The foci of this thesis are the metal oxides Cu2O, ZnO and Fe3O4 and their interaction with water and sulfur dioxide (SO2). The intention is to study SO2-induced atmospheric corrosion on a molecular level. All studies are based on photoelectron spectroscopy (PES) and scanning tunneling microscopy (STM) measurements. The band structure of Cu2O in the Γ-M direction has been probed by angle-resolved PES (ARPES). It reveals a more detailed picture of the bulk band structure than earlier data and gives the first experimental evidence of a dispersive hybridized Cu 3d-Cu 4s state. The experimental data is compared to band structure calculations. The structure of clean metal oxide surfaces and impact of sample preparation have been studied. Oxygen vacancies can form a (√3x√3)R30° reconstruction on Cu2O(111). Oxygen atoms adjacent to copper vacancies, steps or kinks are shown to be adsorption sites for both water and SO2. Annealing temperature influences the defect density and hydrogen content in ZnO, which can have large impact on the surface properties of ZnO(0001). Water is shown to adsorb dissociatively on ZnO(0001) and partly dissociatively on Cu2O(111). The dissociation occurs at undercoordinated oxygen sites on both surfaces. Water stays adsorbed on ZnO(0001) at room temperature but on Cu2O(111), all water has desorbed at 210 K. SO2 interacts with one or two undercoordinated O-sites on all studied oxide surfaces forming SO3 or SO4 species respectively. SO4 on Fe3O4(100) follows the (√2x√2)R45° reconstruction. On Cu2O(111) and ZnO(0001), SO2 adsorbs on defect sites. An SO3 to SO4 transition is observed on Cu2O(111) when heating an SO3 adsorbate layer from 150 K to 280K. Coadsorption of water and SO2 on ZnO(0001) and Fe3O4(100) has been studied briefly. Water blocks SO2 adsorption sites on ZnO(0001). On Fe3O4(100) and on one type of reduced ZnO(0001) sample, SO2 dissociation to atomic sulfur or sulfide occurs to a higher extent on water exposed surfaces than on clean surfaces. Water thus appears to increase the charge density on some surfaces. Further studies are needed to reveal the cause of this unexpected effect. / <p>QC 20110516</p>

In the growing field of spintronics there is a strong need for development of flexible lightweight semi-conducting magnets. Molecular organic-based magnets are attractive candidates since it is possible to tune their properties by organic chemistry, making them so-called “designer magnets”. Vanadium tetracyanoethylene, V(TCNE)x, is particularly interesting since it is a semiconductor with Curie temperature above room temperature (TC~400 K). The main problem with these organic-based magnets is that they are extremely air sensitive. This thesis reports on the frontier electronic structure of the V(TCNE)x by characterization with photoelectron spectroscopy (PES) and near edge x-ray absorption fine structure (NEXAFS) spectroscopy. It also presents a new and more flexible preparation method of this class of organic-based thin film magnets. The result shows improved air stability of the V(TCNE)x prepared with this method as compared to V(TCNE)x prepared by hitherto used methods.

Organic electronics is a rapidly evolving field with vast number of applications having high potential for commercial success. Although a great progress has been made, many organic electronic applications: organic light-emitting diodes (OLEDs), organic fieldeffect transistors (OFETs), organic solar cells, etc; still require further optimization to fulfill the requirements for successful commercialization. For many applications, available at this time organic materials do not provide satisfactory performance and stability, which hinders the possibility of a large-scale production. Therefore, the key ingredient needed for a successful improvement in performance and stability of organic electronic devices is in-depth knowledge of physical and chemical properties of molecular and polymeric materials. Since many applications encompass several thin film layers made of organics, and often also inorganic materials, the understanding of both organic-organic and hybrid interfaces is yet another important issue necessary for the successful development of organic electronics. The research presented in this thesis is based mainly on photoelectron spectroscopy, which is an experimental technique especially suited to study both surfaces and interfaces of materials. In the thesis, the properties of one of the most successful polymeric materials, poly(3,4-ethylenedioxythiophene), often abbreviated as PEDOT, have been extensively studied. The research was done in close cooperation with an industrial partner – AGFA Gevaert, Belgium. The study was focused on the exploration of the intrinsic properties of the material, such as stability, morphology and conductivity. In addition, however, a possibility of alternation of these properties was also explored. This thesis reports also about investigations of the properties of various organic-organic and hybrid interfaces. The energy level alignment at such interfaces plays important role in charge injection and performance of the thin film organic-based devices. The conditions for different energy level alignment regimes at the various interfaces have been studied. The studies on interfaces were performed in close collaboration with the R&amp;D division of DuPont Corporation, USA. This work led to the significant advances in understanding of the interface energetics and properties of industryrelevant organic materials, as represented not only by published scientific papers, but also patent applications.

