Growth, magnetic and transport properties of InSb and II-IV-As2 semiconductors doped with manganese

This thesis is devoted to growth and investigations of Mn-doped InSb and II-IV-As2 semiconductors, including Cd1-xZnxGeAs2:Mn, ZnSiAs2:Mn bulk crystals, ZnSiAs2:Mn/Si heterostructures. Bulk crystals were grown by direct melting of starting components followed by fast cooling. Mn-doped ZnSiAs2/Si heterostructures were grown by vacuum-thermal deposition of ZnAs2 and Mn layers on Si substrates followed by annealing. The compositional and structural properties of samples were investigated by different methods. The samples consist of micro- and nano- sizes clusters of an additional ferromagnetic Mn-X phases (X = Sb or As). Influence of magnetic precipitations on magnetic and electrical properties of the investigated materials was examined. With relatively high Mn concentration the main contribution to magnetization of samples is by MnSb or MnAs clusters. These clusters are responsible for high temperature behavior of magnetization and relatively high Curie temperature: up to 350 K for Mn-doped II-IV-As2 and about 600 K for InMnSb. The low-field magnetic properties of Mn-doped II-IV-As2 semiconductors and ZnSiAs2:Mn/Si heterostructures are connected to the nanosize MnAs particles. Also influence of nanosized MnSb clusters on low-field magnetic properties of InMnSb have been observed. The contribution of paramagnetic phase to magnetization rises at low temperatures or in samples with low Mn concentration. Source of this contribution is not only isolated Mn ions, but also small complexes, mainly dimmers and trimmers formed by Mn ions, substituting cation positions in crystal lattice. Resistivity, magnetoresistance and Hall resistivity properties in bulk Mn-doped II-IV-As2 and InSb crystals was analyzed. The interaction between delocalized holes and 3d shells of the Mn ions together with giant Zeeman splitting near the cluster interface are respond for negative magnetoresistance. Additionally to high temperature critical pointthe low-temperature ferromagnetic transition was observed Anomalous Hall effect was observed in Mn doped samples and analyzed for InMnSb. It was found that MnX clusters influence significantly on magnetic scattering of carriers.

The effects of real time control of welding parameters on weld quality in plasma arc keyhole welding

Joints intended for welding frequently show variations in geometry and position, for which it is unfortunately not possible to apply a single set of operating parameters to ensure constant quality. The cause of this difficulty lies in a number of factors, including inaccurate joint preparation and joint fit up, tack welds, as well as thermal distortion of the workpiece. In plasma arc keyhole welding of butt joints, deviations in the gap width may cause weld defects such as an incomplete weld bead, excessive penetration and burn through. Manual adjustment of welding parameters to compensate for variations in the gap width is very difficult, and unsatisfactory weld quality is often obtained. In this study a control system for plasma arc keyhole welding has been developed and used to study the effects of the real time control of welding parameters on gap tolerance during welding of austenitic stainless steel AISI 304L. The welding tests demonstrated the beneficial effect of real time control on weld quality. Compared with welding using constant parameters, the maximum tolerable gap width with an acceptable weld quality was 47% higher when using the real time controlled parameters for a plate thickness of 5 mm. In addition, burn through occurred with significantly larger gap widths when parameters were controlled in real time. Increased gap tolerance enables joints to be prepared and fit up less accurately, saving time and preparation costs for welding. In addition to the control system, a novel technique for back face monitoring is described in this study. The test results showed that the technique could be successfully applied for penetration monitoring when welding non magnetic materials. The results also imply that it is possible to measure the dimensions of the plasma efflux or weld root, and use this information in a feedback control system and, thus, maintain the required weld quality.

Syntheses of niobium oxide in the presence of magnetic field and determination of physical properties

Now when the technology fast developing it is very important to control the formation of materials with better properties. In the scientific literature there is a number of works describing the influence of magnetic field on the properties and process of formation of materials. The goal of this master's thesis is to analyze the process of electrochemical synthesis of niobium oxide in the present of magnetic field, to compare properties of formed oxide films and to estimate the influence of magnetic field on the process and on the result of synthesis.

