbon-nanotube field-effect transistors (s-SWNT FETs) is important to promote their application in logic devices. The methods to turn the intrinsically ambipolar s-SWNT FETs into unipolar devices that have been proposed until now require extra fabrication steps that make preparation longer and more complex. It is demonstrated that by starting from a highly purified ink of semiconducting single-walled carbon nanotubes sorted by a conjugated polymer, and mixing them with additives, it is possible to achieve unipolar charge transport. The three additives used are benzyl viologen (BV), 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI), which give rise to n-type field-effect transistors, and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F-4-TCNQ) which gives rise to p-type transistors. BV and N-DMBI transform the s-SWNTs transistors from ambipolar with mobility of the order of 0.7 cm(2) V-1 s(-1) to n-type with mobility up to 5 cm(2) V-1 s(-1). F-4-TCNQ transform the ambipolar transistors in p-type with mobility up to 16 cm(2) V-1 s(-1).

The availability of purely semiconducting single-walled carbon nanotube (s-SWCNT) dispersions has prompted their widespread application in solution-processed thin-film transistors with excellent device performance but has also raised the question of how their precise composition influences charge transport properties in random networks. Here, we compare hole and electron transport in three different polymer-sorted s-SWCNT networks from nearly monochiral (6,5) nanotubes (diameter 0.76 nm) to mixed networks of s-SWCNTs with medium (0.8–1.3 nm) and large (1.2–1.6 nm) diameters. Temperature-dependent field-effect mobilities are extracted from gated four-point probe measurements that exclude any contributions by contact resistance and indicate thermally activated transport. The mobility data can be fitted to the fluctuation-induced tunneling model, although with significant differences between the network compositions. The network with the broadest diameter and thus bandgap range results in the strongest tempe...

The aggregation-induced emission (AIE) phenomenon provides a new direction for the development of organic light-emitting devices. Here, we present a new class of emitters based on 4,4-difluoro-4-bora-3 a ,4 a -diaza- s -indacene (BODIPY), functionalized at different positions with tetraphenylethylene (TPE), which is one of the most famous AIE luminogens. Thanks to this modification, we were able to tune the photoluminescence of the BODIPY moiety from the green to the near-infrared (NIR) spectral range and achieve PL efficiencies of ~50% in the solid state. Remarkably, we observed an enhancement of the AIE and up to ~100% photoluminescence efficiencies by blending the TPE-substituted BODIPY fluorophores with a poly[(9,9-di- n -octylfluorene-2,7-diyl)- alt -(benzo[2,1,3]thiadiazol-4,7-diyl)] (F8BT) matrix. By incorporating these blends in organic light-emitting diodes (OLEDs), we obtained electroluminescence peaked in the range 650–700 nm with up to 1.8% external quantum efficiency and ~2 mW/cm2 radiance, a remarkable result for red/NIR emitting and solution-processed OLEDs.

Dense layers of semiconducting single-walled carbon nanotubes (SWNTs) serve as electrochromic (EC) materials in the near-infrared with high optical density and high conductivity. EC cells with tunable notch filter properties instead of broadband absorption are created via highly selective dispersion of specific semiconducting SWNTs through polymer-wrapping followed by deposition of thick films by aerosol-jet printing. A simple planar geometry with spray-coated mixed SWNTs as the counter electrode renders transparent metal oxides redundant and facilitates complete bleaching within a few seconds through iongel electrolytes with high ionic conductivities. Monochiral (6,5) SWNT films as working electrodes exhibit a narrow absorption band at 997 nm (full width at half-maximum of 55–73 nm) with voltage-dependent optical densities between 0.2 and 4.5 and a modulation depth of up to 43 dB. These (6,5) SWNT notch filters can retain more than 95% of maximum bleaching for several hours under open-circuit conditions. In addition, different levels of transmission can be set by applying constant low voltage (1.5 V) pulses with modulated width or by a given number of fixed short pulses.