Nanomaterials because of their small size, may have special properties unlikely to be seen in ordinary types of materials. Nanomaterials like nanotubes,nanowires and nanoparticles are best studied at the nanoscale, vital but also problematic. In this thesis we use a transmission electron microscope (TEM)combined with a scanning tunneling microscope probe. This system allows TEM images to be captured and recorded into a movie together with recordedelectrical data for real time analysis. Using this method we found that the electrical conductivity of molybdenumbased nanowires Mo6S3I6 can be improved by current induced transformation. This might be a general method of improving nanowires which is of high valueif the wires are to be used in electrical circuits or field emission devices. The bending modulus for these nanowires were also determined, by an electromechanical resonance method, to 4.9 GPa. The sintering phase of silver nanoparticles, used in electrical conductive ink for printing electrical circuits, were studied by the in-situ TEM probing method. We observed that percolation path ways are formed and that the dispersive agent of the particles can be pyrolysed into a net of carbon with characteristics similar to graphite. We also developed a method for decorating nanowires and nanotubes with gold nanoparticles. Nanowire particle composites are often used in assembling more complex devices (electronic circuits) or for linking to organic molecules (biosensor applications) and existing particle decoration methods are either difficult or with low yield. By in situ TEM probing we found that carbon nanocages can be grown onto these gold nanoparticles. The size of the gold nanoparticles is controllable an thus the size of the nanocages. These nanocages may be used in medicine- or hydrogen storage-applications. / Nanomaterial har givits stort intresse under det senaste årtiondet, detta på grund av deras unika egenskaper som gör att de i många hänseenden överträffar traditionella material. Egenskaperna beror till största del på storlek och därför är det nödvändigt att studera dessa material på nanonivå, något som är problematiskt. För sådana studier krävs ett instrument med tillräckligt hög upplösning på nanonivå samt ett system med en prob som möjligör selektion och karakterisering utav individuella byggstenar. I denna avhandling används ett transmissionselektronmikroskop (TEM) tillsammans med ett sveptunnelmikroskop (STM) där det senare används som prob. Systemet medger studier på nanonivå och karakterisering av enskilda byggstenar under realtids avbildning (in situ). Metoden medger en bättre överblick och hanterbarhet vid nanomanipulering än vad till exempel atomkraftmikroskopi medger. Piezodrivna probar kan även användas i svepelektronmikroskop men dessa medger inte samma upplösning som transmissionselektronmikroskopet. Nanotrådar av Mo6S3I6 är ett alternativt material till kolnanorör och överträffar dessa i form av löslighet i båda organiska såväl som polära lösningsmedel. De är enkla att syntetisera men deras elektriska konduktivitet är låg. Mo6S3I6 nanotrådar studerades med in situ TEM probing. Vi fann att genom att driva en tillräckligt hög elektrisk ström genom nanotråden så resulterade detta i en omvandling till en solid metallisk molybden nanotråd med en konduktivitet nära värdet för bulkmaterialet. Resultat är intressant då nanotrådar kan användas i t.ex. fältemission, men resultatet visar också på att det kan vara en generell metod för att förbättra nanotrådar överlag. På dessa nanotrådar har även en elektromekanisk resonans studie utförts där böjmodulen för materialet bestämdes till 4.9 GPa. Med in situ-TEM-probing metoden har även silvernanobläck studerats under en sintringsprocess. Studien visade att vid sintringen så bildas perkulativa vägar genom bläckets silvernanopartiklar samt att vid hög sinteringstemperatur förkolnades det lösningsmedel som silvernanopartiklarna är lösta i. Förkolningen av lösningsmedlet resulterade i ett kolnät med liknande egenskaper som för grafit. Förståelse utav sinteringsprocessen är nödvändig eftersom vid tryckning av elektriskt ledande banor på papper används sintring för att höja ledningsförmågan. Genom att växa nanopartiklar på nanotrådar förändras deras egenskaper och tillämpningar. Existerande metoder är endera komplicerade eller ger dåligt ut- byte. Ett enkelt recept för att växa guldnanopartiklar på kolnanorör och Mo6S3I6 nanotrådar har därför tagits fram. Dessa kolnanorör och nanotrådar har sedan studerats med in-situ-TEM-probing metoden som visade att utanpå dessa guldnanopartiklar kan burar av kol skapas. Eftersom partiklarnas storlek kan kontrolleras kan även kolnanoburarnas storlek kontrolleras. Burarna har användningsområden t.ex. inom medicin och vid lagring av vätgas. / The thesis covers six scientific papers

