Quantum transport phenomena and shallow impurity states in CdSb

This work is dedicated to investigation of the energy spectrum of one of the most anisotropic narrow-gap semiconductors, CdSb. At the beginning of the present studies even the model of its energy band structure was not clear. Measurements of galvanomagnetic effects in wide temperature range (1.6 - 300 K) and in magnetic fields up to 30 T were chosen for clarifying of the energy spectrum in the intentionally undoped CdSb single crystals and doped with shallow impurities (In, Ag). Detection of the Shubnikov - de Haas oscillations allowed estimating the fundamental energy spectrum parameters. The shapes of the Fermi surfaces of electrons (sphere) and holes (ellipsoid), the number of the equivalent extremums for valence band (2) and their positions in the Brillouin zone were determined for the first time in this work. Also anisotropy coefficients, components of the tensor of effective masses of carriers, effective masses of density of states, nonparabolicity of the conduction and valence bands, g-factor and its anisotropy for n- and p-CdSb were estimated for the first time during these studies. All the results obtained are compared with the cyclotron resonance data and the corresponding theoretical calculations for p-CdSb. This is basic information for the analyses of the complex transport properties of CdSb and for working out the energy spectrum model of the shallow energy levels of defects and impurities in this semiconductor. It was found out existence of different mechanisms of hopping conductivity in the presence of metal - insulator transition induced by magnetic field in n- and p-CdSb. Quite unusual feature opened in CdSb is that different types of hopping conductivity may take place in the same crystal depending on temperature, magnetic field or even orientation of crystal in magnetic field. Transport properties of undoped p-CdSb samples show that the anisotropy of the resistivity in weak and strong magnetic fields is determined completely by the anisotropy of the effective mass of the holes. Temperature and magnetic field dependence of the Hall coefficient and magnetoresistance is attributed to presence of two groups of holes with different concentrations and mobilities. The analysis demonstrates that below Tcr ~ 20 K and down to ~ 6 - 7 K the low-mobile carriers are itinerant holes with energy E2 ≈ 6 meV. The high-mobile carriers, at all temperatures T < Tcr, are holes activated thermally from a deeper acceptor band to itinerant states of a shallower acceptor band with energy E1 ≈ 3 meV. Analysis of temperature dependences of mobilities confirms the existence of the heavy-hole band or a non-equivalent maximum and two equivalent maxima of the light-hole valence band. Galvanomagnetic effects in n-CdSb reveal the existence of two groups of carriers. These are the electrons of a single minimum in isotropic conduction band and the itinerant electrons of the narrow impurity band, having at low temperatures the energies above the bottom of the conduction band. It is found that above this impurity band exists second impurity band of only localized states and the energy of both impurity bands depend on temperature so that they sink into the band gap when temperature is increased. The bands are splitted by the spin, and in strong magnetic fields the energy difference between them decreases and redistribution of the electrons between the two impurity bands takes place. Mobility of the conduction band carriers demonstrates that scattering in n-CdSb at low temperatures is strongly anisotropic. This is because of domination from scattering on the neutral impurity centers and increasing of the contribution to mobility from scattering by acoustic phonons when temperature increases. Metallic conductivity in zero or weak magnetic field is changed to activated conductivity with increasing of magnetic field. This exhibits a metal-insulator transition (MIT) induced by the magnetic field due to shift of the Fermi level from the interval of extended states to that of the localized states of the electron spectrum near the edge of the conduction band. The Mott variablerange hopping conductivity is observed in the low- and high-field intervals on the insulating side of the MIT. The results yield information about the density of states, the localization radius of the resonant impurity band with completely localized states and about the donor band. In high magnetic fields this band is separated from the conduction band and lies below the resonant impurity bands.

