Ellipsometric Determination of Cation Disorder in Magnetically Ordered Spinel Ferrite Thin Films

In this investigation, the cation distribution in ferrites of spinel-type structure is spectroscopically investigated with respect to the observed magnetic behavior. The ferrite thin films were fabricated by pulsed laser deposition and consequently annealed at different temperatures as well as atmospheres. Structural properties were determined with various methods and the crystalline quality was examined. The dielectric function line-shape was parametrized based on empirical evidence and was found to be dominated by electronic transitions between d orbitals of Fe2+ cations as well as transitions from O 2p to 3d and 4s orbitals of iron and zinc cations. The strongest magneto-optical response was observed for transitions involving cations, which correspond to lattice disorder and inversion within the normal spinel structure. With the decrease in the substrate temperature during fabrication, a decrease in the magnetic response was observed. The diminishing ferrimagnetic order was directly correlated to the decrease in strength of the transitions, involving Fe3+ on tetrahedral lattice sites. After thermal treatment in argon atmosphere and at a temperature below the deposition temperature, the increase in the magnetic response was explained through the facilitation of oxygen vacancies. With the increase in treatment temperature, a decrease in ferrimagnetic order was related to the recrystallization of the disordered spinel structure toward a more stable normal configuration, evident in the dielectric function spectra. The cationic configuration distribution in the surface as well as the bulk region, as a function of Zn concentration, was determined from approximation of the XPS and the dielectric function spectra, respectively. The difference in the cation configuration distribution, in films of predominantly inverse configuration, was related to the weak magnetic response, as opposed to films of predominantly normal spinel configuration. Our results demonstrate that a defect-rich surface region could serve as a possible explanation for the ferrimagnetic order in a nominally non-magnetic normal spinel ZnFe2O4. In combination with structural property determination, the net magnetic behavior is explained through the local cationic disorder, determined from the parametrization of the dielectric function spectra in a wide spectral range.:1 Introduction 2 Theoretical background and fundamental considerations 2.1 Spinel ferrite crystal structure 2.2 Crystal field stabilization energy 2.3 Band structure description 2.4 Verwey transition 2.5 Magnetic exchange interactions 3 Sample preparation and modification 3.1 Macroscopic spinel film formation 3.2 Pulsed laser deposition 3.3 Thermal treatment 3.4 Sample overview 4 Methods and general properties 4.1 Structure characterization techniques 4.1.1 X-ray diffraction 4.1.2 X-ray reflectivity 4.1.3 Energy dispersive X-ray spectroscopy 4.1.4 Focused ion beam and scanning electron microscopy 4.1.5 Raman spectroscopy 4.2 Surface properties 4.2.1 Atomic force microscopy 4.2.2 X-ray photoelectron spectroscopy 4.3 Dielectric tensor properties 4.4 Spectroscopic ellipsometry 4.5 Magneto-optical Kerr effect 4.6 Magneto-static properties 5 Results and discussion 5.1 Magnetic and optical properties of Fe3O4 thin film and single crystal 5.2 Magneto-optical properties of ZnxFe3−xO4 thin films 5.3 Fabrication temperature dependent ferrimagnetic order 5.4 Thermally induced structural stabilization 5.5 Cation configuration in dependence on the Zn concentration 5.5.1 Structural property determination 5.5.2 Composition characterization 5.5.3 Magneto-static behavior 5.5.4 Section summary and discussion 6 Summary and outlook Bibliography List of article contributions Selbstständigkeitserklärung Acknowledgment

Impact of defects on magnetic properties of spinel zinc ferrite thin films

The recent developments in the study of magnetic properties in the spinel zinc ferrite system are explored. Engineering of ionic valence and site distribution allows tailoring of magnetic interactions. Recent literature is reviewed, and own investigations are presented for a conclusive understanding of the mechanisms responsible for the magnetic behavior in this material system. By varying the Zn-to-Fe ratio, the deposition, as well as thermal annealing conditions, ZnFe2O4 thin films with a wide range of crystalline quality are produced. In particular, the focus is on the magnetic structure in relation to spectroscopic properties of disordered ZnFe2O4 thin films. Comparing the cation distribution in film bulk (optical transitions in the dielectric function) and near-surface region (X-ray absorption), it is found that an inhomogeneous cation distribution leads to a weaker magnetic response in films of inverse configuration, whereas defects in the normal spinel are likely to be found at the film surface. The results show that it is possible to engineer the defect distribution in the magnetic spinel ferrite film structure and tailor their magnetic properties on demand. It is demonstrated that these properties can be read out optically, which allows controlled growth of the material and applications in future magneto-optical devices