The experimental work presented in this thesis is based on a wide assortment of very advanced and highly sophisticated photoelectron spectroscopy (PES) techniques. The objective of the present study has been to reveal and understand the electronic structure and electron dynamics in a broad spectrum of materials, ranging from wide band gap oxides, via semiconductors along with metals, and finally high-temperature superconductors. The first part of the thesis concerns laser-based pump-and-probe PES. This unique experimental technique has permitted a study of the excited electronic structure and the electron dynamics of several semiconductor surfaces. An insight into details of the adatom to restatom charge-transfer of the Ge(111)c(2x8) surface is presented, as well as an estimate for the timescale in which the dynamic adatoms of the Ge(111):Sn(sqrt3xsqrt3)R30deg surface operate. Further results comprise a novel unoccupied surface state at the GaSb(001) surface as well as a time-resolved study of the charge accumulation layer at the InAs(111)A/B surfaces. In the second part, high-resolution synchrotron based angle-resolved PES (ARPES) data from the cuprate high-temperature superconductor La(2-x)Sr(x)CuO(4) (LSCO) is presented. This extensive study, reveals detailed information about how the Fermi surface and electronic excitations evolve with doping in the superconducting state. The results comprise support for a connection between high- and low-energy electronic responses, the characteristics of the superconducting gap, and indication of a quantum phase transition between two different superconducting phases. In the third group of experiments we move away from the two-dimensional systems and concentrate on fully three-dimensional compounds. By the use of soft x-ray ARPES it is possible to extract the three-dimensional electronic structure in a straightforward manner with increased k(perpendicular)-resolution. As a result the first high-quality ARPES data from Cu2O is presented, as well as a novel method for extracting the (real space) electron density by ARPES. These experiments clearly display the advantages of using soft x-ray ARPES. If the material and type of experiment is chosen wisely, the benefit of the increased k||-window and the free electron final state, surpass the drawbacks of decreased count-rate and inferior energy resolution. Finally we return to the high-temperature superconductors (NCCO &amp; Nd-LSCO) and make use of the increased bulk-sensitivity. From an evident change in the shape of the Fermi surface when moving from low to high photon energies, the durface to bulk difference in electronic structure is highlighted. / QC 20100810

The high pressure and high temperature (HPHT) behavior of Ti1-xAlxN coatings on cutting tool inserts have been of interest for this diploma work. A literature study of HPHT techniques as well as measurement methods has been done. A diamond anvil cell (DAC) would be a good device to achieve high pressure and high temperature conditions on small samples. Another way to obtain these conditions would be a cutting test, which has been performed on a Ti1-xAlxN coated cutting tool insert with x = 0.67. Also a cubic press could be used to apply HPHT on a     Ti1-xAlxN sample or a large volume press on a whole cutting tool insert. To measure hardness on thin coatings a nanoindentor could be used, which have been done on heat-treated Ti0.33Al0.67N and TiN samples. X-ray diffraction (XRD) is a suitable method to measure phase composition of a sample and was performed on the cutting tested insert as well as on an untreated reference insert. Three ways to continue this project have been outlined all starting with more comprehensive cutting tests.

