Molecular Weight Tuning of Organic Semiconductors for Curved Organic-Inorganic Hybrid X-Ray Detectors

Curved X-ray detectors have the potential to revolutionize diverse sectors due to benefits such as reduced image distortion and vignetting compared to their planar counterparts. While the use of inorganic semiconductors for curved detectors are restricted by their brittle nature, organic-inorganic hybrid semiconductors which incorporated bismuth oxide nanoparticles in an organic bulk heterojunction consisting of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl C71 butyric acid methyl ester (PC70BM) are considered to be more promising in this regard. However, the influence of the P3HT molecular weight on the mechanical stability of curved, thick X-ray detectors remains less well understood. Herein, high P3HT molecular weights (>40 kDa) are identified to allow increased intermolecular bonding and chain entanglements, resulting in X-ray detectors that can be curved to a radius as low as 1.3 mm with low deviation in X-ray response under 100 repeated bending cycles while maintaining an industry-standard dark current of mu C Gy(-1) cm(-2). This study identifies a crucial missing link in the development of curved detectors, namely the importance of the molecular weight of the polymer semiconductors used

Tissue Equivalent Curved Organic X-ray Detectors Utilizing High Atomic Number Polythiophene Analogues

Organic semiconductors are a promising material candidate for X-ray detection. However, the low atomic number (Z) of organic semiconductors leads to poor X-ray absorption thus restricting their performance. Herein, the authors propose a new strategy for achieving high-sensitivity performance for X-ray detectors based on organic semiconductors modified with high –Z heteroatoms. X-ray detectors are fabricated with p-type organic semiconductors containing selenium heteroatoms (poly(3-hexyl)selenophene (P3HSe)) in blends with an n-type fullerene derivative ([6,6]-Phenyl C71 butyric acid methyl ester (PC70BM). When characterized under 70, 100, 150, and 220 kVp X-ray radiation, these heteroatom-containing detectors displayed a superior performance in terms of sensitivity up to 600 ± 11 nC Gy−1 cm−2 with respect to the bismuth oxide (Bi2O3) nanoparticle (NP) sensitized organic detectors. Despite the lower Z of selenium compared to the NPs typically used, the authors identify a more efficient generation of electron-hole pairs, better charge transfer, and charge transport characteristics in heteroatom-incorporated detectors that result in this breakthrough detector performance. The authors also demonstrate flexible X-ray detectors that can be curved to a radius as low as 2 mm with low deviation in X-ray response under 100 repeated bending cycles while maintaining an industry-standard ultra-low dark current of 0.03 ± 0.01 pA mm−2

Singlet Fission in Pechmann Dyes: Planar Chromophore Design and Understanding.

Singlet fission in organic chromophores holds the potential for enhancing photovoltaic efficiencies beyond the single-junction limit. The most basic requirement of a singlet fission material is that it has a large energy gap between its first singlet and triplet excited states. Identifying such compounds is not simple and has been accomplished either through computational screening or by subtle modifications of previously known fission materials. Here, we propose an approach that leverages ground and excited-state aromaticity combined with double-bond conformation to establish simple qualitative design rules for predicting fundamental optical properties without the need for computational modeling. By investigating two Pechmann dye isomers, we demonstrate that although their planarity and degree of charge transfer are similar, singlet fission is active in the isomer with a trans-conformation, while the cis-isomer exhibits greater favorability for polaronic processes, experimentally validated using ultrafast and electron spin resonance spectroscopy. Our results offer a new design perspective that provides a rational framework for tailoring optoelectronic systems to specific applications such as singlet fission or triplet-triplet annihilation

Mixed Small-Molecule Matrices Improve Nanoparticle Dispersibility in Organic Semiconductor-Nanoparticle Films.

Controlling the dispersibility of nanocrystalline inorganic quantum dots (QDs) within organic semiconductor (OSC):QD nanocomposite films is critical for a wide range of optoelectronic devices. This work demonstrates how small changes to the OSC host molecule can have a dramatic detrimental effect on QD dispersibility within the host organic semiconductor matrix as quantified by grazing incidence X-ray scattering. It is commonplace to modify QD surface chemistry to enhance QD dispersibility within an OSC host. Here, an alternative route toward optimizing QD dispersibilities is demonstrated, which dramatically improves QD dispersibilities through blending two different OSCs to form a fully mixed OSC matrix phase

Understanding local and macroscopic electron mobilities in the fullerene network of conjugated polymer-based solar cells : time-resolved microwave conductivity and theory

