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Innovations in resistive switching devices constitute a core objective for the development of ultralow-power computing devices. Forming-free resistive switching is a type of resistive switching that eliminates the need for an initial high voltage for the formation of conductive filaments and offers promising opportunities to overcome the limitations of traditional resistive switching devices. Here, we demonstrate mixed charge state oxygen vacancy-engineered electroforming-free resistive switching in NiFe2O4 (NFO) thin films, fabricated as asymmetric Ti/NFO/Pt heterostructures, for the first time. Using pulsed laser deposition in a controlled oxygen atmosphere, we tune the oxygen vacancies together with the cationic valence state in the nickel ferrite phase, with the latter directly affecting the charge state of the oxygen vacancies. The structural integrity and chemical composition of the films are confirmed by X-ray diffraction and hard X-ray photoelectron spectroscopy, respectively. Electrical transport studies reveal that resistive switching characteristics in the films can be significantly altered by tuning the amount and charge state of the oxygen vacancy concentration during the deposition of the films. The resistive switching mechanism is seen to depend upon the migration of both singly and doubly charged oxygen vacancies formed as a result of changes in the nickel valence state and the consequent formation/rupture of conducting filaments in the switching layer. This is supported by the existence of an optimum oxygen vacancy concentration for efficient low-voltage resistive switching, below or above which the switching process is inhibited. Along with the filamentary switching mechanism, the Ti top electrode also enhances the resistive switching performance due to interfacial effects. Time-resolved measurements on the devices display both long- and short-term potentiation in the optimized vacancy-engineered NFO resistive switches, ideal for solid-state synaps

Innovations in resistive switching devices constitute a core objective for the development of ultralow-power computing devices. Forming-free resistive switching is a type of resistive switching that eliminates the need for an initial high voltage for the formation of conductive filaments and offers promising opportunities to overcome the limitations of traditional resistive switching devices. Here, we demonstrate mixed charge state oxygen vacancy-engineered electroforming-free resistive switching in NiFe2O4 (NFO) thin films, fabricated as asymmetric Ti/NFO/Pt heterostructures, for the first time. Using pulsed laser deposition in a controlled oxygen atmosphere, we tune the oxygen vacancies together with the cationic valence state in the nickel ferrite phase, with the latter directly affecting the charge state of the oxygen vacancies. The structural integrity and chemical composition of the films are confirmed by X-ray diffraction and hard X-ray photoelectron spectroscopy, respectively. Electrical transport studies reveal that resistive switching characteristics in the films can be significantly altered by tuning the amount and charge state of the oxygen vacancy concentration during the deposition of the films. The resistive switching mechanism is seen to depend upon the migration of both singly and doubly charged oxygen vacancies formed as a result of changes in the nickel valence state and the consequent formation/rupture of conducting filaments in the switching layer. This is supported by the existence of an optimum oxygen vacancy concentration for efficient low-voltage resistive switching, below or above which the switching process is inhibited. Along with the filamentary switching mechanism, the Ti top electrode also enhances the resistive switching performance due to interfacial effects. Time-resolved measurements on the devices display both long- and short-term potentiation in the optimized vacancy-engineered NFO resistive switches, ideal for solid-state synaps

Innovations in resistive switching devices constitute a core objective for the development of ultralow-power computing devices. Forming-free resistive switching is a type of resistive switching that eliminates the need for an initial high voltage for the formation of conductive filaments and offers promising opportunities to overcome the limitations of traditional resistive switching devices. Here, we demonstrate mixed charge state oxygen vacancy-engineered electroforming-free resistive switching in NiFe2O4 (NFO) thin films, fabricated as asymmetric Ti/NFO/Pt heterostructures, for the first time. Using pulsed laser deposition in a controlled oxygen atmosphere, we tune the oxygen vacancies together with the cationic valence state in the nickel ferrite phase, with the latter directly affecting the charge state of the oxygen vacancies. The structural integrity and chemical composition of the films are confirmed by X-ray diffraction and hard X-ray photoelectron spectroscopy, respectively. Electrical transport studies reveal that resistive switching characteristics in the films can be significantly altered by tuning the amount and charge state of the oxygen vacancy concentration during the deposition of the films. The resistive switching mechanism is seen to depend upon the migration of both singly and doubly charged oxygen vacancies formed as a result of changes in the nickel valence state and the consequent formation/rupture of conducting filaments in the switching layer. This is supported by the existence of an optimum oxygen vacancy concentration for efficient low-voltage resistive switching, below or above which the switching process is inhibited. Along with the filamentary switching mechanism, the Ti top electrode also enhances the resistive switching performance due to interfacial effects. Time-resolved measurements on the devices display both long- and short-term potentiation in the optimized vacancy-engineered NFO resistive switches, ideal for solid-state synaps

Innovations in resistive switching devices constitute a core objective for the development of ultralow-power computing devices. Forming-free resistive switching is a type of resistive switching that eliminates the need for an initial high voltage for the formation of conductive filaments and offers promising opportunities to overcome the limitations of traditional resistive switching devices. Here, we demonstrate mixed charge state oxygen vacancy-engineered electroforming-free resistive switching in NiFe2O4 (NFO) thin films, fabricated as asymmetric Ti/NFO/Pt heterostructures, for the first time. Using pulsed laser deposition in a controlled oxygen atmosphere, we tune the oxygen vacancies together with the cationic valence state in the nickel ferrite phase, with the latter directly affecting the charge state of the oxygen vacancies. The structural integrity and chemical composition of the films are confirmed by X-ray diffraction and hard X-ray photoelectron spectroscopy, respectively. Electrical transport studies reveal that resistive switching characteristics in the films can be significantly altered by tuning the amount and charge state of the oxygen vacancy concentration during the deposition of the films. The resistive switching mechanism is seen to depend upon the migration of both singly and doubly charged oxygen vacancies formed as a result of changes in the nickel valence state and the consequent formation/rupture of conducting filaments in the switching layer. This is supported by the existence of an optimum oxygen vacancy concentration for efficient low-voltage resistive switching, below or above which the switching process is inhibited. Along with the filamentary switching mechanism, the Ti top electrode also enhances the resistive switching performance due to interfacial effects. Time-resolved measurements on the devices display both long- and short-term potentiation in the optimized vacancy-engineered NFO resistive switches, ideal for solid-state synaps

UV sensors hold significant promise for various applications in both military and civilian domains. However, achieving exceptional detectivity, responsivity, and rapid rise/decay times remains a notable challenge. In this study, we address this challenge by investigating the photodetection properties of CdS thin films and the influence of surface-deposited gold nanoparticles (AuNPs) on their performance. CdS thin films were produced using the pulsed laser deposition (PLD) technique on glass substrates, with CdS layers at a 100, 150, and 200 nm thickness. Extensive characterization was performed to evaluate the thin films’ structural, morphological, and optical properties. Photodetector devices based on CdS and AuNPs/CdS films were fabricated, and their performance parameters were evaluated under 365 nm light illumination. Our findings demonstrated that reducing CdS layer thickness enhanced performance concerning detectivity, responsivity, external quantum efficiency (EQE), and photocurrent gain. Furthermore, AuNP deposition on the surface of CdS films exhibited a substantial influence, especially on devices with thinner CdS layers. Among the configurations, AuNPs/CdS(100 nm) demonstrated the highest values in all evaluated parameters, including detectivity (1.1×1012 Jones), responsivity (13.86 A/W), EQE (47.2%), and photocurrent gain (9.2)., Dynamics of Micro and Nano Systems

The metal–insulator transition (MIT) observed in vanadium dioxide has been a topic of great research interest for past decades, with the underlying physics yet not fully understood due to the complex electron interactions and structures involved. The ability to understand and tune the MIT behavior is of vital importance from the perspective of both underlying fundamental science as well as potential applications. In this work, scanning transmission electron microscopy (STEM) is used to investigate cross-section lamella of the VO2 films deposited using pulsed laser deposition on three substrates: c-cut sapphire, TiO2(101) and TiO2(001). Advanced STEM imaging is performed in which also the oxygen atom columns are resolved. The overall film quality and structures on atomic and nanoscale are linked to the electrical transition characteristics. Relatively poor MIT characteristics are observed on c-sapphire due to the presence of very small domains with six orientation variants, and on TiO2 (001) due to the presence of cracks induced by stress relaxation. However, the MIT on TiO2 (101) behaves favorably, despite similar stress relaxation which, however, only leads to domain boundaries but no cracks.

