11. PHOTO-EXCITATION ENERGY INFLUENCE ON THE PHOTOCONDUCTIVITY OF ORGANIC SEMICONDUCTORSNadiia 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
Celotno besedilo (4,56 MB) |
12. Giant magneto–electric coupling in 100 nm thick Co capped by ZnO nanorodsGiovanni Vinai, Barbara Ressel, Piero Torelli, Federico Loi, Benoit Gobaut, Regina Ciancio, Barbara Casarin, Antonio Caretta, Luca Capasso, Fulvio Parmigiani, Francesco Cugini, Massimo Solzi, Marco Malvestuto, Roberta Ciprian, 2018, izvirni znanstveni članek Ključne besede: ZnO nanorods, Cobalt, X-rays absorption near edge spectroscopy Objavljeno v RUNG: 07.02.2018; Ogledov: 5117; Prenosov: 0 Gradivo ima več datotek! Več... |
13. New strategy for magnetic gas sensingRoberta Ciprian, Piero Torelli, Angelo Giglia, B Gobaut, Barbara Ressel, Janez Štupar, Matija Stupar, Antonio Caretta, Giovanni De Ninno, Tommaso Pincelli, Barbara Casarin, Ganesh Adhikari, G Sberviglieri, C Baratto, Marco Malvestuto, 2016, izvirni znanstveni članek Ključne besede: hybrid nanostructures, sensor, absorption spectroscopy Objavljeno v RUNG: 05.02.2018; Ogledov: 5215; Prenosov: 0 Gradivo ima več datotek! Več... |
14. Design of a highly photocatalytically active ZnO/CuWO4 nanocompositeSaim 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 Gradivo ima več datotek! Več... |
15. Operando characterization of batteries using x-ray absorption spectroscopy: advances at the beamline XAFS at synchrotron ElettraGiuliana 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 Gradivo ima več datotek! Več... |
16. Photocatalytic Activity of Zirconium- and Manganese- Codoped Titania in Aqueous Media: The Role of the Metal Dopant and its Incorporation SiteO. 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 Gradivo ima več datotek! Več... |
17. |
18. Chemical and structural investigation of the cobalt phthalocyanineMatija 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
Celotno besedilo (2,96 MB) |