Biodiesel is a sustainable alternative to petroleum diesel produced by transesterification of vegetable oils in the presence of a catalyst. The present study investigates heterogeneous transesterification of algal oil to biodiesel using novel calcium-doped zinc oxide nanocatalysts synthesized using a UV shaker. The developed catalyst was under different light sources, UV and non-UV; different calcium concentrations (0.01, 0.03, 0.05 M); and different calcination temperatures (600, 700, 800 degrees C). The catalyst has been characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and energy-dispersive spectroscopy (EDS). The effects of the different parameters used in catalyst preparation were studied for transesterification of algal oil. The catalyst of 0.05 M calcium loading and 700 degrees C calcination temperature synthesized in UV light is considered as the most suitable nanocatalyst, which achieved 99.18% yield of biodiesel. The catalyst was used three times effectively with 76% yield. The chemical properties of biodiesel have been investigated using gas chromatography (GC).

In the emerging field of organic bioelectronics, conducting polymers and ion-selective membranes are combined to form resistors, diodes, transistors, and circuits that transport and process both electronic and ionic signals. Such bioelectronics concepts have been explored in delivery devices that translate electronic addressing signals into the transport and dispensing of small charged biomolecules at high specificity and spatiotemporal resolution. Manufacturing such "iontronic" devices generally involves classical thin film processing of polyelectrolyte layers and insulators followed by application of electrolytes. This approach makes miniaturization and integration difficult, simply because the ion selective polyelectrolytes swell after completing the manufacturing. To advance such bioelectronics/iontronics and to enable applications where relatively larger molecules can be delivered, it is important to develop a versatile material system in which the charge/size selectivity can be easily tailormade at the same time enabling easy manufacturing of complex and miniaturized structures. Here, we report a one-pot synthesis approach with minimal amount of organic solvent to achieve cationic hyperbranched polyglycerol films for iontronics applications. The hyperbranched structure allows for tunable pre multi-functionalization, which combines available unsaturated groups used in crosslinking along with ionic groups for electrolytic properties, to achieve a one-step process when applied in devices for monolithic membrane gel formation with selective electrophoretic transport of molecules.

Progress in synthesis technologies and advances in fundamental understanding of materials with low dimensionality has led to the birth of a new scientific field, nanoscience, and to strong expectations of multiple applications of nanomaterials. The physical properties of small particles are unique, bridging the gap between atoms and molecules, on one side, and bulk materials on the other side. The work presented in this thesis investigates the potential of using magnetic nanoparticles as the next generation of contrast agents for biomedical imaging. The focus is on gadolinium-based nanoparticles and cellular activity including the uptake, morphology and production of reactive oxygen species.

Gd ion complexes, like Gd chelates, are used today in the clinic, world-wide. However, there is a need for novel agents, with improved contrast capabilities and increased biocompatibility. One avenue in their design is based on crystalline nanoparticles. It allows to reduce the total number of Gd ions needed for an examination. This can be done by nanotechnology, which allows one to improve and fine tune the physico- chemical properties on the nanomaterial in use, and to increase the number of Gd atoms at a specific site that interact with protons and thereby locally increase the signal. In the present work, synthesis, purification and surface modification of crystalline Gd2O3-based nanoparticles have been performed. The nanoparticles are selected on the basis of their physical properties, that is they show enhanced magnetic properties and therefore may be of high potential interest for applications as contrast agents.

The main synthesis method of Gd₂O₃ nanoparticles in this work was the modified “polyol” route, followed by purification of as-synthesized DEG-Gd2O3 nanoparticles suspensions. In most cases the purification step involved dialysis of the nanoparticle samples. In this thesis, organosilane were chosen as an exchange agent for further functionalization. Moreover, several paths have been explored for modification of the nanoparticles, including Tb³⁺ doping and capping with sorbitol.

Biocompatibility of the newly designed nanoparticles is a prerequisite for their use in medical applications. Its evaluation is a complex process involving a wide range of biological phenomena. A promising path adopted in this work is to study of nanoparticle interactions with isolated blood cells. In this way one could screen nanomaterial prior to animal studies.

The primary cell type considered in the thesis are polymorphonuclear neutrophils (PMN) which represent a type of the cells of human blood belonging to the granulocyte family of leukocytes. PMNs act as the first defense of the immune system against invading pathogens, which makes them valuable for studies of biocompatibility of newly synthesized nanoparticles. In addition, an immortalized murine alveolar macrophage cell line (MH-S), THP-1 cell line, and Ba/F3 murine bone marrow-derived cell line were considered to investigate the optimization of the cell uptake and to examine the potential of new intracellular contrast agent for magnetic resonance imaging.

In paper I, the nanoparticles were investigated in a cellular system, as potential probes for visualization and targeting intended for bioimaging applications. The production of reactive oxygen species (ROS) by means of luminol-dependent chemiluminescence from human neutrophils was studied in presence of Gd₂O₃ nanoparticles. In paper II, a new design of functionalized ultra-small rare earth-based nanoparticles was reported. The synthesis was done using polyol method followed by PEGylation, and dialysis. Supersmall gadolinium oxide (DEG-Gd2O3) nanoparticles, in the range of 3-5 nm were obtained and carefully characterized. Neutrophil activation after exposure to this nanomaterial was studied by means of fluorescence microscopy. In paper III, cell labeling with Gd₂O₃ nanoparticles in hematopoietic cells was monitored by magnetic resonance imaging (MRI). In paper IV, ultra-small gadolinium oxide nanoparticles doped with terbium ions were synthesized as a potentially bifunctional material with both fluorescent and magnetic contrast agent properties. Paramagnetic behavior was studied. MRI contrast enhancement was received, and the luminescent/ fluorescent property of the particles was attributable to the Tb³⁺ ion located on the crystal lattice of the Gd₂O₃ host. Fluorescent labeling of living cells was obtained. In manuscript V, neutrophil granulocytes were investigated with rapid cell signaling communicative processes in time frame of minutes, and their response to cerium-oxide based nanoparticles were monitored using capacitive sensors based on Lab-on-a-chip technology. This showed the potential of label free method used to measure oxidative stress of neutrophil granulocytes. In manuscript VI, investigations of cell-(DEGGd₂O₃) nanoparticle interactions were carried out. Plain (DEG-Gd₂O₃) nanoparticles, (DEG-Gd₂O₃) nanoparticles in presence of sorbitol and (DEG-Gd₂O₃) nanoparticles capped with sorbitol were studied. Relaxation studies and measurements of the reactive oxygen species production by neutrophils were based on chemiluminescence. Cell morphology was evaluated as a parameter of the nanoparticle induced inflammatory response by means of the fluorescence microscopy.

The thesis demonstrates high potential of novel Gd₂O₃-based nanoparticles for development of the next generation contrast agents, that is to find biocompatible compounds with high relaxivity that can be detected at lower doses, and in the future enable targeting to provide great local contrast.

Sunlight responsible mono-and co-doped TiO2 nanoparticles (Con+ and Fen+) were prepared via sol-gel technique. The X-ray diffraction (XRD) results showed no phase change of TiO2 was observed after the addition of Con+ and Fen+ ions. Diffuse reflectance spectra (DRS) results showed a significant red-shift of the absorption edge after doping TiO2 by Co(n )and Fen+ and the band gap energy reduced sharply from 3.10 to 1.72 eV. X-ray photoelectron spectroscopy (XPS) results emphasized the existence of multivalent states of Co2+, Co3+, Fe2+ and Fe3+. The results of ultraviolet photoelectron spectroscopy (UPS), work function, electron spin resonance (ESR) illustrated the Fe3O4/Co3O4-TiO2 formed of ternary hetero-junctions. The photocatalytic performance of the prepared photocatalysts was determined for photodegradation of tetracycline (TC) and phenol (Pl) and production of hydrogen. The results illustrated the existence of multivalent states of Fe and Co ions (Co2+, Co3+, Fe2+ and Fe3+) together improved the solar light absorption, inhibited the recombination of photo -generated charges and consequently enhanced the photocatalytic efficiency of TiO2 compared with mono-doped TiO2 (Co3O4/TiO2 and Fe3O4/TiO2). The sample with 5%Fe3O4/ Co(3)O(4)4-TiO2 showed the highest photoactivity. The mineralization (TOC), photodegradation mechanism and reusability of prepared photocatalysts were also studied. The Fe3O4/Co3O4-TiO2 nanoparticles showed high photoactivity and stability and can be adopted as a promising materials for different environmental and H-2 production applications. (C) 2022 The Author(s). Published by Elsevier B.V.

FeMoO4 and rGO/FeMoO4 nanocomposites were successfully prepared by a facile hydro-thermal method. The XRD results confirmed that the FeMoO4 has a monometallic b-FeMoO4 crystalline phase while the rGO/FeMoO4 showed both monometallic a-and b-FeMoO4 phases where b-FeMoO4 is the predominant phase. The reduction of graphene oxide (GO) to reduced graphene oxide (rGO) was performed without using any chemical reductions. UV-Vis results showed that the visible light absorption and band gap energy were enhanced after the addition of rGO. The prepared samples were successfully applied for degradation of malachite green (MG) and phenol (Ph) and for H2 evolution under natural solar light irradiation. All the nanocomposites showed higher photocatalytic activities compared with pure FeMoO4 photocatalyst, and the 10%rGO/FeMoO4 gave the highest photodegradation performance for MG and Ph and for H2 evolution. The photodegradation results revealed that the rGO content played the crucial factor in the photodegradation of MG and Ph, and H2 evolution. The mineralization (TOC), photodegradation mechanism and degradation kinetics of MG and Ph were discussed.