Developing of AC magnetometer and investigation of magnetic properties of LSMO

In this work AC magnetometer was developed and primary test measurements were performed for temperature range from 77 K up to 350 K in frequency range from 1 kHz up to 20 kHz. In the course of the present work dependencies of magnetization on temperature for Lao7Sr03Mni _yFeyO3 with y = 0.15, 0.20, 0.25 were obtained in DC magnetic field using SQUID magnetometer and in AC magnetic field using the developed AC magnetometer. Lai.XSrXMnO3 (LSMO) compounds belong to the class of Mn perovskites, which demonstrate very high degree of spin polarization. These materials are of great importance for nowadays applications in spintronics, where spin polarized electron transport is used. Spin glass like behavior was found as a characteristic feature of these solid solutions with the freezing temperature in the range 65 — 210 K.

Magnetic and transport properties of II-V diluted magnetic semiconductors doped with manganese and nickel

This thesis is devoted to investigations of three typical representatives of the II-V diluted magnetic semiconductors, Zn1-xMnxAs2, (Zn1-xMnx)3As2 and p-CdSb:Ni. When this work started the family of the II-V semiconductors was presented by only the compounds belonging to the subgroup II3-V2, as (Zn1-xMnx)3As2, whereas the rest of the materials mentioned above were not investigated at all. Pronounced low-field magnetic irreversibility, accompanied with a ferromagnetic transition, are observed in Zn1-xMnxAs2 and (Zn1-xMnx)3As2 near 300 K. These features give evidence for presence of MnAs nanosize magnetic clusters, responsible for frustrated ground magnetic state. In addition, (Zn1-xMnx)3As2 demonstrates large paramagnetic response due to considerable amount of single Mn ions and small antiferromagnetic clusters. Similar paramagnetic system existing in Zn1-xMnxAs2 is much weaker. Distinct low-field magnetic irreversibility, accompanied with a rapid saturation of the magnetization with increasing magnetic field, is observed near the room temperature in p- CdSb:Ni, as well. Such behavior is connected to the frustrated magnetic state, determined by Ni-rich magnetic Ni1-xSbx nanoclusters. Their large non-sphericity and preferable orientations are responsible for strong anisotropy of the coercivity and saturation magnetization of p- CdSb:Ni. Parameters of the Ni1-xSbx nanoclusters are estimated. Low-temperature resistivity of p-CdSb:Ni is governed by a hopping mechanism of charge transfer. The variable-range hopping conductivity, observed in zero magnetic field, demonstrates a tendency of transformation into the nearest-neighbor hopping conductivity in non-zero magnetic filed. The Hall effect in p-CdSb:Ni exhibits presence of a positive normal and a negative anomalous contributions to the Hall resistivity. The normal Hall coefficient is governed mainly by holes activated into the valence band, whereas the anomalous Hall effect, attributable to the Ni1-xSbx nanoclusters with ferromagnetically ordered internal spins, exhibits a low-temperature power-law resistivity scaling.

Magnetic sputtering of complex oxides

HTSC materials are relevant in modern microelectronics, because of their transformation from the normal state to the superconducting. That is why the idea of producing HTSC in industrial amounts is actual nowadays. To decrease cost of their production it is important to use magnetron sputtering systems which give the best results for essential parameters. Modeling is the simplest and the fastest way to determine optimum sputtering condition. This thesis concentrates on determination the phases of the whole sputtering process and to find out basic factors of each phase using the modeling. It was find out, that the main factors which influence on the mode of occurrence of the initial stages are the current density of the magnetron discharge and the pressure of sputtering gas. With the modeling also velocity dependences were obtained for YBCO and SmFeAsO. These were compared and difference between them was examined. To support represented model comparison was made with experimental results. This showed that the model gives good results, very similar to the experimental ones. The results of this work were published in annual conference of the finnish physical society.

