Les concepts de matériaux multiferroïques et/ou magnétoélectriques permettent d’envisager de nouveaux dispositifs de mémoires plus performants et moins consommateurs d’énergie. Malheureusement de tels matériaux présentant ces propriétés à température ambiante ne sont pour l’instant pas disponibles. Les matériaux qui font l’objet des études présentées dans ce manuscrit, les ferrites de gallium Ga2-xFexO3, 0,7 ≤ x ≤ 1,4, sont d’excellents candidats. Le présent travail de thèse en a étudié les propriétés électriques, tant sur matériaux massifs que couches minces. Nous avons mesuré une polarisation sur composés massifs du même ordre de grandeur que celle précédemment déterminée par calculs ab initio. Une considérable réduction des courants de fuite habituellement observés en couches minces a été possible grâce à la substitution de Fe2+ par Mg2+. Une polarisation réversible et un effet magnétoélectrique ont alors pu être mis en évidence. Compte tenu du caractère ferrimagnétique à température ambiante des couches minces considérées, ceci constitue la première manifestation d’un matériau multiferroïque et magnétoélectrique à réel intérêt applicatif. / Concepts of multiferroic and magnetoelectric materials allow designing new memory devices with better performances and less energy consumption. Unfortunately, such materials with room temperature applicability are not yet available.The material concerned by this study, gallium ferrites Ga2-xFexO3, 0.7 ≤ x ≤ 1.4, are excellent candidates for such applications. This work aimed at studying the electrical properties of the bulk material, as well as in thin films. We have measured a polarization on the bulk samples comparable to the value estimated by first principle calculations. A considerable reduction of the leakage currents usually observed in oxide thin films has been achieved by the doping by substitution of Fe2+ in the structure, using Mg2+. A switchable polarization and a magnetoelectric effect at room temperature in thin films have been observed. Considering the room temperature ferrimagnetic behavior of this compound, this is the first manifestation of a multiferroic and magnetoelectric with real potential and technological applications.

Cette thèse concerne l’étude de l’effet du dopage au chrome sur les propriétés structurales, électriques et optiques des films de dioxyde de vanadium. Ces films V(1-x)CrxO2 (x allant de 0 à 25%) de 110 nm d’épaisseur ont été déposés par dépôt par ablation laser (PLD) multicibles sur substrat saphir c. Ils ont été caractérisés grâce à des techniques d’analyse morphologique, structurale, électrique et optique. Les différentes phases présentes dans les films V(1-x)CrxO2 ont été identifiées par DRX, spectroscopie Raman et comparées au diagramme de phase du matériau massif. Les phases M1, M2 et M3, un mélange M2 + M3 et la phase R ont été identifiées. En revanche la phase M4 n’a pas été détectée pour des dopages supérieurs à 8%, montrant une réelle différence entre diagrammes de phase du matériau massif et des films. Le dopage au chrome a permis d’augmenter la température de transition isolant-métal de 68 à 102°C. En revanche, la dynamique de cette transition, déterminée par mesure de transmission optique ou par mesure de résistivité électrique, est souvent diminuée. Enfin, des dispositifs à deux terminaux à base de films V(1-x)CrxO2 ont été réalisés. Leurs caractérisations courant-tension montrent que le dopage au chrome influence fortement le seuil d’activation de la transition entre les états isolant et métallique. / This thesis presents a study of the effect of chromium doping on structural, electrical and optical properties of thin films of vanadium dioxide. These V(1-x)CrxO2 thin films (x from 0 to 25%) of 110 nm thick have been deposited on c sapphire substrate by multi target Pulsed Laser Deposition method. Their morphological, structural, electrical and optical properties have been studied. Different phases for V(1-x)CrxO2 have been identified by XRD and Raman analysis and compared to those of bulk material. M1, M2, M3, a mixture M2 + M3 and R phases are present. The M4 phase has not been detected for doping above 8%, showing a real difference between phase diagram of bulk and thin films. Chromium doping also increases the metal-insulator transition temperature from 68°C to 102°C. Moreover, the transition dynamics, determined using optical transmission and electrical resistivity measurements, decreases. Finally, two terminal switches based on V(1-x)CrxO2 thin films have been fabricated. Their current-voltage characterization showed that chromium doping affects the activation threshold voltage of the metal to insulator transition.