Innovations in resistive switching devices constitute a core objective for the development of ultralow-power computing devices. Forming-free resistive switching is a type of resistive switching that eliminates the need for an initial high voltage for the formation of conductive filaments and offers promising opportunities to overcome the limitations of traditional resistive switching devices. Here, we demonstrate mixed charge state oxygen vacancy-engineered electroforming-free resistive switching in NiFe2O4 (NFO) thin films, fabricated as asymmetric Ti/NFO/Pt heterostructures, for the first time. Using pulsed laser deposition in a controlled oxygen atmosphere, we tune the oxygen vacancies together with the cationic valence state in the nickel ferrite phase, with the latter directly affecting the charge state of the oxygen vacancies. The structural integrity and chemical composition of the films are confirmed by X-ray diffraction and hard X-ray photoelectron spectroscopy, respectively. Electrical transport studies reveal that resistive switching characteristics in the films can be significantly altered by tuning the amount and charge state of the oxygen vacancy concentration during the deposition of the films. The resistive switching mechanism is seen to depend upon the migration of both singly and doubly charged oxygen vacancies formed as a result of changes in the nickel valence state and the consequent formation/rupture of conducting filaments in the switching layer. This is supported by the existence of an optimum oxygen vacancy concentration for efficient low-voltage resistive switching, below or above which the switching process is inhibited. Along with the filamentary switching mechanism, the Ti top electrode also enhances the resistive switching performance due to interfacial effects. Time-resolved measurements on the devices display both long- and short-term potentiation in the optimized vacancy-engineered NFO resistive switches, ideal for solid-state synaps

Pulsed laser deposition (PLD) has already been adopted as a low damage deposition technique of transparent conducting oxides on top of sensitive organic charge transport layers in optoelectronic devices. Herein, SnO2 deposition is demonstrated as buffer layer in p–i–n perovskite solar cells (PSCs) via wafer-scale (4 inch) PLD at room temperature. The PLD SnO2 properties, its interface with perovskite/C60, and device performance are compared to atomic layer deposited (ALD) SnO2, i.e., state-of-the-art buffer layer in perovskite-based single junction and tandem photovoltaics. The PLD SnO2-based solar cells exhibit on par efficiencies (17.8%) with that of SnO2 fabricated using ALD. The solvent-free room temperature processing and wafer-scale approach of PLD open up possibilities for buffer layer formation with increased deposition rates while mitigating potential thermal or physical damage to the top organic layers. This is a promising outlook for fully physical vapor-processed halide PSCs and optoelectronic devices requiring low thermal budget.

Various copper oxide stoichiometries have been grown by Pulsed Laser Deposition (PLD) on MgO (100). The role of oxygen pressure on the structural and physical properties of the films was investigated in the 1·10 –5 Pa – 1 Pa range. Positron annihilation spectroscopy revealed positrons trapped at vacancies and large vacancy clusters with lifetimes ranging from 400 ps to 500 ps. Different stoichiometries were found to be dominated by characteristic vacancies. Single copper vacancies V Cu are found for CuO phase with good indication for p-type applications while for the Cu 2 O complexes of copper vacancies coupled with oxygen vacancies (V Cu + V O and V Cu + 2V O ) are seen. Particular O 2 atmosphere conditions induce a mixture of copper oxide phases with the CuO crystals growing on top of Cu 2 O films. The deposition process was monitored with in situ diagnostic techniques based on optical emission spectroscopy and Langmuir probe method. The kinetics of the plasma during the deposition process are well correlated with the properties of the deposited films. The monitoring tools define clear energetic threshold for the formation of CuO or Cu 2 O phases.

Epitaxial films of metal oxides deposited on silicon substrates represent a new type of material that could be used as protective (or electroactive) layer in the photoelectrochemical water splitting. To understand the influence of crystalline and interfacial properties of oxide layer on the water splitting process a ~10 nm strontium titanate (STO) films have been grown using the PLD method on bare and reduced graphene oxide (rGO) buffered silicon substrate. Our approach relied on the oxide-silicon integration using combination of SrO-assisted deoxidation and controllable coverage of silicon surface with a mono- to threelayer of spin-coated GO. The STO films have been grown at 515 and 700 °C and various experimental techniques were used to examine the surface and crystalline properties of grown films (reflection high energy electron diffraction, atomic force microscopy, scanning electron microscopy, X-ray diffraction, X-ray reflectivity and X-ray photoelectron spectroscopy). The results show that the best the crystallinity of the STO thin films was obtained on rGO/SrO deoxidized silicon surface at 515 °C. Future studies will be devoted to electrochemical characterization of the grown films, that will help to establish clearer link on how the interface and crystalline parameters affect the water splitting process.

This bachelor's thesis focuses on the application of pulsed laser deposition for the fabrication of thin films that are used to enhance the quality of medical materials. It provides a detailed description of the PLD process, its mechanism, and equipment for a better understanding of how this technique functions. Additionally, it showcases specific studies where PLD has been successfully applied to deposit various materials, serving as examples of its effectiveness in the field of medical materials., Tato bakalářská práce se zaměřuje na aplikaci pulzní laserové depozice pro výrobu tenkých vrstev, které se používají ke zvýšení kvality medicinálních materiálů. Poskytuje podrobný popis procesu PLD, jeho mechanismu a vybavení pro lepší pochopení toho, jak tato technika funguje. Kromě toho předvádí konkrétní studia, kde PLD technika byla úspěšně aplikována při depozici různých materiálů, což slouží jako příklady účinnosti dané techniky v oblasti medicinálních materiálů., Fakulta chemicko-technologická, Příklady dalších depozičních technik, přístrojové vybavení, Dokončená práce s úspěšnou obhajobou

We investigated the integration of transient liquid-assisted growth (TLAG) approach for epitaxial YBa2Cu3O7−x (YBCO) films by physical deposition methodologies (pulsed laser deposition (PLD)), as an additional opportunity for high-throughput growth of YBCO. As a prerequisite, highly flat and amorphous YBCO precursor films were deposited by PLD at temperatures below 400 °C on single-crystalline SrTiO3 (STO) and LaMnO3 (LMO)/STO, as well as industrial coated conductor architectures. Contrary to TLAG based on chemical solution deposition, where BaCO3 elimination is a key factor for the YBCO growth, TLAG-PLD growth is controlled by the transformation of Ba-Cu-O (s) to a transient liquid. High-quality c-axis YBCO films were successfully grown on different substrates, as demonstrated by high-resolution x-ray diffraction and transmission electron microscopy. In-situ resistance measurements revealed that the growth rates around 1000 nm s−1 can be achieved, outperforming the capabilities of standard PLD growth of REBa2Cu3O7 films by few orders of magnitude. Experimental conditions such as temperature, oxygen partial pressure, and heating ramp, were optimized to obtain critical temperature (T c) values up to 90 K. Critical current densities of 15 MA cm−2 at 5 K and 1.7 MA cm−2 at 77 K were obtained for YBCO films of 450 nm on LMO/STO.