The efficient synthesis of a new solution-processable n-type conjugated polymer network (PNT1) is reported through palladium-catalyzed Stille cross-coupling reaction conditions following the A3 + B2 synthetic approach. A benzo[1,2-b:3,4-b′:5,6-b″]trithiophene derivative is used as the A3 knot and an alkyl functionalized naphthalenediimide is utilized as the B2 linker. The thermal, optical, and electrochemical properties are examined in detail, showing high thermal stability, absorbance in the visible part of the solar spectrum, and reversible reduction characteristics similar to those of the fullerene derivative [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM). PNT1 is employed as the electron acceptor in solution-processed bulk heterojunction organic solar cells, demonstrating the potential of this new type of materials for optoelectronic applications.

It is demonstrated that α,β-unsubstituted meso-positioning thienyl BODIPY is an electron deficient unit that leads to the development of ultra low optical band gap (Eoptg < 1 eV) π-conjugated D–A quarterthiophene polymers. Furthermore, it is revealed that the optoelectronic, electrochemical and charge transporting properties of the resulting α,β-unsubstituted meso-positioning thienyl BODIPY quaterthiophene-based polymers are alkyl side chain positioning dependent. Tail-to-tail (TT) positioning of the alkyl side chains at the two central thiophenes of the quaterthiophene segment results in lower Eoptg, higher energy levels and increased hole mobility as compared to head-to-head (HH) positioning. Finally, even though the synthesized polymers exhibit high electron affinity, higher even than that of the fullerene derivative [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM), they present only p-type behaviour in field effect transistors (FETs) independent of the alkyl side chain positioning.

We employ photoluminescence and pumpprobe spectroscopy on films of semiconducting single-walled carbon nanotubes (CNTs) of different chirality wrapped with either a wide band gap polyfluorene derivative (PF12) or a polythiophene with narrower gap (P3DDT) to elucidate the excited states interplay between the two materials. Excitation above the polymer band gap gives way to an ultrafast electron transfer from both polymers toward the CNTs. By monitoring the hole polaron on the polymer via its mid infrared signature, we show that also illumination below the polymer band gap leads to the formation of this fingerprint and infer that holes are also transferred toward the polymer. As this contradicts the standard way of discussing the involved energy levels, we propose that polymer-wrapped CNTs should be considered as a single hybrid system, exhibiting states shared between the two components. This proposition is validated through quantum chemical calculations that show hybridization of the first excited states, especially for the thiopheneCNT sample.

We acknowledge financial support from FP7 project “Laser Induced Synthesis of Polymeric Nanocomposite Materials and Development of Micro-Patterned Hybrid Light Emitting Diodes (LED) and Transistors (LET)”-LAMP (Project G.A.247928). A.K.B. and I.D.W.S. also acknowledge financial support from EPSRC Programme “Challenging the Limits of Photonics: Structured Light” Grant EP/J01771X/1. Quantum dots are of growing interest as emissive materials in light emitting devices. Here first we report the formation of highly luminescent organic capped colloidal cadmium sulfide (CdS) nanoparticles having the highest photoluminescence quantum yield of 69% in solutions and 34% in neat thin films in the near-infrared range. Second, we also show efficient electroluminescence in the near-infrared from solution processed hybrid light emitting diodes (LEDs) based on such colloidal CdS quantum dots embedded in an organic semiconductor matrix forming a nanocomposite active layer. We also discuss the device structure and role of the doped active layer in efficiency improvement. With optimized active layer thickness and concentration of QDs, the device exhibits an external electroluminescence quantum efficiency of 0.62% at a peak emission wavelength of 760 nm, providing a route to solution processable flexible light sources for biosensors and medicine. Publisher PDF

