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.

Atomikerroskasvatuksen soveltaminen kemiantekniikassa

Tässä kirjallisuustyössä tutkittiin atomikerroskasvatuksen (ALD) soveltamista kemiantekniikassa. Työn alussa kerrottiin atomikerroskasvatuksesta, sen toimintaperiaatteista ja prosessitekniikasta. Tämän jälkeen tutkittiin viittä eri kemiantekniikan sovellusta, jotka olivat polymeerien pinnoittaminen, heterogeenisten katalyyttien syntetisointi, membraanien modifiointi, korroosionesto ja kaasunilmaisimet. ALD on ohutkalvotekniikka, jolla voidaan valmistaa nanometrin tai jopa Ångströmin (1 Å = 0.1 nm) tarkkuudella epäorgaanisia materiaalikerroksia, jotka yleensä ovat metallioksideja, kuten alumiinioksidi. ALD perustuu kaasu-kiintoainereaktioihin, joissa kaasumaiset kemialliset prekursorit reagoivat vuorotellen kasvualustan kanssa. Tyypilliset prekursorit ovat metalliligandi ja vesi, joka on yleisin hapen lähde ALD-reaktioissa. ALD−reaktiot suoritetaan yleensä matalassa paineessa (100−200 Pa) ja korkeassa lämpötilassa (200–400 °C) suljetussa reaktorikammiossa. ALD-prosesseissa voidaan hyödyntää myös plasmaa alentamaan reaktiolämpötiloja. Plasman avulla prekursoreista luodaan hyvin reaktiivisia radikaaleja, jotka voivat reagoida jopa huoneenlämmössä. Lämpöherkkiä polymeerejä voidaan pinnoittaa ohutkalvoilla, joilla voidaan lisätä esimerkiksi pakkausmateriaalien suojaa happea ja vesihöyryä vastaan. ALD:llä voidaan syntetisoida tarkasti nanomittakaavan heterogeenisiä katalyyttejä, joilla on korkea dispersio tukimateriaalin pinnalla. ALD:n avulla voidaan säästää katalyyttimateriaalia menettämättä katalyytin aktiivisuutta, mikä on tärkeää monien katalyyttisovellusten taloudellisuuden kannalta, esimerkiksi polttokennot. ALD soveltuu hyvin membraanien modifiointiin, koska kaasumaiset prekursorit leviävät tasaisesti membraanin huokosiin. Membraanien pinnoittamisella pyritään vaikuttamaan, selektiivisyyteen, hydrofiilisyyteen, liuotinkestävyyteen, huokoskokoon ja sen jakaumaan. Lisäksi membraaneja voidaan pinnoittaa katalyyttisillä ohutkalvoilla, mikä on tärkeää nanoreaktoreiden kehityksen kannalta. ALD:llä voidaan pinnoittaa esimerkiksi terästä, ja vähentää täten teräksen korroosiota. Puolijohtavia metallioksideja voidaan käyttää kaasunilmaisimina, joiden valmistuksessa ALD:n tarkkuudesta on suurta hyötyä.

Climate driven changes in temperature, pH and food quality : effects on copepod reproduction

