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.

Finnish Critical Industries, Maritime Transport Vulnerabilities and societal Implications

Maritime transports are very essential for Finland as over 80% of the foreign trade in the country is seaborne and possibilities to carry out these transports by are limited. Any disruption in maritime transports has negative consequences to many sectors in the Finnish economy. Maritime transport thus represents critical infrastructure for Finland. This report focuses on the importance of maritime transports on security of supply in Finland and for the so called critical industries in particular. The report summarizes the results of the Work Package 2 of the research project STOCA – “Study of cargo flows in the Gulf of Finland in emergency situations”. The aim of the research was to analyze the cargo flows and infrastructure that are vital for maintaining security of supply in Finland, as well as the consequences of disruptions in the maritime traffic for the Finnish critical industries and for the Finnish society. In the report we give a presentation of the infrastructure and transport routes which are critical for maintaining security of supply in Finland. We discuss import dependency of the critical industries, and the importance of the Gulf of Finland ports for Finland. We assess vulnerabilities associated with the critical material flows of the critical industries, and possibilities for alternative routings in case either one or several of the ports in Finland would be closed. As a concrete example of a transport disruption we analyze the consequences of the Finnish stevedore strike at public ports (4.3.–19.3.2010). The strike stopped approximately 80% of the Finnish foreign trade. As a result of the strike Finnish companies could not export their products and/or import raw materials, components and spare parts, or other essential supplies. We carried out personal interviews with representatives of the companies in Finnish critical industries to find out about the problems caused by the strike, how companies carried out they transports and how they managed to continue their operations during the strike. Discussions with the representatives of the companies gave us very practical insights about companies’ preparedness towards transport disruptions in general. Companies in the modern world are very vulnerable to transport disruptions because companies regardless of industries have tried to improve their performance by optimizing their resources and e.g. by reducing their inventory levels. At the same time they have become more and more dependent on continuous transports. Most companies involved in foreign trade have global operations and global supply chains, so any disruption anywhere in the world can have an impact on the operations of the company causing considerable financial loss. The volcanic eruption in Iceland in April 2010 stopping air traffic in the whole Northern Europe and most recently the earth quake causing a tsunami in Japan in March 2011 are examples of severe disruptions causing considerable negative impacts to companies’ supply chains. Even though the Finnish stevedore strike was a minor disruption compared to the natural catastrophes mentioned above, it showed the companies’ vulnerability to transport disruptions very concretely. The Finnish stevedore strike gave a concrete learning experience of the importance of preventive planning for all Finnish companies: it made them re-think their practical preparedness towards transport risks and how they can continue with their daily operations despite the problems. Many companies realized they need to adapt their long-term countermeasures against transport disruptions. During the strike companies did various actions to secure their supply chains. The companies raised their inventory levels before the strike began, they re-scheduled or postponed their deliveries, shifted customer orders between production plants among their company’s production network or in the extreme case bought finished products from their competitor to fulfil their customers’ order. Our results also show that possibilities to prepare against transport disruptions differ between industries. The Finnish society as a whole is very dependent on imports of energy, various raw materials and other supplies needed by the different industries. For many of the Finnish companies in the export industries and e.g. in energy production maritime transport is the only transport mode the companies can use due to large volumes of materials transported or due to other characteristics of the goods. Therefore maritime transport cannot be replaced by any other transport mode. In addition, a significant amount of transports are concentrated in certain ports. From a security of supply perspective attention should be paid to finding ways to decrease import dependency and ensuring that companies in the critical industries can ensure the continuity of their operations.

Charge transport in disordered materials : simulations, theory, and numerical modeling of hopping transport and electron-hole recombination

