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11.
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: 7332; Prenosov: 173
.pdf Celotno besedilo (4,56 MB)

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Design of a highly photocatalytically active ZnO/CuWO4 nanocomposite
Saim Emin, Matjaž Valant, 2017, objavljeni povzetek znanstvenega prispevka na konferenci (vabljeno predavanje)

Opis: We report the synthesis, photocatalytic activity and mechanistic study of a novel heterostructure (HTS) with an efficient charge separation. A ZnO/CuWO4 HTS material is reported for the first time. The nanocomposite (NC) consists of CuWO4 nanoparticles (ca. 200-400 nm) decorated with ZnO nanorods (ca. 30 nm, 100 nm length) and is shown to be a highly active photocatalyst for decomposition of model contaminants including methyl orange and terephthalic acid. The ZnO/CuWO4 interface is shown to be the key for controlling the enhanced activity of the composite material. Transient absorption spectroscopy studies demonstrated that a photoinduced charge transfer across the ZnO/CuWO4 interface increased electron-hole lifetime by 3 orders of magnitude, from < 20 s in ZnO to 30 ms in the ZnO/CuWO4 NC sample. Our findings show that through interface design efficient HTS materials can be prepared for a wide range of photocatalytic applications.
Ključne besede: CuWO4, nanocomposite, transient absorption spectroscopy
Objavljeno v RUNG: 28.08.2017; Ogledov: 6540; Prenosov: 0
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15.
Operando characterization of batteries using x-ray absorption spectroscopy: advances at the beamline XAFS at synchrotron Elettra
Giuliana Aquilanti, marco Giorgetti, Robert Dominko, Lorenzo Stievano, Iztok Arčon, Nicola Novello, Luca Ivanc Olivieri, 2017, izvirni znanstveni članek

Opis: X-ray absorption spectroscopy is a synchrotron radiation based technique that is able to provide information on both local structure and electronic properties in a chemically selective manner. It can be used to characterize the dynamic processes that govern the electrochemical energy storage in batteries, and to shed light on the redox chemistry and changes in structure during galvanostatic cycling to design cathode materials with improved properties. Operando XAS studies have been performed at beamline XAFS at Elettra on different systems. For Li-ion batteries, a multiedge approach revealed the role of the different cathode components during the charge and discharge of the battery. In addition, Li-S batteries for automotive applications were studied. Operando sulfur K-edge XANES and EXAFS analysis was used to characterize the redox chemistry of sulfur, and to relate the electrochemical mechanism to its local structure.
Ključne besede: operando studies, x-ray absorption spectroscopy, Li-ion batteries, Li-S batteries
Objavljeno v RUNG: 03.03.2017; Ogledov: 7458; Prenosov: 0
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16.
Photocatalytic Activity of Zirconium- and Manganese- Codoped Titania in Aqueous Media: The Role of the Metal Dopant and its Incorporation Site
O. L. Pliekhov, Iztok Arčon, Nataša Novak Tušar, Urška Lavrenčič Štangar, 2016, izvirni znanstveni članek

Opis: The development of efficient TiO2-based photocatalysts for water treatment is mainly performed by doping with transition metals or by establishing junctions between different phases, metal–semiconductor or semiconductor–semiconductor. We present, for the first time, the synthesis of Zr- and Mn-modified TiO2 by a redesigned sol–gel technique that allows the formation of heterometallic bridges on the TiO2 surface. Cations of the doping metals are located in the pores of mesoporous anatase and attached to the crystalline TiO2 walls. The presence of the Zr enhances the photoactivity of the TiO2 catalyst. However, the introduction of Mn decreases the photocatalytic efficiency in a nonadditive manner. The inhibition effect was assigned to the side reaction between hydroxyl radicals and Mn ions. The fact that Mn effectively scavenges the hydroxyl radicals and, consequently, inhibits the whole oxidation process is direct proof that hydroxyl radicals are the main reactive species in the photocatalytic oxidative processes on TiO2 surfaces in aqueous media and the process of COH generation is the rate-determining step, which was confirmed using a method based on the decolorization of a commercial dye Bezaktiv Blau in a reaction with Fenton’s reagent as a source of hydroxyl radicals.
Ključne besede: doping, manganese, oxidation, X-ray absorption spectroscopy, zirconium
Objavljeno v RUNG: 21.07.2016; Ogledov: 5283; Prenosov: 0
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17.
Operando (micro) XAFS analysis
Iztok Arčon, Robert Dominko, Katarina Vogel-Mikuš, 2016, objavljeni povzetek znanstvenega prispevka na konferenci (vabljeno predavanje)

Opis: In the talk the principles of XAS methods were presented with practical examples which illustrate the possibilities and advanced approaches for their use in structural analysis of different types of materials. The emphasis will be on to the use of XAS spectroscopy in operando mode and in combination with X-ray microscopy.
Ključne besede: X-ray absorption spectroscopy, X-ray microscopy, EXAFS, XANES, opearndo mode
Objavljeno v RUNG: 25.03.2016; Ogledov: 8867; Prenosov: 168
.pdf Celotno besedilo (18,40 MB)

18.
Chemical and structural investigation of the cobalt phthalocyanine
Matija Stupar, 2015, magistrsko delo

Opis: In the last two decades, studies on organic molecules mimicking substances of fundamental importance in nature, like chlorophyll or hemoglobin, have attracted researchers’ attention. These molecules are building blocks for a family of materials also referred to as “organic semiconductors”. Such compounds can be implemented in numerous applications, ranging from data-storage to light harvesting. Some of their fundamental advantages include low cost, light weight, relatively easy engineering and mechanical flexibility, compatible with bending plastic substrates. In this thesis work we investigated the chemical, structural and electronic properties of cobalt phthalocyanines (CoPc). These molecules have promising applications in the field of magnetic data storage and spintronics in general, due to the ferromagnetic properties of the cobalt atom. Several techniques like photoemission core-level spectroscopy and valence band spectroscopy, together with X-ray absorption, have been used in order to determine the CoPc properties in gaseous phase, i.e. in the absence of interaction with the surrounding environment. Another set of experiments was devoted to the commissioning of the CITIUS time-resolved photoemission setup, that will be used in future studies of CoPc molecules on surfaces.
Ključne besede: Cobalt phthalocyanine (CoPc), photoemission spectroscopy (PES), X-ray absorption spectroscopy (XAS), synchrotron radiation, laser, high order harmonic generation (HHG), time resolved spectroscopy
Objavljeno v RUNG: 29.09.2015; Ogledov: 10366; Prenosov: 286
.pdf Celotno besedilo (2,96 MB)

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