Nanostructured materials for visible light driven photo-processes such as photodegradation of organic pollutants and photoelectrochemical (PEC) water oxidation for hydrogen production are very attractive because of the positive impact on the environment. Metal oxides-based nanostructures are widely used in these photoprocesses due to their unique properties. But single nanostructured metal oxide material might suffer from low efficiency and instability in aqueous solutions under visible light. These facts make it important to have an efficient and reliable nanocomposite for the photo-processes. The combination of different nanomaterials to form a composite configuration can produce a material with new properties. The new properties which are due to the synergetic effect, are a combination of the properties of all the counterparts of the nanocomposite. Zinc oxides (ZnO) have unique optical and electrical properties which grant it to be used in optoelectronics, sensors, solar cells, nanogenerators, and photocatalysis activities. Although ZnO absorbs visible light from the sun due to the deep level band, it mainly absorbs ultraviolet wavelengths which constitute a small portion of the whole solar spectrum range. Also, ZnO has a problem with the high recombination rate of the photogenerated electrons. These problems might reduce its applicability to the photo-process. Therefore, our aim is to develop and investigate different nanocomposites materials based on the ZnO nanostructures for the enhancement of photocatalysis processes using the visible solar light as a green source of energy. Two photo-processes were applied to examine the developed nanocomposites through photocatalysis: (1) the photodegradation of organic dyes, (2) PEC water splitting. In the first photo-process, we used the ZnO nanoparticles (NPs), Magnesium (Mg)-doped ZnO NPs, and plasmonic ZnO/graphene-based nanocomposite for the decomposition of some organic dyes that have been used in industries. For the second photo-process, ZnO photoelectrode composite with different silver-based semiconductors to enhance the performance of the ZnO photoelectrode was used for PEC reaction analysis to perform water splitting. The characterization and photocatalysis experiment results showed remarkable enhancement in the photocatalysis efficiency of the synthesized nanocomposites. The observed improved properties of the ZnO are due to the synergetic effects are caused by the addition of the other nanomaterials. Hence, the present thesis attends to the synthesis and characterization of some nanostructured materials composite with ZnO that are promising candidates for visible light-driven photo-processes.  

Doped semiconductors nanostructures (NSs) have shown great interest as a potential for green and efficient photocatalysis activities. Magnesium (Mg)-doped zinc oxide (ZnO) nanoparticles (NPs) has been synthesized by a one-step chemical low temperature (60 °C) co-precipitation method without further calcination and their photocatalytic performance for photodegradation of Methylene blue (MB) dye under the illumination of solar light is investigated. The crystal structure of the synthesized NPs is examined by X-ray diffraction (XRD). XRD data indicates a slight shift towards higher 2θ angle in Mg-doped samples as compared to the pure ZnO NPs which suggest the incorporation of Mg2+ into ZnO crystal lattice. X-ray photoelectron spectroscopy (XPS), UV–Vis spectrophotometer and cathodoluminescence (CL) spectroscopy, were used to study electronics, and optical properties, respectively. The XPS analysis confirms the substitution of the Zn2+ by the Mg2+ into the ZnO crystal lattice in agreement with the XRD data. The photocatalytic activities showed a significant enhancement of the Mg-doped ZnO NPs in comparison with pure ZnO NPs. Hole/radical scavengers were used to reveal the mechanism of the photodegradation. It was found that the addition of the Mg to the ZnO lattices increases the absorption of the hydroxyl ions at the surface of the NPs and hence acts as a trap site leading to decrease the electron-hole pair and consequently enhancing the photodegradation.

For an active hydrogen gas generation through water dissociation, the sluggish oxygen evolution reaction (OER) kinetics due to large overpotential is a main hindrance. Herein, a simple approach is used to produce composite material based on TiO2/Co3O4 for efficient OER and overpotential is linearly reduced with increasing amount of TiO2. The scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) investigations reveal the wire like morphology of composite materials, formed by the self-assembly of nanoparticles. The titania nanoparticles were homogenously distributed on the larger Co3O4 nanoparticles. The powder x-ray diffraction revealed a tetragonal phase of TiO2 and the cubic phase of Co3O4 in the composite materials. Composite samples with increasing TiO2 content were obtained (18%, 33%, 41% and 65% wt.). Among the composites, cobalt oxide-titanium oxide with the highest TiO2 content (CT-20) possesses the lowest overpotential for OER with a Tafel slope of 60 mV dec(-1) and an exchange current density of 2.98 x 10(-3)A/cm(2). The CT-20 is highly durable for 45 h at different current densities of 10, 20 and 30 mA/cm(2). Electrochemical impedance spectroscopy (EIS) confirmed the fast charge transport for the CT-20 sample, which potentially accelerated the OER kinetics. These results based on a two-step methodology for the synthesis of TiO2/Co3O4 material can be useful and interesting for various energy storage and energy conversion systems. (C) 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

The fabrication of efficient, alkaline-stable and nonprecious electrocatalysts for the oxygen evolution reaction is highly needed; however, it is a challenging task. Herein, we report a noble metal-free advanced catalyst, i.e. the chemically reduced mixed transition metal oxide CuO-Co3O4 composite, with outstanding oxygen evolution reaction activity in alkaline media. Sodium borohydride (NaBH4) was used as a reducing agent for the mixed transition metal oxide CuO-Co3O4. The chemically reduced composite carried mixed valence states of Cu and Co, which played a dynamic role in driving an excellent oxygen evolution reaction process. The X-ray photo-electron spectroscopy (XPS) study confirmed high density of active sites in the treated sample with a large number of oxygen vacancies. The developed electrocatalyst showed the lowest overpotential of 144.5 mV vs. the reversible hydrogen electrode (RHE) to achieve the current density of 40 mA cm(-2) and remained stable for 40 hours throughout the chronoamperometry test at the constant potential of 1.39 V vs. RHE. Moreover, the chemically reduced composite was highly durable. Electrochemical impedance spectroscopy (EIS) confirmed the low charge transfer resistance of 13.53 ohms for the chemically reduced composite, which was 50 and 26 times smaller than that of Co3O4 and untreated CuO-Co3O4, respectively. The electrochemically active surface area for the chemically reduced composite was found to be greater than that for pristine CuO, Co3O4 and untreated pristine CuO-Co3O4. These findings reveal the possibility of a new gateway for the capitalization of a chemically reduced sample into diverse energy storage and conversion systems such as lithium-ion batteries and supercapacitors.

The water oxidation in alkaline media is a kinetically sluggish process and it requires an active electrocatalyst for overall water splitting which is a challenging task to date. Herein, we formulate a platform for the design of efficient NiCo2S4/C nanocomposite using earth abundant and nonprecious materials. The nanocomposites are prepared by scale up hydrothermal method using different carbon contents from acid dehydrated sucrose. They are structurally and morphologically characterized by various analytic techniques. The scanning electron microscopy has shown few microns flower-like morphology of nanocomposite and hexagonal crystalline phase is identified by X-ray diffraction (XRD). Further, high-resolution transmission electron microscopy supported the XRD results, and C, Ni, Co and O elements were found in the composition nanocomposite as investigated by energy-dispersive spectroscopy. The most active nanocomposite reaches a current density of 20 mA center dot cm(-2) at potential of 285 mV vs reversible hydrogen electrode. The nanocomposite is kinetically supported by 61 mV center dot dec(-1) as small Tafel slope. The nanocomposite is stable and durable for 40 h. The electrochemical impedance spectroscopy described a small charge transfer resistance of 188.4 omega. These findings suggest that the NiCo2S4/C nanocomposite could be used as a promising material for an extended range of applications particularly in energy technology.

There are many challenges associated with the fabrication of efficient, inexpensive, durable and very stable nonprecious metal catalysts for the hydrogen evolution reaction (HER). In this study, we have designed a facile strategy by tailoring the concentration of precursors to successfully obtain nickel-cobalt bimetallic sulfide (NiCo2S4) using a simple hydrothermal method. The morphology of the newly prepared NiCo(2)S(4)comprised a mixture of microparticles and nanorods, which were few microns in dimension. The crystallinity of the composite sample was found to be excellent with a cubic phase. The sample that contained a higher amount of cobalt compared to nickel and produced single-phase NiCo(2)S(4)exhibited considerably improved HER performance. The variation in the salt precursor concentration during the synthesis of a material is a simple methodology to produce a scalable platinum-free catalyst for HER. The advantageous features of the multiple active sites of cobalt in the CN-21 sample as compared to that for pristine CoS and NiS laid the foundation for the provision of abundant active edges for HER. The composite sample produced a current density of 10 mA cm(-2)at an overpotential of 345 mV. Also, it exhibited a Tafel value of 60 mV dec(-1), which predominantly ensured rapid charge transfer kinetics during HER. CN-21 was highly durable and stable for 30 hours. Electrochemical impedance spectroscopy showed that the charge transfer resistance was 21.88 ohms, which further validated the HER polarization curves and Tafel results. CN-21 exhibited a double layer capacitance of 4.69 mu F cm(-2)and a significant electrochemically active surface area of 134.0 cm(2), which again supported the robust efficiency for HER. The obtained results reveal that our developed NiCo(2)S(4)catalyst has a high density of active edges, and it is a non-noble metal catalyst for the hydrogen evolution reaction. The present findings provide an alternative strategy and an active nonprecious material for the development of energy-related applications.