Rare-earth (RE)-Oxygen-Hydrogen compounds are versatile materials whose composition and properties can be significantly varied by changing the relative O and H contents. Among them hydrides and oxyhydrides have been thoroughly investigated due to its photochromic properties. Instead, research of RE-hydroxides and oxyhydroxides (RE-OH and RE-OOH) is scarce although they show promising properties as light emitters. However, their use and integration in solid state devices have been hindered so far because their usual chemical synthesis routes yield materials in bulk or powder configurations. In this work we demonstrate a physical deposition route based on pulsed laser deposition that results in the unprecedented preparation of high-quality Eu oxyhydroxide (EuOOH) thin films. The synthetized EuOOH films show a well-defined monoclinic structure, are optically active and show a robust red emission related to the intra-f transitions of the Eu3+ ions. The excellent quality of these crystalline films has allowed us to obtain relevant properties of the monoclinic EuOOH phase not previously reported such as its refractive index and its Raman spectrum, including the identification of the characteristic phonon modes. These novel EuOOH films have been prepared both on Si and fused silica substrates, and thus are ready for potential integration in solid state optoelectronic components and devices. © 2023 The Authors

Integration of the prototypical GeSbTe (GST) ternary alloys, especially on the GeTe-Sb2 Te3 tie-line, into non-volatile memory and nanophotonic devices is a relatively mature field of study. Nevertheless, the search for the next best active material with outstanding properties is still ongoing. This search is relatively crucial for embedded memory applications where the crystallization temperature of the active material has to be higher to surpass the soldering threshold. Increasing the Ge content in the GST alloys seems promising due to the associated higher crystallization temperatures. However, homogeneous Ge-rich GST in the as-deposited condition is thermodynamically unstable, and phase separation upon annealing is unavoidable. This phase separation reduces endurance and is detrimental in fully integrating the alloys into active memory devices. This work investigated the phase separation of Ge-rich GST alloys, specifically Ge5 Sb2 Te3 or GST523, into multiple (meta)stable phases at different length scales in melt-quenched bulk and annealed thin film. Electron microscopy-based techniques were used in our work for chemical mapping and elemental composition analysis to show the formation of multiple phases. Our results show the formation of alloys such as GST213 and GST324 in all length scales. Furthermore, the alloy compositions and the observed phase separation pathways agree to a large extent with theoretical results from density functional theory calculations.

In this work, Ag-doped ZnO nanoparticles are obtained via pulsed laser ablation of the Ag-coated ZnO target in water. The ratio of Ag dopant in ZnO nanoparticles strongly depends on the thickness of the Ag layer at the ZnO target. Synthesized nanoparticles were characterized by XRD, XPS, SEM, EDS, ICP-OES, and UV–VIS spectrophotometry to obtain their crystal structure, elemental composition, morphology and size distribution, mass concentration, and optical properties, respectively. The photocatalytic studies showed photodegradation of methylene blue (MB) under UV irradiation. Different ratios of Ag dopant in ZnO nanoparticles influence the photodegradation rate. The ZnO nanoparticles doped with 0.32% silver show the most efficient photodegradation rate, with the chemical reaction constant of 0.0233 min−1. It exhibits an almost twice as large photodegradation rate compared to pure ZnO nanoparticles, showing the doping effect on the photocatalytic activity.

Binary ZrCu nanocomposite amorphous films are synthetized by pulsed laser deposition (PLD) under vacuum (2 x 10-3 Pa) and 10 Pa He pressure, leading to fully amorphous compact and nanogranular morphologies, respectively. Then, post-thermal annealing treatments are carried out to explore thermal stability and crystallization phenomena together with the evolution of mechanical properties. Compact films exhibit larger thermal stability with partial crystallization phenomena starting at 420 °C, still to be completed at 550 °C, while nanogranular films exhibit early-stage crystallization at 300 °C and completed at 485 °C. The microstructural differences are related to a distinct evolution of mechanical properties and residual stress, with compact TFMGs showing the highest values of Young’s modulus (157 GPa), hardness (12 GPa), strain rate sensitivity (0.096), and local residual stress (+691 MPa) upon annealing at 550 °C, while nanogranular films reach the maximum values of mechanical properties at 485 °C followed by relaxation at higher temperatures due to complete crystallization. We show that PLD in combination with post-thermal annealing can generate different families of amorphous films with varying nanoscale morphologies, resulting in tunable mechanical properties and thermal stability, which can thus be used for designing novel film configurations for different fields of application.

L’augmentation continue de nos besoins énergétiques et le réchauffement climatique sont les facteurs principaux qui poussent les scientifiques à chercher des sources énergétiques plus robustes, non polluantes, durables et peu chères. Les piles à combustibles à base d’ammoniaque sont l’une des solutions prometteuses dues aux propriétés remarquables de l’ammoniac. En effet, par rapport à l’hydrogène, ce dernier possède une densité énergétique plus élevée, un stockage et un transport moins couteux et plus sécuritaires, et son oxydation donne des produits non polluants. Cependant, les anodes des présentes piles sont caractérisées par une faible densité de courant, un potentiel d’activation élevé, une faible stabilité et sont couteuses. Des études ont montré que le platine est l’élément le plus actif pour la réaction d’électro oxydation de l’ammoniaque. De plus, cette réaction est fortement favorisée par les larges terrasses orientées (100). D’autres travaux ont trouvé que l’ajout d’éléments du groupe du platine, particulièrement l’iridium et lerhodium, ont tendance à améliorer la densité de courant anodique maximal, réduire le potentiel d’activation de cette réaction et augmenter la stabilité des électrodes. À partir de cela, on s’est demandé : (i) s’il était possible de déposer par ablation laser pulsé des films à base de l’alliage ternaire Pt1-x-yIrxRhy et des films sandwichs Pt/Ir/Pt orientés (100) ainsi que des siliciures polycristallins à base des métaux du groupe du platine; et (ii) s’ils étaient la solution aux faibles caractéristiques cités ci-dessus. Les résultats obtenus à travers notre étude montrent que non seulement il est possible d’obtenir de tels films, mais aussi que des activités trois fois plus élevées et des potentiels d’activation jusqu’à 0.150V plus négatifs que le platine peuvent être atteint. AbstractThe continuous increase of our energy needs accompanied by the dramatic consequence of global warming are the main factors that push scient

Physical vapor deposition (PVD) refers to the removal of atoms from a solid or a liquid by physical means, followed by deposition of those atoms on a nearby surface to form a thin film or coating. Various approaches and techniques are applied to release the atoms including thermal evaporation, electron beam evaporation, ion-driven sputtering, laser ablation, and cathodic arc-based emission. Some of the approaches are based on a plasma discharge, while in other cases the atoms composing the vapor are ionized either due to the release of the film-forming species or they are ionized intentionally afterward. Here, a brief overview of the various PVD techniques is given, while the emphasis is on sputtering, which is dominated by magnetron sputtering, the most widely used technique for deposition of both metallic and compound thin films. The advantages and drawbacks of the various techniques are discussed and compared., QC 20220930