Temperature dependence of the dielectric tensor of monoclinic Ga2O3 single crystals in the spectral range 1.0–8.5 eV

The full dielectric tensor of monoclinic Ga2O3 (β-phase) was determined by generalized spectroscopic ellipsometry in the spectral range from 1.0 eV up to 8.5 eV and temperatures in the range from 10K up to 300K. By using the oriented dipole approach, the energies and broadenings of the excitonic transitions are determined as a function of the temperature, and the exciton-phonon coupling properties are deduced

Ellipsometric investigation of ZnFe2O4 thin films in relation to magnetic properties

We report an influence of disorder on structural and magnetic properties of ZnFe2O4 thin films grown at temperatures ranging from 400°C to 600°C by pulsed laser deposition in O2 atmosphere on SrTiO3 (100) substrates evidenced by properties of electronic transitions observed in the dielectric function. Inversion of the normal spinel structure was found to be one of the main mechanisms responsible for the increase in the magnetic response for the lowest growth temperature. The enhanced feature in the dielectric function located at ~3.5 eV, related to the transition involving tetrahedrally coordinated Fe3+ cations, corresponds to the dominating magnetic coupling between the octahedral and tetrahedral lattice sites, responsible for the overall ferrimagnetic behaviour of the film grown at the lowest temperature

Dielectric function in the spectral range (0.5–8.5)eV of an (Alx Ga1−x )2O3 thin film with continuous composition spread

We determined the dielectric function of the alloy system (AlxGa1−x)2O3 by spectroscopic ellipsometry in the wide spectral range from 0.5 eV to 8.5 eV and for Al contents ranging from x = 0.11 to x = 0.55. For the composition range x<0.4, we observe single phase material in the b-modification and for larger Al content also the occurrence of γ-(Al,Ga)2O3. We derived spectra of the refractive index and the absorption coefficient as well as energy parameters of electronic bandband transitions by model analysis of the dielectric function. The dependence of the dielectric functions lineshape and the energy parameters on x is highly continuous, reflecting theoretical expectations. The data presented here provide a basis for a deeper understanding of the electronic properties of this material system and may be useful for device engineering

Lasing in cuprous iodide microwires

We report on the observation of lasing in cuprous iodide (CuI) microwires. A vapor-phase transport growth procedure was used to synthesize CuI microwires with low defect concentration. The crystal structure of single microwires was determined to be of zincblende-type. The high optical quality of single microwires is indicated by the observed series of excitonic emission lines as well as by the formation of gain under optical excitation. Lasing of triangular whispering-gallery modes in single microwires is demonstrated for fs- and ns-excitation from cryogenic temperatures up to 200 K. Timeresolved micro-photoluminescence studies reveal the dynamics of the laser process on the time scale of several picoseconds

Mid- and far-infrared localized surface plasmon resonances in chalcogen-hyperdoped silicon

Plasmonic sensing in the infrared region employs the direct interaction of the vibrational fingerprints of molecules with the plasmonic resonances, creating surface-enhanced sensing platforms that are superior than the traditional spectroscopy. However, the standard noble metals used for plasmonic resonances suffer from high radiative losses as well as fabrication challenges, such as tuning the spectral resonance positions into mid- to far-infrared regions, and the compatibility issue with the existing complementary metal-oxide-semiconductor (CMOS) manufacturing platform. Here, we demonstrate the occurrence of mid-infrared localized surface plasmon resonances (LSPR) in thin Si films hyperdoped with the known deep-level impurity tellurium. We show that the mid-infrared LSPR can be further enhanced and spectrally extended to the far-infrared range by fabricating two-dimensional arrays of micrometer-sized antennas in a Te-hyperdoped Si chip. Since Te-hyperdoped Si can also work as an infrared photodetector, we believe that our results will unlock the route toward the direct integration of plasmonic sensors with the one-chip CMOS platform, greatly advancing the possibility of mass manufacturing of high-performance plasmonic sensing systems.Comment: 20 pages, 5 figure