Printed random networks of polymer-wrapped multi-chiral semiconducting carbon nanotubes (s-SWCNTs) are an opportunity for mass-manufacturable, high-performance large-area electronics. To meet this goal, a deeper understanding of charge-transport mechanisms in such mixed networks is crucial. Here, charge transport in field-effect transistors based on inkjet-printed s-SWCNTs networks is investigated, obtaining direct evidence for the phases probed by charge in the accumulated channel, which is critical information to rationalize the different transport properties obtained for different printing conditions. In particular, when the fraction of nanotubes with smaller bandgaps is efficiently interconnected, the sparse network provides efficient charge percolation for band-like transport, with a charge mobility as high as 20.2 cm(2) V-1 s(-1). However, when the charges are forced by a less efficient morphology, to populate also higher bandgap nanotubes and and/or the wrapping polymer, thermally activated transport takes place and mobility drops. As a result, a trade-off between network density and charge transport properties is identified for device current optimization, in both p- and n-type regimes. These findings shed light on the fundamental aspects related to charge transport in printed s-SWCNT mixed networks and contribute to devise appropriate strategies for the formulation of inks and processes towards cost-effective mass production schemes of high-performance large-area electronics.

The authors acknowledge financial support from FP7 project “Laser Induced Synthesis of Polymeric Nanocomposite Materials and Development of Micro‐patterned Hybrid Light Emitting Diodes (LED) and Transistors (LET)” – LAMP project (G.A. 247928). M.T.S., A.R., and I.D.W.S. acknowledge support from the European Research Council (EXCITON grant 321305). I.D.W.S. acknowledges a Royal Society Wolfson Research Merit Award. The authors are grateful to EPSRC for an equipment grant (EP/L017008/1). Exciton diffusion plays an important role in functional materials used in organic optoelectronic devices, such as solar cells, organic light emitting diodes, and lasers. Here we explore how exciton diffusion can be controlled in highly fluorescent blue‐emitting polyfluorene materials by changing the length and type of side chains. We find that the exciton diffusion coefficient (D) decreases from 1.2 × 10−3 cm2 s−1 to 0.2×10−3 cm2 s−1 when the side chain length is increased from 8 to 12 carbon atoms. Other changes to the side chains led to enhancement of D up to 1.6 × 10−3 cm2 s−1. Our results show that small adjustments to the molecular structure can be helpful for the future development of high‐brightness organic light emitting devices. Postprint Postprint

Semiconducting single‐walled carbon nanotubes (s‐SWNTs) are used as a protective interlayer between the lead sulfide colloidal quantum dot (PbS CQD) active layer and the anode of the solar cells (SCs). The introduction of the carbon nanotubes leads to increased device stability, with 85% of the initial performance retained after 100 h exposure to simulated solar light in ambient condition. This is in sharp contrast with the behavior of the device without s‐SWNTs, for which the photoconversion efficiency, the open circuit voltage, the short‐circuit current, and the fill factor all experiencing a sharp decrease. Therefore, the inclusion of s‐SWNT as interlayer in CQD SCs, give rise to SCs of identical efficiency (above 8.5%) and prevents their performance degradation. ISSN:2196-7350

Noncovalent functionalization of single-walled carbon nanotubes (SWNTs) using π-conjugated polymers has become one of the most effective techniques to select semiconducting SWNTs (s-SWNTs). Several conjugated polymers are used, but their ability to sort metallic and semiconducting species, as well as the dispersions yields, varies as a function of their chemical structure. Here, three polymers are compared, namely, poly[2,6-(4,4-bis-(2-dodecyl)-4H-cyclopenta[2,1-b;3,4b′]dithiophene)-alt-4,7(2,1,3-ben-zothiadiazole)] (P12CPDTBT), poly(9,9-di-n-dodecylfluorenyl-2,7-diyl) (PF12), and poly(3-dodecylthiophene-2,5-diyl) (P3DDT) in their ability to select two types of carbon nanotubes comprising small (≈1 nm) and large (≈1.5 nm) diameters. P12CPDTBT is a better dispersant than PF12 for small diameter nanotubes, while both polymers are good dispersants of large diameter nanotubes. However, these dispersions contain metallic species. P3DDT, instead presents the best overall performance regarding the selectivity toward semiconducting species, with a dispersion yield for s-SWNTs of 15% for small and 21% for large diameter nanotubes. These results are rationalized in terms of electronic and chemical structure showing that: (i) the binding energy is stronger when more alkyl lateral chains adsorb on the nanotube surface; (ii) the binding energy is stronger when the polymer backbone is more flex-ible; (iii) the purity of the dispersions seems to depend on a strong polymer– nanotube interaction.

