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41.
Photothermal lens technique: a comparison between conventional and self-mixing schemes
Humberto 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, izvirni znanstveni članek

Opis: 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.
Ključne besede: thermal lens, photothermal spectroscopy, self-mixing effect, trace detection
Objavljeno v RUNG: 05.04.2019; Ogledov: 3590; Prenosov: 0
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42.
Determination of Dissolved Iron Redox Species in Freshwater Sediment using DGT Technique Coupled to BDS
Hanna Budasheva, Aleksander Kravos, Dorota Korte, Arne Bratkič, Yue Gao, Mladen Franko, 2019, izvirni znanstveni članek

Opis: 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.
Ključne besede: Beam deflection spectroscopy, diffusive gradients in thin-film technique, iron redox species, photothermal techniques, sediment
Objavljeno v RUNG: 26.02.2019; Ogledov: 3887; Prenosov: 114
.pdf Celotno besedilo (452,58 KB)

43.
First principles vibrational spectra of tetrahedrally-bonded glasses: sio2, geo2 and gese2
Luigi Giacomazzi, 2007, doktorska disertacija

Ključne besede: Silica, Germania, Chalcogenide Glasses, Vibrational Spectra, Raman Spectroscopy, Infrared, First-principles
Objavljeno v RUNG: 31.01.2019; Ogledov: 4418; Prenosov: 0
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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: 5727; Prenosov: 166
.pdf Celotno besedilo (4,56 MB)

49.
Amorphous nanocomposite of polycarbosilanes and aluminum oxide
Andraž Mavrič, 2018, doktorska disertacija

Opis: 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.
Ključne besede: 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
Objavljeno v RUNG: 19.07.2018; Ogledov: 6397; Prenosov: 218
.pdf Celotno besedilo (5,07 MB)

50.
Determination of iron species in Arctic water by optimized photothermal beam deflection spectroscopy
Hanna Budasheva, Dorota Korte, Arne Bratkič, Mladen Franko, 2018, objavljeni povzetek znanstvenega prispevka na konferenci

Ključne besede: phototermal beam deflection spectroscopy, arctic water, iron species
Objavljeno v RUNG: 16.07.2018; Ogledov: 4379; Prenosov: 0
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