Magnetic and transport properties of LaMnO3+δ, La1-xCaxMnO3, La1-xCaxMn1-yFeyO3 and La1-xSrxMn1-yFeyO3

Interest to hole-doped mixed-valence manganite perovskites is connected to the ‘colossal’ magnetoresistance. This effect or huge drop of the resistivity, ρ, in external magnetic field, B, attains usually the maximum value near the ferromagnetic Curie temperature, TC. In this thesis are investigated conductivity mechanisms and magnetic properties of the manganite perovskite compounds LaMnO3+, La1-xCaxMnO3, La1-xCaxMn1-yFeyO3 and La1- xSrxMn1-yFeyO3. When the present work was started the key role of the phase separation and its influence on the properties of the colossal magnetoresistive materials were not clear. Our main results are based on temperature dependencies of the magnetoresistance and magnetothermopower, investigated in the temperature interval of 4.2 - 300 K in magnetic fields up to 10 T. The magnetization was studied in the same temperature range in weak (up to 0.1 T) magnetic fields. LaMnO3+δ is the parent compound for preparation of the hole-doped CMR materials. The dependences of such parameters as the Curie temperature, TC, the Coulomb gap, Δ, the rigid gap, γ, and the localization radius, a, on pressure, p, are observed in LaMnO3+δ. It has been established that the dependences above can be interpreted by increase of the electron bandwidth and decrease of the polaron potential well when p is increased. Generally, pressure stimulates delocalization of the electrons in LaMnO3+δ. Doping of LaMnO3 with Ca, leading to La1-xCaxMnO3, changes the Mn3+/Mn4+ ratio significantly and brings an additional disorder to the crystal lattice. Phase separation in a form of mixture of the ferromagnetic and the spin glass phases was observed and investigated in La1- xCaxMnO3 at x between 0 and 0.4. Influence of the replacement of Mn by Fe is studied in La0.7Ca0.3Mn1−yFeyO3 and La0.7Sr0.3Mn1−yFeyO3. Asymmetry of the soft Coulomb gap and of the rigid gap in the density of localized states, small shift of the centre of the gaps with respect to the Fermi level and cubic asymmetry of the density of states are obtained in La0.7Ca0.3Mn1−yFeyO3. Damping of TC with y is connected to breaking of the double-exchange interaction by doping with Fe, whereas the irreversibility and the critical behavior of the magnetic susceptibility are determined by the phase separation and the frustrated magnetic state of La0.7Sr0.3Mn1−yFeyO3.

Negative refractive index materials and propagation

Negative refractive index materials and propagation of electromagnetic waves in them started to draw attention of scientists not so long ago. This review highlights historically important and recent papers on practical and theoretical aspects related to these issues. Namely, basic properties and peculiarities of such materials related to both their design and wave propagation in them, experimental verification of predictions theoretically made for them, possible practical applications and prospects in this area are considered.

Magnetic properties of multi-walled nanotubes on polysterene substrate

Nanotubes are one of the most perspective materials in modern nanotechologies. It makes present investigation very actual. In this work magnetic properties of multi-walled nanotubes on polystyrene substrate are investigated by using quantum magnetometer SQUID. Main purpose was to obtain magnetic field and temperature dependences of magnetization and to compare them to existing theoretical models of magnetism in carbon-bases structures. During data analysis a mathematical algorithm for obtained data filtration was developed because measurement with quantum magnetometer assume big missives of number data, which contain accidental errors. Nature of errors is drift of SQUID signal, errors of different parts of measurement station. Nanotube samples on polystyrene substrate were studied with help of atomic force microscope. On the surface traces of nanotube were found contours, which were oriented in horizontal plane. This feature was caused by rolling method for samples. Detailed comparison of obtained dependences with information of other researches on this topic allows to obtain some conclusions about nature of magnetism in the samples. It emphasizes importance and actuality of this scientific work.