The efficiency of bulk heterojunction (BHJ) organic photovoltaics is sensitive to the morphology of the fullerene network that transports electrons through the device. This sensitivity makes it difficult to distinguish the contrasting roles of local electron mobility (how easily electrons can transfer between neighboring fullerene molecules) and macroscopic electron mobility (how well-connected is the fullerene network on device length scales) in solar cell performance. In this work, a combination of density functional theory (DFT) calculations, flash-photolysis time-resolved microwave conductivity (TRMC) experiments, and space-charge-limit current (SCLC) mobility estimates are used to examine the roles of local and macroscopic electron mobility in conjugated polymer/fullerene BHJ photovoltaics. The local mobility of different pentaaryl fullerene derivatives (so-called ‘shuttlecock’ molecules) is similar, so that differences in solar cell efficiency and SCLC mobilities result directly from the different propensities of these molecules to self-assemble on macroscopic length scales. These experiments and calculations also demonstrate that the local mobility of phenyl-C₆₀ butyl methyl ester (PCBM) is an order of magnitude higher than that of other fullerene derivatives, explaining why PCBM has been the acceptor of choice for conjugated polymer BHJ devices even though it does not form an optimal macroscopic network. The DFT calculations indicate that PCBM's superior local mobility comes from the near-spherical nature of its molecular orbitals, which allow strong electronic coupling between adjacent molecules. In combination, DFT and TRMC techniques provide a tool for screening new fullerene derivatives for good local mobility when designing new molecules that can improve on the macroscopic electron mobility offered by PCBM.9 page(s

Structure and conductivity of semiconducting polymer hydrogels

Poly(fluorene-alt-thiophene) (PFT) is a conjugated polyelectrolyte that self-assembles into rod-like micelles in water, with the conjugated polymer backbone running along the length of the micelle. At modest concentrations (∼10 mg/mL in aqueous solutions), PFT forms hydrogels, and this work focuses on understanding the structure and intermolecular interactions in those gel networks. The network structure can be directly visualized using cryo electron microscopy. Oscillatory rheology studies further tell us about connectivity within the gel network, and the data are consistent with a picture where polymer chains bridge between micelles to hold the network together. Addition of tetrahydrofuran (THF) to the gels breaks those connections, but once the THF is removed, the gel becomes stronger than it was before, presumably due to the creation of a more interconnected nanoscale architecture. Small polymer oligomers can also passivate the bridging polymer chains, breaking connections between micelles and dramatically weakening the hydrogel network. Fits to solution-phase small-angle X-ray scattering data using a Dammin bead model support the hypothesis of a bridging connection between PFT micelles, even in dilute aqueous solutions. Finally, time-resolved microwave conductivity measurements on dried samples show an increase in carrier mobility after THF annealing of the PFT gel, likely due to increased connectivity within the polymer network.10 page(s

Polariton condensation in an organic microcavity utilising a hybrid metal-DBR mirror

We have developed a simplified approach to fabricate high-reflectivity mirrors suitable for applications in a strongly-coupled organic-semiconductor microcavity. Such mirrors are based on a small number of quarter-wave dielectric pairs deposited on top of a thick silver film that combine high reflectivity and broad reflectivity bandwidth. Using this approach, we construct a microcavity containing the molecular dye BODIPY-Br in which the bottom cavity mirror is composed of a silver layer coated by a SiO2 and a Nb2O5 film, and show that this cavity undergoes polariton condensation at a similar threshold to that of a control cavity whose bottom mirror consists of ten quarter-wave dielectric pairs. We observe, however, that the roughness of the hybrid mirror—caused by limited adhesion between the silver and the dielectric pair—apparently prevents complete collapse of the population to the ground polariton state above the condensation threshold

Long-lived photoinduced polaron formation in conjugated polyelectrolyte-fullerene assemblies

The efficiency of biological photosynthesis results from the exquisite organization of photoactive elements that promote rapid movement of charge carriers out of a critical recombination range. If synthetic organic photovoltaic materials could mimic this assembly, charge separation and collection could be markedly enhanced. We show that micelle-forming cationic semiconducting polymers can coassemble in water with cationic fullerene derivatives to create photoinduced electron-transfer cascades that lead to exceptionally long-lived polarons. The stability of the polarons depends on the organization of the polymer-fullerene assembly. Properly designed assemblies can produce separated polaronic charges that are stable for days or weeks in aqueous solution

Exploring Nanoscale Structure in Perovskite Precursor Solutions Using Neutron and Light Scattering