Increased emissions of greenhouse gases into the atmosphere are causing an anthropogenic climate change. The resulting global warming challenges the ability of organisms to adapt to the new temperature conditions. However, warming is not the only major threat. In marine environments, dissolution of carbon dioxide from the atmosphere causes a decrease in surface water pH, the so called ocean acidification. The temperature and acidification effects can interact, and create even larger problems for the marine flora and fauna than either of the effects would cause alone. I have used Baltic calanoid copepods (crustacean zooplankton) as my research object and studied their growth and stress responses using climate predictions projected for the next century. I have studied both direct temperature and pH effects on copepods, and indirect effects via their food: the changing phytoplankton spring bloom composition and toxic cyanobacterium. The main aims of my thesis were: 1) to find out how warming and acidification combined with a toxic cyanobacterium affect copepod reproductive success (egg production, egg viability, egg hatching success, offspring development) and oxidative balance (antioxidant capacity, oxidative damage), and 2) to reveal the possible food quality effects of spring phytoplankton bloom composition dominated by diatoms or dinoflagellates on reproducing copepods (egg production, egg hatching, RNA:DNA ratio). The two copepod genera used, Acartia sp. and Eurytemora affinis are the dominating mesozooplankton taxa (0.2 – 2 mm) in my study area the Gulf of Finland. The 20°C temperature seems to be within the tolerance limits of Acartia spp., because copepods can adapt to the temperature phenotypically by adjusting their body size. Copepods are also able to tolerate a pH decrease of 0.4 from present values, but the combination of warm water and decreased pH causes problems for them. In my studies, the copepod oxidative balance was negatively influenced by the interaction of these two environmental factors, and egg and nauplii production were lower at 20°C and lower pH, than at 20°C and ambient pH. However, presence of toxic cyanobacterium Nodularia spumigena improved the copepod oxidative balance and helped to resist the environmental stress, in question. In addition, adaptive maternal effects seem to be an important adaptation mechanism in a changing environment, but it depends on the condition of the female copepod and her diet how much she can invest in her offspring. I did not find systematic food quality difference between diatoms and dinoflagellates. There are both good and bad diatom and dinoflagellate species. Instead, the dominating species in the phytoplankton bloom composition has a central role in determining the food quality, although copepods aim at obtaining as a balanced diet as possible by foraging on several species. If the dominating species is of poor quality it can cause stress when ingested, or lead to non-optimal foraging if rejected. My thesis demonstrates that climate change induced water temperature and pH changes can cause problems to Baltic Sea copepod communities. However, their resilience depends substantially on their diet, and therefore the response of phytoplankton to the environmental changes. As copepods are an important link in pelagic food webs, their future success can have far reaching consequences, for example on fish stocks.

Power cycling lifetime estimation of IGBT power modules based on chip temperature modeling

In this doctoral thesis, methods to estimate the expected power cycling life of power semiconductor modules based on chip temperature modeling are developed. Frequency converters operate under dynamic loads in most electric drives. The varying loads cause thermal expansion and contraction, which stresses the internal boundaries between the material layers in the power module. Eventually, the stress wears out the semiconductor modules. The wear-out cannot be detected by traditional temperature or current measurements inside the frequency converter. Therefore, it is important to develop a method to predict the end of the converter lifetime. The thesis concentrates on power-cycling-related failures of insulated gate bipolar transistors. Two types of power modules are discussed: a direct bonded copper (DBC) sandwich structure with and without a baseplate. Most common failure mechanisms are reviewed, and methods to improve the power cycling lifetime of the power modules are presented. Power cycling curves are determined for a module with a lead-free solder by accelerated power cycling tests. A lifetime model is selected and the parameters are updated based on the power cycling test results. According to the measurements, the factor of improvement in the power cycling lifetime of modern IGBT power modules is greater than 10 during the last decade. Also, it is noticed that a 10 C increase in the chip temperature cycle amplitude decreases the lifetime by 40%. A thermal model for the chip temperature estimation is developed. The model is based on power loss estimation of the chip from the output current of the frequency converter. The model is verified with a purpose-built test equipment, which allows simultaneous measurement and simulation of the chip temperature with an arbitrary load waveform. The measurement system is shown to be convenient for studying the thermal behavior of the chip. It is found that the thermal model has a 5 C accuracy in the temperature estimation. The temperature cycles that the power semiconductor chip has experienced are counted by the rainflow algorithm. The counted cycles are compared with the experimentally verified power cycling curves to estimate the life consumption based on the mission profile of the drive. The methods are validated by the lifetime estimation of a power module in a direct-driven wind turbine. The estimated lifetime of the IGBT power module in a direct-driven wind turbine is 15 000 years, if the turbine is located in south-eastern Finland.

Reliability of SMD interconnections on flexible low-temperature substrates with inkjet-printed conductors

julkaisumaa: NLD

Topochemistry of physical and chemical pretreatments of biomass as investigated by FE-SEM, XPS and ToF-SIMS