Chemical derivatization of galactoglucomannan for functional materials

In the framework of the biorefinery concept researchers aspire to optimize the utilization of plant materials, such as agricultural wastes and wood. For most of the known processes, the first steps in the valorisation of biomass are the extraction and purification of the individual components. The obtained raw products by means of a controlled separation can consecutively be modified to result in biofuels or biogas for energy production, but also in value-added products such as additives and important building blocks for the chemical and material industries. Considerable efforts are undertaken in order to substitute the use of oil-based starting materials or at least minimize their processing for the production of everyday goods. Wood is one of the raw materials, which have gained large attention in the last decades and its composition has been studied in detail. Nowadays, the extraction of water-soluble hemicelluloses from wood is well known and so for example xylan can be obtained from hardwoods and O-acetyl galactoglucomannans (GGMs) from softwoods. The aim of this work was to develop water-soluble amphiphilic materials of GGM and to assess their potential use as additives. Furthermore, GGM was also applied as a crosslinker in the synthesis of functional hydrogels for the removal of toxic metals and metalloid ions from aqueous solutions. The distinguished products were obtained by several chemical approaches and analysed by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), size exclusion chromatography (SEC), thermal gravimetric analysis (TGA), scanning electron microscope SEM, among others. Bio-based surfactants were produced by applying GGM and different fatty acids as starting materials. On one hand, GGM-grafted-fatty acids were prepared by esterification and on the other hand, well-defined GGM-block-fatty acid derivatives were obtained by linking amino-functional fatty acids to the reducing end of GGM. The reaction conditions for the syntheses were optimized and the resultant amphiphilic GGM derivatives were evaluated concerning their ability to reduce the surface tension of water as surfactants. Furthermore, the block-structured derivatives were tested in respect to their applicability as additives for the surface modification of cellulosic materials. Besides the GGM surfactants with a bio-based hydrophilic and a bio-based hydrophobic part, also GGM block-structured derivatives with a synthetic hydrophobic tail, consisting of a polydimethylsiloxane chain, were prepared and assessed for the hydrophobization of surface of nanofibrillated cellulose films. In order to generate GGM block-structured derivatives containing a synthetic tail with distinguished physical and chemical properties, as well as a tailored chain length, a controlled polymerization method was used. Therefore, firstly an initiator group was introduced at the reducing end of the GGM and consecutively single electron transfer-living radical polymerization (SET-LRP) was performed by applying three different monomers in individual reactions. For the accomplishment of the synthesis and the analysis of the products, challenges related to the solubility of the reactants had to be overcome. Overall, a synthesis route for the production of GGM block-copolymers bearing different synthetic polymer chains was developed and several derivatives were obtained. Moreover, GGM with different molar masses were, after modification, used as a crosslinker in the synthesis of functional hydrogels. Hereby, a cationic monomer was used during the free radical polymerization and the resultant hydrogels were successfully tested for the removal of chromium and arsenic ions from aqueous solutions. The hydrogel synthesis was tailored and materials with distinguished physical properties, such as the swelling rate, were obtained after purification. The results generated in this work underline the potential of bio-based products and the urge to continue carrying out research in order to be able to use more green chemicals for the manufacturing of biorenewable and biodegradable daily products.

Modified nano- and microcellulose based adsorption materials in water treatment

In recent decades, industrial activity growth and increasing water usage worldwide have led to the release of various pollutants, such as toxic heavy metals and nutrients, into the aquatic environment. Modified nanocellulose and microcellulose-based adsorption materials have the potential to remove these contaminants from aqueous solutions. The present research consisted of the preparation of five different nano/microcellulose-based adsorbents, their characterization, the study of adsorption kinetics and isotherms, the determination of adsorption mechanisms, and an evaluation of adsorbents’ regeneration properties. The same well known reactions and modification methods that were used for modifying conventional cellulose also worked for microfibrillated cellulose (MFC). The use of succinic anhydride modified mercerized nanocellulose, and aminosilane and hydroxyapatite modified nanostructured MFC for the removal of heavy metals from aqueous solutions exhibited promising results. Aminosilane, epoxy and hydroxyapatite modified MFC could be used as a promising alternative for H2S removal from aqueous solutions. In addition, new knowledge about the adsorption properties of carbonated hydroxyapatite modified MFC as multifunctional adsorbent for the removal of both cations and anions ions from water was obtained. The maghemite nanoparticles (Fe3O4) modified MFC was found to be a highly promising adsorbent for the removal of As(V) from aqueous solutions due to its magnetic properties, high surface area, and high adsorption capacity . The maximum removal efficiencies of each adsorbent were studied in batch mode. The results of adsorption kinetics indicated very fast removal rates for all the studied pollutants. Modeling of adsorption isotherms and adsorption kinetics using various theoretical models provided information about the adsorbent’s surface properties and the adsorption mechanisms. This knowledge is important for instance, in designing water treatment units/plants. Furthermore, the correspondence between the theory behind the model and properties of the adsorbent as well as adsorption mechanisms were also discussed. On the whole, both the experimental results and theoretical considerations supported the potential applicability of the studied nano/microcellulose-based adsorbents in water treatment applications.