The authors acknowledge financial support from the UK EPSRC (Grants EP/E065066/1, EP/E062636/1, EP/J009318/1 and EP/J009019/1), from the EPSRC Scottish Centre for Doctoral training in Condensed Matter Physics and from the European Union Seventh Framework Programme under Grant Agreement 321305. Electronic energy transfer (EET) in organic materials is a key mechanism that controls the efficiency of many processes, including light harvesting antennas in natural and artificial photosynthesis, organic solar cells, and biological systems. In this paper we have examined EET in solid-state thin-films of polyfluorene, a prototypical conjugated polymer, with ultrafast photoluminescence experiments and theoretical modeling. We observe EET occurring on a 680 ± 300 fs time scale by looking at the depolarisation of photoluminescence. An independent, predictive microscopic theoretical model is built by defining 125 000 chromophores containing both spatial and energetic disorder appropriate for a spin-coated thin film. The model predicts time-dependent exciton dynamics, without any fitting parameters, using the incoherent Förster-type hopping model. Electronic coupling between the chromophores is calculated by an improved version of the usual line-dipole model for resonant energy transfer. Without the need for higher level interactions, we find that the model is in general agreement with the experimentally observed 680 ± 300 fs depolarisation caused by EET. This leads us to conclude that femtosecond EET in polyfluorene can be described well by conventional resonant energy transfer, as long as the relevant microscopic parameters are well captured. The implications of this finding are that dipole-dipole resonant energy transfer can in some circumstances be fully adequate to describe ultrafast EET without needing to invoke strong or intermediate coupling mechanisms. Postprint

A new ultra low band gap (LBG) α,β-unsubstituted BODIPY-based conjugated polymer has been synthesized by conventional cross coupling polymerization techniques (Stille cross coupling) for the first time. The polymer exhibits a panchromatic absorption spectrum ranging from 300 nm to 1100 nm and an optical band gap (Eoptg) of 1.15 eV, suitable for near infrared (NIR) organic photovoltaic applications as electron donor. Preliminary power conversion efficiency (PCE) of 1.1% in polymer : [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) 1 : 3 weight ratio bulk heterojunction (BHJ) solar cells has been achieved, demonstrating very interesting and promising photovoltaic characteristics, such as good fill factor (FF) and open circuit voltage (Voc). These results showing that by the proper chemical design, new α,β-unsubstituted BODIPY-based NIR copolymers can be developed in the future with suitable energy levels matching those of PC71BM towards more efficient NIR organic photovoltaics (OPVs).

Organic pi-conjugated polymers are deemed to be soft materials with strong electron-phonon coupling, which results in the formation of polarons, i.e., charge carriers dressed by self-localized distortion of the nuclei. Universal signatures for polarons are optical resonances below the band gap and intense vibrational modes (IVMs), both found in the infrared (IR) spectral region. Here, we study p-doped conjugated homo- and copolymers by combining first-principles modelling and optical spectroscopy from the far-IR to the visible. Polaronic IVMs are found to feature absorption intensities comparable to purely electronic transitions and, most remarkably, show only loose resemblance to the Raman or IR-active modes of the neutral polymer. The IVM frequency is dramatically scaled down (up to 50%) compared to the backbone carbon-stretching modes in the pristine polymers. The very large intensity of IVMs is associated with displacement of the excess positive charge along the backbone driven by specific vibrational modes. We propose a quantitative picture for the identification of these polaron shifting modes that solely based on structural information, directly correlates with their IR intensity. This finding finally discloses the elusive microscopic mechanism behind the huge IR intensity of IVMs in doped polymeric semiconductors.

