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31.
Characterisation of charge carrier transport in thin organic semiconductor T layers by time-of-flight photocurrent measurements
Gvido Bratina, Egon Pavlica, 2019, pregledni znanstveni članek

Opis: The paper reviews recent advances in characterisation of charge carrier transport in organic semiconductor layers by time-of-flight photocurrent measurements, with the emphasis on the measurements of the samples with co-planar electrodes. These samples comprised an organic semiconductor layer whose thickness is on the order of a μm or less, and thus mimic the structures of organic thin film transistors. In the review we emphasise the importance of considering spatial variation of electric field in these, essentially two-dimensional structures, in interpretation of photocurrent transients. We review the experimental details of this type of measurements and give examples that demonstrate exceptional sensitivity of the method to minute concentration of electrically active defects in the organic semiconductors as well as the capability of probing charge transport along the channels of different mobility that reside in the same sample.
Ključne besede: organic semiconductors, time of flight, mobiulity
Objavljeno v RUNG: 24.10.2018; Ogledov: 3658; Prenosov: 0
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32.
PHOTO-EXCITATION ENERGY INFLUENCE ON THE PHOTOCONDUCTIVITY OF ORGANIC SEMICONDUCTORS
Nadiia Pastukhova, 2018, doktorska disertacija

Opis: In this work, we experimentally studied the influence of photoexcitation energy influence on the charge transport in organic semiconductors. Organic semiconductors were small molecules like corannulene, perylene and pentacene derivatives, polymers such as polythiophene and benzothiophene derivatives, and graphene, along with combinations of these materials in heterojunctions or composites. The first part of this study is focused on the photoexcitation energy influence on the transient photoconductivity of non-crystalline curved π-conjugated corannulene layers. The enhanced photoconductivity, in the energy range where optical absorption is absent, is deduced from theoretical predictions of corannulene gas-phase excited state spectra. Theoretical analysis reveals a consistent contribution involving transitions to Super Atomic Molecular Orbitals (SAMOs), a unique set of diffuse orbitals typical of curved π-conjugated molecules. More, the photoconductivity of the curved corannulene was compared to the π-conjugated planar N,N′-1H,1H- perfluorobutyldicyanoperylene-carboxydi-imide (PDIF-CN2), where the photoexcitation energy dependence of photocurrent closely follows the optical absorption spectrum. We next characterized charge transport in poly(3-hexylthiophene) (P3HT) layers deposited from solution. Our results indicate that time-of-flight (TOF) mobility depends on the photoexcitation energy. It is 0.4× 10 −3 cm 2 /Vs at 2.3 eV (530 nm) and doubles at 4.8 eV (260 nm). TOF mobility was compared to field-effect (FET) mobility of P3HT field-effect transistors (OFETs). The FET mobility was similar to the 2.3 eV excitation TOF mobility. In order to improve charge mobility, graphene nanoparticles were blended within a P3HT solution before the deposition. We found that the mobility significantly improves upon the addition of graphene nanoparticles of a weight ratio as low as 0.2 %. FET mobility increases with graphene concentration up to a value of 2.3× 10 −2 cm 2 /Vs at 3.2 %. The results demonstrate that phase segregation starts to influence charge transport at graphene concentration of 0.8 % and above. Hence, the graphene cannot form a bridged conduction channel between electrodes, which would cancel the semiconducting effect of the polymer composite. An alternative approach to enhance mobility is to optimize the molecular ordering of organic semiconductors. For that purpose, we studied an innovative nanomesh device. Free-standing nanomesh devices were used to form nanojunctions of N,N′- iiDioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) nanowires and crystalline bis(triisopropylsilylethinyl)pentacene (TIPS-PEN). We characterized the photocurrent response time of this novel nanomesh scaffold device. The photoresponse time depends on the photon energy. It is between 4.5 − 5.6 ns at 500 nm excitation wavelength and between 6.7 − 7.7 ns at 700 nm excitation wavelength. In addition, we found that thermal annealing reduces charge carrier trapping in crystalline nanowires. This confirms that the structural defects are crucial to obtaining high photon-to-charge conversion efficiency and subsequent transport from pn junction in heterostructured materials. Structural defects also influence the power conversion efficiency of organic heterostructured photovoltaics (OPVs). Anticipating that polymers with different backbone lengths produce different level of structural defects, we examined charge transport dependence on the molecular weight of poly[4,8-bis(5-(2- ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2- ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl] (PTB7-Th) from 50 kDa to 300 kDa. We found p-type hopping transport in PTB7-Th, characterized by 0.1 – 3× 10 −2 cm 2 /Vs mobility, which increases with temperature and electric field. The polymer molecular weight exhibits a non-trivial influence on charge transport. FET mobility in the saturation regime increases with molecular weight. A similar trend is observed in TOF mobility and FET mobility in the linear regime, except for the 100kDa polymer, which manifests in the highest mobility due to reduced charge trapping. The lowest trapping at the dielectric interface of OFET is observed at 200 kDa. In addition, the 200 kDa polymer exhibits the lowest activation energy of the charge transport. Although the 100 kDa polymer indicates the highest mobility, OPVs using the 200 kDa polymer exhibit the best performance in terms of power conversion efficiency.
Ključne besede: organic semiconductors, optical absorption spectroscopy, time-of-flight photoconductivity, transient photocurrent spectroscopy, organic thin film transistors, atomic force microscopy, superatomic molecular orbitals, pn heterojunction, organic nanowires, graphene, composites, charge mobility, charge trapping, temperature dependence, photodetector, photovoltaic, solar cell, organic electronics
Objavljeno v RUNG: 08.10.2018; Ogledov: 5389; Prenosov: 163
.pdf Celotno besedilo (4,56 MB)