Filled skutterudites are currently studied as promising thermoelectric materials due to their high power factor and low thermal conductivity. The latter property, in particular, can be enhanced by adding scattering centers, such as the ones deriving from low dimensionality and the presence of interfaces. This work reports on the synthesis and characterization of thin films belonging to the Sm-y(FexNi1-x)(4)Sb-12-filled skutterudite system. Films were deposited under vacuum conditions by the pulsed laser deposition (PLD) method on fused silica substrates, and the deposition temperature was varied. The effect of the annealing process was studied by subjecting a set of films to a thermal treatment for 1 h at 423 K. Electrical conductivity sigma and Seebeck coefficient S were acquired by the four-probe method using a ZEM-3 apparatus performing cycles in the 348-523 K temperature range, recording both heating and cooling processes. Films deposited at room temperature required three cycles up to 523 K before being stabilized, thus revealing the importance of a proper annealing process in order to obtain reliable physical data. XRD analyses confirm the previous result, as only annealed films present a highly crystalline skutterudite not accompanied by extra phases. The power factor of annealed films is shown to be lower than in the corresponding bulk samples due to the lower Seebeck coefficients occurring in films. Room temperature thermal conductivity, on the contrary, shows values comparable to the ones of doubly doped bulk samples, thus highlighting the positive effect of interfaces on the introduction of scattering centers, and therefore on the reduction of thermal conductivity.

The pulsed laser deposition (PLD) technique was used to deposit CZTS thin films onto SLG/Mo substrates via the KrF-laser ablation of a composite target consisting of Cu2ZnSnS4 pellet onto which Zn strips were purposely affixed. The effect of the substrate temperature (Tsub) of the PLD-CZTS films on their structure and properties was systematically studied over the 25–500 °C temperature range. The Zn content of the films was found to increase mainly when Tsub is raised from 300 to 500 °C. While both XRD and Raman analyses confirmed that the films consist of the kësterite-single-phase of which crystallinity improves when Tsub is increased (from RT up to 400 °C), the near resonant Raman (at 325 nm) revealed the presence of ZnS phase at high Tsub (> 400 °C). The optical energy band gap (Eg) of the PLD-CZTS films was consistently found to decrease from 1.9 to 1.4 eV when Tsub is increased from RT to 500 °C. Our results pointed out the Tsub = 400 °C as the optimal deposition temperature that meets at best the properties required for the PLD-CZTS films for PV application. The post-annealing (in presence of S and Sn vapors at 560 °C) of the PLD-CZTS films has improved further their crystallinity and led to the formation of some ZnS secondary phase at their surface. By appropriately integrating these post-annealed films into SLG/Mo/CZTS/CdS/ZnO/ITO photovoltaic devices, we were able to demonstrate their photoconversion ability with a PCE of 3.3 % (Voc = 512 mV, Jsc = 12.5 mA/cm2 and a FF = 51.5 %). The analysis of their EQE spectrum suggests that the effective carrier collection length in the CZTS absorption layer needs to be extended further to achieve higher photoconversion efficiencies., Peer Reviewed, Postprint (author's final draft)

In ABO₃ perovskite oxide ferroelectrics, electrical conductivity ranges from insulator- to superconductor-type and is virtually critical for all applications of these materials. Compared to bulk ceramics and crystals, ferroelectric thin films can enable advanced control of the conductivity. Here, small-polaron hopping conductivity was evidenced and examined in various pulsed-laser-deposited films of ferroelectric BaTiO₃ and reference films of SrTiO₃. For this, AC conductivity was studied in a broad range of temperatures and frequencies for films sandwiched between the bottom and top electrodes. In the BaTiO₃ films, with increasing temperature, a significant increase in activation energy for small-polaron hopping was found and ascribed to strong electron–phonon coupling and complex lattice oscillations therein. Plain relations of the activation energy to microstructure, composition, or phase transitions were lacking, which corroborated the critical role of phonons. Additionally, a phonon-less transport was detected. It was anticipated that owing to strong electron–phonon coupling, rich phonon ensembles, and coexistence of phonon-stimulated and phonon-less processes, the small-polaron conductivity can heavily vary in ferroelectric films that necessitates further studies.

Positron annihilation lifetime spectroscopy data from beamtime at ELBE

In dieser Arbeit werden das Wachstum und die Charakterisierung der Heterostruktur eines FeFET auf der Grundlage von BaSnO3, LaInO3 und (K,Na)NbO3 Schichten untersucht. Für jedes Material wurden die Wachstumsbedingungen bestimmt und im Hinblick auf die strukturellen und elektrischen Eigenschaften optimiert. Epitaktische BaSnO3 Filme, die auf SrTiO3 Substraten gewachsen sind, weisen eine hohe Dichte an Versetzungen auf, die ihre elektrischen Eigenschaften beeinträchtigen. Die Verwendung von NdScO3 Substraten und Einführung einer SrSnO3 Pufferschicht verbesserten die strukturellen und elektrischen Eigenschaften der BaSnO3 Schichten. Dies ermöglichte schließlich Untersuchungen an der LaInO3/BaSnO3 Grenzfläche. Schon eine geringe La-Dotierung der BaSnO3 Schicht von 0,3 % führte zur Bildung eines 2DEG nach der Grenzflächenbildung und damit zum Einschluss von Elektronen an der Grenzfläche. Dies konnte durch C-V, Van-der-Pauw und Hall-Effekt-Messungen eindeutig nachgewiesen werden. Eine deutliche Verbesserung der strukturellen und elektrischen Eigenschaften der BaSnO3 Schichten wurde durch die Verwendung von LaInO3:Ba Substraten erreicht. Diese sind gitterangepasst an BaSnO3, sodass zum ersten Mal vollständig verspannte Schichten ohne Versetzungen gewachsen werden konnten. Strukturelle und elektrische Eigenschaften von (K,Na)NbO3 Schichten wurden auf SrRuO3/DyScO3 und SrTiO3:Nb-Substraten untersucht. Auf diese Weise wurden der Einfluss der Gitterdehnung auf die kritische Schichtdicke und die Prozesse der plastischen Relaxation des Gitters bestimmt. Die elektrische Charakterisierung ergab einen hohen Leckstrom, der durch strukturelle Defekte verursacht wird. Die gesamte FeFET Heterostruktur wurde auf LaInO3:Ba Substraten gewachsen und untersucht. BaSnO3 und LaInO3 Schichten wuchsen kohärent, während (K,Na)NbO3 Schichten eine plastische Gitterrelaxation aufwiesen. Das führte zur Bildung von Strukturdefekten und zu einer Verschlechterung der ferroelektrischen Eigenschaften., In this thesis, the design, growth and characterisation of the heterostructure of a FeFET based on BaSnO3, LaInO3 and (K,Na)NbO3 thin films are investigated. For each material, the growth conditions were determined and optimised with respect to their structural and electrical properties. Epitaxial BaSnO3 thin films grown on SrTiO3 substrates exhibit a high density of threading dislocations, which degrade their electrical properties. The use of NdScO3 substrates and the introduction of a SrSnO3 buffer layer improved the structural and electrical properties of the BaSnO3 thin films. This finally allowed investigations on the LaInO3/BaSnO3 heterointerface. Even a low La doping of the BaSnO3 layer of 0.3 % led to the formation of a 2DEG after interface formation and thus to the confinement of electrons at the interface. This could be clearly demonstrated by C-V, Van-der-Pauw and Hall effect measurements. A significant improvement of the structural and electrical properties of the BaSnO3 thin films was achieved by using LaInO3:Ba substrates. These are lattice-matched to BaSnO3 so that, for the first time, fully strained thin films could be grown without dislocations. Structural and electrical properties of (K,Na)NbO3 thin films were investigated on SrRuO3/DyScO3 and SrTiO3:Nb substrates. In this way, the influence of lattice strain on the critical film thickness and plastic lattice relaxation were determined. Their electrical characterisation revealed a high leakage current caused by structural defects. Therefore, the entire FeFET heterostructure was grown and investigated on LaInO3:Ba substrates. The BaSnO3 and LaInO3 thin films were grown coherently, while the (K,Na)NbO3 thin films exhibited plastic lattice relaxation. This led to the formation of structural defects and consequently to a deterioration of their ferroelectric properties.