Defects in Persistent Luminescence Materials

Persistent luminescence materials can store energy from solar radiation or artificial lighting and release it over a period of several hours without a continuous excitation source. These materials are widely used to improve human safety in emergency and traffic signalization. They can also be utilized in novel applications including solar cells, medical diagnostics, radiation detectors and structural damage sensors. The development of these materials is currently based on methods based on trial and error. The tailoring of new materials is also hindered by the lack of knowledge on the role of their intrinsic and extrinsic lattice defects in the appropriate mechanisms. The goal of this work was to clarify the persistent luminescence mechanisms by combining ab initio density functional theory (DFT) calculations with selected experimental methods. The DFT approach enables a full control of both the nature of the defects and their locations in the host lattice. The materials studied in the present work, the distrontium magnesium disilicate (Sr₂MgSi₂O₇) and strontium aluminate (SrAl₂O₄) are among the most efficient persistent luminescence hosts when doped with divalent europium Eu²⁺ and co-doped with trivalent rare earth ions R³⁺ (R: Y, La-Nd, Sm, Gd-Lu). The polycrystalline materials were prepared with the solid state method and their structural and phase purity was confirmed by X-ray powder diffraction. Their local crystal structure was studied by high-resolution transmission electron microscopy. The crystal and electronic structure of the nondoped as well as Eu²⁺, R^2+/3+ and other defect containing materials were studied using DFT calculations. The experimental trap depths were obtained using thermoluminescence (TL) spectroscopy. The emission and excitation of Sr₂MgSi₂O₇:Eu²+,Dy³⁺ were also studied. Significant modifications in the local crystal structure due to the Eu²⁺ ion and lattice defects were found by the experimental and DFT methods. The charge compensation effects induced by the R³⁺ co-doping further increased the number of defects and distortions in the host lattice. As for the electronic structure of Sr₂MgSi₂O₇ and SrAl₂O₄, the experimental band gap energy of the host materials was well reproduced by the calculations. The DFT calculated Eu²⁺ and R^2+/3+ 4fn as well as 4f^n-15d¹ ground states in the Sr₂MgSi₂O₇ band structure provide an independent verification for an empirical model which is constructed using rather sparse experimental data for the R³⁺ and especially the R²⁺ ions. The intrinsic and defect induced electron traps were found to act together as energy storage sites contributing to the materials’ efficient persistent luminescence. The calculated trap energy range agreed with the trap structure of Sr₂MgSi₂O₇ obtained using TL measurements. More experimental studies should be carried out for SrAl₂O₄ to compare with the DFT calculations. The calculated and experimental results show that the electron traps created by both the rare earth ions and vacancies are modified due to the defect aggregation and charge compensation effects. The relationships between this modification and the energy storage properties of the solid state materials are discussed.

Computational modeling of the properties of TiO2 nanoparticles

In this study we discuss the electronic, structural, and optical properties of titanium dioxide nanoparticles, and also the properties of Ni(II) diimine dithiolato complexes as dyes in dye-sensitized TiO2 based solar cells. The abovementioned properties have been modeled by using computational codes based on the density functional theory. The results achieved show slight evidence on the structure-dependent band gap broadening, and clear blue-shifts in absorption spectra and refractive index functions of ultra-small TiO2 particles. It is also shown that these properties are strongly dependent on the shape of the nanoparticles. Regarding the Ni(II) diimine dithiolato complexes as dyes in dye-sensitized TiO2 based solar cells, it is shown that based on the experimental electrochemical investigation and DFT studies all studied diimine derivatives could serve as potential candidates for the light harvesting, but the e ciencies of the dyes studied are not very promising.

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.

Age and size structure of gap-dynamic, old-growth boreal forest stands in Newfoundland

[Abstract]

Paperitehtaan kunnossapitoprosessien gap -analyysi

Tässä diplomityössä käsitellään paperitehtaan kunnossapitoprosessien hallintaa ja niiden uudistamista yrityksen strategisista lähtökohdista. Diplomityön tavoitteena on etsiä merkittävimmät poikkeamat toimintojen nykytilan ja strategiassa määritellyn tavoitetilan välillä, ja tämän perusteella esittää kehitysehdotuksia toimintojen parantamiseksi. Tutkimuksen kirjallisessa osassa tutkimusongelmaa käsitellään prosessien kuvaamisen, ydinprosessien määrittelemisen ja toimintamallimuutoksen käyttöönoton näkökulmasta. Lisäksi kirjallisissa lähteissä hyödynnetään kunnossapidon johtamisen ajatuksia. Diplomityön empiirisessä osassa toteutetaan haastattelututkimus kohdeyrityksen kunnossapito-organisaatiossa sekä benchmark -tyyppinen haastattelu ulkopuolisessa yrityksessä. Tutkimuksen tulokset osoittavat, että kunnossapitotoimintojen toteuttaminen on hajanaista niin yrityksen strategiaan kuin osastojen väliseen toimintaan suhteutettuna. Näiden tulosten perusteella suositellaan johdolle aktiivisempaa otetta toimintamallimuutoksen loppuunsaattamiseen.