Surface chemistry is of great importance in plant biomass engineering and applications. The surface chemical composition of biomass which includes lignin, carbohydrates and extractives influences its interactions with chemical agents, such as pulp processing/papermaking chemicals, or enzymes for different purposes. In this thesis, the changes in the surface chemical composition of lignocellulosic biomass after physical modification for the improvement of resulting paper properties and chemical treatment for the enhancement of enzymatic hydrolysis were investigated. Low consistency (LC) refining was used as physical treatment of bleached softwood and hardwood pulp samples, and the surface chemistry of refined samples was investigated. The refined pulp was analysed as whole pulp while the fines-free fibre samples were characterized separately. The fines produced in LCrefining contributed to an enlarged surface specific area as well as the change of surface coverage by lignin and extractives, as investigated by X-ray photoelectron spectroscopy (XPS). The surface coverage by lignin of the whole pulp decreased after refining while the surface coverage by extractives increased both for pine and eucalyptus. In the case of pine, the removal of fines resulted in reduction of the surface coverage by extractives, while the surface coverage by lignin increased on fibre sample (without fines). In the case of eucalyptus, the surface coverage by lignin of fibre samples decreased after the removal of fines. In addition, the surface distribution of carbohydrates, lignin and extractives of pine and eucalyptus samples was determined by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). LC-refining increased the amounts of pentose, hexose and extractives on the surface of pine samples. ToF-SIMS also gave clear evidence about xylan deposition and reduction of surface lignin distribution on the fibre of eucalyptus. However, the changes in the surface chemical composition during the physical treatment has led to an increase in the adsorption of fluorescent whitening agents (FWAs) on fibres due to a combination of electro-static forces, specific surface area of fibres and hydrophobic interactions. Various physicochemical pretreatments were conducted on wood and non-wood biomass for enhancing enzymatic hydrolysis of polysaccharides, and the surface chemistry of the pretreated and enzymatically hydrolysed samples was investigated by field emission scanning electron microscopy (FE-SEM), XPS and ToF-SIMS. A hydrotrope was used as a relatively novel pretreatment technology both in the case of wood and non-wood biomass. For comparison, ionic liquid and hydrothermal pretreatments were applied on softwood and hardwood as well. Thus, XPS analysis showed that the surface lignin was more efficiently removed by hydrotropic pretreatment compared to ionic liquid or hydrothermal pretreatments. SEM analysis also found that already at room temperature the ionic liquid pretreatments were more effective in swelling the fibres compared with hydrotropic pretreatment at elevated temperatures. The enzymatic hydrolysis yield of hardwood was enhanced due to the decrease in surface coverage of lignin, which was induced by hydrotropic treatment. However, hydrotropic pretreatment was not appropriate for softwood because of the predominance of guaiacyl lignin structure in this material. In addition, the reduction of surface lignin and xylan during pretreatment and subsequent increase in cellulose hydrolysis by enzyme could be observed from ToF-SIMS results. The characterisation of the non-wood biomass (e.g. sugarcane bagasse and common reed) treated by hydrotropic method, alkaline and alkaline hydrogen peroxide pretreatments were carried out by XPS and ToF-SIMS. According to the results, the action for the removal of the surface lignin of non-wood biomass by hydrotropic pretreatment was more significant compared to alkaline and alkaline hydrogen peroxide pretreatments, although a higher total amount of lignin could be removed by alkaline and alkaline hydrogen peroxide pretreatment. Furthermore, xylan could be remarkably more efficiently removed by hydrotropic method. Therefore, the glucan yield achieved from hydrotropic treated sample was higher than that from samples treated with alkaline or alkaline hydrogen peroxide. Through the use of ToF-SIMS, the distribution and localization of lignin and carbohydrates on the surface of ignocelluloses during pretreatment and enzymatic hydrolysis could be detected, and xylan degradation during enzymatic hydrolysis could also be assessed. Thus, based on the results from XPS and ToF-SIMS, the mechanism of the hydrotropic pretreatment in improving the accessibility of enzymes to fibre and further ameliorating of the enzymatic saccharification could be better elucidated.

Modeling of temperature regimes in a furnace of bubbling fluidized bed boiler

The work is mainly focused on the technology of bubbling fluidized bed combustion. Heat transfer and hydrodynamics of the process were examined in the work in detail. Special emphasis was placed on the process of heat exchange in a freeboard zone of bubbling fluidized bed boiler. Operating mode of bubbling fluidized bed boiler depends on many parameters. To assess the influence of some parameters on a temperature regime inside the furnace a simplified method of zonal modeling was used in the work. Thus, effects of bed material fineness, excess air ratio and changes in boiler load were studied. Besides the technology of combustion in bubbling fluidized bed, other common technologies of solid fuels combustion were reviewed. In addition, brief survey of most widely used types of solid fuel was performed in the work.