No description available.

Perovskite based artificial superlattices has recently been extensively investigated due to the immense promise in various device applications. The major applications include non-volatile random access memories, microwave devices, phase shifters voltage tunable capacitor applications etc. In this thesis we have taken up the investigation of two different types of symmetric superlattices, viz. BaZrO3/BaTiO3 and SrTiO3/BaZrO3, with possible applicability to voltage tunable devices. Chapter 1 deals with the introduction to the perovskite based functional oxides. Their various applications and the specific requirements for voltage tunable device applications has also been discussed in detail. The basic properties of BaTiO3 and SrTiO3, which are well documented in the literature, have been reviewed. The fundamental physics of interfacial interactions that influence the properties of superlattices is also discussed using existing models. The reason behind the choice of constructing artificial superlattices of BaZrO3/BaTiO3 and SrTiO3/BaZrO3 and the motivation behind this thesis is outlined. Chapter 2 gives a brief description of the basic characterization techniques that has been employed for studying the thin films. These include pulsed laser deposition of oxide thin films, structural characterization using X-Ray Diffraction and Atomic Force Microscope and electrical characterization of thin film metal-insulator-metal structures. The basic principle behind the techniques has also been included in various sections of this chapter. Chapter 3 introduces the reader to basic properties of the less studied perovskite material BaZrO3, one of the parent components of Ba(Zr,Ti)O3 based ceramics for high frequency applications. BaZrO3 is the common material in both the types of superlattices studied in this thesis. Initially the growth of polycrystalline BaZrO3 on (111)Pt/TiO2/SiO2/Si has been elaborated in this chapter. After characterizing the crystalline quality of the films and optimizing the growth conditions, epitaxial BaZrO3 films has been grown on (001) SrTiO3 substates. Dielectric properties of epitaxial BaZrO3 film have been measured as a function of temperature and frequencies. The electric field tunability of BaZrO3 films has been calculated from capacitance-voltage data for comparison with superlattice structures. Chapter 4 deals with the basic considerations involving growth of artificial superlattices and multilayers using pulsed laser ablation technique. The fundamental differences between formation of multilayers and superlattices have also been discussed, and the basic considerations for optimizing growth parameters are analyzed in this chapter. X-ray θ-2θ and φ-scans have been performed to investigate crystal quality of superlattices. The growth rates calculated from the satellite reflections in X-ray θ-2θ scans indicate fair degree of control over the growth and φ-scans confirms epitaxial cube-on cube growth of both types of superlattices. Atomic Force microscopy has been used to hcaracterize the film quality and surface morphology of superlattice structures and it has been found that the films have a very smooth surface with rms roughness of the order of few nanometres. Chapter5 deals with the detailed electrical characterization of both types of superlattices structures. Dielectric response showed nearly temperature invariance for both types of superlattices. Polarization measurements show that the heterostructures are in paraelectric state. Even for paraelectric/ferroelectric BaZrO3/BaTiO3 superlattices, stress induced stabilization of the paraelectric state is exhibited in low period superlattices. Paraelectric/paraelectric-SrTiO3/BaZrO3 superlattices exhibited a tunability of ~20% at intermediate modulation periods and an extremely stable dissipation factor with respect to temperature which is very attractive for device application point of view. A maximum tunability of ~40% has been observed for lowest period BaZrO3/BaTiO3 superlattice. Relatively high Quality Factors has been observed for both type of superlattices and their dependence on the modulation periods has been analyzed. Dielectric relaxation data showed that Maxwell-Wanger type of behaviour is exhibited but the presence of a conductance component G had to be realized in the equivalent circuit representation, which originates from the observation of a square law dependence of the alternating current on the frequency. Finally DC electrical characteristics were investigated as a function of temperature to determine the type of conduction mechanism that is involoved. The data has been analyzed using existing theories of high field conduction in thin dielectric films and it has been found that at different temperature ranges, the conduction mechanism varied from bulk limited Poole-Frenkel to Space Charge limited conduction. The activation energy calculation indicate that the physical processes responsible for dielectric relaxation and dc conduction are identical.