Strong magnetic field pulse generator

High magnetic fields and extremely low temperatures are essential in the study of new semiconductor materials for example in the field of spintronics. Typical phenomenons that arise in such conditions are: Hall Effect, Anomalous Hall effect and Shubnikov de-Haas effect. In this thesis a device capable for such conditions was described. A strong magnetic field pulse generator situated in the laboratory of physics and the Lappeenranta University of Technology was studied. The device is introduced in three parts. First one is the pulsed field magnetic generator, which is responsible for generating the high magnetic field. Next one is the measurement systems, which are responsible for monitoring the sample and the system itself. The last part describes the cryostat system, which allows the extremely cold temperatures in the system.

Emission, kinetic and magnetic phenomena in rare-earth and transition metal doped ZnSe single crystals

In this work emission, optical, electrical and magnetic properties of the d- and f- elements doped zinc selenide crystals were investigated within a wide temperature range. Doping was performed in various technological processes: during the growth by chemical vapor transport method; by thermal diffusion from the Bi or Zn melt. Concentration of the doping impurity in the crystals was controlled by amount of the dopant in the source material or by its concentration in the doping media. Special interest in the work was paid to the influence of the different concentrations of Cr and Yb impurities on ZnSe crystals’ properties, correlations between observed effects and similarities with the Ni, Mn and Gd dopants are analysed. Possibility of formation of the excitons bound to the doping d-ions was shown. In contrast to this, it was observed that f-elements do not bound excitons, but prevent formation of excitons bound to some uncontrolled impurities. A mechanism of Cr doping impurity interaction with background impurities and zinc selenide structural defects was proposed based on experimental data. An assumption about resonant energy transfer between double charged chromium ions and complexes based on crystals’ vacancy defects was made. A correlation between emission and magnetic properties of the d- ions doped samples was established. Based on this correlation a mechanism explaining the concentration quench of the emission was proposed. It was found that f-ions bind electrically active shallow and deep donor and acceptor states of background impurity to electrically neutral complexes. This may be observed as “purification” of ZnSe crystals by doping with the rare-earth elements, resulting i tendency of the properties of f-ion doped crystals to the properties of intrinsic crystals, but with smaller concentration of uncontrolled native and impurity defects. A possible interpretation of this effect was proposed. It was shown that selenium substituting impurities decrease efficiency of the Yb doping. Based on this experimental results an attempt to determine ytterbium ion surroundings in the crystal lattice was made. It was shown that co-doping of zinc selenide crystals with the d- and f- ions leads to the combination of the impurities influence on the material’s properties. On the basis of obtained data an interaction mechanism of the d- and f-elements co-dopants was proposed. Guided by the model of the ytterbium ion incorporation in the selenide sublattice of the ZnSe crystals, an assumption about stabilization of single charged chromium ions in the zinc sublattice crystal nodes, by means of formation of the local charge compensating clusters, was made.

