1. Two-layer hybrid sol-gel system's thermal parameters investigated with the optical nondestructive photoacoustic method in the frequency domainŁukasz Chrobak, Mirosław Maliński, Dorota Korte, 2023, original scientific article Keywords: optical spectroscopy, nondestructive testing, photoacoustic method, thermal parameters, hybrid sol-gel layers, thin film characterization Published in RUNG: 24.05.2023; Views: 2759; Downloads: 13 Full text (2,37 MB) This document has many files! More... |
2. Time-of-flight photoconductivity investigation of high charge carrier mobility in ▫$Ti_3C_2T_x$▫ MXenes thin-filmJurij 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, original scientific article Abstract: 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. Keywords: charge transport, multilayered network, flakes, time-of-flight photoconductivity, MXene exfoliation, high-mobility solution-cast thin-film, semiconducting MXene Published in RUNG: 31.03.2023; Views: 2295; Downloads: 9 Full text (1,97 MB) |
3. Deposition of porphyrin thin films by electrophoresisAndraž Mavrič, Tina Škorjanc, Mads Nybo Sørensen, Changzhu Wu, Matjaž Valant, 2022, published scientific conference contribution abstract Abstract: 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. Keywords: porphyrin, thin film, electrophoresis Published in RUNG: 26.09.2022; Views: 1992; Downloads: 0 This document has many files! More... |
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5. Thermal diffusivity downscaling of molybdenum oxide thin film through annealing temperature-induced nano-lamelle formation: a photothermal beam deflection studyS. Soumya, Vimal Raj, Mohanachandran Nair Sindhu Swapna, Sankaranarayana Iyer Sankararaman, 2021, original scientific article Abstract: 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. Keywords: thermal diffusivity, molybdenum oxide, thin film, nano-lamelle, photothermal beam deflection Published in RUNG: 04.07.2022; Views: 2101; Downloads: 27 Link to full text This document has many files! More... |
6. Charge transport characterization of P3HT thin-film organic semiconductor : Written report: in fulfilment of diploma seminar 1FAF29 requirementMatija Filipčič, 2021, research project (high school) Abstract: 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. Keywords: charge transport, P3HT, thin-film organic semiconductor Published in RUNG: 15.09.2021; Views: 3506; Downloads: 0 This document has many files! More... |
7. The role of charge transfer at reduced graphene oxide/organic semiconductor interface on the charge transport propertiesGvido Bratina, Egon Pavlica, 2019, original scientific article Abstract: 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. Keywords: organic semiconductors, reduced graphene oxide, time-resolved photocurrent measurements, organic thin film transistors Published in RUNG: 28.10.2019; Views: 4966; Downloads: 1 This document has many files! More... |
8. 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: 4783; Downloads: 117 Full text (452,58 KB) |
9. 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: 4868; Downloads: 0 This document has many files! More... |
10. 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: 6963; Downloads: 170 Full text (4,56 MB) |