Die vorliegende Arbeit beschreibt den Verlauf der Forschung von der Entwicklung einer neuartigen Methode der gepulsten Laser-Plasmaabscheidung (PLD) über die Untersuchung der ternären In- und Al-Legierungssysteme von metastabilem orthorhombischen κ-Ga2O3 auf der Basis dieser Methode hin zu Multi-Quantengraben (QW) Supergitter (SL) Heterostrukturen für transparente Quantengrabeninfrarotphotodetektoren (QWIPs). Im ersten Teil wird die Methode, welche vertical continuous composition spread (VCCS) PLD genannt wird, eingeführt und am MgxZn1−xO Legierungssystem erprobt. Die Methode erlaubt die Kontrolle der Komposition von Dünnfilmen über die radiale Position des PLD Laserspots auf der Targetoberfläche. Das ist eine wichtige Voraussetzung für die Bestimmung der kompositionsabhängigen Eigenschaften der Legierungssysteme und für präzise Profile der physikalischen Eigenschaften in Wachstumsrichtung für das Design von Bauelementen. Die Dünnfilme mit 0 ≤ x ≤ 0.4 zeigen die gleichen Eigenschaften wie solche, die mit Standard-PLD abgeschieden wurden. Numerische Modelle werden präsentiert, welche die Dünnfilmkomposition exakt vorhersagen. Im zweiten Teil werden κ-Ga2O3 Dünnfilme durch die Beigabe von Zinn während des PLD Prozesses stabilisiert. Die Dünnfilme weisen hohe kristalline Qualität, glatte Oberflächen und große Bandlücken (Eg ≈ 4.9 eV) auf. Ein Wachstumsmodell wird präsentiert, welches Zinn als Oberflächenschicht beschreibt. Im dritten Teil werden die In- und Al-Legierungssysteme von κ-Ga2O3 mittels VCCS PLD untersucht. Die Löslichkeitsgrenzen xIn <~ 0.35 und xAl <~ 0.65 sind die höchsten bislang berichteten. In- und out-of-plane Gitterkonstanten wurden in Abhängigkeit der Zusammensetzung bestimmt und Eg konnte von 4.1 eV bis 6.4 eV variiert werden. Die Position des Valenzbandmaximums wird als unabhängig von der Komposition gezeigt, womit die Variation in Eg den Leitungsbandunterschieden gleicht und Detektionsbereiche vom fernen IR bis in das Sichtbare für QWIP-Anwendungen bedeutet. Berechnungen anhand dieser Ergebnisse ergeben Polarisationsladungsdichten an Grenzflächen von Heterostrukturen gleich oder höher derer im etablierten AlGaN/GaN System, welche wichtig zur Polarisationsdotierung zur Besetzung des Grundzustandes in QWIPs sind. Dies bestätigt das große Potential der κ-Phase. Im letzten Teil werden erste kohärent gewachsene κ-(AlxGa1−x)2O3/Ga2O3 SL Strukturen untersucht. Glatte Grenzflächen im Bereich weniger Monolagen werden gezeigt und es konnten kritische Dicken für die κ-Ga2O3 QW Schichten bestimmt werden, die für QWIP-Anwendungen genügen. / The presented thesis describes the research path from the development of a novel pulsed laser deposition (PLD) technique over the exploration of the ternary In- and Al-alloy systems of metastable orthorhombic κ-Ga2O3 employing this technique towards multi-quantum well (QW) superlattice (SL) heterostructures for solar-blind quantum well infrared photodetector (QWIP) applications. In the first part, the PLD technique called vertical continuous composition spread (VCCS) PLD employing radially-segmented targets is established and tested on the well-known MgxZn1−xO alloy system. The technique enables direct control of the chemical composition of thin films by a variation of the radial position of the PLD laser spot on the target surface. This is a prerequisite for a discrete compositional screening of alloy properties and the exact tailoring of physical parameters in growth direction for heterostructure device design. The resulting thin films with 0 ≤ x ≤ 0.4 exhibit the same quality as thin films deposited by standard PLD and numerical models are presented that precisely predict the thin film composition. In the second part, κ-Ga2O3 thin films are stabilized by the addition of tin in the PLD process. The thin films show a high crystalline quality, smooth surfaces and large bandgaps (Eg ≈ 4.9 eV). A growth model is proposed based on tin acting as surfactant. In the third part, the In- and Al-alloy systems of κ-Ga2O3 are explored by VCCS PLD. Solubility limits of xIn <~ 0.35 and xAl <~ 0.65 are the highest reported to date. In- and out-of-plane lattice constants were determined as function of alloy composition and bandgap engineering from 4.1 eV to 6.4 eV is feasible within these limits. The energetic position of the valence band maximum was found independent on chemical composition such that the change in bandgap equals the conduction band offset rendering wavelength ranges from far IR to the visible spectral range in QWIP applications possible. Calculations based on these results found polarization charge densities at the interfaces of corresponding heterostructures on par or larger than for the established AlGaN/GaN system important for polarization doping to populate the ground state in QWIPs. This corroborates the high potential of the κ-phase. In the last part, first coherently grown κ-(AlxGa1−x)2O3/Ga2O3 SL heterostructures are presented. Smooth interfaces of the order of a few monolayers are confirmed and critical thicknesses for coherent growth of the Ga2O3 QW layer are found to be sufficient for QWIP applications.