International audience; The influence of annealing temperature on the structural and electrical properties of conjugated poly(dodecyl-quaterthiophene) (PQT-12) polymer films is exploited. The temperature induced changes of structural parameters are monitored by in situ grazing incident X-ray diffraction (GIXD) and the conductivity. They are complemented by studies of the dielectric properties using variable angle spectroscopic ellipsometry (VASE). An increase of the scattered intensity, the size of the crystalline domains, and the current response is observed for a first thermal cycle with stepwise heating up to 90 degrees C, which revealed two polymorphs with different degrees of interdigitation in PQT-12. Irreversible changes are observed for the second cycle with a higher thermal budget up to 140 degrees C and are connected with a transition from the highly ordered to powder-like disordered phase for the main PQT-12 form whereas the second polymorph with stronger interdigitation completely vanished. In agreement with these observations high-temperature VASE studies demonstrated a blue shift of the transitions with a reduction in the conjugation length caused by an increase in the twist and torsion of the backbone. Combined GIRD, VASE, and electrical characterizations show that PQT-12 exhibits a complex interplay between two polymorphs with a strong influence on the charge carrier transport depending on the thermal budget employed.

In this paper, the fabrication of carbon nanotubes field effect transistors by chemical self-assembly of semiconducting single walled carbon nanotubes (s-SWNTs) on prepatterned substrates is demonstrated. Polyfluorenes derivatives have been demonstrated to be effective in selecting s-SWNTs from raw mixtures. In this work the authors functionalized the polymer with side chains containing thiols, to obtain chemical self-assembly of the selected s-SWNTs on substrates with prepatterned gold electrodes. The authors show that the full side functionalization of the conjugated polymer with thiol groups partially disrupts the s-SWNTs selection, with the presence of metallic tubes in the dispersion. However, the authors determine that the selectivity can be recovered either by tuning the number of thiol groups in the polymer, or by modulating the polymer/SWNTs proportions. As demonstrated by optical and electrical measurements, the polymer containing 2.5% of thiol groups gives the best s-SWNT purity. Field-effect transistors with various channel lengths, using networks of SWNTs and individual tubes, are fabricated by direct chemical self-assembly of the SWNTs/thiolated-polyfluorenes on substrates with lithographically defined electrodes. The network devices show superior performance (mobility up to 24 cm(2) V-1 s(-1)), while SWNTs devices based on individual tubes show an unprecedented (100%) yield for working devices. Importantly, the SWNTs assembled by mean of the thiol groups are stably anchored to the substrate and are resistant to external perturbation as sonication in organic solvents.

We take advantage of a recent breakthrough in the synthesis of α,β-unfunctionalised 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) moieties, which we symmetrically conjugate with oligothienyls in an unexpectedly stable form, and produce a “metal-free” A-D-A (acceptor-donor-acceptor) oligomer emitting in the near-infrared (NIR) thanks to delocalisation of the BODIPY low-lying lowest unoccupied molecular orbital (LUMO) over the oligothienyl moieties, as confirmed by density functional theory (DFT). We are able to retain a PL efficiency of 20% in the solid state (vs. 30% in dilute solutions) by incorporating such a dye in a wider gap polyfluorene matrix and demonstrate organic light-emitting diodes (OLEDs) emitting at 720 nm. We achieve external quantum efficiencies (EQEs) up to 1.1%, the highest value achieved so far by a “metal-free” NIR-OLED not intentionally benefitting from triplet-triplet annihilation. Our work demonstrates for the first time the promise of A-D-A type dyes for NIR OLEDs applications thereby paving the way for further optimisation.