Numerical and ExperimentalModelling of Gas Flow and Heat Transfer in the Air Gap of An Electric Machine

This work deals with the cooling of high-speed electric machines, such as motors and generators, through an air gap. It consists of numerical and experimental modelling of gas flow and heat transfer in an annular channel. Velocity and temperature profiles are modelled in the air gap of a high-speed testmachine. Local and mean heat transfer coefficients and total friction coefficients are attained for a smooth rotor-stator combination at a large velocity range. The aim is to solve the heat transfer numerically and experimentally. The FINFLO software, developed at Helsinki University of Technology, has been used in the flow solution, and the commercial IGG and Field view programs for the grid generation and post processing. The annular channel is discretized as a sector mesh. Calculation is performed with constant mass flow rate on six rotational speeds. The effect of turbulence is calculated using three turbulence models. The friction coefficient and velocity factor are attained via total friction power. The first part of experimental section consists of finding the proper sensors and calibrating them in a straight pipe. After preliminary tests, a RdF-sensor is glued on the walls of stator and rotor surfaces. Telemetry is needed to be able to measure the heat transfer coefficients at the rotor. The mean heat transfer coefficients are measured in a test machine on four cooling air mass flow rates at a wide Couette Reynolds number range. The calculated values concerning the friction and heat transfer coefficients are compared with measured and semi-empirical data. Heat is transferred from the hotter stator and rotor surfaces to the coolerair flow in the air gap, not from the rotor to the stator via the air gap, althought the stator temperature is lower than the rotor temperature. The calculatedfriction coefficients fits well with the semi-empirical equations and precedingmeasurements. On constant mass flow rate the rotor heat transfer coefficient attains a saturation point at a higher rotational speed, while the heat transfer coefficient of the stator grows uniformly. The magnitudes of the heat transfer coefficients are almost constant with different turbulence models. The calibrationof sensors in a straight pipe is only an advisory step in the selection process. Telemetry is tested in the pipe conditions and compared to the same measurements with a plain sensor. The magnitudes of the measured data and the data from the semi-empirical equation are higher for the heat transfer coefficients than thenumerical data considered on the velocity range. Friction and heat transfer coefficients are presented in a large velocity range in the report. The goals are reached acceptably using numerical and experimental research. The next challenge is to achieve results for grooved stator-rotor combinations. The work contains also results for an air gap with a grooved stator with 36 slots. The velocity field by the numerical method does not match in every respect the estimated flow mode. The absence of secondary Taylor vortices is evident when using time averagednumerical simulation.

Investigation of interaction between native and impurity defects in ZnSe

Zinc selenide is a prospective material for optoelectronics. The fabrication of ZnSe­based light-emitting diodes is hindered by complexity of p-type doping of the component materials. The interaction between native and impurity defects, the tendency of doping impurity to form associative centres with native defects and the tendency to self-compensation are the main factors impeding effective control of the value and type of conductivity. The thesis is devoted to the study of the processes of interaction between native and impurity defects in zinc selenide. It is established that the Au impurity has the most prominent amphoteric properties in ZnSe among Cu, Ag and Au impurities, as it forms a great number of both Au; donors and Auz„ acceptors. Electrical measurements show that Ag and Au ions introduced into vacant sites of the Zn sublattice form simple single-charged Agz„+ and Auzn+ states with d1° electron configuration, while Cu ions can form both single-charged Cuz„ (d1) and double-charged Cuzr`+ (d`o) centres. Amphoteric properties of Ag and Au transition metals stimulated by time are found for the first time from both electrical and luminescent measurements. A model that explains the changes in electrical and luminescent parameters by displacement of Ag ions into interstitial sites due to lattice deformation forces is proposed. Formation of an Ag;-donor impurity band in ZnSe samples doped with Ag and stored at room temperature is also studied. Thus, the properties of the doped samples are modified due to large lattice relaxation during aging. This fact should be taken into account in optoelectronic applications of doped ZnSe and related compounds.