No description available.

This diploma thesis deals with the preparation of the very thin films and their investigation by scanning probe microscopy methods. The ultrathin films of Pt on Pt(111) were created by pulsed laser deposition and the ultrathin films of Co on Pt(111) were deposited by thermal evaporation. The coverage of the substrate was much smaller than one monolayer (in order of hundredths of monolayer). The nucleation theory was verified by these experiments using so-called Onset method. Further graphene sheets were prepared on layer of Si/SiO2 by the mechanical exfoliation from the graphite crystal. The fabricated graphene sheets were studied by micro-Raman spectroscopy, microreflectometry, atomic force microscopy and similar techniques. These methods proved the thinnest graphite layers were consisted of two graphene monolayers.

L'intégration d'oxydes ferroélectriques permet la réduction des dimensions de dispositifs électroniques pour des applications en télécommunications, tout en leur apportant la reconfigurabilité. Parmi ces matériaux multifonctionnels, KxNa1-xNbO3 (KNN) se présente comme un candidat oxyde sans plomb prometteur pour un grand nombre d'applications. L'objectif de cette thèse est l'élaboration de couches minces de KNN et l'étude de leurs propriétés diélectriques en hyperfréquences en vue de leur intégration dans des antennes miniatures et reconfigurables. La permittivité εr, les pertes tanδ et l'agilité seront caractérisées à partir de couches minces de KNN déposées par la technique d'ablation laser. De plus, les avancements sur les dépôts par pulvérisation cathodique seront présentés. Après une étude sur la composition du matériau, l'influence des propriétés structurales sur les propriété diélectriques à travers l'utilisation de deux types de substrats a permis l'obtention d'une agilité de 20% sous un champ Ebias de 90 kV/cm. Une caractérisation diélectrique en température aura permis d'observer, à 10 GHz, une augmentation de la permittivité de 360 à 20°C jusqu'à 1000 à 240°C au niveau de la transition de phase polymorphique. Lors de ces travaux, la phase bronze de tungstène tétragonale (TTB), encore très peu étudiée dans le système K-Na-Nb-O a été préparée en couches minces fortement orientées et une permittivité élevée a été obtenue à basses (~200 à 10 kHz) et hautes fréquences (~130 à 10 GHz). Enfin la conception, la réalisation et la mesure d'antennes miniatures intégrant du KNN ont été effectuées. / Ferroelectric materials are a solution for reducing the size of electronic devices for telecommunication applications while also enabling reconfigurability. Among the multifunctional materials, KxNa1-xNbO3 (KNN) is a promising lead-free oxide for a large number of applications. The main goal of this work is the elaboration of KNN thin films and their dielectric characterisations in order to integrate the thin film to obtain miniature reconfigurable antennas. The permittivity εr, the loss tanδ and the tunability, at microwave frequencies, of the KNN were retrieved from thin films prepared by pulsed laser deposition. Also, the progress on the deposition of KNN thin films by RF magnetron sputtering will be presented. After the investigation of the effect of the composition and the structural properties of the KNN thin films on their dielectric properties, the tunability has been increased up to 20% under a 90 kV/cm electric field for x = 0.5. A dielectric characterisation of depending on the temperature, at 10 GHz, has shown an increase of the permittivity value from 360 at 20°C up to 1000 at 240°C, indicating the polymorphic phase transition. The tetragonal tungsten bronze phase (TTB), barely studied in the K-Na-Nb-O system, has been prepared in thin film and exhibiting high values of permittivity at both low and microwave frequencies (~200 à 10 kHz and ~130 à 10 GHz). Finally the design, realisation and measurements of miniature antennas integrating KNN has been done.