One of the key aspects to achieve high efficiency in ternary bulk-hetorojunction solar cells is the physical and chemical compatibility between the donor materials. Here, we report the synthesis of a novel conjugated polymer (P1) containing alternating pyridyl[2,1,3] thiadiazole between two different donor fragments, dithienosilole and indacenodithienothiophene (IDTT), used as a sensitizer in a host system of indacenodithieno[3,2-b]thiophene, 2,3-bis(3-(octyloxy)phenyl)quinoxaline (PIDTTQ) and [6,6]-phenyl C-70 butyric acid methyl ester (PC71BM). We found that the use of the same IDTT unit in the host and guest materials does not lead to significant changes in the morphology of the ternary blend compared to the host binary. With the complementary use of optoelectronic characterizations, we found that the ternary cells suffer from a lower mobility-lifetime (mu tau) product, adversely impacting the fill factor. However, the significant light harvesting in the near infrared region improvement, compensating the transport losses, results in an overall power conversion efficiency enhancement of similar to 7% for ternary blends as compared to the PIDTTQ:PC71BM devices.

In the past years, high-quality semiconducting single-walled carbon nanotube (s-SWCNT) inks obtained by conjugated polymer wrapping using toluene as solvent have been used for the fabrication of high-performance field-effect transistors. Charge-carrier mobilities up to 50 cm(2) V-1 s(-1) and on/off ratios above 10(8) have been reported for devices based on networks of s-SWCNT. However, devices fabricated from inks that are only a few weeks old generally show a marked decrease in performance, indicating the limited shelf life of toluene-based inks. The use of o-xylene as applicator solvent to obtain high quality and very stable s-SWCNT inks is reported. The charge carrier mobility of field-effect transistors fabricated with this new ink show a twofold increase in magnitude compared to devices prepared from a toluene solution. More importantly, the device-to-device performance shows improved reproducibility, which is ascribed to the higher degree of homogeneity of the s-SWCNT network deposited from o-xylene with respect to the one from toluene. Finally, the o-xylene inks maintain their initial properties for longer than one year. This very long shelf life is an important pre-condition for the industrial use of s-SWCNT inks.

The recent development of donor–acceptor copolymers has led to an enormous improvement in the performance of organic solar cells and organic field-effect transistors. Here we describe the synthesis, detailed characterisation, and application of a series of structurally modified copolymers to investigate fundamental structure–property relationships in this class of conjugated polymers. The interplay between chemical structure and optoelectronic properties is investigated. These are further correlated to the charge transport and solar cell performance, which allows us to link their chemical structure to the observed physical properties.

Low-bandgap near-infrared polymers are usually synthesized using the common donor-acceptor (D-A) approach. However, recently polymer chemists are introducing more complex chemical concepts for better fine tuning of their optoelectronic properties. Usually these studies are limited to one or two polymer examples in each case study so far, though. In this study, the dependence of optoelectronic and macroscopic (device performance) properties in a series of six new D-A

Five different poly(arylene-diarylvinylene)s have been synthesized by reductive polyolefination starting from the corresponding bis(α,α-dichlorobenzyl)-substituted monomers and dicobaltoctacarbonyl as reducing agent. The resulting polymers all contain main chain tetraphenylethylene units. Thanks to the aggregation-induced emission effect, the corresponding polymer films show remarkably high photoluminescence quantum yields (PLQYs) of 32%-73%. The polymer with the highest PLQY is tested as solid state sensing material for the PL-quenching-based detection of nitroaromatic analytes (1,3,5-trinitrobenzene as prototypical analyte).

This work is part of the TIRAMISU project, funded by the European Commission’s Seventh Framework Programme (FP7/2007-2013) under grant agreement n◦284747 and the Engineering and Physical Sciences Research Council (EPSRC) grants EP/J009016/1 and EP/F059922/1. I.D.W.S. and P.J.S. are Royal Society Wolfson Research Merit Award holders. The density of organic semiconductor films is an important quantity because it is related to intermolecular spacing which in turn determines the electronic and photophysical properties. We report thin film density and refractive index measurements of polyfluorenes and star-shaped oligofluorene truxene molecules. An ellipsometer and a procedure using a spectrophotometer were used to determine film thickness and mass of spin-coated films, respectively. We present a study of the effect of alkyl side-chain length on the volumetric mass density and refractive index of the materials studied. The density measured for poly(9,9-di-n-octylfluorene) (PF8) was 0.88 ± 0.04 g/cm3 and decreased with longer alkyl side chains. For the truxene molecule with butyl side chains (T3 butyl), we measured a density of 0.90 ± 0.04 g/cm3, which also decreased with increasing side-chain length. Postprint