Hydrogen evolution reaction (HER) has been identified as a sustainable and environment friendly technology for a wide range of energy conversion and storage applications. The big barrier in realizing this green technology requires a highly efficient, earth-abundant, and low-cost electrocatalyst for HER. Various HER catalysts have been designed and reported, still, their performance is not up to the mark of Pt. Among them, cobalt-based, especially cobalt disulfide (CoS2) has shown significant HER activity and found suitable candidature for HER due to its low cost, simple to prepare, and exhibits good stability. Herein, we synthesized various nanostructured materials including pure CoS2, Co3O4 and their composites by wet chemical methods and found them active for HER. The scanning electron microscopy (SEM) has revealed a morphology of composite as a mixture of nanowires and round shape spherical nanoparticles with several microns in dimension. The X-ray diffraction (XRD) confirmed the cubic phase of CoS2 and cubic phase of Co3O4 in the composite materials. The chemical deposition of CoS2 onto Co3O4 has tailored the HER activity of CoS2@Co3O4 composite material. Two CoS2@Co3O4 composite materials were produced with varying amounts of Co3O4 and labeled as samples 1 and 2. The Co3O4 reduced the adsorption energy for hydrogen, decreased the aggregation of CoS2 and uplifted the stability of CoS2@Co3O4 a composite material in alkaline media. Sample 1 requires an overpotential of 320 mV to reach a current density of 10 mA/cm(2) and it exhibits a Tafel slope of 42 mVdec(-1) which is the key indicator for the fast HER kinetics on sample 1. The sample 1 is highly durable for 50 h and also it has excellent stability. The electrochemical impedance spectroscopy (EIS) revealed a small charge transfer resistance of 28.81 Ohms for the sample 1 with high capacitance double-layer value of 0.81 mF. EIS has supported polarization and Tafel slope results. Based on the partial physical characterization and the electrochemical results, the as-obtained sample 1 (CoS2@Co3O4 composite material) will find potential applications in an extended range of energy conversion and storage devices owing to its low cost, high abundance, and excellent efficiency. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Electrodeposition of NiP composite coatings with nano and sub-micron sized SiC has been carried out to investigate the possibility of replacing hard chromium coatings. The composition and structure of the coatings were evaluated by energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) analysis, respectively. Microhardness was measured by Vickers indentation and polarization measurements were carried out to study the corrosion behavior of the coatings. The results showed that submicron particles can be codeposited with a higher content as compared to nano sized ones. However, even if a smaller amount of the nano-sized SiC particles are incorporated in the coating, the contribution to an increasing microhardness was comparable with the submicron sized particles, which can be related to the higher density of codeposited particles. SiC particles did not change the anodic polarization behavior of NiP coatings in a 3.5% NaCl solution. Finally, the effect of heat-treatment on the coatings properties at 400 degrees C for 1 h was studied to investigate the contribution of particles and heat-treatment on hardness and corrosion properties. It was found that the heat-treatment doubled the microhardness and changed the anodic polarization behavior of the coatings from passive to active with respect to the asplated conditions. (C) 2018 Elsevier B.V. All rights reserved.

Carbon-based substrates are widely used as current collectors for high-performance energy storage materials in supercapacitors. However, these substrates exhibit negligible charge storage due to inferior electrochemical activity and small surface area. Herein, electrochemical activation is utilized to enhance the electrochemical activity of - inherently inactive - commercial graphite sheets for supercapacitive applications. The results reveal that the electrochemically activated graphite sheets render a 30-fold increase in areal capacitance, i.e., from 22 to 447 mF cm(-2), which can be ascribed to the activation of graphite oxide functional groups on the surface. Also, the influence of electrochemical activation time on electrochemical performance is explored in detail, followed by the fabrication and characterization of symmetric supercapacitors based on the optimum process parameters in single-cell and tandem configurations, demonstrating the potential of electrochemically activated graphite sheets in practical applications.

MXenes hold immense potential given their superior electrical properties. The practical adoption of these promising materials is, however, severely constrained by their oxidative susceptibility, leading to significant performance deterioration and lifespan limitations. Attempts to preserve MXenes have been limited, and it has not been possible thus far to reverse the materials performance. In this work, we show that subjecting oxidized micron or nanometer thickness dry MXene films-even those constructed from nanometer-order solution-dispersed oxidized flakes-to just one minute of 10 MHz nanoscale electromechanical vibration leads to considerable removal of its surface oxide layer, whilst preserving its structure and characteristics. Importantly, electrochemical performance is recovered close to that of their original state: the pseudocapacitance, which decreased by almost 50% due to its oxidation, reverses to approximately 98% of its original value, with good capacitance retention ( approximate to 93%) following 10,000 charge-discharge cycles at 10 A g(-1). These promising results allude to the exciting possibility for rejuvenating the material for reuse, therefore offering a more economical and sustainable route that improves its potential for practical translation. Despite their vast potential, the practical deployment of MXenes has been hampered by their tendency to be oxidized. Here, the authors show that simply vibrating MXene films in just a minute can remove the oxide layer formed and restore their electrochemical performance close to its original state.

Owing to their large surface area and high uptake capacity, metal-organic frameworks (MOFs) have attracted considerable attention as potential materials for gas storage, energy conversion, and electrocatalysis. Various strategies have recently been proposed to manipulate the MOF surface chemistry to facilitate exposure of the embedded metal centers at the crystal surface to allow more effective binding of target molecules to these active sites. Nevertheless, such strategies remain complex, often requiring strict control over the synthesis conditions to avoid blocking pore access, reduction in crystal quality, or even collapse of the entire crystal structure. In this work, we exploit the hydrodynamics and capillary resonance associated with acoustically-driven dynamically spreading and nebulizing thin films as a new method for ultrafast synthesis of swordlike Cu-3(1,3,5-benzenetricarboxylate)(n) (Cu-BTC) MOFs with unique monoclinic crystal structures (P2(1)/n) distinct to that obtained via conventional bulk solvothermal synthesis, with swordlike morphologies whose lengths far exceed their thicknesses. Through pulse modulation and taking advantage of the rapid solvent evaporation associated with the high nebulisation rates, we are also able to control the thicknesses of these large aspect ratio (width and length with respect to the thickness) crystals by arresting their vertical growth, which, in turn, allows exposure of the metal active sites at the crystal surface. An upshot of such active site exposure on the crystal surface is the concomitant enhancement in the conductivity of the MOF, evident from the improvement in its current density by two orders of magnitude.

Diffusion, nucleation and growth provide the fundamental access to control nanostructure growth. In this study, the temperature activated diffusion of Xe at and between different compartments of an on-surface metal organic coordination network on Cu(111) has been visualized in real space. Xe atoms adsorbed at lower energy sites become mobile with increased temperature and gradually populate energetically more favourable binding sites or remain in a delocalized fluid form confined to diffusion along a topological subset of the on-surface network. These diffusion pathways can be studied individually under kinetic control via the chosen thermal energy kT of the sample and are determined by the network and sample architecture. The spatial distribution of Xe in its different modes of mobility and the time scales of the motion is revealed by Scanning Tunneling Microscopy (STM) at variable temperatures up to 40 K and subsequent cooling to 4 K. The system provides insight into the diffusion of a van der Waals gas on a complex structured surface and its nucleation and coarsening/growth into larger condensates at elevated temperature under thermodynamic conditions.

Hydrogenated diamondlike carbon (DLC:H) thin films exhibit many interesting properties that can be tailored by controlling the composition and energy of the vapor fluxes used for their synthesis. This control can be facilitated by high electron density and/or high electron temperature plasmas that allow one to effectively tune the gas and surface chemistry during film growth, as well as the degree of ionization of the film forming species. The authors have recently demonstrated by adding Ne in an Ar-C high power impulse magnetron sputtering (HiPIMS) discharge that electron temperatures can be effectively increased to substantially ionize C species [Aijaz et al., Diamond Relat. Mater. 23, 1 (2012)]. The authors also developed an Ar-C2H2 HiPIMS process in which the high electron densities provided by the HiPIMS operation mode enhance gas phase dissociation reactions enabling control of the plasma and growth chemistry [Aijaz et al., Diamond Relat. Mater. 44, 117 (2014)]. Seeking to further enhance electron temperature and thereby promote electron impact induced interactions, control plasma chemical reaction pathways, and tune the resulting film properties, in this work, the authors synthesize DLC: H thin films by admixing Ne in a HiPIMS based Ar/C2H2 discharge. The authors investigate the plasma properties and discharge characteristics by measuring electron energy distributions as well as by studying discharge current characteristics showing an electron temperature enhancement in C2H2 based discharges and the role of ionic contribution to the film growth. These discharge conditions allow for the growth of thick (amp;gt;1 mu m) DLC: H thin films exhibiting low compressive stresses (similar to 0.5 GPa), high hardness (similar to 25 GPa), low H content (similar to 11%), and density in the order of 2.2 g/cm(3). The authors also show that film densification and change of mechanical properties are related to H removal by ion bombardment rather than subplantation. (C) 2016 American Vacuum Society.

Lignin, a byproduct from the pulp industry, is one of the redox active biopolymers being investigated as a component in the electrodes for sustainable energy storage applications. Due to its insulating nature, it needs to be combined with a conductor such as carbon or conducting polymer for efficient charge storage. Here, the lignin/carbon composite electrodes manufactured via mechanical milling (ball milling) are reported. The composite formation, correlation between performance and morphology is studied by comparison with manual mixing and jet milling. Superior charge storage capacity with approximate to 70% of the total contribution from the Faradaic process involving the redox functionality of lignin is observed in a mechanically milled composite. In comparison, manual mix shows only approximate to 30% from the lignin storage participation while the rest is due to the electric double layer at the carbon-electrolyte interface. The significant participation of lignin in the ball milled composite is attributed to the homogeneous, intimate mixing of the carbon and the lignin leading the electronic carrier transported in the carbon phase to reach most of the redox group of lignin. A maximum capacity of 49 mAh g(-1) is obtained at charge/discharge rate of 0.25 A g(-1) for the sample milled for 60 min.