Reducing contact resistance in graphene devices

In this thesis, the contact resistance of graphene devices was investigated because high contact resistance is detrimental to the performance of graphene field-effect transistors (GFET). Method for increasing so-called edge-contact area was applied in device fabrication process, as few nanometers thick Ni layer was used as a catalytic etchant during the annealing process. Finally, Ni was also used as a metal for contact. GFETs were fabricated using electron beam lithography using graphene fabricated by chemical vapor deposition (CVD). Critical part of the fabrication process was to preserve the high quality of the graphene channel while etching the graphene at contact areas with Ni during the annealing. This was achieved by optimizing the combination of temperature and gas flows. The structural properties of graphene were studied using scanning electron microscopy, scanning confocal μ-Raman spectroscopy and optical microscopy. Evaluation of electric transport properties including contact resistance was carried out by transmission line method and four-probe method. The lowest contact resistance found was about at 350 Ωμm. In addition, different methods to transfer CVD graphene synthesized on copper were studied. Typical method using PMMA as a supporting layer leaves some residues after its removal, thus effecting on the performance of a graphene devices. In a metal assisted transfer method, metal is used as an interfacial layer between PMMA and graphene. This allows more effective removal of PMMA. However, Raman spectra of graphene transferred by metal assisted method showed somewhat lower quality than the PMMA assisted method

Track of HSMS Sophia tracing the extent of navigable water along the main northern ice between Spitzbergen and Greenland September 1868 : also showing the nature of the ice and temperature and depth of the sea

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Een eenfalligh Kennedoom af nödtorftelighe articklar vthdraghne aff then Helga schrifft / Laurentius Olai Gestricius. (Coll. 762, Aholansaari Foundation's deposition)

Quire structure: 9xIV⁷² + (IV–1)⁷⁹. Text in one column, on (mostly) 26–33 lines, not ruled. Catchwords frequently used at the foot of each page to indicate the next word when a sentence continues on the next page. Not foliated. Gothic Cursive in one saec. XVI² hand. The first initial of the book has been touched with what looks like red pencil. This may be a later addition, as also the green tint to the outer edges of the block. Titles and rubrics distinguished, if at all, through layout only. A note fol. [47]v (see also the main text on fol. [31]v) indicates that the text was copied in 1580. The Anti-Papist poem mentions the Jesuit Antonio Possevino, active in Sweden in 1577–1580 (Kiiskinen ed. 2010, 25, 27). The texts appear to be copies of printed works, with the possible exception of the Anti-Papist poem. The publication of Eric Falck’s Een Tröstbook is known, but apparently no printed copies survive; Laurentius Olai Gestricius’ catechism is otherwise unknown. He was a teacher in Gävle from 1557 or 1558, then curate of Västerås from 1561 and of Stockholm in 1562, where he died in 1565 (Kiiskinen ed. 2010, 15, 349; Collijn ed. 1927–1938, vol. 2, 324).

Transformation of carbon dioxide to diethyl carbonate over ceria and ceria-supported catalysts