Min avhandling behandlar hur oordnade material leder elektrisk ström. Bland materialen som studeras finns ledande polymerer, d.v.s. plaster som leder ström, och mer allmänt organiska halvledare. Av de här materialen har man kunnat bygga elektroniska komponenter, och man hoppas på att kunna trycka hela kretsar av organiska material. För de här tillämpningarna är det viktigt att förstå hur materialen själva leder elektrisk ström. Termen oordnade material syftar på material som saknar kristallstruktur. Oordningen gör att elektronernas tillstånd blir lokaliserade i rummet, så att en elektron i ett visst tillstånd är begränsad t.ex. till en molekyl eller ett segment av en polymer. Det här kan jämföras med kristallina material, där ett elektrontillstånd är utspritt över hela kristallen (men i stället har en väldefinierad rörelsemängd). Elektronerna (eller hålen) i det oordnade materialet kan röra sig genom att tunnelera mellan de lokaliserade tillstånden. Utgående från egenskaperna för den här tunneleringsprocessen, kan man bestämma transportegenskaperna för hela materialet. Det här är utgångspunkten för den så kallade hopptransportmodellen, som jag har använt mig av. Hopptransportmodellen innehåller flera drastiska förenklingar. Till exempel betraktas elektrontillstånden som punktformiga, så att tunneleringssannolikheten mellan två tillstånd endast beror på avståndet mellan dem, och inte på deras relativa orientation. En annan förenkling är att behandla det kvantmekaniska tunneleringsproblemet som en klassisk process, en slumpvandring. Trots de här grova approximationerna visar hopptransportmodellen ändå många av de fenomen som uppträder i de verkliga materialen som man vill modellera. Man kan kanske säga att hopptransportmodellen är den enklaste modell för oordnade material som fortfarande är intressant att studera. Man har inte hittat exakta analytiska lösningar för hopptransportmodellen, därför använder man approximationer och numeriska metoder, ofta i form av datorberäkningar. Vi har använt både analytiska metoder och numeriska beräkningar för att studera olika aspekter av hopptransportmodellen. En viktig del av artiklarna som min avhandling baserar sig på är att jämföra analytiska och numeriska resultat. Min andel av arbetet har främst varit att utveckla de numeriska metoderna och applicera dem på hopptransportmodellen. Därför fokuserar jag på den här delen av arbetet i avhandlingens introduktionsdel. Ett sätt att studera hopptransportmodellen numeriskt är att direkt utföra en slumpvandringsprocess med ett datorprogram. Genom att föra statisik över slumpvandringen kan man beräkna olika transportegenskaper i modellen. Det här är en så kallad Monte Carlo-metod, eftersom själva beräkningen är en slumpmässig process. I stället för att följa rörelsebanan för enskilda elektroner, kan man beräkna sannolikheten vid jämvikt för att hitta en elektron i olika tillstånd. Man ställer upp ett system av ekvationer, som relaterar sannolikheterna för att hitta elektronen i olika tillstånd i systemet med flödet, strömmen, mellan de olika tillstånden. Genom att lösa ekvationssystemet fås sannolikhetsfördelningen för elektronerna. Från sannolikhetsfördelningen kan sedan strömmen och materialets transportegenskaper beräknas. En aspekt av hopptransportmodellen som vi studerat är elektronernas diffusion, d.v.s. deras slumpmässiga rörelse. Om man betraktar en samling elektroner, så sprider den med tiden ut sig över ett större område. Det är känt att diffusionshastigheten beror av elfältet, så att elektronerna sprider sig fortare om de påverkas av ett elektriskt fält. Vi har undersökt den här processen, och visat att beteendet är väldigt olika i endimensionella system, jämfört med två- och tredimensionella. I två och tre dimensioner beror diffusionskoefficienten kvadratiskt av elfältet, medan beroendet i en dimension är linjärt. En annan aspekt vi studerat är negativ differentiell konduktivitet, d.v.s. att strömmen i ett material minskar då man ökar spänningen över det. Eftersom det här fenomenet har uppmätts i organiska minnesceller, ville vi undersöka om fenomenet också kan uppstå i hopptransportmodellen. Det visade sig att det i modellen finns två olika mekanismer som kan ge upphov till negativ differentiell konduktivitet. Dels kan elektronerna fastna i fällor, återvändsgränder i systemet, som är sådana att det är svårare att ta sig ur dem då elfältet är stort. Då kan elektronernas medelhastighet och därmed strömmen i materialet minska med ökande elfält. Elektrisk växelverkan mellan elektronerna kan också leda till samma beteende, genom en så kallad coulombblockad. En coulombblockad kan uppstå om antalet ledningselektroner i materialet ökar med ökande spänning. Elektronerna repellerar varandra och ett större antal elektroner kan leda till att transporten blir långsammare, d.v.s. att strömmen minskar.

Future prospects of short distance rail based passenger transport in Northern Europe

The worlds’ population is increasing and cities have become more crowded with people and vehicles. Communities in the fringe of metropolitans’ increase the traffic done with private cars, but also increase the need for public transportation. People have typically needs traveling to work located in city centers during the morning time, and return to suburbs in the afternoon or evening. Rail based passenger transport is environmentally friendly transport mode with high capacity to transport large volume of people. Railways have been regulated markets with national incumbent having monopoly position. Opening the market for competition is believed to have a positive effect by increasing the efficiency of the industry. National passenger railway market is opened for competition only in few countries, where as international traffic in EU countries was deregulated in 2010. The objective of this study is to examine the passenger railway market of three North European countries, Sweden, Denmark and Estonia. The interest was also to get an understanding of the current situation and how the deregulation has proceeded. Theory of deregulation is unfolded with literature analyses and empirical part of the study is constructed from two parts. Customer satisfaction survey was chosen as a method to collect real life experiences from the passengers and measure their knowledge of the market situation and possible changes appeared. Interviews of experts from the industry and labor unions give more insights and able better understanding for example of social consequences caused from opening the market for competition. Expert interviews were conducted by using semi-structured theme interview. Based on the results of this study, deregulation has proceeded quite differently in the three countries researched. Sweden is the most advanced country, where the passenger railway market is open for new entrants. Denmark and Estonia are lagging behind. Opening the market is considered positive among passengers and most of the experts interviewed. Common for the interviews were the labour unions negative perspective concerning deregulation. Despite the fact deregulation is considered positive among the respondents of the customer satisfaction survey, they could not name railway undertakings operating in their country. Generally respondents were satisfied with the commuter trains. Ticket price, punctuality of trains and itinerary affect the most to customer satisfaction.

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.

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