Tailoring the solution chemistry of metal halide perovskites requires a detailed understanding of precursor aggregation and coordination. In this work, we use various scattering techniques, including dynamic light scattering (DLS), small angle neutron scattering (SANS), and spin-echo SANS (SESANS) to probe the nanostructures from 1 nm to 10 μm within two different lead-halide perovskite solution inks (MAPbI 3and a triple-cation mixed-halide perovskite). We find that DLS can misrepresent the size distribution of the colloidal dispersion and use SANS/SESANS to confirm that these perovskite solutions are mostly comprised of 1-2 nm-sized particles. We further conclude that if there are larger colloids present, their concentration must be <0.005% of the total dispersion volume. With SANS, we apply a simple fitting model for two component microemulsions (Teubner-Strey), demonstrating this as a potential method to investigate the structure, chemical composition, and colloidal stability of perovskite solutions, and we here show that MAPbI 3solutions age more drastically than triple cation solutions. RST/Technici PoolInstrumenten groe

Autonominen videokuvan siirtoon soveltuva tietoverkkoratkaisu viranomaisajoneuvoihin

Työn tavoitteena oli luoda tutkielma, jossa huomioidaan olosuhteita ja tilanteita, joita voi tulla eteen videokuvan siirrossa kenttäolosuhteissa. Kenttäolosuhteissa toimittaessa on yhteyksien toimivuusvarmuuteen kiinnitettävä erityistä huomiota. Toimivista tietoliikenneyhteyksistä saattaa olla kiinni ihmishenkien tai materiaalien pelastuminen. Insinöörityössä tutkittiin eri kuvansiirtotapoja viranomaisajoneuvojen välillä. Työssä tutkittiin neljää erilaista tiedonsiirtotapaa, kahta kaapelitoteutusta ja kahta langatonta versiota. Tutkimus oli luonteeltaan teoreettinen, lukuun ottamatta WLAN mittauksia. Työssä pohditaan pääsääntöisesti erinäisiä ratkaisuja ja toteutustapoja. Langattoman lähiverkon (WLAN) toimivuus kenttäolosuhteissa on sidoksissa moneen käyttäjästä riippumattomaan asiaan kuten säähän, rakenteisiin ja maaston muotoihin. Tästä syystä langatonta lähiverkkoa ei voida pitää ensisijaisena tiedonsiirtomuotona. Tätä asiaa tukivat myös suoritetut mittaukset. WLAN:ia voidaan kuitenkin käyttää muodostettaessa verkko ajoneuvon lähietäisyydelle esimerkiksi kameraa tai tietokonetta varten. Työssä tutkittiin kotimaisen Ajeco Oy:n 4Com -monikanavareitittimen ominaisuuksia ja todettiin sen soveltuvan hyvin viranomaisajoneuvon kuvansiirron runkolaitteeksi. Johtopäätöksenä voidaan todeta, että kaapeliyhteydet ovat tiedonsiirto-ominaisuuksiltaan varmempia kuin langattomat vaihtoehdot. Kaapeliyhteyksien käyttökuntoon saattaminen on kuitenkin hitaampaa. Mahdollisissa jatkotutkimuksissa olisi huomioitava pidemmän matkan langattomien tiedonsiirtotapojen, kuten esimerkiksi WIMAXin, käyttömahdollisuuksia.This thesis aims to describe the effects of field operations on video transmission. Under field conditions, the functionality of data communications requires special attention. Problems in data connections may lead to material losses and in the worst case prevent saving human lives. The thesis examines different methods of transferring image between two vehicles. In detail, four different data transmission methods are compared; two cable implementations and two wireless versions. Problems and challenges are approached from a theoretical aspect. Specific implementation solutions are compared and their strengths and weaknesses are demonstrated. There are numerous different aspects that affect wireless LAN (WLAN) performance in field conditions. These aspects include the weather, infrastructure and terrain. For this reason, a wireless LAN cannot be considered as the primary option for video transmission. These concerns were proven justified via attenuation measurements of the WLAN signal. Nevertheless, WLAN may be used in forming a close range network around the vehicle, for example to connect cameras, computers and PDAs. For longer range video transfer it could be determined that a domestic Ajeco Ltd 4Com multi-channel router is an adequate device. It can be concluded that in order to provide stable, reliable and secure data transfer between vehicles, it is necessary to use wired connections. Wired connections are slower to setup than wireless connections, but wired connections are clearly a better choice due to the numerous challenges that are encountered with wireless connections. For future research it would be worthwile to study the possibilities of long-distance wireless communication methods such as Wi-MAX