Carbon dioxide is regarded, nowadays, as a primary anthropogenic greenhouse gas leading to global warming. Hence, chemical fixation of CO2 has attracted much attention as a possible way to manufacture useful chemicals. One of the most interesting approaches of CO2 transformations is the synthesis of organic carbonates. Since conventional production technologies of these compounds involve poisonous phosgene and carbon monoxide, there is a need to develop novel synthetic methods that would better match the principles of "Green Chemistry" towards protection of the environment and human health. Over the years, synthesis of dimethyl carbonate was under intensive investigation in the academia and industry. Therefore, this study was entirely directed towards equally important homologue of carbonic esters family namely diethyl carbonate (DEC). Novel synthesis method of DEC starting from ethanol and CO2 over heterogeneous catalysts based on ceria (CeO2) was studied in the batch reactor. However, the plausible drawback of the reaction is thermodynamic limitations. The calculated values revealed that the reaction is exothermic (ΔrHØ298K = ─ 16.6 J/ ) and does not occur spontaneously at rooms temperature (ΔrGØ 298K = 35.85 kJ/mol). Moreover, co-produced water easily shifts the reaction equilibrium towards reactants excluding achievement of high yields of the carbonate. Therefore, in-situ dehydration has been applied using butylene oxide as a chemical water trap. A 9-fold enhancement in the amount of DEC was observed upon introduction of butylene oxide to the reaction media in comparison to the synthetic method without any water removal. This result confirms that reaction equilibrium was shifted in favour of the desired product and thermodynamic boundaries of the reaction were suppressed by using butylene oxide as a water scavenger. In order to obtain insight into the reaction network, the kinetic experiments were performed over commercial cerium oxide. On the basis of the selectivity/conversion profile it could be concluded that the one-pot synthesis of diethyl carbonate from ethanol, CO2 and butylene oxide occurs via a consecutive route involving cyclic carbonate as an intermediate. Since commercial cerium oxide suffers from the deactivation problems already after first reaction cycle, in-house CeO2 was prepared applying room temperature precipitation technique. Variation of the synthesis parameters such as synthesis time, calcination temperature and pH of the reaction solution turned to have considerable influence on the physico-chemical and catalytic properties of CeO2. The increase of the synthesis time resulted in high specific surface area of cerium oxide and catalyst prepared within 50 h exhibited the highest amount of basic sites on its surface. Furthermore, synthesis under pH 11 yielded cerium oxide with the highest specific surface area, 139 m2/g, among all prepared catalysts. Moreover, CeO2─pH11 catalyst demonstrated the best catalytic activity and 2 mmol of DEC was produced at 180 oC and 9 MPa of the final reaction pressure. In addition, ceria-supported onto high specific surface area silicas MCM-41, SBA-15 and silica gel were synthesized and tested for the first time as catalysts in the synthesis of DEC. Deposition of cerium oxide on MCM-41 and SiO2 supports resulted in a substantial increase of the alkalinity of the carrier materials. Hexagonal SBA-15 modified with 20 wt % of ceria exhibited the second highest basicity in the series of supported catalysts. Evaluation of the catalytic activity of ceria-supported catalysts showed that reaction carried out over 20 wt % CeO2-SBA-15 generated the highest amount of DEC.

Bumblebees in a Changing Climate: Evaluating the Effects of Temperature on Queen Performance

Bumblebees are a very essential group of pollinating insects, but their populations have declined drastically during the past decades. We need to understand why their numbers are decreasing and what can be done to reverse this trend. Climate change-related phenomena, such as changes in the overwintering temperatures and spring conditions, are among the most prominent threats to bumblebees. Queens have a special role in the lifecycle of bumblebees because they overwinter and start new colonies the next year. Their successful performance: survival, overwintering ability, longevity, immune competence, and nest establishing capability in spring, is highly important for bumblebee populations. However, the effects of climate change on bumblebee queen performance remain unknown. The main objective of this thesis was to assess how temperature affects the performance of bumblebee queens during and after overwintering. The effects of warm temperature predicted by climate change scenarios on queen survival and stress-tolerance were studied by a four-month artificial diapause of bumblebee queens at two temperatures (9°C and 1.8°C). Bumblebee colonies were also reared in a laboratory and factors affecting colony characteristics were examined. In addition, queen performance during spring was studied in a starvation experiment using two temperatures (15°C as normal; 24°C as warmer than average) and queens collected from nature right after their emergence. My research revealed how temperature affects queen performance, and queen size was found to be an important factor determining the direction of some of these effects. We found a 0.4g weight threshold for bumblebee queens to be able to survive overwintering. In addition, during mild winters, larger queens have a higher chance than smaller ones to survive through winter and also to cope with immunological stresses after overwintering. During cold conditions, which are normal in the current climatic situation, this advantage disappears. In the spring starvation experiment, the starved queens survived approximately eight days longer in 15°C than in 24°C, which means that starvation risk rises significantly with increasing spring temperature, in a situation where food is scarce due to for example frost damage or asynchrony between bumblebees and their important food plants. These results could mean that in the future climate, larger queens are better able to survive the winter, initiate their nests and start rearing their offspring. This may be problematic, because I also detected two alternative strategies of colony development that differ between large and small queens; larger queens start to lay eggs earlier at nest initiation, their colonies mature later, they produce more workers, and they have a more strongly male biased sex allocation compared with smaller queens. If larger queens have a greater change of producing offspring after a mild winter, this could lead to a significant decline in the total production of new queens at a population level. Thus, it seems that queen size could act as one mechanism regulating the population level outcomes in different temperatures. The new information presented in my thesis reinforces that basic research, monitoring, and local species conservation of bumblebees both in Finland and globally must be increased to ensure that this highly important pollinator group survives in the face of climate change.