SAHAUSTEKNOLOGIA TEOLLISILLA SAHALAITOKSILLA NYT JA TULEVAISUUDESSA

Diplomityössä on selvitetty teollisen sahaustekniikan nykytilaa ja sahausprosessissa käytettävien sahakoneiden teknistä kehitystä Pohjois- ja Keski-Euroopassa. Sahakonevalmistajia on tutkittu niiden tuottamien laitteiden kautta sekä yleisen saatavilla olevan taloudellisen ja tieteellisten tutkimusten tarjoaman informaation avulla. Tutkimuksessa mukana oleviin sahakoneisiin tutustuminen suoritettiin sahalaitosvierailuilla suomalaisilla sahalaitoksilla kevään 2002 aikana. Tieteellisten julkaisujen tietoja verrattiin samalla vallitsevaan tilanteeseen sahoilla. Samalla tehtyjen haastatteluiden avulla selvitettiin sahakoneisiin liittyvien investointien vaikuttimia. Haastatteluiden kohteena olivat sahateollisuuden tuotannosta ja teknisestä suunnittelusta sekä johtamisesta vastaavia henkilöitä erikokoisista sahateollisuusyrityksistä. Myös muutamat sahakonevalmistajien edustajat antoivat haastattelun omia laitteitaan koskien. Sahaustuotannon raaka-ainetilannetta tutkittiin tutkimusalueella maakohtaisesti. Sahaustekniikkana nelisahaus on vallitseva työstömuoto. Siinä käytettävät sahakoneet ovat pelkkahakkuri, joka hakettaa tukin sivut sivutuotehakkeeksi, profilointiyksiköt, jotka työstävät tukin tai pelkan pintaan sivutavarakappaleiden leveyden ennen tai jälkeen pyörösahayksiköitä, jotka erottavat sahatavarakappaleet toisistaan. Merkittävimmät oheislaitteet ovat tukin ja pelkan mittauslaitteet sekä tukinsyöttölaitteet, joiden perusteella puun käytön optimointi sahausprosessissa ja suuntaus sahakoneisiin tapahtuu. Mittatarkimmat ja tuotantonopeudeltaan nopeimmat pyörösahayksiköt ovat kaksiakselisia, profiloivia sahakoneita. Näillä ominaisuuksilla on suurin painoarvo myös sahojen investointisuunnittelussa nopean käyntiinajon lisäksi. Sahakoneiden kehitykseen vaikuttavia seikkoja ovat tulevaisuudessa tukkien koon pieneneminen istutusmetsien jalostuksen lisääntyessä ja suurten aarniometsien vähetessä. Terätekniikan kehitys on tuottaa edelleen ohuempia teriä teräohjaimin, luomalla teriin sisäisiä jännityksiä tai kehittämällä uusia terägeometrioita.

Big band -sovitus kappaleesta "(Surrounded by) Zip-Zip" : Sovituksen analysoiminen puhallinsektioiden näkökulmasta

Opinnäytetyö käsittelee big bandia sekä sille sovittamista. Keskityn tarkastelemaan ennen kaikkea 1930-40-lukujen musiikillista murrosta, jolloin syntyi uusi tapa käsitellä useasti suurimpien orkestereiden kokoonpanoon kuuluneita puhaltimia. Tuona ajanjaksona orkestereiden puhallinryhmistä sekä komppisoittimista alettiin yleisesti muodostaa sektioita. Tämä kokoonpano sai nimekseen ”big band”. Opinnäytetyön tavoitteena oli syventää tietojani big bandin puhallinsektioiden toiminnasta sekä niiden yleisimmistä tehtävistä. Tehtäviä selventääkseni tein big band -sovituksen omasta kappaleestani, missä peilasin 1930-40-luvuilla yleistynyttä tyyliä sovittaa. Sovitustyön valmistuminen pohjautui kolmeen seikkaan: historian tuntemus, sovitussuunnitelman teko sekä musiikin teorian tuntemus. Historian tuntemus loi pohjan sovitussuunnitelmalle, minkä avulla loin kehykset sovitustyön tekemiselle. Sovituksen tekninen suoritus sekä valmistuminen pohjautuivat musiikin teorian ymmärtämiseen sekä kokemukseeni sovittajana. Sovitukseni analyysi-osiossa käyn sovituksen läpi osa kerrallaan, selventäen kuinka puhallinsektiot kussakin osassa toimivat. Opinnäytetyön suunnittelu sekä tiukka rajaus eivät poissulkeneet täysin aiheen moniulotteisuutta. Pelkkiin puhallinsektioihin keskittyminen aiheutti ongelmallisia tilanteita, jotka vaativat suurien kompromissien tekemistä. Muun muassa teorian ja reharmonisoinnin syvempi analysoiminen tässä jää tekemättä. Sovituksellisten sekä soinnullisien ratkaisuiden olemassaolo vaatisi yleensä rinnalleen syvempää perustelua. Näin varsinkin nyt, kun ratkaisut harmoniassa ovat aika ajoin jopa radikaaleja. Tulin kuitenkin siihen päätelmään, että kaikki tekstissä ilmenevä tieto mikä ei koskisi puhallinsektioiden käyttäytymistä olisi irrelevanttia. Lopputuloksen oli tarkoitus olla jäsennelty esittely siitä, mitä big bandin puhallinsektiot ovat ja tekevät. Käyn opinnäytteessäni lyhyesti läpi myös sovitukseni esikuvat. Tämä lyhyt historia-osuus kertoo tiivistetysti mistä ajalta mallintamani sovitustyyli on peräisin ja ketkä ovat edesauttaneet sen yleistymisessä. Historia osuus toimii mainiosti suppeana avainsanastona aiheesta enemmän kiinnostuneelle.

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.