The exploration for thermoelectric thin films of complex oxides such as SrTiO3-based oxides is driven by the need for miniaturized harvesting devices for powering the Internet of Things (IoT). However, there is still not a clear consensus in the literature for the underlying influence of film thickness on thermoelectric properties. Here, we report the fabrication of epitaxial thin films of 6% Nb-doped SrTiO3 on (001) (LaAlO3)0.3(Sr2AlTaO6)0.7 (LSAT) single crystal using pulsed laser deposition (PLD) where the film thickness was varied from 2 nm to 68 nm. The thickness dependence shows a subtle increase of tetragonality of the thin film lattice and a gradual drop of the electrical conductivity, the density of charge carriers, and the thermoelectric Seebeck coefficient as the film thickness decreases. DFT-based calculations show that ∼2.8% increase in tetragonality results in an increased splitting between t2g and eg orbitals to ∼42.3 meV. However, experimentally observed tetragonality for films between 68 to 13 nm is only 0.06%. Hence, the effect of thickness on tetragonality is neglected. We have discussed the decrease of conductivity and the Seebeck coefficient based on the decrease of carriers and change in the scattering mechanism, respectively.

Lithium titanium oxide thin films are increasingly popular anode materials in microbatteries and hybrid supercapacitors, due to their improved safety, cost, and cycle lifetime. So far, research efforts have mainly focused on the pure spinel phase Li4Ti5O12 (LTO) and only a small fraction is dedicated to a broader spectrum of titanium-based metal oxide thin films. In this work, pulsed laser deposition is used in a multilayer approach by alternating LTO and Li2O ablations to create a heterogeneous landscape in the titania-based micro-anodes. This rich microstructure enables the safe extension of the accessible electrochemical window down to 0.2 V. This leads to extraordinary high specific capacities of 250–300 mAh/g at 1 C, maintaining a stable discharge capacity of 180 mAh/g at 16 C. Operando spectroscopic ellipsometry and Raman spectroscopy are used to track optical and structural changes as a function of the discharge voltage down to 0.01 V. A kinetically limited degradation mechanism based on the effective trapping of Li-ions at the octahedral 16c positions is proposed when cycling in the range of 0.2–0.01 V. In essence, our work contributes to titania-based nanoshapes as anodes of increased specific capacity due to a higher Li-site occupation, while maintaining their good stability and safety.

We have developed a pulsed laser deposition (PLD) geometry for the growth of uniform BaF2 nanoscale thin films, through control of the deposition conditions. Our goal is to use the BaF2 layers with controllable structure as component layers in layered optical nanocomposites. The structure of the BaF2 nanolayer evolves as a function of the layer thickness: BaF2 grows via a layer-by-layer growth mode on Al2O3; the layers are amorphous for a thickness < 3 nm, and then become nanocrystalline as the layer thickness increases. The BaF2 nanocrystals have an FCC crystal structure with a weak <111> texture that becomes stronger for thicker films. We then demon- strate that our BaF2 films can be introduced into layered Al2O3/BaF2/EuOx nanocomposite films, which allows for control of the relative position of the Eu ions and the BaF2 layer. Cross-section samples of the multilayered films show interfacial intermixing between the layers, which is related to implantation during the PLD process. This intermixing enables the incorporation of Eu ions into BaF2 layers and form a thin Eu-doped BaF2 nanolayer at the interface. The layered nanocomposite films show photoluminescence (PL) emission from Eu3+ ions, and the PL intensity changes can be correlated with the crystallinity and crystal size changes in the BaF2 layer. Our results provide guidance for achieving thin film nanocomposite materials with controllable structure and pho- toluminescence behavior for light emitting diodes, photovoltaics and other optical applications.

Pulsed UV laser deposition was exploited for the preparation of thin Sn50-xAsxSe50 (x = 0, 0.05, 0.5, and 2.5) films with the aim of investigating the influence of low arsenic concentration on the properties of the deposited layers. It was found that the selected deposition method results in growth of a highly (h00) oriented orthorhombic SnSe phase. The thin films were characterized by different techniques such as X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, atomic force microscopy, Raman scattering spectroscopy, and spectroscopic ellipsometry. From the results, it can be concluded that thin films containing 0.5 atom % of As exhibited extreme values regarding crystallite size, unit cell volume, or refractive index that significantly differ from those of other samples. Laser ablation with quadrupole ion trap time-of-flight mass spectrometry was used to identify and compare species present in the plasma originating from the interaction of a laser pulse with solid-state Sn50-xAsxSe50 materials in both forms, i.e. parent powders as well as deposited thin films. The mass spectra of both materials were similar; particularly, signals of SnmSen+ clusters with low m and n values were observed., Pulzní UV laserová depozice byla využita pro přípravu tenkých vrstev Sn50-xAsxSe50 (x = 0, 0,05, 0,5 a 2,5) s cílem prozkoumat vliv nízké koncentrace arsenu na vlastnosti deponovaných vrstev. Bylo zjištěno, že zvolená metoda depozice vede k růstu vysoce (h00) orientované orthorhombické fáze SnSe. Tenké vrstvy byly charakterizovány různými technikami, jako je rentgenová difrakce, rastrovací elektronová mikroskopie s energiově disperzní rentgenovou spektroskopií, mikroskopie atomárních sil, spektroskopie Ramanova rozptylu a spektroskopická elipsometrie. Z výsledků lze usoudit, že tenké vrstvy obsahující 0,5 at. % As vykazovaly extrémní hodnoty týkající se velikosti krystalitů, objemu základní buňky nebo indexu lomu, které se významně liší od ostatních vzorků. Laserová ablace s kvadrupólovou iontovou pastí time-of-flight hmotnostní spektrometrie byla použita k identifikaci a porovnání klastrů přítomných v plazmatu pocházejícího z interakce laserového pulzu s Sn50-xAsxSe50 v obou formách, tj. prášcích i nanesených tenkých vrstvách. Hmotnostní spektra obou materiálů byla podobná; zejména byly pozorovány signály klastrů SnmSen+ s nízkými hodnotami m a n.

Thin films of silicon carbide (SiC) on Si (100) and SrTiO (100) substrates have been grown by nanosecond pulsed laser deposition (PLD) with a Q-switched Nd:YAG laser operating at the wavelengths of 1064, 532 and 266 nm. The deposits obtained consisted of smooth and uniform layers of amorphous SiC, free of holes and cracks, with thicknesses in the range of 30–100 nm and average roughness substantially lower than 1 nm. The role of laser wavelength and of substrate temperature (300 K vs. 1025 K) on morphology, crystallinity and composition of the deposits was assessed. The films were analyzed by X-ray diffraction, micro-Raman spectroscopy and X-ray photoelectron spectroscopy. In addition, optical emission spectroscopy was employed to evaluate the characteristics of the ablation plasma and its correlation with the film growth.