Modification of commercial poly-lactide for extrusion coated food packaging applications

Poly-L-lactide (PLLA) is a widely used sustainable and biodegradable alternative to replace synthetic non-degradable plastic materials in the packaging industry. Conversely, its processing properties are not always optimal, e.g. insufficient melt strength at higher temperatures (necessary in extrusion coating processes). This thesis reports on research to improve properties of commercial PLLA grade (3051D from NatureWorks), to satisfy and extend end-use applications, such as food packaging by blending with modified PLLA. Adjustment of the processability by chain branching of commercial poly-L-lactide initiated by peroxide was evaluated. Several well-defined branched structures with four arms (sPLLA) were synthesized using pentaerythritol as a tetra-functional initiator. Finally, several block copolymers consisting of polyethylene glycol and PLLA (i.e. PEGLA) were produced to obtain a well extruded material with improved heat sealing properties. Reactive extrusion of poly-L-lactide was carried out in the presence of 0.1, 0.3 and 0.5 wt% of various peroxides [tert-butyl-peroxybenzoate (TBPB), 2,5-dimethyl-2,5-(tert-butylperoxy)-hexane (Lupersol 101; LOL1) and benzoyl peroxide (BPO)] at 190C. The peroxide-treated PLLAs showed increased complex viscosity and storage modulus at lower frequencies, indicating the formation of branched/cross linked architectures. The material property changes were dependent on the peroxide, and the used peroxide concentration. Gel fraction analysis showed that the peroxides, afforded different gel contents, and especially 0.5 wt% peroxide, produced both an extremely high molar mass, and a cross linked structure, not perhaps well suited for e.g. further use in a blending step. The thermal behavior was somewhat unexpected as the materials prepared with 0.5 wt% peroxide showed the highest ability for crystallization and cold crystallization, despite substantial cross linking. The peroxide-modified PLLA, i.e. PLLA melt extruded with 0.3 wt% of TBPB and LOL1 and 0.5 wt% BPO was added to linear PLLA in ratios of 5, 15 and 30 wt%. All blends showed increased zero shear viscosity, elastic nature (storage modulus) and shear sensitivity. All blends remained amorphous, though the ability of annealing was improved slightly. Extrusion coating on paperboard was conducted with PLLA, and peroxide-modified PLLA blends (90:10). All blends were processable, but only PLLA with 0.3 wt% of LOL1 afforded a smooth high quality surface with improved line speed. Adhesion levels between fiber and plastic, as well as heat seal performance were marginally reduced compared with pure 3051D. The water vapor transmission measurements (WVTR) of the blends containing LOL1 showed acceptable levels, only slightly lower than for comparable PLLA 3051D. A series of four-arm star-shaped poly-L-lactide (sPLLA) with different branch length was synthesized by ring opening polymerization (ROP) of L-lactide using pentaerythritol as initiator and stannous octoate as catalyst. The star-shaped polymers were further blended with its linear resin and studied for their melt flow and thermal properties. Blends containing 30 wt% of sPLLA with low molecular weight (30 wt%; Mwtotal: 2500 g mol-1 and 15000 g mol-1) showed lower zero shear viscosity and significantly increased shear thinning, while at the same time slightly increased crystallization of the blend. However, the amount of crystallization increased significantly with the higher molecular weight sPLLA, therefore the star-shaped structure may play a role as nucleating agent. PLLA-polyethylene glycol–PLLA triblock copolymers (PEGLA) with different PLLA block length were synthesized and their applicability as blends with linear PLLA (3051D NatureWorks) was investigated with the intention of improving heat-seal and adhesion properties of extrusion-coated paperboard. PLLA-PEG-PLLA was obtained by ring opening polymerization (ROP) of L-lactide using PEG (molecular weight 6000 g mol-1) as an initiator, and stannous octoate as catalyst. The structures of the PEGLAs were characterized by proton nuclear magnetic resonance spectroscopy (1H-NMR). The melt flow and thermal properties of all PEGLAs and their blends were evaluated using dynamic rheology, and differential scanning calorimeter (DSC). All blends containing 30 wt% of PEGLAs showed slightly higher zero shear viscosity, higher shear thinning and increased melt elasticity (based on tan delta). Nevertheless, no significant changes in thermal properties were distinguished. High molecular weight PEGLAs were used in extrusion coating line with 3051D without problems.