We introduce a new and simple method to quantify the effective extraction mobility in organic solar cells at low electric fields and charge carrier densities comparable to operation conditions under one sun illumination. By comparing steady-state carrier densities at constant illumination intensity and under open-circuit conditions, the gradient of the quasi-Fermi potential driving the current is estimated as a function of external bias and charge density. These properties are then related to the respective steady-state current to determine the effective extraction mobility. The new technique is applied to different derivatives of the well-known low-band-gap polymer PCPDTBT blended with PC70BM. We show that the slower average extraction due to lower mobility accounts for the moderate fill factor when solar cells are fabricated with mono- or difluorinated PCPDTBT. This lower extraction competes with improved generation and reduced nongeminate recombination, rendering the monofluorinated derivative the most efficient donor polymer.

We report on the investigation of the temperature effect on the selective dispersion of single-walled carbon nanotubes (SWNTs) by Poly(3-dodecylthiophene-2,5-diy1) wrapping. The interaction mechanism between polymer chains and SWNTs is studied by controlling the polymer aggregation via variation of the processing temperature. Optical absorption and photoluminescence measurements including time resolved photoluminescence spectroscopy are employed to study the degree of interaction between the polymer in different aggregation states and the carbon nanotubes. At low processing temperatures, results are consistent with the planarization of the polymer chains and with SWNTs working as seeds for polymer aggregation. The formation of small clusters due to the inter-digitation of alkyl tails between neighboring polymer-wrapped SWNTs allows the formation of the SWNT bundles, as experimentally evidenced and investigated by molecular dynamics simulations. The interaction between the tubes within the bundles, which is reflected in the variation of the photoluminescence dynamics of the polymer, can be suppressed by warming up the sample. (C) 2014 Elsevier Ltd. All rights reserved.

Molecular doping of conjugated polymers represents an important strategy for improving organic electronic devices. However, the widely reported low efficiency of doping remains a crucial limitation to obtain high performance. Here we investigate how charge transfer between dopant and donor-acceptor copolymers is affected by the spatial arrangement of the dopant molecule with respect to the copolymer repeat unit. We p-dope a donor-acceptor copolymer and probe its charge-sensitive molecular vibrations in films by infrared spectroscopy. We find that, compared with a related homopolymer, a four times higher dopant/polymer molar ratio is needed to observe signatures of charges. By DFT methods, we simulate the vibrational spectra, moving the dopant along the copolymer backbone and finding that efficient charge transfer occurs only when the dopant is close to the donor moiety. Our results show that the donor-acceptor structure poses an obstacle to efficient doping, with the acceptor moiety being inactive for p-type doping.

Nanostructured composites of inorganic and organic materials are attracting extensive interest for electronic and optoelectronic device applications. Here we report a novel method for the fabrication and patterning of metal selenide nanoparticles in organic semiconductor films that is compatible with solution processable large area device manufacturing. Our approach is based upon the controlled in situ decomposition of a cadmium selenide precursor complex in a film of the electron transporting material 1,3,5-tris(N-phenyl-benzimidazol-2-yl)-benzene (TPBI) by thermal and optical methods. In particular, we show that the photoluminescence quantum yield (PLQY) of the thermally converted CdSe quantum dots (QDs) in the TPBI film is up to 15%. We also show that laser illumination can form the QDs from the precursor. This is an important result as it enables direct laser patterning (DLP) of the QDs. DLP was performed on these nanocomposites using a picosecond laser. Confocal microscopy shows the formation of emissive QDs after laser irradiation. The optical and structural properties of the QDs were also analysed by means of UV-Vis, PL spectroscopy and transmission electron microscopy (TEM). The results show that the QDs are well distributed across the film and their emission can be tuned over a wide range by varying the temperature or irradiated laser power on the blend films. Our findings provide a route to the low cost patterning of hybrid electroluminescent devices. This journal is © The Royal Society of Chemistry.