Organic polymer thermoelectrics (TE) as well as transition metal (TM) silicides are two thermoelectric class of materials of interest because they are composed of atomic elements of high abundatice; which is a prerequisite for mass implementation of thermoelectric (TE) solutions for solar and waste heat recovery. But both materials have drawbacks when it comes to finding low-cost manufacturing. The metal silicide needs high temperature (amp;gt;1000 degrees C) for creating TE legs in a device from solid powder, but it is easy to achieve long TE legs in this case. On the contrary, organic TEs are synthesized at low temperature from solution. However, it is difficult to form long legs or thick films because of their low solubility. In this work, we propose a novel method for the room temperature synthesis of TE composite containing the microparticles of chromium disilicide; CrSi2 (inorganic filler) in an organic matrix of nanofibrillated cellulose-poly(3,4-ethyelenedioxythiophene)-polystyrene sulfonate (NFC-PEDOT:PSS). With this method, it is easy to create long TE legs in a room temperature process. The originality of the approach is the use of conducting polymer aerogel microparticles mixed with CrSi2 microparticles to obtain a composite solid at room temperature under pressure. We foresee that the method can be scaled up to fabricate and pattern TE modules. The composite has an electrical conductivity (sigma) of 5.4 +/- 0.5 S/cm and the Seebeck coefficient (a) of 88 +/- 9 mu V/K, power factor (alpha(2)sigma) of 4 +/- 1 mu Wm(-1) K-2 at room temperature. At a temperature difference of 32 degrees C, the output power/unit area drawn across the load, with the resistance same as the internal resistance of the device is 0.6 +/- 0.1 mu W/cm(2). (C) 2017 Elsevier B.V. All rights reserved.

We demonstrate the fabrication, by exclusive means of inkjet-printing, of capacitive relative humidity sensors on flexible, plastic substrate. These sensors can be successfully used for the measurement of relative-humidity in both air and common soil. We also show that the same technique may be used for the fabrication of the same type of sensors on the surface of the leaves of El AE gnus Ebbingei (silverberry).Our results demonstrate the suitability of leaves as substrate for printed electronics and pave the way to the next generation of sensors to be used in fields such as agriculture and flower farming.

We report spectroelectrochemical studies to investigate the charge storage mechanism of composite polypyrrole/lignin electrodes. Renewable bioorganic electrode materials were produced by electropolymerization of pyrrole in the presence of a water-soluble lignin derivative acting as a dopant. The resulting composite exhibited enhanced charge storage abilities due to a lignin-based faradaic process, which was expressed after repeated electrochemical redox of the material. The in situ FTIR spectroelectrochemistry results show the formation of quinone groups, and reversible oxidation-reduction of these groups during charge-discharge experiments in the electrode materials. The most significant IR bands include carbonyl absorption near 1705 cm(-1), which is attributed to the creation of quinone moieties during oxidation, and absorption at 1045 cm(-1) which is due to hydroquinone moieties.

The mass implementation of renewable energies is limited by the absence of efficient and affordable technology to store electrical energy. Thus, the development of new materials is needed to improve the performance of actual devices such as batteries or supercapacitors. Herein, the facile consecutive chemically oxidative polymerization of poly(1-amino-5-chloroanthraquinone) (PACA) and poly(3,4-ethylenedioxythiophene (PEDOT) resulting in a water dispersible material PACA-PEDOT is shown. The water-based slurry made of PACA-PEDOT nanoparticles can be processed as film coated in ambient atmosphere, a critical feature for scaling up the electrode manufacturing. The novel redox polymer electrode is a nanocomposite that withstands rapid charging (16 A g−1) and delivers high power (5000 W kg−1). At lower current density its storage capacity is high (198 mAh g−1) and displays improved cycling stability (60% after 5000 cycles). Its great electrochemical performance results from the combination of the redox reversibility of the quinone groups in PACA that allows a high amount of charge storage via Faradaic reactions and the high electronic conductivity of PEDOT to access to the redox-active sites. These promising results demonstrate the potential of PACA-PEDOT to make easily organic electrodes from a water-coating process, without toxic metals, and operating in non-flammable aqueous electrolyte for large scale pseudocapacitors. 

A trihybrid bioelectrode composed of lignin, poly(3,4-ethylenedioxythiophene) (PEDOT), and poly(aminoanthraquinone) (PAAQ) is prepared by a two-step galvanostatic electropolymerization, and characterized for supercapacitor applications. Using PEDOT/Lignin as a base layer, followed by the consecutive deposition of PAAQ, the hybrid electrode PEDOT/Lignin/PAAQ shows a high specific capacitance of 418 F g(-1) with small self-discharge. This trihybrid electrode material can be assembled into symmetric and asymmetric super-capacitors. The asymmetric supercapacitor uses PEDOT + Lignin/PAAQ as positive electrode and PEDOT/PAAQ as negative electrode, and exhibits superior electrochemical performance due to the synergistic effect of the two electrodes, which leads to a specific capacitance of 74 F g(-1). It can be reversibly cycled in the voltage range of 0-0.7 V. More than 80% capacitance is retained after 10 000 cycles. These remarkable features reveal the exciting potential of a full organic energy storage device with long cycle life.

Daily and seasonally fluctuating energy supply and demand requires adequate energy storage solutions. In recent years electrochemical supercapacitors have attracted considerable attention due to their ability to both store and deliver electrical energy efficiently. Our efforts are focused on developing and optimizing sustainable organic electrode materials for supercapacitors based on renewable bioorganic materials, offering a cheap, environmentally friendly and scalable alternative to store energy. In particular, we are using the second most abundant biopolymer in nature, lignin (Lig), which is an insulating material. However, when used in combination with electroactive and conducting polymers such as polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene) (PEDOT), the biohybrid electrodes PPy/Lig and PEDOT/Lig display significantly enhanced energy storage performance as compared to the pristine conducting polymers without the lignin. Redox cyclic voltammetry and galvanostatic charge/discharge measurements indicate that the enhanced performance is due to the additional pseudocapacitance generated by the quinone moieties in lignin. Moreover, a conjugated redoxpolymer poly(aminoanthraquinone) PAAQ, with intrinsic quinone functions and excellentstability, has been combined with lignin and PEDOT resulting in a trihybrid bioelectrode. PEDOT compensates the low conductivity of PAAQ and provides electrical pathways to the quinone groups. The electrochemically generated quinones undergo a two electron, two protonredox process within the biohybrid electrodes as revealed by FTIR spectroelectrochemistry.These remarkable features reveal the exciting potential of a full organic energy storage device with long cycle life. Therefore, supercapacitor devices were designed in symmetric or asymmetric two electrode configuration. The best electrochemical performance was achieved by the asymmetric supercapacitor based on PEDOT+Lignin/PAAQ as the positive electrode and PEDOT/PAAQ as the negative electrode. This device exhibits superior electrochemical performance and outstanding stability after 10000 charge/discharge cycles due to the synergistic effect of the two electrodes. Finally, we have characterized the response of this supercapacitor device when charged with the intermittent power supply from an organic photovoltaic module. We have designed charging/discharging conditions such that reserve power was available in the storage device at all times. This work has resulted in an inexpensive fully organic system witht he dual function of energy conversion and storage.

Polyvinylidene difluoride (PVDF) derivatives in metal/PVDF/metal (MPM) sandwich structures have been studied extensively since 1969. Cousin copolymers of the same family have been discovered with fascinating piezoelectric, pyroelectric, electrocaloric, and ferroelectric properties. Solution processing, flexibility, lightweight, and thermal stability make this class of materials complementary to inorganics. Thus, PVDF based polymers potentially compete with inorganic materials for a broad range of technologies such as energy generators, loudspeakers, coolers, and memories. However, the stable non-electroactive α-phase and hydrophobic nature of PVDF are the main barriers for developoing high performing and robust MPM devices in electronic applications. In this review, we present an up-to-date overview on different methods to induce the electroactive β-phase and improve the adhesion strength with metals to ensure robust and durable MPM devices. We go through advantages and disadvantages of several methods and pinpoint future opportunities in this research area. A special attention is paid to wearable piezoelectric nanogenerators for energy harvesting from human body motion, where flexible PVDF derivatives are compared with rigid piezoelectric ceramics. While the piezoelectric coefficient of PVDF (d₃₃ ~ 24–34 pm/V) is one order lower than ceramic materials, novel co-polymers of PVDF display d₃₃ > 1000 pm/V upon bias. This shows promise to bring piezoelectrics to flexible and large-area applications such as smart textiles. We also discussed challenges to improve wearability, such as light weight, breathability, and flexibility.

Perovskite solar cells (per-SCs) with high performance and cost-effective solution processing have been the center of interest for researchers in the past decade. Power conversion efficiencies (PCEs) have been gradually improved up to 25.2% with relatively improved stability, which is an unparalleled progress in all generations of solar cell (SC) technology. However, there are still some prevailing challenges regarding the stability and upscaling of these promising devices. Recently, 2D layered materials (LMs) have been extensively explored to overcome the prevailing challenges of poor stability (under moisture, light soaking and high temperature), halide segregation, hysteresis, involvement of toxic materials (i.e., lead), and upscaling of devices. A critical review addressing the recent developments in the use of 2D materials, especially transition metal dichalcogenides (TMDCs), is hence necessary. The development of novel synthesis and deposition techniques including liquid-metal synthesis and ultrasonic assisted spray pyrolysis has offered more efficient fabrication of 2D-LMs with controlled thickness and morphology. Effective functionalization approaches to increase the dispersability of 2D-LMs in non-polar solvents has boosted their potential application in solar cell technology as well. Moreover, compositing 2D TMDCs with suitable organic/inorganic compounds has enabled superior charge kinetics in all functional parts of per-SCs. In addition, newly developed materials such as graphyne and graphdyine along with 2D metal organic frameworks (MOFs) and covalent organic frameworks (COFs) have been employed in per-SCs to achieve PCEs up to 20%. This review summarizes the recent progress and challenges in the application of 2D-LMs in per-SCs and outlines the future pathways to further extend the PCE of per-SCs beyond 25%. This review particularly focuses on 2D-LMs as electrode materials and additives, the underlying charge (electron-hole) transport phenomenon in the functional layers, and their chemical and structural stability.