Deposition of alumina thin films in the presence of fluorine as a method for reducing thehydrogen incorporation in the films was investigated in this thesis. Hydrogen incorporated in alumina thin films have been shown to cause a lower density and refractive index in amorphous films, assist electrical conduction through thin amorphous films as well as inhibiting the formation of the thermally stable α-phase. The depositions were made in a ultra high vacuum system where high vacuum conditions were simulated by leaking water vapor into the system. No substrate heating or substratebias was applied. Films were deposited at a range of fluorine partial pressures, from 2,5×10-6- 5×10-5 Torr, and were analyzed by elastic recoil detection analysis, nuclear reaction analysis, scanning electron microscopy and x-ray diffraction. Mass spectrometry measurements were done during the depositions to analyze the deposition process. The mass spectrometry investigations show that there is a trend of increasing O2 partial pressures with increasing fluorine partial pressures during the depositions. This is attributed to the well known reaction: 2H2O+F2→O2+4HF. However, no trend in the measured water partial pressures can be observed. The increase in the O2 partial pressure is therefore attributed to a reaction between water and fluorine on the chamber walls. The chemical analysis show that the hydrogen incorporation in the films were lowered from ~10 at.% when deposited in the presence of water vapor to ~3 at.% when deposited in the presence of water vapor and 2×10-5 Torr fluorine. The hydrogen incorporation stabilize at ~3 at.% at higher fluorine partial pressures. However, there is also a large amount of fluorine incorporated in the films, ~20 at.% with a fluorine partial pressure during the deposition of 2×10-5 Torr and ~46 at.% with a fluorine partial pressure of 5×10-5 Torr. There is a slight increase in the aluminum concentration in the films deposited with fluorine. This is attributed to bonding the hydrogen in aluminum hydroxide while the reminder forms Al2O3 or Al leading to an increase in the aluminum concentration in the film. A linear decrease in the deposition rate with increasing fluorinepartial pressures during the deposition was observed, this can be explained by sputter etching of AlFx and AlOxFy by energetic O- ions. The XRD investigation show that the films deposited with the highest fluorine partial pressures were x-ray amorphous, the films with deposited with lower fluorine partial pressures are therefore also assumed to be amorphous.