Photoluminescent cadmium sulphide (CdS) quantum dots (QDs) were successfully obtained by a single-source route via a non-injection one-pot approach using octadecene (ODE) as a non-coordinating solvent and myristic acid (MA) as capping agent. The synthetic scheme makes use of two metal-organic molecules belonging to the xanthate family, cadmium diethyl-xanthate (CdDEX) and cadmium dibutyl-xanthate (CdDBX) single-source precursors. The thermal conversion of both xanthates was explored in the temperature range of 150 °C-180 °C. Following this heat treatment material made from both precursors showed photoluminescence from the direct band gap having a PLQY from 5% (CdDEX) to 13% (CdDBX). The nucleation and growth of CdS nanoparticles in thin solid films was studied by transmission electron microscopy. The surface topography and morphology of the thin films was observed by atomic force microscopy.

We report our investigations of the photophysical properties of a so-called “donor-acceptor” (D-A) electroluminescent polymer incorporating N-alkyl-4,7-di(thien-2-yl)-2,1,3-benzothiadiazole-5,6-dicarboxylic imide (DI) as the electron acceptor and benzo[1,2-b:4,5-b′]dithiophene (BDT) acceptor units. Polymer light-emitting diodes (PLEDs) based on this copolymer give the best efficiency (external quantum efficiency EQE∼0.04%) and show a pure near-infrared (NIR) electroluminescence (EL) with a peak at 870 nm.

Poly(3-alkylthiophenes) are one of the most frequently used conjugated polymer classes in organic photovoltaics. Here, a generalized packing model for the polythiophene main chains in the crystalline form I of high molecular weight regioregular poly(3-alkylthiophenes) with extended side chains (pentyl through octyl) is reported. The model is based on structural constraints from solid-state NMR: short internuclear distances of less than 4.0 A of neighboring thiophene protons parallel to the stacking direction and the isotropic chemical shift for the thiophene protons is high-field shifted by 0.9 ± 0.1 ppm. Nucleus-independent chemical shift calculations show that only the most recent structure for P3HT (space group P21/c) is compatible with these structural constraints. On this basis, a generalized packing model is developed, showing that slipping parallel to the stacked polymer chains of up to 1.5 A is allowed, while out-of-plane tilts perpendicular to the stacked chains are only tolerated up to 20°.

Low-bandgap near-infrared polymers are usually synthesized using the common donor-acceptor (D-A) approach. However, recently polymer chemists are introducing more complex chemical concepts for better fine tuning of their optoelectronic properties. Usually these studies are limited to one or two polymer examples in each case study so far, though. In this study, the dependence of optoelectronic and macroscopic (device performance) properties in a series of six new D-A1 -D-A2 low bandgap semiconducting polymers is reported for the first time. Correlation between the chemical structure of single-component polymer films and their optoelectronic properties has been achieved in terms of absorption maxima, optical bandgap, ionization potential, and electron affinity. Preliminary organic photovoltaic results based on blends of the D-A1 -D-A2 polymers as the electron donor mixed with the fullerene derivative [6,6]-phenyl-C71 -butyric acid methyl ester demonstrate power conversion efficiencies close to 4% with short-circuit current densities (J sc ) of around 11 mA cm-2 , high fill factors up to 0.70, and high open-circuit voltages (V oc s) of 0.70 V. All the devices are fabricated in an inverted architecture with the photoactive layer processed in air with doctor blade technique, showing the compatibility with roll-to-roll large-scale manufacturing processes.

A demonstration of ambipolar transistors of polymer-wrapped single-walled carbon nanotubes (SWNTs) provides an opportunity to scrutinize transport mechanism of electrons and holes in this system. Anomalous temperature-dependent nonlinear transport behavior is observed in large diameter SWNTs. This suggests an interplay between the intrinsic transport of individual tubes and the percolative network properties, highlighting the nature of polymer-wrapped SWNTs as a complex hybrid material.