CuO microstructures are produced in the presence of water-soluble amino acids by hydrothermal method. The used amino acids include isoleucine, alpha alanine, and arginine as a soft template and are used for tuning the morphology of CuO nanostructures. The crystalline and morphological investigations were carried out by x-ray diffraction (XRD) and scanning electron microscopy techniques. The XRD study has shown that CuO material obtained in the presence of different amino acids is of high purity and all have the same crystal phase. The CuO microstructures prepared in the presence of arginine were used for the development of sensitive and selective glucose biosensor. The linear range for the glucose detection are from 0.001 mM to 30 mM and limit of detection was found to be 0.0005 mM. The sensitivity was estimated around 77 mV/decade. The developed biosensor is highly selective, sensitive, stable and reproducible. The glucose biosensor was used for the determination of real human blood samples and the obtained results are satisfactory. The CuO material is functional therefore can be capitalized in wide range of applications such as lithium ion batteries, all oxide solar cells and supercapacitors.

Poor wettability and weak graphene/Cu interface limit the mechanical properties' enhancement in graphene/Cu composites. This study devised an interface enhancement approach by Ag decoration of graphene nanoplatelets (Ag-GNPs) and Ag decorated nitrogen doped graphene (Ag-N-GNP) without oxide (during decoration) and carbide (during sintering) formation. Sonication was used to functionalize GNPs for decoration with Ag nanoparticles (NPs) and Cu composites (Ag-GNP/Cu and Ag-N-GNP/Cu) were fabricated using cold pressing (low-pressure) and sintering. 2-Ag-GNP/Cu (2 vol% of Ag-GNPs) and 2Ag-N-GNP/Cu (2 vol% of Ag-N-GNPs) possessed highest sintered density. In addition, 2-Ag-GNP/Cu and 1-Ag-N-GNP/Cu showed highest microhardness and tensile strength (theoretical), respectively. Higher concentration of Ag NPs on GNPs in Ag-N-GNP (oxygen and nitrogen functionalization) showed lower mechanical properties for Ag-N-GNP/Cu compared to Ag-GNP/Cu with limited Ag NPs on GNPs (oxygen functionalization). Interface modification strategy with noble metal NPs bridging between GNP and Cu suggests controlled functionalization and noble metal NPs' attachment on GNPs for effective mechanical properties' enhancement in graphene Cu composites. (c) 2024 The Society of Powder Technology Japan. Published by Elsevier BV and The Society of Powder Technology Japan. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Phase formation, morphology, and optical properties of Ti(O,N) thin films with varied oxygen-to- nitrogen ration content were investigated. The films were deposited by magnetron sputtering at 500 & DEG;C on Si(100) and c-plane sapphire substrate. A competition between a NaCl B1 structure TiN1-xOx, a rhombohedral structure Ti-2(O1-yNy)(3), and an anatase structure Ti(O1-zNz)(2) phase was observed. While the N-rich films were composed of a NaCl B1 TiN1-xOx phase, an increase of oxygen in the films yields the growth of rhombohedral Ti-2(O1-yNy)(3) phase and the oxygen-rich films are comprised of a mixture of the rhombohedral Ti-2(O1-yNy)(3) phase and anatase Ti(O1-zNz)(2) phase. The optical properties of the films were correlated to the phase composition and the observation of abrupt changes in terms of refractive index and absorption coefficient. The oxide film became relatively transparent in the visible range while the addition of nitrogen into films increases the absorption. The oxygen rich-samples have bandgap values below 3.75 eV, which is higher than the value for pure TiO2, and lower than the optical bandgap of pure TiN. The optical properties characterizations revealed the possibility of adjusting the band gap and the absorption coefficient depending on the N-content, because of the phases constituting the films combined with anionic substitution.

Ca-Si-O-N thin films were deposited on commercial soda-lime silicate float glass, silica wafers and sapphire substrates by RF magnetron co-sputtering from Ca and Si targets in an Ar/N-2/O-2 gas mixture. Chemical composition, surface morphology, hardness, reduced elastic modulus and optical properties of the films were investigated using X-ray photoelectron spectroscopy, scanning electron microscopy, nanoindentation, and spectroscopic ellipsometry. It was found that the composition of the films can be controlled by the Ca target power, predominantly, and by the reactive gas flow. Thin films in the Ca-Si-O-N system are composed of N and Ca contents up to 31 eq. % and 60 eq. %, respectively. The films thickness ranges from 600 to 3000 nm and increases with increasing Ca target power. The films surface roughness varied between 2 and 12 nm, and approximately decreases with increasing power of Ca target. The hardness (4-12 GPa) and reduced elastic modulus (65-145 GPa) of the films increase and decrease with the N and Ca contents respectively. The refractive index (1.56-1.82) is primarily dictated by the N content. The properties are compared with findings for bulk glasses in the Ca-Si-(Al)-O-N systems, and it is concluded that Ca-Si-O-N thin films have higher values of hardness, elastic modulus and refractive index than bulk glasses of similar composition. (C) 2017 Elsevier B.V. All rights reserved.

Additive manufacturing (AM) or industrial three-dimensional (3D) printing drives a new spectrum of design and production possibilities; pushing the boundaries both in the application by production of sophisticated products as well as the development of next-generation materials. AM technologies apply a diversity of feedstocks, including plastic, metallic, and ceramic particle powders with distinct size, shape, and surface chemistry. In addition, powders are often reused, which may change the particles' physicochemical properties and by that alter their toxic potential. The AM production technology commonly relies on a laser or electron beam to selectively melt or sinter particle powders. Large energy input on feedstock powders generates several byproducts, including varying amounts of virgin microparticles, nanoparticles, spatter, and volatile chemicals that are emitted in the working environment; throughout the production and processing phases. The micro and nanoscale size may enable particles to interact with and to cross biological barriers, which could, in turn, give rise to unexpected adverse outcomes, including inflammation, oxidative stress, activation of signaling pathways, genotoxicity, and carcinogenicity. Another important aspect of AM-associated risks is emission/leakage of mono- and oligomers due to polymer breakdown and high temperature transformation of chemicals from polymeric particles, both during production, use, and in vivo, including in target cells. These chemicals are potential inducers of direct toxicity, genotoxicity, and endocrine disruption. Nevertheless, understanding whether AM particle powders and their byproducts may exert adverse effects in humans is largely lacking and urges comprehensive safety assessment across the entire AM lifecycle-spanning from virgin and reused to airborne particles. Therefore, this review will detail: 1) brief overview of the AM feedstock powders, impact of reuse on particle physicochemical properties, main exposure pathways and protective measures in AM industry, 2) role of particle biological identity and key toxicological endpoints in the particle safety assessment, and 3) next-generation toxicology approaches in nanosafety for safety assessment in AM. Altogether, the proposed testing approach will enable a deeper understanding of existing and emerging particle and chemical safety challenges and provide a strategy for the development of cutting-edge methodologies for hazard identification and risk assessment in the AM industry.

The conversion of layered transition metal carbides and/or nitrides (MXenes) into zero-dimensional structures with thicknesses and lateral dimensions of a few nanometers allows these recently discovered materials with exceptional electronic properties to exploit the additional benefits of quantum confinement, edge effects, and large surface area. Conventional methods for the conversion of MXene nanosheets and quantum dots, however, involve extreme conditions such as high temperatures and/or harsh chemicals that, among other disadvantages, lead to significant degradation of the material as a consequence of their oxidation. Herein, we show that the large surface acceleration.on the order of 10 million gs.produced by high-frequency (10 MHz) nanometer-order electromechanical vibrations on a chipscale piezoelectric substrate is capable of efficiently nebulizing, and consequently dimensionally reducing, a suspension of multilayer Ti3C2Tz (MXene) into predominantly monolayer nanosheets and quantum dots while, importantly, preserving the material from any appreciable oxidation. As an example application, we show that the high-purity MXene quantum dots produced using this room-temperature chemical-free synthesis method exhibit superior performance as electrode materials for electrochemical sensing of hydrogen peroxide compared to the highly oxidized samples obtained through conventional hydrothermal synthesis. The ability to detect concentrations as low as 5 nM is a 10-fold improvement to the best reported performance of Ti3C2Tz MXene electrochemical sensors to date.

One-dimensional (1D) nanostructures (NSs) of Zinc Oxide (ZnO) such as nanorods (NRs) have recently attracted considerable research attention due to their potential for the development of optoelectronic devices such as ultraviolet (UV) photodetectors and light-emitting diodes (LEDs). The potential of ZnO NRs in all these applications, however, would require synthesis of high crystal quality ZnO NRs with precise control over the optical and electronic properties. It is known that the optical and electronic properties of ZnO NRs are mostly influenced by the presence of native (intrinsic) and impurities (extrinsic) defects. Therefore, understanding the nature of these intrinsic and extrinsic defects and their spatial distribution is critical for optimizing the optical and electronic properties of ZnO NRs. However, identifying the origin of such defects is a complicated matter, especially for NSs, where the information on anisotropy is usually lost due to the lack of coherent orientation.

Thus, the aim of this thesis is towards the optimization of the lowtemperature solution-based synthesis of ZnO NRs for device applications. In this connection, we first started with investigating the effect of the precursor solution stirring durations on the deep level defects concentration and their spatial distribution along the ZnO NRs. Then, by choosing the optimal stirring time, we studied the influence of ZnO seeding layer precursor’s types, and its molar ratios on the density of interface defects. The findings of these investigations were used to demonstrate ZnO NRs-based heterojunction LEDs. The ability to tune the point defects along the NRs enabled us further to incorporate cobalt (Co) ions into the ZnO NRs crystal lattice, where these ions could occupy the vacancies or interstitial defects through substitutional or interstitial doping. Following this, high crystal quality vertically welloriented ZnO NRs have been demonstrated by incorporating a small amount of Co into the ZnO crystal lattice. Finally, the influence of Co ions incorporation on the reduction of core-defects (CDs) in ZnO NRs was systematically examined using electron paramagnetic resonance (EPR).