Ce travail de doctorat porte sur la croissance par ablation laser pulsée de films ultrafins de Grenat de Fer et d’Yttrium dopés au Bismuth (BiYIG). Ces films d’épaisseur nanométriques sont caractérisés puis utilisés pour des applications magnon-spintroniques. Cette thèse englobe deux thématiques différentes de la physique : la science des matériaux et les applications magnon-spintroniques.La motivation de cette thèse repose sur le besoin, venant de la communauté magnon-spintronique, d’un nouveau matériau magnétique ultrafin à anisotropie ajustable. En effet, au court des dernières années, une avancée majeure dans le domaine a été l’obtention d’auto-oscillations magnétiques induites par un courant de charge dans un isolant magnétique. Ce résultat a été rendu possible grâce à l’utilisation d’un film ultrafin (20 nm) de Grenat de Fer et d’Yttrium (YIG) possédant de très faibles pertes magnétiques. Ces films ultrafins de YIG sont également intéressants pour la magnonique puisqu’il est aussi possible d’y propager et de manipuler des ondes de spin sur de grandes distances. Cependant, la direction facile d’aimantation dans ces films est fixée par l’anisotropie de forme et n’est pas un paramètre ajustable. Pour pousser plus loin les possibilités dans le domaine de la magnon-spintronique un matériau ultrafin, présentant des pertes magnétiques similaires au YIG, dans lequel il serait possible de stabiliser une anisotropie perpendiculaire serait désirable.La croissance par épitaxie en phase liquide de films de YIG substitués de plusieurs microns d’épaisseur a permis de mettre en évidence que l’anisotropie magnétique pouvait être modifiée par dopage. Notamment que la substitution des atomes d’Yttrium par les atomes de Bismuth sur les sites atomiques dodécaédriques permet d’obtenir une direction facile d’aimantation hors du plan, le BiYIG est également reconnu pour sa forte activité magnéto-optique. Cette thèse présente la croissance par ablation laser pulsée de films ultrafins (7 à 50 nm d’épaisseur) de BiYIG. Dans ces films l’anisotropie magnétique a deux origines : l’anisotropie de croissance et l’anisotropie de contrainte. Dans ces films grâce à la contrainte les deux types anisotropies magnétique (planaire ou perpendiculaire) peuvent être obtenues. La caractérisation dynamique des films montre que la substitution d’Yttrium par le Bismuth n’augmente pas les pertes magnétiques et que l’amortissement de Gilbert dans le BiYIG est comparable à celui du YIG. De plus l’augmentation de l’activité magnéto optique du BiYIG par rapport à celle du YIG rend ce nouveau matériau très intéressant pour des techniques expérimentales impliquant l’interaction lumière/ moment magnétique (BLS, Kerr microscope…).Pour observer des phénomènes spintronique nous avons déposé une couche de Pt. Des mesures de transport comme la magnetoresistance Hall de spin, l’effet Hall de spin inverse ou l’effet Hall anormal témoignent d’un transfert de courant de spin a l’interface BiYIG-Pt. Grâce à l’anisotropie perpendiculaire, il est également possible d’observer de nouveaux phénomènes comme la génération d’onde de spin cohérent à partir d’auto-oscillations. Ce nouvel isolant magnétique combinant une faible épaisseur, un faible amortissement magnétique et une anisotropie magnétique modifiable est donc un matériau prometteur pour des applications magnon-spintroniques et ouvre de nouvelles possibilités pour le domaine. / This PhD work focuses on the Pulsed Laser Deposition (PLD) growth of Bismuth doped Iron Garnet nanometer thick films. Those films are charcterised and used for magnon-spintronics applications. This PhD has two main focuses : material science and magnon-spintronics applications.The aim of this PhD is to fill up the need in the magnon-spintronics community of an ultrathin magnetic material combining low magnetic losses and tunable magnetic anisotropy. Indeed the recent breakthrough in the domain was the ability of generating magnetic auto-oscillations from a charge current in a magnetic insulator. This result has been obtained by using an 20 nm thick film of Yttrium Iron Garnet (YIG) with low magnetic losses (α=2⋅〖10〗^(-4) ). Those