41. Photothermal lens technique: a comparison between conventional and self-mixing schemesHumberto Cabrera, Imrana Ashraf, Fatima Matroodi, Evelio E. Ramírez-Miquet, Jehan Akbar, Jose Juan Suárez-Vargas, John Fredy Barrera Ramírez, Dorota Korte, Hanna Budasheva, Joseph J. Niemela, 2019, original scientific article Abstract: This work focuses on assessing the analytical capabilities of a new photothermal lens method based on the self-mixing effect to reliably measure metallic traces in water-ethanol solutions. We compare it with the conventional thermal lens scheme, considering the low detection limit and versatility. A theoretical model is presented to describe the laser power variations as a function of the photothermal parameters of the analyzed sample. The experimental results demonstrate that the laser intensity variations, induced by the external optical feedback, are governed by
the photothermal lens effect. Measurements of Fe(II)-1,10-phenanthroline in water–ethanol solutions show a favourable correspondence and agreement with the theory. The low detection limits obtained by the two analytic techniques also agree very well. Nevertheless, our instrument presents advantages regarding compactness and simplicity, suggesting that this platform could be potentially useful as a robust analytical tool for metallic trace detection. In addition, calibration of the method is performed by measuring the so-called self-mixing constant. Keywords: thermal lens, photothermal spectroscopy, self-mixing effect, trace detection Published in RUNG: 05.04.2019; Views: 3292; Downloads: 0 This document has many files! More... |
42. Determination of Dissolved Iron Redox Species in Freshwater Sediment using DGT Technique Coupled to BDSHanna Budasheva, Aleksander Kravos, Dorota Korte, Arne Bratkič, Yue Gao, Mladen Franko, 2019, original scientific article Abstract: In this work we have developed a novel method for determination of iron redox species by the use of diffusive gradients in thin-film (DGT) technique coupled to photothermal beam deflection spectroscopy (BDS). The combination of both methods achieved low limit of detection (LOD) of 0.14 μM for Fe (II) ions. The total Fe concentration determined in the Vrtojbica river sediment (Slovenia, Rožna Dolina, 5000 Nova Gorica) was 49.3 μgL–1. The Fe (II) and Fe (III) concentra- tion amounted to 12.8 μgL–1 and 39.9 μgL–1, respectively. Such an approach opens new opportunities for monitoring the content of iron species in natural waters and sediments and provides highly sensitive chemical analysis and an accurate qualitative and quantitative characteristic of the materials under study. Keywords: Beam deflection spectroscopy, diffusive gradients in thin-film technique, iron redox species, photothermal techniques, sediment Published in RUNG: 26.02.2019; Views: 3610; Downloads: 114 Full text (452,58 KB) |
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44. Growth, morphology and stability of Au in contact with the Bi[sub]2Se[sub]3(0 0 0 1) surfaceMattia Fanetti, Iuliia Mikulska, Katja Ferfolja, Paolo Moras, Polina M. Sheverdyaeva, M. Panighel, A. Lodi-Rizzini, I. Píš, S. Nappini, Matjaž Valant, Sandra Gardonio, 2018, original scientific article Keywords: metal contact, topological insulator contact, growth mode, electronic properties, chemical properties, photoemission spectroscopy, microscopy Published in RUNG: 05.12.2018; Views: 3580; Downloads: 0 This document has many files! More... |
45. Optimization of DGT technique for determination of iron species in natural water and sediments by photothermal beam deflection spectroscopyHanna Budasheva, Arne Bratkič, Dorota Korte, Mladen Franko, 2018, published scientific conference contribution abstract Keywords: beam deflection spectroscopy, diffusive gradients in thin-film technique, iron redox species, photothermal techniques, natural water, sediments Published in RUNG: 23.11.2018; Views: 3695; Downloads: 0 This document has many files! More... |