This review celebrates the width and depth of electron microscopy methods and how these have enabled massive research efforts on MXenes. MXenes constitute a powerful recent addition to 2-dimensional materials, derived from their parent family of nanolaminated materials known as MAX phases. Owing to their rich chemistry, MXenes exhibit properties that have revolutionized ranges of applications, including energy storage, electromagnetic interference shielding, water filtering, sensors, and catalysis. Few other methods have been more essential in MXene research and development of corresponding applications, compared with electron microscopy, which enables structural and chemical identification at the atomic scale. In the following, the electron microscopy methods that have been applied to MXene and MAX phase precursor research are presented together with research examples and are discussed with respect to advantages and challenges.

Low temperature aqueous chemical synthesis (LT-ACS) of zinc oxide (ZnO) nanorods (NRs) has been attracting considerable research interest due to its great potential in the development of light-emitting diodes (LEDs). The influence of the molar ratio of the zinc acetate (ZnAc): KOH as a ZnO seed layer precursor on the density of interface defects and hence the presence of non-radiative recombination centers in LT-ACS of ZnO NRs/GaN LEDs has been systematically investigated. The material quality of the as-prepared seed layer as quantitatively deduced by the X-ray photoelectron spectroscopy is found to be influenced by the molar ratio. It is revealed by spatially resolved cathodoluminescence that the seed layer molar ratio plays a significant role in the formation and the density of defects at the n-ZnO NRs/p-GaN heterostructure interface. Consequently, LED devices processed using ZnO NRs synthesized with molar ratio of 1:5M exhibit stronger yellow emission (similar to 575 nm) compared to those based on 1:1 and 1:3M ratios as measured by the electroluminescence. Furthermore, seed layer molar ratio shows a quantitative dependence of the non-radiative defect densities as deduced from light-output current characteristics analysis. These results have implications on the development of high-efficiency ZnO-based LEDs and may also be helpful in understanding the effects of the ZnO seed layer on defect-related non-radiative recombination. Published by AIP Publishing.

The present study used ultra-sonication approach to manufacture ZnO/NiFe2O4 (ZNF) and casting technique to prepare ZnO/NiFe2O4-Cs/PVP nanocomposite films. The successful creation of these nanocomposites with a significant decrease in the % crystallinity of the polymer blend with doping agent was verified by XRD results. ZNF and the Cs/PVP chains interacted in the polymer nanocomposites, as seen by the spectra of the FTIR. To determine the direct and indirect optical band gaps, tauc graphs were studied using data from UV-Vis analysis. The results indicate that while the Urbach energy was found to increase, the optical band gaps decreased as the weight percentage of the nanofiller increased. Using a thermogravimetric approach, the thermal stability of the produced PNCs has been investigated. Conductivity experiments demonstrated that when the nanofiller ZNF content increased to 2.5 wt%, so did AC conductivity, the dielectric loss, and the dielectric constant. The correlation between the mechanism of conduction and the amount of nanoparticles indicates that an increase in the percentage of ZNF in nanocomposites could increase their conductivity, with values ranging from 3.72 x 10-12 for pure blend to 7.72 x 10-8 S/cm for 2.5%ZNF-Cs/PVP at 100 Hz. The dielectric measurements for the nanocomposite films showed an increase in dielectric losses and dielectric constant, which is indicative of the films' enhanced dielectric polarization. The results of characterization point to possible uses of these polymer nanocomposites in flexible optoelectronic and magneto-electronic applications and energy storage devices.

In this study, a cast synthesis approach was used to create flexible nanocomposite films made of polyacrylamide (PAM), chitosan (Cs), and zinc ferrite nanoparticles (ZnFe2O4 NPs). XRD analysis was used to examine the composite structure. They demonstrated the effective interaction between ZnFe2O4 NPs and PAM/Cs blend. As the concentration of nanomaterial in the host polymer matrix grew, it was observed that the PAM/Cs matrix's direct and indirect energy band gaps decreased while its absorbance of ultraviolet-visible radiations increased. The nanocomposite's AC conductivity was significantly higher than that of the blend, and 2.5 wt percent of the nanocomposite showed the highest electrical conductivity. It was observed that as frequency raised, the epsilon ' and epsilon '' declined though the concentration of nanoparticles enhanced these characteristics. Because of the high dielectric permittivity of ZnFe2O4, the values of epsilon ' and epsilon '' raised as ZnFe2O4 were higher. The outcome of the vibrating sample magnetometer (VSM) demonstrated the ferromagnetic property of the produced nanocomposites. Furthermore, the VSM study shows that as the nanoparticles content increases, the PAM/Cs/ZnFe2O4 nanocomposites' Ms, Hc, and Mr also increase. These PAM/Cs/ZnFe2O4 films were shown by the experimental results to be promising candidates for bandgap-regulated materials, electromagnetic interference shielders, frequency tunable nanodielectric, and flexible dielectric substrates for future microelectronic, optoelectronic technologies, and capacitive energy storage.

N-type semiconducting polymers have been recently utilized in thermoelectric devices, however they have typically exhibited low electrical conductivities and poor device stability, in contrast to p-type semiconductors, which have been much higher performing. This is due in particular to the n-type semiconductors low doping efficiency, and poor charge carrier mobility. Strategies to enhance the thermoelectric performance of n-type materials include optimizing the electron affinity (EA) with respect to the dopant to improve the doping process and increasing the charge carrier mobility through enhanced molecular packing. Here, we report the design, synthesis and characterization of fused electron-deficient n-type copolymers incorporating the electron withdrawing lactone unit along the backbone. The polymers were synthesized using metal-free aldol condensation conditions to explore the effect of enlarging the central phenyl ring to a naphthalene ring, on the electrical conductivity. When n-doped with N-DMBI, electrical conductivities of up to 0.28 S cm(-1), Seebeck coefficients of -75 mu V K-1 and maximum Power factors of 0.16 mu W m(-1) K-2 were observed from the polymer with the largest electron affinity of -4.68 eV. Extending the aromatic ring reduced the electron affinity, due to reducing the density of electron withdrawing groups and subsequently the electrical conductivity reduced by almost two orders of magnitude.

Three lactone-based rigid semiconducting polymers were designed to overcome major limitations in the development of n-type organic thermoelectrics, namely electrical conductivity and air stability. Experimental and theoretical investigations demonstrated that increasing the lactone group density by increasing the benzene content from 0 % benzene (P-0), to 50 % (P-50), and 75 % (P-75) resulted in progressively larger electron affinities (up to 4.37 eV), suggesting a more favorable doping process, when employing (N-DMBI) as the dopant. Larger polaron delocalization was also evident, due to the more planarized conformation, which is proposed to lead to a lower hopping energy barrier. As a consequence, the electrical conductivity increased by three orders of magnitude, to achieve values of up to 12 S cm and Power factors of 13.2 mu Wm(-1) K-2 were thereby enabled. These findings present new insights into material design guidelines for the future development of air stable n-type organic thermoelectrics.

We propose a new facile electrochemical sensing platform for determination of urea, based on a glassy carbon electrode (GCE) modified with nickel cobalt oxide (NiCo2O4) nanoneedles. These nanoneedles are used for the first time for highly sensitive determination of urea with the lowest detection limit (1 mu M) ever reported for the non-enzymatic approach. The nanoneedles were grown through a simple and low-temperature aqueous chemical method. We characterized the structural and morphological properties of the NiCo2O4 nanoneedles by TEM, SEM, XPS and XRD. The bimetallic nickel cobalt oxide exhibits nanoneedle morphology, which results from the self-assembly of nanoparticles. The NiCo2O4 nanoneedles are exclusively composed of Ni, Co, and O and exhibit a cubic crystalline phase. Cyclic voltammetry was used to study the enhanced electrochemical properties of a NiCo2O4 nanoneedle-modified GCE by overcoming the typical poor conductivity of bare NiO and Co3O4. The GCE-modified electrode is highly sensitive towards urea, with a linear response (R-2 = 0.99) over the concentration range 0.01-5 mM and with a detection limit of 1.0 mu M. The proposed non-enzymatic urea sensor is highly selective even in the presence of common interferents such as glucose, uric acid, and ascorbic acid. This new urea sensor has good viability for urea analysis in urine samples and can represent a significant advancement in the field, owing to the simple and cost-effective fabrication of electrodes, which can be used as a promising analytical tool for urea estimation.

Designing a nanocomposite with sensitive and selective determination of ascorbic acid is challenging task. It is possible through the exploitation of attractive features of nanoscience and nanotechnology for the synthesis of nanostructured materials. Herein, we report the decoration of nanoparticle of MoSx on the surface of Co3O4 nanowires by hydrothermal method. The MoSx nanoparticles shared the large surface on the Co3O4 nanowires, thus it supported in the development enzyme free ascorbic acid sensor. Non-enzymatic sensor based on MoSx-Co3O4 composite was found very selective for the determination of ascorbic acid (AA) in phosphate buffer solution of pH 7.4. The MoSx-Co3O4 nanocomposite was used to modify the glassy carbon electrode to measure AA from variety of practical samples. The MoSx-Co3O4 nanocomposite was used to modify the glassy carbon electrode and it has shown the attractive analytical features such as a low working potential +0.3 V, linear range of concentration from 100-7000 mu M, low limit of detection 14 mu M, and low limit of quantification (LOQ) of 42 mu M. The developed sensor is highly selective and stable. Importantly, it was applied successfully for the practical applications such as detection of AA from grapefruit, tomato and lemon juice. The excellent electrochemical properties of fabricated MoSx-Co3O4 nanocomposite can be attributed to the increasing electro active surface area of MoSx. The presented nanocomposite is earth abundant, environment friendly and inexpensive and it holds promising features for the selective and sensitive determination of AA from practical applications. The nanocomposite can be capitalized into the wide range of biomedical applications.