ultrafin films of YIG can also be used for spin waves propagation over micrometeter distances. However the easy magnetic axis in those films is set to in plane due to the shape anisotropy and it is not a tunable parameter. To go further in terms of magnon-spintronics applications a perpendicularly easy magnetized low losses ultra-thin magnetic material would be desirable. Liquid Phase Epitaxy growth of micrometer thick doped YIG during the 70’s evidenced that the magnetic anisotropy could be modified by doping or substitution. Especially the substitution of Yttrium atoms by Bismuth ones on the dodecaedric atomic sites allows to stabilise out of plane magnetic anisotropy. Morevover the BiYIG is also known to posses high magneto optical activity.This PhD presents the growth by Pulsed Laser Deposition of ultrathin BiYIG films (7 to 50 nm thick). In those films the uniaxial magnetic anisotropy has two main origins : the magneto elastic and the growth induced anisotropy. Using the strain in those films it is possible to obtain both out of plane and in plane magnetic anisotropy. The dynamical characterisation shows that magnetic losses in the perpendicular easy magnetized films are comparable to the one of YIG ultrathin films. The high magneto optical activity in those films makes the BiYIG ultrathin films suitable for ligth based detection technics involving ligth/magnetism interaction. By sputtering a Pt sublayer on the top of BiYIG ultra thin films we could observ different spintronic phenomena evidencing the transfer of spin current from the metal to the insulator. Low losses and nanometer thickness in perpendicularly easy magnetized BiYIG films allow to observ current induced magnetic auto oscillation in the same fashion as what was previously done with ultrathin YIG. The perpendicular magnetic anisotropy allows however to couple those auto oscillation to spin waves, which was not possible for in plane magnetized YIG fims. This new phenomena is related to the unique properties of the ultrathin BiYIG.BiYIG ultrathin films are thus opening new perspectives in the magnon spintronic commnutiy due to their low thickness and tunable magnetic anisotropy.

In this thesis, the structural, optical, and electrical properties of wurtzite MgxZn1-xO:Al and MgxZn1-xO:Ga thin films have been investigated in dependence on Mg and dopant concentration. Among the transparent conductive oxides (TCOs), ZnO based compounds have gained renewed interest as a transparent electrode for large scale applications such as defroster windows, at panel displays, touch screens, and thin film solar cells due to low material and processing cost, non-toxicity, and suitable physical properties. In general, these applications require transparent electrodes with lowest possible resistivity of rho < 10^-3 Ohmcm and lower [1]. Recently, it has been reported that Ga and Al doped ZnO thin films can be deposited with respective resistivity of 5x10^-5 Ohmcm [2] and 3 x10^-5 Ohmcm [3] which are similar to the data obtained for other practical TCOs, i.e. the resistivity of about 4x 10^-5 Ohmcm for Sn doped In2O3 (ITO) thin films [4]. Moreover, the bandgap of ZnO can be increased by alloying with Mg offering band alignment between transparent electrode and active (or buffer) layer of the device, e.g. Cu(In,Ga)Se2 solar cells [5]. The tunable bandgap of these transparent electrodes can further increase the efficiency of the devices by avoiding energy losses in the interface region of the layers. From this point of view, this work has been aimed to investigate the doping efficiency and limits in transparent conductive (Mg,Zn)O alloys. For this purpose, the samples investigated in this work have been grown by pulsed-laser deposition (PLD) using a novel, continuous composition spread method (CCS). In general, this method allows to grow thin films with lateral composition gradient(s) [6, 7]. All MgxZn1-xO:Al and MgxZn1-xO:Ga thin films have been deposited on 2-inch in diameter glass, c- or r-plane sapphire substrates using threefold segmented PLD targets in order to grow thin films with two perpendicular, lateral composition gradients, i.e. the Mg composition is varied in one direction whereas the Al/Ga concentration is varied in a perpendicular direction [7, 8]. In order to investigate the influence of the temperature, samples grown at different substrate temperatures in the range of 25 to 600 C were investigated. The optical and electrical measurements have been carried out on (5x 5)mm^2 samples that were cut from the CCS wafers along the respective composition gradients, i.e. Mg and Al/Ga contents. Subsequently, physical properties of thin films have been analyzed for a large range of Al/Ga content between 0.5 and 7 at.