In this work, Ag-doped ZnO nanoparticles are obtained via pulsed laser ablation of the Ag-coated ZnO target in water. The ratio of Ag dopant in ZnO nanoparticles strongly depends on the thickness of the Ag layer at the ZnO target. Synthesized nanoparticles were characterized by XRD, XPS, SEM, EDS, ICP-OES, and UV–VIS spectrophotometry to obtain their crystal structure, elemental composition, morphology and size distribution, mass concentration, and optical properties, respectively. The photocatalytic studies showed photodegradation of methylene blue (MB) under UV irradiation. Different ratios of Ag dopant in ZnO nanoparticles influence the photodegradation rate. The ZnO nanoparticles doped with 0.32% silver show the most efficient photodegradation rate, with the chemical reaction constant of 0.0233 min−1. It exhibits an almost twice as large photodegradation rate compared to pure ZnO nanoparticles, showing the doping effect on the photocatalytic activity.

Vanadium redox flow batteries (VRFBs) are appealing large-scale energy storage systems due to their unique properties of independent energy/power design. The VRFBs stack design is crucial for technology deployment in power applications. Besides the design, the stack suffers from high voltage losses caused by the electrodes. The introduction of active sites into the electrode to facilitate the reaction kinetic is crucial in boosting the power rate of the VRFBs. Here, an O-rich layer has been applied onto structured graphite felt (GF) by depositing WO3 to increase the oxygen species content. The oxygen species are the active site during the positive reaction (VO2+/VO2+) in VRFB. The increased electrocatalytic activity is demonstrated by the monoclinic (m)-WO3/GF electrode that minimizes the voltage losses, yielding excellent performance results in terms of power density output and limiting current density (556 mWcm−2@800 mAcm−2). The results confirm that the m-WO3/GF electrode is a promising electrode for high-power in VRFBs, overcoming the performance-limiting issues in a positive half-reaction.

Integration of the prototypical GeSbTe (GST) ternary alloys, especially on the GeTe-Sb2 Te3 tie-line, into non-volatile memory and nanophotonic devices is a relatively mature field of study. Nevertheless, the search for the next best active material with outstanding properties is still ongoing. This search is relatively crucial for embedded memory applications where the crystallization temperature of the active material has to be higher to surpass the soldering threshold. Increasing the Ge content in the GST alloys seems promising due to the associated higher crystallization temperatures. However, homogeneous Ge-rich GST in the as-deposited condition is thermodynamically unstable, and phase separation upon annealing is unavoidable. This phase separation reduces endurance and is detrimental in fully integrating the alloys into active memory devices. This work investigated the phase separation of Ge-rich GST alloys, specifically Ge5 Sb2 Te3 or GST523, into multiple (meta)stable phases at different length scales in melt-quenched bulk and annealed thin film. Electron microscopy-based techniques were used in our work for chemical mapping and elemental composition analysis to show the formation of multiple phases. Our results show the formation of alloys such as GST213 and GST324 in all length scales. Furthermore, the alloy compositions and the observed phase separation pathways agree to a large extent with theoretical results from density functional theory calculations.

Frequency-dependent AC susceptibility measurements have been used to estimate the critical current densities and pinning potential of two 1.1-mu m-thick YBCO films with nanoengineered pinning centres. The films were grown by pulsed laser deposition using a target with 4 % BaZrO3 nanoinclusions. Data were analysed in the framework of the Anderson-Kim model, collective pinning model, and a model due to Zeldov that implies a logarithmic dependence of pinning potential on the current density. It was found that the latter describes better our experimental data, and that the resulting pinning potential has reasonable high values in high magnetic field up to 9 T, indicating a high current-carrying capability in high magnetic fields., EU Marie Curie Excellence Grant "NanoTechPinningHTS"; UEFISCDI RomaniaConsiliul National al Cercetarii Stiintifice (CNCS)Unitatea Executiva pentru Finantarea Invatamantului Superior, a Cercetarii, Dezvoltarii si Inovarii (UEFISCDI) [138/2012]; Center of Excellence for Superconductivity Research, Ankara UniversityAnkara University, Work in Birmingham has been supported by the EU Marie Curie Excellence Grant "NanoTechPinningHTS". Work at NIMP Bucharest has been supported by UEFISCDI Romania, under Grant PN II PCCA No. 138/2012. Most of the data analysis and fitting has been done during a workshop at the Spring School and Educational Courses, International Conference on Superconductivity and Magnetism, Antalya, Turkey, 21 April-2 May 2014. Support of the Center of Excellence for Superconductivity Research, Ankara University, is also gratefully acknowledged.

Les piles à combustible (PC) peuvent aider à atténuer les effets délétères de l'utilisation de combustibles fossiles sur l'environnement, mais leur coût élevé et leur fonctionnement limité à long terme entravent leur commercialisation. Pour résoudre ces problèmes, de nouveaux matériaux d'électrode sont nécessaires pour remplacer le platine (Pt) dans les PC, en particulier à la cathode. Des charges élevées de Pt sont utilisées comme électrocatalyseur de réaction de réduction d'oxygène (RRO) dans cette électrode. L'RRO est une réaction lente et complexe, et même sur les surfaces Pt, elle se déroule loin de son potentiel thermodynamique, provoquant des pertes d'énergie. Les voies pour résoudre ces problèmes sont soit d'améliorer les performances du Pt, soit de développer de nouveaux matériaux pour le remplacer. Pour concevoir de nouveaux matériaux pour l'RRO, les descripteurs d'activité doivent être bien compris. Dans cette perspective, les études de réactions électrochimiques sur des surfaces ayant une structure bien définie - c'est-à-dire les études modèles - représentent un outil important dans l'élucidation des mécanismes de réaction, pour l'identification des sites actifs et pour permettre la déconvolution de la réponse électrochimique des surfaces. Ainsi, les études sur des surfaces modèles ouvrent la voie au progrès d'électrocatalyse. Concernant l'RRO, traditionnellement, ces études sont menées à l'aide de monocristaux et de méthodes hydrodynamiques. Cependant, certains matériaux ne peuvent pas être évalués en utilisant les voies conventionnelles, et pour ces cas, nous avons besoin de voies alternatives pour étudier l'ORR. Dans ce contexte, l'objectif principal de cette thèse est de proposer une voie alternative pour réaliser des études électrocatalytiques de l’RRO sur des surfaces modèles. A cet effet, des films minces à orientation épitaxiale déposés par dépôt laser pulsé (DLP) sont présentés comme des surfaces modèles appropriées. Des films minces de Pt et Au

This thesis explores topological defects and topological defect transitions in epitaxial ultrathin ferroelectric heterostructures. Geometrical confinements in ultrathin films has enabled the realisation of several nontrivial topological polarisation arrangements in ferroelectrics, categorised as a range of topological defects such as bubble, meron, vortex, flux-closure domain, etc. These ferroelectric topological defects can be engineered by tuning depolarisation field, mechanical and electrical boundary conditions. Our model system is an ultrathin (001) oriented PbZrxTi1-xO3/ SrTiO3/ PbZrxTi1-xO3 heterostructure fabricated on La0.67Sr0.33MnO3 buffered SrTiO3 substrates. Several topological defects are realised under specific mechanical and electrical boundary conditions. Topological defect transitions are also achieved using different routes such as electric field, thickness variation, mechanical pressure and thin film milling.These topological defects have also gained immense technological interest on account of their emergent properties. This thesis further studies the functional properties in topological defects such as electrical conductivity in bubble domains. The motion of these bubble domains is also investigated.The results herein offer new insights on how to engineer topological defects and topological defect transitions in order to design multifunctional ferroelectric/multiferroic devices with enhanced operational speed, sensitivity and energy-efficiencies.