The communication outposts of the emerging Internet of Things are embodied by ordinary items, which desirably include all-printed flexible sensors, actuators, displays and akin organic electronic interface devices in combination with silicon-based digital signal processing and communication technologies. However, hybrid integration of smart electronic labels is partly hampered due to a lack of technology that (de)multiplex signals between silicon chips and printed electronic devices. Here, we report all-printed 4-to-7 decoders and seven-bit shift registers, including over 100 organic electrochemical transistors each, thus minimizing the number of terminals required to drive monolithically integrated all-printed electrochromic displays. These relatively advanced circuits are enabled by a reduction of the transistor footprint, an effort which includes several further developments of materials and screen printing processes. Our findings demonstrate that digital circuits based on organic electrochemical transistors (OECTs) provide a unique bridge between all-printed organic electronics (OEs) and low-cost silicon chip technology for Internet of Things applications.

Thin films provide a remarkable asset, as depositing a thin surface layer can completely alter a material’s characteristics and provide new, inexpensive, and valuable properties. In 2020, a new Chemical Vapour Deposition (CVD) approach was developed at Linköping University, using plasma electrons as reducing agents for the deposition of metallic thin films. To understand the CVD approach, comprehension of the deposition chemistry is crucial. In this thesis, I have performed a theoretical examination of the gas phase and surface chemistry of ferrocene in the recently developed CVD method to form metallic iron thin films, using plasma electrons as reducing agents. Results show that ferrocene anion formation and dissociation are probable in the gas phase, depending on the energy of the plasma electrons. It gets successively easier to dissociate the complex after gaining electrons. The most probable gas phase species leading to film formation was determined as FeCp2-, FeCp, and Cp− under the normal deposition parameters. An electron energy above 220 kJ/mol would suffice for ion formation and dissociation to form FeCp and Cp− fragments. On the surface, ferrocene’s vertical and horizontal adsorption is equally probable, with energies around -72 kJ/mol. Cp, Fe, and FeCp with Fe facing towards the surface interacts stronger with the surface than ferrocene, with adsorption energies of -179, -279 kJ/mol, and -284 kJ/mol. FeCp with Fe facing up from the surface had adsorption energy of -23 kJ/mol. As the surface bonding of Fe and FeCp with Fe facing the surface is stronger than for the other species, this poses a possible way of tuning the CVD method to limit carbon impurities. By providing above 180 kJ/mol energy, for example in the form of heating the substrate, the unwanted species FeCp2, Cp, and FeCp with the ring facing downwards would desorb from the surface, leaving the Fe and FeCp fragments with iron facing towards the surface still adsorbed. This poses a possible way of reducing carbon impurities.

The surface immobilization of the parent Dawson polyoxometalate (POM) as a counter-ion for the electropolymerization of polypyrrole (PPy) or as an electrode-adhered solid was utilized for voltammetric studies of the surface adhered POM in room temperature ionic liquids (RTIL). Illustrating the efficiency of intermediate stabilization, voltammetry at POM-modified electrodes in a PF6-based RTIL revealed richer redox behaviour and higher stabilization in comparison with aqueous electrolytes and with BF4-based RTIL, respectively. High stability of the POM-doped PPy towards continuous charge-discharge voltammetric redox cycles was confirmed by minor changes in film morphology observed after the cycling in RTILs. (c) 2017 Elsevier Ltd. All rights reserved.

Tin oxide (SnO2) has been considered as one of the most promising anodes for advanced rechargeable batteries due to its advantages such as high energy density, earth abundance and environmental friendly. However, its large volume change during the Li-Sn/Na-Sn alloying and de-alloying processes will result in a fast capacity degradation over a long term cycling. To solve this issue, in this work we design and synthesize a novel honeycomb-like composite composing of carbon encapsulated SnO2 nanospheres embedded in carbon film by using dual templates of SiO2 and NaCl. Using these composites as anodes both in lithium ion batteries and sodium-ion batteries, no discernable capacity degradation is observed over hundreds of long term cycles at both low current density (100 mA g(-1)) and high current density (500 mA g(-1)). Such a good cyclic stability and high delivered capacity have been attributed to the high conductivity of the supported carbon film and hollow encapsulated carbon shells, which not only provide enough space to accommodate the volume expansion but also prevent further aggregation of SnO2 nanoparticles upon cycling. By engineering electrodes of accommodating high volume expansion, we demonstrate a prototype to achieve high performance batteries, especially high-power batteries. (C) 2017 Elsevier B.V. All rights reserved.

In this study, NiO nanostructures were synthesized via a hydrothermal process using ascorbic acid as doping agent in the presence of ammonia. As prepared nanostructures were characterized using Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Brunauer-Emmett-Teller (BET) specific surface area analysis, and thermogravimetric analysis (TGA). These analyses showed that these nanostructures are in the form of cotton-like porous material and crystalline in nature. Furthermore, the average size of these NiO crystallites was estimated to be 3.8 nm. These nanostructures were investigated for their potential to be a highly sensitive and selective enzyme-free sensor for detection of urea after immobilizing on a glassy carbon electrode (GCE) using 0.1% Nafion as binder. The response of this as developed amperometric sensor was linear in the range of 100-1100 mu M urea with a R-2 value of 0.990 and limit of detection (LOD) of 10 mu M. The sensor responded negligibly to various interfering species including glucose, uric acid, and ascorbic acid. This sensor was applied successfully for determining urea in real water samples such as mineral water, tap water, and river water with acceptable recovery.

The construction of visible-light-driven hybrid heterostructure photocatalysts is of great significance for environmental remediation, although the utilization of strong visible-light response photocatalysts with high efficiency and stability remains a major challenge. Defect engineering is an excellent way to introduce metal cation vacancies in materials, thereby ensuing in highly enhanced catalytic performance. Inspired by this, we effectively constructed a built-in interface alpha-MnO2/Bi2WO6 heterostructure with abundant intimate interfaces and defective Mn3+/Mn4+ active sites for photocatalytic tetracycline hydrochloride (TC-HCl), hexavalent chromium Cr6+ reduction, and Escherichia coli (E. coli) inactivation. The experimental results, such as the active species test and X-ray photoelectron spectroscopy, indicated that the defective sites Mn3+/Mn4+, surface oxygen vacancies, and Bi(3+x)+ boosted the visible light absorption, and highly enhanced the photoinduced charge separation/transfer. Furthermore, experimental and DFT calculations reveal the high charge density at the built-in interface heterostructure and the Z-scheme charge transfer mechanism during the photocatalytic process. The results further reveal that O-2(-) and O-1(2) are the main reactive active species contributing to the photocatalytic reaction. The exceptional TC-HCl decomposition activity of the alpha-MnO2/Bi2WO6 heterostructure (97.56%, 2.31, and 2.04 times higher than bulk), enhanced reaction kinetics (K-app = 0.041 min(-1), 6.4, and 5.2 times higher than bulk), removal rate of 80.3%, Cr6+ reduction to Cr3+ (98.56%, K-app = 0.0599 min(-1)), and almost 100% bacterial inactivation compared to bulk alpha-MnO2 (42.22%) and Bi2WO6 (47.76%), were mainly due to the enhanced charge separation/transfer at the built-in interface and high charge density. This study opens new horizons for constructing Z-scheme MnO-based interface heterostructures with abundant defect sites for exceptional photocatalytic applications.

Development of silicon based electronics have revolutionized our every day life during the last five decades. Nowadays silicon based devices operate close to their theoretical limits that is becoming a bottleneck for further progress. In particular, for the growing field of high frequency and high power electronics, silicon cannot offer the required properties. Development of materials capable of providing high current densities, carrier mobilities and high breakdown fields is crucial for further progress in state of the art electronics.

Epitaxial graphene grown on semi-insulating silicon carbide substrates has a high potential to be integrated in current planar device technologies. High electron mobilities and sheet carrier densities make graphene extremely attractive for high frequency analog applications. One of the remaining challenges is the interaction of epitaxial graphene with the substrate. Typically, much lower free charge carrier mobilities, compared to free standing graphene, and doping, due to charge transfer from the substrate, is reported. Thus, a good understanding of the intrinsic free charge carriers properties and the factors affecting them is very important for further development of epitaxial graphene.

Group III-nitrides have been extensively studied and already have proven their high efficiency as light emitting diodes for short wavelengths. High carrier mobilities and breakdown electric fields were demonstrated for group III-nitrides, making them attractive for high frequency and high power applications. Currently, In-rich InGaN alloys and AlGaN/GaN high electron mobility structures are of high interest for the research community due to open fundamental questions such as free charge carrier properties at high temperatures and wavefunction hybridization in AlGaN/GaN heterostructures.

Electrical characterization techniques, commonly used for the determination of free charge carrier properties, require good ohmic and Schottky contacts, which in certain cases can be difficult to achieve. Access to electrical properties of buried conductive channels in multilayered structures requires modification of samples and good knowledge of the electrical properties of all electrical junctions within the structure. Moreover, the use of contacts to electrically characterize two-dimensional electronic materials, such as graphene, can alter their intrinsic properties. Furthermore, the determination of effective mass parameters commonly employs cyclotron resonance and Shubnikov-de Haas oscillations measurements, which require long scattering times of free charge carriers, high magnetic fields and low temperatures.

The optical Hall effect is an external magnetic-field induced birefringence of conductive layers due to the free charge carriers interaction with long-wavelength electromagnetic waves under the influence of the Lorentz force. The optical Hall effect can be measured by generalized ellipsometry and provides a powerful method for the determination of free charge carrier properties in a non-destructive and contactless manner. The optical Hall effect measurements can provide quantitative information about free charge carrier type, concentration, mobility and effective mass parameters at temperatures ranging from few kelvins to room temperature and above. It further allows to differentiate the free charge carrier properties of individual layers in multilayer samples. The employment of a backside cavity for transparent samples can enhance the optical Hall effect and allows to access free charge carrier properties at relatively low magnetic fields using permanent magnet.