%, which corresponds to doping concentrations between 2x 10^20 and 3x 10^21 cm^-3, for different Mg contents x(Mg) ranging from 0.01 to 0.1. It has been found that practically the limiting the dopant concentrations is about 2 x10^21 cm^-3. Further, the electrical data suggests, that the compensating intrinsic defect is doubly chargeable hinting to the zinc vacancy (V_Zn) as microscopic origin. Increasing the dopant concentration above 2 x10^21 cm^-3 leads to a degradation of electrical and structural properties [8]. Further, the influence of growth and annealing temperatures on structural, electrical and optical properties of the films has been studied. For that purpose, Al and Ga doped (2.5 at.% = 1x10^21 cm^-3) Mg0.05Zn0.95O thin films have been chosen from CCS samples grown at T_g = (25 - 600) C . For both doping series, the samples grown at higher temperatures exhibit better crystalline quality compared to the samples grown at lower growth temperatures. As a result, samples grown at higher temperatures reveal higher Hall mobility. For the Al-doping series, the highest free charge carrier density of n = 8.2x 10^20 cm^-3 was obtained for an Mg0.05Zn0.95O:Al thin film grown at 200 C, with corresponding Hall mobility of mu = 13.3 cm^2/Vs, a resistivity of rho = 5.7x10^-4 Ohmcm, and optical bandgap of E_g = 3.8 eV. Interestingly, the free charge carrier density of n = (5 - 8) x 10^20 cm^-3 for samples grown with T_g > 300 C is clearly higher than the value of n = 1.25 x 10^20 cm^-3 that was obtained for the high temperature grown sample, i.e. at T_g = 600 C. Furthermore, for all T_g, Al-doped films have a higher doping efficiency than the Ga-doped counterparts. In order to look deeper into the microscopic origin of this behavior, the samples were post-annealed in vacuum at 400 C. Experimental results showed that the free charge carrier density of Al-doped samples first decreased and saturated afterward with increasing annealing time. On the other hand, the free charge carrier density of the Ga-doped samples first slightly increased and saturated with increasing annealing time. For both doping series, the saturation value of n ~ 1 x 10^20 cm^-3 was very close to the data that has been observed for (i) high temperature grown samples and (ii) the solubility limit of Al in ZnO of 0.3 at.% = 1.2x 10^20 cm^-3, that has been determined by Shirouzu et al. for high temperature grown (T_g > 600 C) Al-doped ZnO [9]. Correspondingly, the optical bandgap also changed, i.e. increased (decreased) for Al- (Ga-) doping series, and approached a constant value of 3.5 0 +- 0.1 eV which is explained by generation of acceptor-like compensating defects, and the solubility limit of the dopants. From XRD data, no secondary phases were found for as-grown and post-annealed films. However, the slight improvement of crystalline quality has been observed on post-annealed samples. Further, it has been shown that the growth and annealing temperatures are important as they strongly affect the metastable state of the solid solution that samples grown at low temperature represent. The low solubility limit of the dopants, i.e. 0.3 at.% for Al in ZnO under equilibrium condition, can be increased by preparing samples by non-equilibrium growth techniques [10]. This is also consistent with experimental results of this work that Al- as well as Ga-doped metastable ZnO and (Mg,Zn)O thin films can be prepared with highest possible doping efficiency for the dopant concentration up to 2.5 at.% when growth or annealing temperatures below 400 C are used.