It is difficult to grow uniform film by pulsed laser deposition because the spatial distribution of the laser-induced plume is a forward-directed cone-shape. A 3D-motional deposition setup was founded, and the correlative mathematical model of the film thickness on the 3D curved surface was deduced. Based on simulation and optimization, the diamond-like carbon (DLC) film was grown onto the large curved silicon substrate. According to the infrared transmittance spectra, the optical constants of the DLC film samples at different regions on the curved substrate were similar, indicating that the DLC film prepared onto the curved surface was homogeneous. Meanwhile, the deviation of average transmittance in the medium infrared band was below 2.3%, which could improve the imaging performance of the infrared detection. This research is useful to expand the application of the pulsed laser deposition in the optical field., It is difficult to grow uniform film by pulsed laser deposition because the spatial distribution of the laser-induced plume is a forward-directed cone-shape. A 3D-motional deposition setup was founded, and the correlative mathematical model of the film thickness on the 3D curved surface was deduced. Based on simulation and optimization, the diamond-like carbon (DLC) film was grown onto the large curved silicon substrate. According to the infrared transmittance spectra, the optical constants of the DLC film samples at different regions on the curved substrate were similar, indicating that the DLC film prepared onto the curved surface was homogeneous. Meanwhile, the deviation of average transmittance in the medium infrared band was below 2.3%, which could improve the imaging performance of the infrared detection. This research is useful to expand the application of the pulsed laser deposition in the optical field.

Materials having an anisotropic crystal structure often exhibit anisotropy in the electrical conductivity. Compared to complex transition-metal oxides (TMOs), simple TMOs rarely show large anisotropic electrical conductivity due to their simple crystal structure. Here, we focus on the anisotropy in the electrical conductivity of a simple TMO, oxygen-deficient tungsten oxide (WOx) with an anisotropic crystal structure. We fabricated several WOx films by the pulsed laser deposition technique on the lattice-matched (110)-oriented LaAlO3 substrate under a controlled oxygen atmosphere. The crystallographic analyses of the WOx films revealed that highly dense atomic defect tunnels were aligned one-dimensionally (1D) along [001] LaAlO3. The electrical conductivity along the 1D atomic defect tunnels was similar to 5 times larger than that across the tunnels. The present approach, introduction of 1D atomic defect tunnels, might be useful to design simple TMOs exhibiting anisotropic electrical conductivity.

A novel class of nanostructured Zr50 Cu50 (%at.) metallic glass films with superior and tunable mechanical properties is produced by pulsed laser deposition. The process can be controlled to synthetize a wide range of film microstructures including dense fully amorphous, amorphous embedded with nanocrys- tals and amorphous nano-granular. A unique dense self-assembled nano-laminated atomic arrangement characterized by alternating Cu-rich and Zr/O-rich nanolayers with different local chemical enrichment and amorphous or amorphous-crystalline composite nanostructure has been discovered, while significant in-plane clustering is reported for films synthetized at high deposition pressures. This unique nanoarchi- tecture is at the basis of superior mechanical properties including large hardness and elastic modulus up to 10 and 140 GPa, respectively and outstanding total elongation to failure ( > 9%), leading to excel- lent strength/ductility balance, which can be tuned by playing with the film architecture. These results pave the way to the synthesis of novel class of engineered nanostructured metallic glass films with high structural performances attractive for a number of applications in microelectronics and coating industry.

Les piles à combustible (PC) peuvent aider à atténuer les effets délétères de l'utilisation de combustibles fossiles sur l'environnement, mais leur coût élevé et leur fonctionnement limité à long terme entravent leur commercialisation. Pour résoudre ces problèmes, de nouveaux matériaux d'électrode sont nécessaires pour remplacer le platine (Pt) dans les PC, en particulier à la cathode. Des charges élevées de Pt sont utilisées comme électrocatalyseur de réaction de réduction d'oxygène (RRO) dans cette électrode. L'RRO est une réaction lente et complexe, et même sur les surfaces Pt, elle se déroule loin de son potentiel thermodynamique, provoquant des pertes d'énergie. Les voies pour résoudre ces problèmes sont soit d'améliorer les performances du Pt, soit de développer de nouveaux matériaux pour le remplacer. Pour concevoir de nouveaux matériaux pour l'RRO, les descripteurs d'activité doivent être bien compris. Dans cette perspective, les études de réactions électrochimiques sur des surfaces ayant une structure bien définie - c'est-à-dire les études modèles - représentent un outil important dans l'élucidation des mécanismes de réaction, pour l'identification des sites actifs et pour permettre la déconvolution de la réponse électrochimique des surfaces. Ainsi, les études sur des surfaces modèles ouvrent la voie au progrès d'électrocatalyse. Concernant l'RRO, traditionnellement, ces études sont menées à l'aide de monocristaux et de méthodes hydrodynamiques. Cependant, certains matériaux ne peuvent pas être évalués en utilisant les voies conventionnelles, et pour ces cas, nous avons besoin de voies alternatives pour étudier l'ORR. Dans ce contexte, l'objectif principal de cette thèse est de proposer une voie alternative pour réaliser des études électrocatalytiques de l’RRO sur des surfaces modèles. A cet effet, des films minces à orientation épitaxiale déposés par dépôt laser pulsé (DLP) sont présentés comme des surfaces modèles appropriées. Des films minces de Pt et Au

Materials having an anisotropic crystal structure often exhibit anisotropy in the electrical conductivity. Compared to complex transition-metal oxides (TMOs), simple TMOs rarely show large anisotropic electrical conductivity due to their simple crystal structure. Here, we focus on the anisotropy in the electrical conductivity of a simple TMO, oxygen-deficient tungsten oxide (WOx) with an anisotropic crystal structure. We fabricated several WOx films by the pulsed laser deposition technique on the lattice-matched (110)-oriented LaAlO3 substrate under a controlled oxygen atmosphere. The crystallographic analyses of the WOx films revealed that highly dense atomic defect tunnels were aligned one-dimensionally (1D) along [001] LaAlO3. The electrical conductivity along the 1D atomic defect tunnels was similar to 5 times larger than that across the tunnels. The present approach, introduction of 1D atomic defect tunnels, might be useful to design simple TMOs exhibiting anisotropic electrical conductivity.

Filled skutterudites are currently studied as promising thermoelectric materials due to their high power factor and low thermal conductivity. The latter property, in particular, can be enhanced by adding scattering centers, such as the ones deriving from low dimensionality and the presence of interfaces. This work reports on the synthesis and characterization of thin films belonging to the Sm-y(FexNi1-x)(4)Sb-12-filled skutterudite system. Films were deposited under vacuum conditions by the pulsed laser deposition (PLD) method on fused silica substrates, and the deposition temperature was varied. The effect of the annealing process was studied by subjecting a set of films to a thermal treatment for 1 h at 423 K. Electrical conductivity sigma and Seebeck coefficient S were acquired by the four-probe method using a ZEM-3 apparatus performing cycles in the 348-523 K temperature range, recording both heating and cooling processes. Films deposited at room temperature required three cycles up to 523 K before being stabilized, thus revealing the importance of a proper annealing process in order to obtain reliable physical data. XRD analyses confirm the previous result, as only annealed films present a highly crystalline skutterudite not accompanied by extra phases. The power factor of annealed films is shown to be lower than in the corresponding bulk samples due to the lower Seebeck coefficients occurring in films. Room temperature thermal conductivity, on the contrary, shows values comparable to the ones of doubly doped bulk samples, thus highlighting the positive effect of interfaces on the introduction of scattering centers, and therefore on the reduction of thermal conductivity.