In orthopaedic practice, fractures are usually stabilised with metal screws or rods. This is done in order to keep the fracture parts in place during the rather slow healing process. The healing time can potentially be reduced by local- or systemic treatment with different bone promoting drugs. In later years, lithium, otherwise used to treat bipolar disease, has shown promise to be such a drug.   The aim of this master thesis was to find a way to coat metal bone screws with lithium and to characterise the coating. The coating was to be designed in such a way that it could release lithium to the surrounding bone tissue.   Lithium chloride was incorporated into a titanate sol-gel and attached to silicon wafers and stainless steel screws by dip coating. Wafers were used for initial in vitro studies of how lithium changed coating characteristics. This was studied using ellipsometry, AFM and SEM. Lithium is most probably physisorbed and not incorporated into the network building up the sol-gel. Coating structure is changed as more lithium is incorporated. For large amounts of lithium, the nanoparticles normally formed when curing the sol-gel are inhibited. One effect of this is reduced bioactivity, seen as a reduced ability for calcium phosphate crystals to nucleate on the coating when immersed in simulated body fluid. Lithium release was investigated using AAS. Lithium is released from the coating, showing a burst effect. By changing the number of coating layers used, the release profile can be partly altered. The coating was also applied to screws, showing good attachment, and the lithium release profile was similar to the one seen from wafers. Finally, a screw model was used in rats to assess the effect of local lithium treatment from screws and systemic lithium treatment on fracture healing. In the model, a screw was inserted in tibia, mimicking a fracture. When the bone around the screw was healed, a pullout test was performed, giving information about the strength of the bone surrounding the screw. No significant difference could be found for either local- or systemic lithium treatment compared to control. However, when evaluating the strength of intact bone in a similar way, a positive effect of systemic lithium treatment could be seen. Therefore, it is still likely that lithium has a positive effect on bone and further studies are needed to fully evaluate its role in fracture healing. / Vid behandling av benbrott stabiliseras vanligtvis frakturen internt med metallskruvar och metallstavar. Detta görs för att hålla brottbitarna på plats under den relativt långsamma läkprocessen. Det är möjligt att minska tiden för frakturläkning genom att lokalt eller systemiskt behandla med olika läkemedel som främjar bentillväxt. På senare år har det presenterats bevis för att litium, som annars används som psykofarmaka, fungerar som ett sådant läkemedel.   Syftet med detta examensarbete var att hitta en metod för att fästa litium på benimplantat. Litium skulle fästas på ett sådant sätt att frisläppning till omgivande vävnad blev möjlig.   Litiumklorid inkorporerades i en titanat-solgel och lager av detta lades på kiselytor och rostfria skruvar genom s.k. ”dip-coating”. Kiselytorna användes för initiala in vitro-studier av hur litium ändrade beläggningens egenskaper. Litium sitter antagligen fast på ytan av det tredimensionella nätverk som utgör solgelen, istället för att sitta inbundet i nätverket. Lagerstrukturen ändras ju mer litium som inkorporeras och vid stora mängder skapas inte de nanopartiklar som vanligtvis finns i en solgel-baserad beläggning. En följd av detta är reducerad bioaktivitet för beläggningen, dvs. en minskad förmåga för kalciumfosfatkristaller att bildas på ytan. Litium frisläpps från beläggningen, dock sker denna frisläppning snabbt. Genom att belägga ytan med flera lager av solgel kan frisläppningskinetiken delvis ändras. Solgelen kunde också med god vidhäftning appliceras på skruvar och frisläppningskinetiken från en skruv är liknande den från en kiselyta. Slutligen användes en skruvmodell i råtta för att undersöka vilken effekt lokal respektive systemisk litiumbehandling har på frakturläkning. I modellen efterliknas ett benbrott genom att en skruv sätts in i skenbenet.  När benvävnaden runt skruven har läkt görs ett utdragstest på skruven vilket ger information om benets styrka. Ingen signifikant skillnad i skruvens utdragskraft kunde ses mellan de båda försöksgrupperna och kontrollgruppen. Däremot hade gruppen som fick systemisk litiumbehandling fått starkare ben totalt, vilket indikerar att litium har effekt på intakt ben. På grund av dessa resultat finns det fortfarande skäl att tro att litium har en positiv påverkan på ben, varför dess effekt på frakturläkning bör undersökas ytterligare.

A new NOx sensor for high-temperature applications has been developed and thouroghly characterised. The sensor layers are a mixed oxide of CoO, MgO and MgO2 deposited by thermal evaporation with a porous platinum gate on top, deposited by thermal evaporation or sputtering. The sensitivity and selectivity of the sensor is promising and is shown to depend upon the ratio between Co and Mg in the film and a number of competing mechanisms are shown to take place on the sensor surface. Response and recovery of the device is still slow and there are some drift, which are suggested to be due to a restructuring sensor surface during operation that was found by SEM-studies. Finally,the oxide surface has been characterized by XPS and a novel process for deposition of the sensor layers by lift-off technique has been developed.

<p>In the growing field of spintronics there is a strong need for development of flexible lightweight semi-conducting magnets. Molecular organic-based magnets are attractive candidates since it is possible to tune their properties by organic chemistry, making them so-called “designer magnets”. Vanadium tetracyanoethylene, V(TCNE)_x, is particularly interesting since it is a semiconductor with Curie temperature above room temperature (T_C~400 K). The main problem with these organic-based magnets is that they are extremely air sensitive. This thesis reports on the frontier electronic structure of the V(TCNE)_x by characterization with photoelectron spectroscopy (PES) and near edge x-ray absorption fine structure (NEXAFS) spectroscopy. It also presents a new and more flexible preparation method of this class of organic-based thin film magnets. The result shows improved air stability of the V(TCNE)_x prepared with this method as compared to V(TCNE)_x prepared by hitherto used methods.</p>