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Time-of-flight photoconductivity investigation of high charge carrier mobility in ▫$Ti_3C_2T_x$▫ MXenes thin-film
Jurij Urbančič, Erika Tomsic, Manisha Chhikara, Nadiia Pastukhova, Vadym Tkachuk, Alex Dixon, Andraž Mavrič, Payam Hashemi, Davood Sabaghi, Ali Shaygan Nia, Gvido Bratina, Egon Pavlica, 2023, izvirni znanstveni članek

Opis: Charge transport through a randomly oriented multilayered network of two-dimensional (2D) Ti3C2Tx (where Tx is the surface termination and corresponds to O, OH and F) was studied using time-of-flight photoconductivity (TOFP) method, which is highly sensitive to the distribution of charge carrier velocities. We prepared samples comprising Ti3C2Tx with thickness of 12 nm or 6-monolayers. MXene flakes of size up to 16 μm were randomly deposited on the surface by spin-coating from water solution. Using TOFP, we have measured electron mobility that reached values up to 279 cm2/Vs and increase with electric-field in a Poole-Frenkel manner. These values are approximately 50 times higher than previously reported field-effect mobility. Interestingly, our zero-electric-field extrapolate approaches electron mobility measured using terahertz absorption method, which represents intra-flake transport. Our data suggest that macroscopic charge transport is governed by two distinct mechanisms. The high mobility values are characteristic for the intra-flake charge transport via the manifold of delocalized states. On the other hand, the observed Poole-Frenkel dependence of charge carrier mobility on the electric field is typical for the disordered materials and suggest the existence of an important contribution of inter-flake hopping to the overall charge transport.
Ključne besede: charge transport, multilayered network, flakes, time-of-flight photoconductivity, MXene exfoliation, high-mobility solution-cast thin-film, semiconducting MXene
Objavljeno v RUNG: 31.03.2023; Ogledov: 1314; Prenosov: 4
.pdf Celotno besedilo (1,97 MB)

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Deposition of porphyrin thin films by electrophoresis
Andraž Mavrič, Tina Škorjanc, Mads Nybo Sørensen, Changzhu Wu, Matjaž Valant, 2022, objavljeni povzetek znanstvenega prispevka na konferenci

Opis: Porphyrins are heterocyclic macrocycles consisting of interconnected pyrrole subunits acting as ligands for metal ions. Metallised metalloporphyrins naturally occur as cofactors in a series of enzymes, acting as active sites for biochemical transformations. Mimicking nature, a variety of functionalized porphyrins have been prepared for different catalytic purposes [1]. These organometallic complexes have isolated metal centers in tailored coordination environments to drive catalytic reactions in homogeneous solutions. The activity and selectivity of isolated metal ions acting as single-atom catalysts are defined by the coordination environment. Depending on the porphyrin structure, the solubility of these macrocycles and their processability in solutions can be altered. While such adjustments to the structure might ease the processability, the catalytic properties might also be altered. Because homogenous catalysis presents challenges with the separation and recyclability of the catalyst, it is common to fix metalloporphyrins into molecular organic frameworks or deposit them onto a substrate. Commonly used deposition techniques face several challenges. For instance, thermal evaporation can cause partial or complete degradation of some thermally-labile functional groups attached to the porphyrins. Similarly, spin coating commonly results in an uneven thickness and uneven morphology of the deposited films. To overcome these difficulties, we present an alternative method for the deposition of porphyrin thin films that is suitable for a wide range of functionalized porphyrins. The electrophoresis can force the molecules to deposit on a conductive substrate such as a metal foil or transparent conductive oxide by applying the electric field generated by a DC power supply. The film thickness can be precisely controlled by changing the voltage value, deposition time, or solution concentration using even a small amount of material [2, 3]. Six different functionalized porphyrin molecules have been successfully deposited onto the copper foil substrate by optimizing key parameters, including applied electric field, the duration of electrophoresis, the size of the copper electrodes, and solvent polarity. To demonstrate the generality of our approach, we have selected a broad range of porphyrins that incorporate the following functional groups: phenyl rings, carboxylic acids, pyridyl rings, methyl benzyl ethers, methyl benzoyl esters, and cobalt (II) metalized macrocycle. The impact of this study extends above catalysis to various applications of porphyrins thin films on conductive substrates such as optoelectronics and sensors.
Ključne besede: porphyrin, thin film, electrophoresis
Objavljeno v RUNG: 26.09.2022; Ogledov: 1222; Prenosov: 0
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4.
Fractal analysis as a potential tool for surface morphology of thin films
Mohanachandran Nair Sindhu Swapna, 2017, izvirni znanstveni članek