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The effect of polymer molecular weight on the performance of PTB7-Th:O-IDTBR non-fullerene organic solar cells
Sebastian F. Hoefler, Egon Pavlica, Gvido Bratina, 2018, izvirni znanstveni članek

Opis: Recent advances in the development of non-fullerene acceptors have increased the power conversion efficiency of organic solar cells to approximately 13%. Fullerene-derivatives and non-fullerene acceptors possess distinctively different structural, optical and electronic properties, which also change the requirements on the polymer donor in non-fullerene organic solar cells. Therefore, in this study, the effect of the molecular weight of the conjugated polymer on the photovoltaic performance, charge carrier mobility, crystallization properties, film morphology, and non-geminate recombination dynamics is systematically investigated in polymer:small molecule organic solar cells using the low bandgap polymer PTB7-Th as the donor and the non-fullerene indacenodithiophene-based small molecule O-IDTBR as the acceptor. Among the examined polymer samples (50–300 kDa), high molecular weights of PTB7-Th (with an optimum molecular weight of 200 kDa) are advantageous to achieve high efficiencies up to 10%, which can be correlated with an increased crystallinity, an improved field-effect hole mobility (1.05 × 10−2 cm2 V−1 s−1), lower charge carrier trapping and a reduced activation energy of charge transport (98 meV). Bias-assisted charge extraction and transient photovoltage measurements reveal higher carrier concentrations (1016 cm−3) and long lifetimes (4.5 μs) as well as lower non-geminate recombination rate constants in the corresponding devices, supporting the high photocurrents (ca. 15.2 mA cm−2) and fill factors (>60%).
Ključne besede: organski polprevodniki, gibljivost, organske sončne celice
Objavljeno v RUNG: 28.05.2018; Ogledov: 4326; Prenosov: 0
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35.
Self-Suspended Nanomesh Scaffold for Ultrafast Flexible Photodetectors Based on Organic Semiconducting Crystals
Gvido Bratina, Egon Pavlica, 2018, izvirni znanstveni članek

Opis: Self-standing nanostructures are of fundamental interest in materials sci- ence and nanoscience and are widely used in (opto-)electronic and photonic devices as well as in micro-electromechanical systems. To date, large-area and self-standing nanoelectrode arrays assembled on flexible substrates have not been reported. Here the fabrication of a hollow nanomesh scaffold on glass and plastic substrates with a large surface area over 1 mm2 and ultralow leakage current density (≈1–10 pA mm−2 @ 2 V) across the empty scaffold is demonstrated. Thanks to the continuous sub-micrometer space formed in between the nanomesh and the bottom electrode, highly crystalline and dendritic domains of 6,13-bis(triisopropylsilylethinyl)pentacene growing within the hollow cavity can be observed. The high degree of order at the supramolecular level leads to efficient charge and exciton transport; the pho- tovoltaic detector supported on flexible polyethylene terephthalate substrates exhibits an ultrafast photoresponse time as short as 8 ns and a signal-to- noise ratio approaching 105. Such a hollow scaffold holds great potential as a novel device architecture toward flexible (opto-)electronic applications based on self-assembled micro/nanocrystals.
Ključne besede: nanostrukture, organski polprevodniki, fotonapetostne komponente
Objavljeno v RUNG: 22.05.2018; Ogledov: 3552; Prenosov: 0
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36.
Negative field‐dependent charge mobility in crystalline organic semiconductors with delocalized transport
Fei Tong, Andrey Kadashchuk, Egon Pavlica, Gvido Bratina, 2018, izvirni znanstveni članek

Opis: Charge-carrier mobility has been investigated by time-of-flight (TOF) transient photocurrent in a lateral transport con- figuration in highly crystalline thin films of 2,7-dioctyl[1]benzothieno [3,2-b][1] benzothiophene (C8-BTBT) grown by a zone-casting alignment technique. High TOF mobility has been revealed that it is consistent with the delocalized nature of the charge transport in this material, yet it featured a positive temperature dependence at T ≥ 295 K. Moreover, the mobility was surprisingly found to decrease with electric field in the high-temperature region. These observations are not compat- ible with the conventional band-transport mechanism. We have elaborated an analytic model based on effective-medium approximation to rationalize the puzzling findings. The model considers the delocalized charge transport within the energy landscape formed by long-range transport band-edge variations in imperfect organic crystalline materials and accounts for the field-dependent effective dimensionality of charge transport percolative paths. The results of the model calculations are found to be in good agreement with experimental data.
Ključne besede: time of flight, organic semiconductors, single crystals
Objavljeno v RUNG: 07.05.2018; Ogledov: 5222; Prenosov: 0
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