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47. Photocatalytic properties of metal modified TiO2 by photothermal techniquesZeinab Ebrahimpour, Olena Pliekhova, Humberto Cabrera, Dorota Korte, Urška Lavrenčič Štangar, Mladen Franko, 2018, published scientific conference contribution abstract Keywords: Thermal lens spectrometry, Photothermal beam deflection spectroscopy, Dye remediation, Photothermal technique, Photocatalytic degradation, Reactive Blue 19, TiO2 modification Published in RUNG: 09.11.2018; Views: 3583; Downloads: 0 This document has many files! More... |
48. PHOTO-EXCITATION ENERGY INFLUENCE ON THE PHOTOCONDUCTIVITY OF ORGANIC SEMICONDUCTORSNadiia Pastukhova, 2018, doctoral dissertation Abstract: 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. Keywords: 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 Published in RUNG: 08.10.2018; Views: 5377; Downloads: 163 Full text (4,56 MB) |
49. Amorphous nanocomposite of polycarbosilanes and aluminum oxideAndraž Mavrič, 2018, doctoral dissertation Abstract: This work presents a paradigm for high temperature stabilization of bulk amorphous aluminium oxide. The thermodynamic stabilization is achieved by preparing a nanocomposite, where polymethylsilane dendritic molecules are dispersed in an aluminium hydroxide gel. Upon heat-treatment the gel transforms to the amorphous aluminium oxide that is stable up to 900°C. The dispersion of the macromolecules and their covalent bonding to the alumina matrix induce homogeneously distributed strain fields that keep the alumina amorphous.
The first part of the thesis focuses on the synthesis, characterization and solubility properties of the dendritic polymethylsilane. The polymethylsilane is synthetized by electrochemical polymerization from trichloromethylsilane monomer. The polymerization mechanism, involving a single polymerization pathway, is identified. The polymer growth proceeds through reduction of the monomers to the silyl anions and their addition to the growing polymer.
The solubility of three chemically related but topologically different polysilanes (linear, dendritic and network) were studied by dynamic light scattering. At room temperature the agglomerates in a range from 500 to 1300 nm are present. They undergo de-agglomeration at slightly elevated temperatures of around 40°C. The de-agglomeration results in formation of stable solutions, where a hydrodynamic diameter of the individual polymer molecules was measured to be in a range from 20 to 40 nm.
The obtained diameters of two dendritic polymethylsilane macromolecules, synthesized under different electrolysis conditions, are much larger than the theoretical size estimated for an ideal dendrimer. We determined by 29Si NMR that the reason for this is in a large number of branching irregularities (defects) contained in the molecular structure. Combining the experimental values obtained by DLS and density measurements with a structural model that considers the branching irregularities, it is shown that the inclusion of the defects allows the dendritic polymer to exceed the sterical limitations and form the hyperbranched dendritic structure. The final size depends on a relative amount of the branching defects.
In the second part, the synthetized polymethylsilane molecules were successfully used for the nanocomposite formation. The aluminium hydroxide gel with the dispersed polymethylsilane molecules was prepared as a precursor. Upon heat-treatment it gives the amorphous aluminium oxide stable up to 900°C. The dispersed macromolecules induce homogeneously distributed strain fields that keep the aluminium oxide amorphous during the thermal treatment the dispersed macromolecules covalently bind to the matrix, inducing the interface strain. The amorphous state was confirmed by the presence of penta-coordinated aluminium detected by 27Al NMR and a low bandgap measured by UV-vis absorption spectroscopy. Keywords: amorphous aluminium oxide, polymethylsilane, nanocomposite, electropolymerization, solubility, agglomeration, de-agglomeration, dendrimer, hyperbranched dendritic structure, dynamic light scattering, thermal analysis, transmission electron microscopy, scanning electron microscopy, X-ray diffraction, infrared spectroscopy, UV-Vis spectroscopy Published in RUNG: 19.07.2018; Views: 6009; Downloads: 210 Full text (5,07 MB) |
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