Ključne besede: Fractals.thin film, AFM, surface morphology
Objavljeno v RUNG: 05.07.2022; Ogledov: 1167; Prenosov: 0
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5.
Thermal diffusivity downscaling of molybdenum oxide thin film through annealing temperature-induced nano-lamelle formation: a photothermal beam deflection study
S. Soumya, Vimal Raj, Mohanachandran Nair Sindhu Swapna, Sankaranarayana Iyer Sankararaman, 2021, izvirni znanstveni članek

Opis: The present work proposes a method of downscaling the thermal diffusivity (α) of MoO3 thin films through annealing temperature-induced nano-lamelle formation. The thermal diffusivity modification of the MoO3 films, prepared by the doctor blade method, is investigated by the sensitive transverse photothermal beam deflection technique. The X-ray diffraction analysis confirms the structural phase transformation from monoclinic to orthorhombic in the films annealed from 300 to 450 °C. The thermal induced anisotropy of the film is evident from the variation of the morphology index and texture coefficient. The field emission scanning electron microscopic analysis unveils the morphology modifications from blocks to the nano-lamelle structure with layers of average thickness ~ 77 nm. The thermal diffusivity measurement reveals a 53% reduction upon annealing the film to 450 °C. The drastic reduction is achieved through the annealing temperature-induced nano-lamelle formation and the phase transformation from monoclinic to orthorhombic in the MoO3 films.
Ključne besede: thermal diffusivity, molybdenum oxide, thin film, nano-lamelle, photothermal beam deflection
Objavljeno v RUNG: 04.07.2022; Ogledov: 1238; Prenosov: 26
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6.
Charge transport characterization of P3HT thin-film organic semiconductor : Written report: in fulfilment of diploma seminar 1FAF29 requirement
Matija Filipčič, 2021, raz. nal. na višji ali visoki šoli

Opis: The focus of this diploma seminar is to describe different types of charge transport theory and models used for finding mobility in semiconductors, more specifically focused on P3HT thin-film organic semiconductor. It also describes the time-of-flight method, which was used to measure the experimental data for P3HT with time dependent current I(t) curve. Another data set was obtained by performing Kinetic Monte Carlo (KMC) simulations using Miller-Abrahams hopping formalism. KMC was used to determine the material disorder, simulate I(t) curve and transit time for every charge carrier. Simulated data, different transit times and mobilities were then finally compared with experimental, in order to find agreements between the two.
Ključne besede: charge transport, P3HT, thin-film organic semiconductor
Objavljeno v RUNG: 15.09.2021; Ogledov: 2392; Prenosov: 0
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7.
The role of charge transfer at reduced graphene oxide/organic semiconductor interface on the charge transport properties
Gvido Bratina, Egon Pavlica, 2019, izvirni znanstveni članek

Opis: The effect of 1-pyrenesulfonicacid sodium salt (1-PSA), tetracyanoethylene (TCNE) and tetrafluoro- tetracyanoquinodimethane (F4-TCNQ) on charge transport properties of reduced graphene oxide (RGO) is examined by measuring the transfer characteristics of field-effect transistors and co-planar time-of-flight photocurrent technique. Evidence of p-type doping and a reduction of mobility of electrons in RGO upon deposition of these materials is observed. Time-resolved photocurrent measurements show a reduction in elec- tron mobility even at submonolayer coverage of these materials. The variation of transit time with different coverages reveals that electron mobility decreases with increasing the surface coverage of 1-PSA, TCNE and F4- TCNQ to a certain extent, while at higher coverage the electron mobility is slightly recovered. All three molecules show the same trend in charge carrier mobility variation with coverage, but with different magnitude. Among all three molecules, 1-PSA acts as weak electron acceptor compared to TCNE and F4-TCNQ. The additional fluorine moieties in F4-TCNQ provides excellent electron withdrawing capability compared to TCNE. The experimental results are consistent with the density functional theory calculations.
Ključne besede: organic semiconductors, reduced graphene oxide, time-resolved photocurrent measurements, organic thin film transistors
Objavljeno v RUNG: 28.10.2019; Ogledov: 3672; Prenosov: 1
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8.
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: 3786; Prenosov: 114
.pdf Celotno besedilo (452,58 KB)

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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: 5611; Prenosov: 165
.pdf Celotno besedilo (4,56 MB)

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