Filled skutterudites are currently studied as promising thermoelectric materials due to their high power factor and low thermal conductivity. The latter property, in particular, can be enhanced by adding scattering centers, such as the ones deriving from low dimensionality and the presence of interfaces. This work reports on the synthesis and characterization of thin films belonging to the Sm-y(FexNi1-x)(4)Sb-12-filled skutterudite system. Films were deposited under vacuum conditions by the pulsed laser deposition (PLD) method on fused silica substrates, and the deposition temperature was varied. The effect of the annealing process was studied by subjecting a set of films to a thermal treatment for 1 h at 423 K. Electrical conductivity sigma and Seebeck coefficient S were acquired by the four-probe method using a ZEM-3 apparatus performing cycles in the 348-523 K temperature range, recording both heating and cooling processes. Films deposited at room temperature required three cycles up to 523 K before being stabilized, thus revealing the importance of a proper annealing process in order to obtain reliable physical data. XRD analyses confirm the previous result, as only annealed films present a highly crystalline skutterudite not accompanied by extra phases. The power factor of annealed films is shown to be lower than in the corresponding bulk samples due to the lower Seebeck coefficients occurring in films. Room temperature thermal conductivity, on the contrary, shows values comparable to the ones of doubly doped bulk samples, thus highlighting the positive effect of interfaces on the introduction of scattering centers, and therefore on the reduction of thermal conductivity.

Filled skutterudites are currently studied as promising thermoelectric materials due to their high power factor and low thermal conductivity. The latter property, in particular, can be enhanced by adding scattering centers, such as the ones deriving from low dimensionality and the presence of interfaces. This work reports on the synthesis and characterization of thin films belonging to the Sm-y(FexNi1-x)(4)Sb-12-filled skutterudite system. Films were deposited under vacuum conditions by the pulsed laser deposition (PLD) method on fused silica substrates, and the deposition temperature was varied. The effect of the annealing process was studied by subjecting a set of films to a thermal treatment for 1 h at 423 K. Electrical conductivity sigma and Seebeck coefficient S were acquired by the four-probe method using a ZEM-3 apparatus performing cycles in the 348-523 K temperature range, recording both heating and cooling processes. Films deposited at room temperature required three cycles up to 523 K before being stabilized, thus revealing the importance of a proper annealing process in order to obtain reliable physical data. XRD analyses confirm the previous result, as only annealed films present a highly crystalline skutterudite not accompanied by extra phases. The power factor of annealed films is shown to be lower than in the corresponding bulk samples due to the lower Seebeck coefficients occurring in films. Room temperature thermal conductivity, on the contrary, shows values comparable to the ones of doubly doped bulk samples, thus highlighting the positive effect of interfaces on the introduction of scattering centers, and therefore on the reduction of thermal conductivity.

The injection of spin-polarized electrons from a magnetic material into semiconductor is currently one of the foremost challenges in semiconductor spin electronics. Here, we have studied the efficient electrical spin injection and detection from nickel doped Fe3O4 (NFO) into the p-Si having (100) crystal orientation via MgO thin insulating tunnel barrier with the help of three-terminal Hanle measurement. The NFO/MgO/p-Si heterojunction has been prepared using pulsed laser deposition (PLD) technique. Clear Hanle and Inverted Hanle signals have been noticed in spin injection and detection condition of the heterojunction. A large value of Hanle signal (Delta V=2.4 mV) has been detected at room temperature (300 K). Pure spin accumulation in p-Si resulted from spin injection from strong ferromagnetic NFO via MgO tunnel barrier has been corroborated by a meticulous experiment incorporating a non-magnetic Ag/MgO/p-Si heterostructure. The bias dependent Delta V and spin lifetime (tau) suggest that the transport of the heterojunction is governed by the spin tunnelling via pin-hole free MgO tunnel barrier. Hence the oxide magnetic materials establish a decent platform in spin injection and detection for the development and improvement of room temperature spin-based electronic devices.

The capacity of direct laser interference patterning (DLIP)to generate periodic surface structures has demonstrated advantages to other structuring techniques such as the large diversity of materials and geometries achievable as well as the simplicity of structuring in only a single processing step(Source). The applicability for generating photocatalytic active surfaces from titanium substrates has been explored in some extend for femtosecond and nanosecond pulsed lasers (Source). The favorable multi-scattering and caption of light due to the surface morphology as well as the superficial chemical modification make the surface photocatalytically active under near UV radiation. The role of the processing variables in the surface physical and chemical modification is not completely understood. In this work pure titanium was structure by DLIP with a picosecond pulsed laser under atmospheric conditions. The influence of the processing parameters in the morphology, topography, chemical composition and photocatalytic activity of the structured surface were evaluated. For this , confocal laser scanning microscopy, scanning electron microscopy, grazing incidence X-ray diffraction, transmission electron microscopy, Raman spectroscopy and diffuse reflected spectroscopy were used. The photocatalytic activity was evaluated by measuring the degradation of an aqueous solution of methylene blue under near UV radiation and local photocatalytic regions were detected by mean the photodeposition of silver. Well defined line-like patterns of 3 and 10 um periodicity were obtained. The height difference between peaks and valleys depends mainly on the periodicity followed by the effect of the accumulated fluence, with a positive relationship. However the roughness ratio showed higher dependency on the accumulated fluence than the periodicity. The accumulated fluence has the greatest effect on the photocatalytic activity and the highest degradations were found for the samples with very high, Outgoing

The interplay of structure, composition and electrical conductivity was investigated for Fe-doped SrTiO3 thin films prepared by pulsed laser deposition. Structural information was obtained by reciprocal space mapping while solution-based inductively-coupled plasma optical emission spectroscopy and positron annihilation lifetime spectroscopy were employed to reveal the cation composition and the predominant point defects of the thin films, respectively. A severe cation non-stoichiometry with Sr vacancies was found in films deposited from stoichiometric targets. The across plane electrical conductivity of such epitaxial films was studied in the temperature range of 250 - 720 °C by impedance spectroscopy. This revealed a pseudo-intrinsic electronic conductivity despite the substantial Fe acceptor doping, i.e. conductivities being several orders of magnitude lower than expected. Variation of PLD deposition parameters causes some changes of the cation stoichiometry, but the films still have conductivities much lower than expected. Targets with significant Sr excess (in the range of several percent) were employed to improve the cation stoichiometry in the films. The use of 7 % Sr-excess targets resulted in near-stoichiometric films with conductivities close to the stoichiometric bulk counterpart. The measurements show that a fine-tuning of the film stoichiometry is required in order to obtain acceptor doped SrTiO3 thin films with bulk-like properties. One can conclude that, although RSM experiments give a first hint whether or not cation non-stoichiometry is present, conductivity measurements are more appropriate for assessing SrTiO3 film quality in terms of cation stoichiometry.

In recent years, molybdenum disulfide (MoS2) has been investigated due to its unique electronic, optical, and mechanical properties with a variety of applications. Sulfurization of pre-deposited MoO3 layers is one of the methods of the preparation of large-area MoS2 thin films. The MoO3 layers have been grown on c-sapphire substrates, using two different techniques (rf sputtering, pulsed laser deposition). The films were subsequently annealed in vapors of sulfur at high temperatures what converted them to MoS2 films. The quality of MoS2 is strongly influenced by the properties of the precursor MoO3 layers. The pre-deposited MoO3, as well as the sulfurized MoS2, have been characterized by several techniques including Raman, Rutherford backscattering spectroscopy, atomic force microscopy, scanning electron microscopy, and X-ray diffraction. Here we compare two types of MoS2 films prepared from different MoO3 layers to determine the most suitable MoO3 layer properties providing good quality MoS2 films for future applications.