The optical Hall effect measurements at mid-infrared spectral range can be used to probe quantum mechanical phenomena such as Landau levels in graphene. The magnetic field dependence of the inter-Landau level transition energies and optical polarization selection rules provide information about coupling properties between graphene layers and the electronic band structure.

Measurement of the optical Hall effect by generalized ellipsometry is an indirect technique requiring subsequent data analysis. Parameterized optical models are fitted to match experimentally measured ellipsometric spectra by varying physically significant model parameters. Analysis of the generalized ellipsometry data at long wavelengths for samples containing free charge carriers by optical models based on the classical Drude formulation, augmented with an external magnetic field contribution, allows to extract carrier concentration, mobility and effective mass parameters.

The development of the integrated FIR and THz frequency-domain ellipsometer at the Terahertz Materials Analysis Center in Linköping University was part of the graduate studies presented in this dissertation. The THz ellipsometer capabilities are demonstrated by determination of Si and sapphire optical constants, and free charge carrier properties of two-dimensional electron gas in GaN-based high electron mobility transistor structures. The THz ellipsometry is further shown to be capable of determining free charge carrier properties and following their changes upon variation of ambient conditions in atomically thin layers with an example of epitaxial graphene.

A potential of the THz OHE with the cavity enhancement (THz-CE-OHE) for determination of the free charge carrier properties in atomically thin layers were demonstrated by the measurements of the carrier properties in monolayer and multilayer epitaxial graphene on Si-face 4H-SiC. The data analysis revealed p-type doping for monolayer graphene with a carrier density in the low 10¹² cm^-2 range and a carrier mobility of 1550 cm²V^-1s^-1. For the multilayer graphene, n-type doping with a carrier density in the low 10¹³ cm^-2 range, a mobility of 470 cm²V^-1s^-1 and an effective mass of (0.14 ± 0.03)m₀ were extracted. Different type of doping among monolayer and multilayer graphene is explained as a result of different hydrophobicity among samples.

Further, we have employed THz-CE-OHE to determine for the first time anisotropic mobility parameter in quasi-free-standing bilayer epitaxial graphene induced by step-like surface morphology of 4H-SiC. Correlation of atomic force microscopy, Raman scattering spectroscopy, scanning probe Kelvin probe microscopy, low energy electron microscopy and diffraction analysis allows us to investigate the possible scattering mechanisms and suggests that anisotropic mobility is induced by varying local mobility parameter due to interaction between graphene and underlaying substrate.

The origin of the layers decoupling in multilayer graphene on C-face 4H-SiC was studied by MIR-OHE, transmission electron microscopy and electron energy loss spectroscopy. The results revealed the decoupling of the layers induced by the increased interlayer spacing which is attributed to the Si atoms trapped between graphene layers.

MIR ellipsometry and MIR-OHE measurements were employed to determine the electron effective mass in a wurtzite In_0.33Ga_0.67N epitaxial layer. The data analysis revealed the effective mass parameters parallel and perpendicular to the c-axis which can be considered as equal within sensitivity of our measurements. The determined effective mass is consistent with linear dependence on the In content.

Analysis of the free charge carrier properties in AlGaN/GaN high electron mobility structures with modified interfaces showed that AlGaN/GaN interface structure has a significant effect on the mobility parameter. A sample with a sharp interface layers exhibits a record mobility of 2332 ± 73 cm²V^-1s^-1. The determined effective mass parameters showed an increase compared to the bulk GaN value, which is attributed to the penetration of the electron wavefunction into the AlGaN barrier layer.

Temperature dependence of free charge carrier properties in GaN-based high electron mobility transistor structures with AlGaN and InAlN barrier layers were measured by terahertz optical Hall effect technique in a temperature range from 7.2 K to 398 K. The results revealed strong changes in the effective mass and mobility parameters. At temperatures below 57 K very high carrier mobility parameters above 20000 cm²V^-1s^-1 for AlGaN-barrier sample and much lower mobilities of ~ 5000 cm²V^-1s^-1 for InAlN-barrier sample were obtained. At low temperatures the effective mass parameters for both samples are very similar to bulk GaN value, while at temperatures above 131 K effective mass shows a strong increase with temperature. The effective masses of 0.344 m0 (@370 K) and 0.439 m0 (@398 K) were obtained for AlGaN- and InAlN-barrier samples, respectively. We discussed the possible origins of effective mass enhancement in high electron mobility transistor structures.  

Development of silicon based electronics have revolutionized our every day life during the last three decades. Nowadays Si based devices operate close to their theoretical limits that is becoming a bottleneck for further progress. In particular, for the growing field of high frequency and high power electronics, Si cannot offer the required properties. Development of materials capable of providing high current densities, carrier mobilities and high breakdown fields is crucial for a progress in state of the art electronics.

Epitaxial graphene grown on semi-insulating silicon carbide substrates has a high potential to be integrated in the current planar device technologies. High electron mobilities and sheet carrier densities make graphene extremely attractive for high frequency analog applications. One of the remaining challenges is the interaction of epitaxial graphene with the substrate. Typically, much lower free charge carrier mobilities, compared to free standing graphene, and doping, due to charge transfer from the substrate, is reported. Thus, a good understanding of the intrinsic free charge carriers properties and the factors affecting them is very important for further development of epitaxial graphene.

III-group nitrides have been extensively studied and already have proven their high efficiency as light sources for short wavelengths. High carrier mobilities and breakdown electric fields were demonstrated for III-group nitrides, making them attractive for high frequency and high power applications. Currently, In-rich InGaN alloys and AlGaN/GaN high electron mobility structures are of high interest for the research community due to open fundamental questions.

Electrical characterization techniques, commonly used for the determination of free charge carrier properties, require good ohmic and Schottky contacts, which in certain cases can be difficult to achieve. Access to electrical properties of buried conductive channels in multilayered structures requires modification of samples and good knowledge of the electrical properties of all electrical contact within the structure. Moreover, the use of electrical contacts to electrically characterize two-dimensional electronic materials, such as graphene, can alter their intrinsic properties. Furthermore, the determination of effective mass parameters commonly employs cyclotron resonance and Shubnikov-de Haas oscillations measurements, which require long scattering times of free charge carriers, high magnetic fields and low temperatures.

The optical Hall effect is an external magnetic field induced optical anisotropy in  conductive layers due to the motion of the free charge carriers under the influence of the Lorentz force, and is equivalent to the electrical Hall effect at optical frequencies. The optical Hall effect can be measured by generalized ellipsometry and provides a powerful method for the determination of free charge carrier properties in a non-destructive and contactless manner. In principle, a single optical Hall effect measurement can provide quantitative information about free charge carrier types, concentrations, mobilities and effective mass parameters at temperatures ranging from few kelvins to room temperature and above. Further, it was demonstrated that for transparent samples, a backside cavity can be employed to enhance the optical Hall effect.

Measurement of the optical Hall effect by generalized ellipsometry is an indirect technique requiring subsequent data analysis. Parameterized optical models are fitted to match experimentally measured ellipsometric data by varying physically significant parameters. Analysis of the optical response of samples, containing free charge carriers, employing optical models based on the classical Drude model, which is augmented with an external magnetic field contribution, provide access to the free charge carrier properties.

The main research results of the graduate studies presented in this licentiate thesis are summarized in the five scientific papers.

Paper I. Description of the custom-built terahertz frequency-domain spectroscopic ellipsometer at Linköping University. The terahertz ellipsometer capabilities are demonstrated by an accurate determination of the isotropic and anisotropic refractive indices of silicon and m-plane sapphire, respectively. Further, terahertz optical Hall effect measurements of an AlGaN/GaN high electron mobility structures were employed to extract the two-dimensional electron gas sheet density, mobility and effective mass parameters. Last, in-situ optical Hall effect measurement on epitaxial graphene in a gas cell with controllable environment, were used to study the effects of environmental doping on the mobility and carrier concentration.

Paper II. Presents terahertz cavity-enhanced optical Hall measurements of the monolayer and multilayer epitaxial graphene on semi-insulating 4H-SiC (0001) substrates. The data analysis revealed p-type doping for monolayer graphene with a carrier density in the low 1012 cm−2 range and a carrier mobility of 1550 cm2/V·s. For the multilayer epitaxial graphene, n-type doping with a carrier density in the low 1013 cm−2 range, a mobility of 470 cm2/V·s and an effective mass of (0.14 ± 0.03) m0 were extracted. The measurements demonstrate that cavity-enhanced optical Hall effect measurements can be applied to study electronic properties of two-dimensional materials.

Paper III. Terahertz cavity-enhanced optical Hall effect measurements are employed to study anisotropic transport in as-grown monolayer, quasi free-standing monolayer and quasi free-standing bilayer epitaxial graphene on semi-insulating 4H-SiC (0001) substrates. The data analysis revealed a strong anisotropy in the carrier mobilities of the quasi freestanding bilayer graphene. The anisotropy is demonstrated to be induced by carriers scattering at the step edges of the SiC, by showing that the mobility is higher along the step than across them. The scattering mechanism is discussed based on the results of the optical Hall effect, low-energy electron microscopy, low-energy electron diffraction and Raman measurements.

Paper IV. Mid-infrared spectroscopic ellipsometry and mid-infrared optical Hall effect measurements are employed to determine the electron effective mass in an In0.33Ga0.67N epitaxial layer. The data analysis reveals slightly anisotropic effective mass and carrier mobility parameters together with the optical phonon frequencies and broadenings.

Paper V. Terahertz cavity-enhanced optical Hall measurements are employed to study the free charge carrier properties in a set of AlGaN/GaN high electron mobility structures with modified interfaces. The results show that the interface structure has a significant effect on the free charge carrier mobility and that the sample with a sharp interface between an AlGaN barrier and a GaN buffer layers exhibits a record mobility of 2332±73 cm2/V·s. The determined effective mass parameters showed an increase compared to the GaN value, that is attributed the the penetration of the electron wavefunction into the AlGaN barrier layer.