Roll-to-roll atomic layer deposition process for flexible electronics applications

Atomic Layer Deposition (ALD) is the technology of choice where very thin and highquality films are required. Its advantage is its ability to deposit dense and pinhole-free coatings in a controllable manner. It has already shown promising results in a range of applications, e.g. diffusion barrier coatings for OLED displays, surface passivation layers for solar panels. Spatial Atomic Layer Deposition (SALD) is a concept that allows a dramatic increase in ALD throughput. During the SALD process, the substrate moves between spatially separated zones filled with the respective precursor gases and reagents in such a manner that the exposure sequence replicates the conventional ALD cycle. The present work describes the development of a high-throughput ALD process. Preliminary process studies were made using an SALD reactor designed especially for this purpose. The basic properties of the ALD process were demonstrated using the wellstudied Al2O3 trimethyl aluminium (TMA)+H2O process. It was shown that the SALD reactor is able to deposit uniform films in true ALD mode. The ALD nature of the process was proven by demonstrating self-limiting behaviour and linear film growth. The process behaviour and properties of synthesized films were in good agreement with previous ALD studies. Issues related to anomalous deposition at low temperatures were addressed as well. The quality of the coatings was demonstrated by applying 20 nm of the Al2O3 on to polymer substrate and measuring its moisture barrier properties. The results of tests confirmed the superior properties of the coatings and their suitability for flexible electronics encapsulation. Successful results led to the development of a pilot scale roll-to-roll coating system. It was demonstrated that the system is able to deposit superior quality films with a water transmission rate of 5x10-6 g/m2day at a web speed of 0.25 m/min. That is equivalent to a production rate of 180 m2/day and can be potentially increased by using wider webs. State-of-art film quality, high production rates and repeatable results make SALD the technology of choice for manufacturing ultra-high barrier coatings for flexible electronics.

The Role of Structural Imperfections in Sr2FeMoO6 Thin Films

In this work, Sr2FeMoO6 (SFMO) thin films were studied with the main focus on their magnetic and magneto-transport properties. The fabrication process of pulsed laser deposited SFMO films was first optimized. Then the effects of strain, film thickness and substrate were thoroughly investigated. In addition to these external factors, the effect of intrinsic defects on the magnetic properties of SFMO were also clarified. Secondly, the magnetoresistivity mechanims of SFMO films were studied and a semiempirical model of the temperature dependence of resistivity was introduced. The films were grown on single crystal substrates using a ceramic target made with sol-gel method. The structural characterization of the films were carried out with X-ray diffraction, atomic force microscopy, transmission electron microscopy and high kinetic energy photoelectron spectroscopy. The magnetic properties were measured with SQUID magnetometer and the magneto-transport properties by magnetometer with a resistivity option. SFMO films with the best combination of structural and magnetic properties were grown in Ar atmosphere at 1050 °C . Their magnetic properties could not be improved by the ex situ post-annealing treatments aside from the treatments in ultra-high vacuum conditions. The optimal film thickness was found to be around 150 nm and only small improvement in the magnetic properties with decreasing strain was observed. Instead, the magnetic properties were observed to be highly dependent on the choice of the substrate due to the lattice mismatch induced defects, which are best avoided by using the SrTiO3 substrate. The large difference in the Curie temperature and the saturation magnetization between the SFMO thin film and polycrystalline bulk samples was connected to the antisite disorder and oxygen vacancies. Thus, the Curie temperature of SFMO thin films could be improved by increasing the amount of oxygen vacancies for example with ultra-high vacuum treatments or improving the B-site ordering by further optimization of the deposition parameters. The magneto-transport properties of SFMO thin films do not follow any conventional models, but the temperature dependence of resistivity was succesfully described with a model of two spin channel system. Also, evidences that the resistivity-temperature behaviour of SFMO thin films is dominated by the structural defects, which reduce the band gap in the majority spin band were found. Moreover, the magnetic field response of the resistivity in SFMO thin films were found to be superposition of different mechanisms that seems to be related to the structural changes in the film.