Max Döbeli

Strain-Induced Ferromagnetism in Antiferromagnetic LuMnO3 Thin Films

Single phase and strained LuMnO(3) thin films are discovered to display coexisting ferromagnetic and antiferromagnetic orders. A large moment ferromagnetism (≈1μ(B)), which is absent in bulk samples, is shown to display a magnetic moment distribution that is peaked at the highly strained substrate-film interface. We further show that the strain-induced ferromagnetism and the antiferromagnetic order are coupled via an exchange field, therefore demonstrating strained rare-earth manganite thin films as promising candidate systems for new multifunctional devices.

Plasma interactions determine the composition in pulsed laser deposited thin films

Plasma chemistry and scattering strongly affect the congruent, elemental transfer during pulsed laser deposition of target metal species in an oxygen atmosphere. Studying the plasma properties of La0.6Sr0.4MnO3, we demonstrate for as grown La0.6Sr0.4MnO3-δ films that a congruent transfer of metallic species is achieved in two pressure windows: ∼10−3 mbar and ∼2 × 10−1 mbar. In the intermediate pressure range, La0.6Sr0.4MnO3-δ becomes cation deficient and simultaneously almost fully stoichiometric in oxygen. Important for thin film growth is the presence of negative atomic oxygen and under which conditions positive metal-oxygen ions are created in the plasma. This insight into the plasma chemistry shows why the pressure window to obtain films with a desired composition and crystalline structure is narrow and requires a careful adjustment of the process parameters.

Pulsed laser deposition of La0.6Ca0.4CoO3(LCCO) films. A promising metal-oxide catalyst for air based batteries

La0.6Ca0.4CoO3 (LCCO) thin films were deposited on MgO(001) and stainless steel substrates by pulsed reactive crossed-beam laser ablation (PRCLA). The film stoichiometry was characterized by Rutherford backscattering spectrometry (RBS). The data confirmed that the material transfer from the target to the substrate is congruent. The thickness and surface roughness of the films is in the range of 200–500 and 2–12 nm, respectively, depending on the deposition conditions. The quality of the deposited film was analyzed by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). Epitaxial and single oriented thin films could be grown. In view of the importance of the surface composition in electrochemistry, X-ray photoelectron spectroscopy (XPS) measurements were performed. The electrochemical activity of the LCCO films is influenced by the crystallinity of the film.

Scalable, ultra-resistant structural colors based on network metamaterials

Structural colors have drawn wide attention for their potential as a future printing technology for various applications, ranging from biomimetic tissues to adaptive camouflage materials. However, an efficient approach to realize robust colors with a scalable fabrication technique is still lacking, hampering the realization of practical applications with this platform. Here, we develop a new approach based on large-scale network metamaterials that combine dealloyed subwavelength structures at the nanoscale with lossless, ultra-thin dielectric coatings. By using theory and experiments, we show how subwavelength dielectric coatings control a mechanism of resonant light coupling with epsilon-near-zero regions generated in the metallic network, generating the formation of saturated structural colors that cover a wide portion of the spectrum. Ellipsometry measurements support the efficient observation of these colors, even at angles of 70°. The network-like architecture of these nanomaterials allows for high mechanical resistance, which is quantified in a series of nano-scratch tests. With such remarkable properties, these metastructures represent a robust design technology for real-world, large-scale commercial applications.

Influence of La and Mn vacancies on the electronic and magnetic properties of LaMnO3 thin films grown by pulsed laser deposition

and magnetic properties. Specifically, we show that the Mn/La ratio can be systematically varied from 0.92 at 0.11 mbar to 1.09 at 0.30 mbar of oxygen. The cationic vacancies have markedly different effects that become most pronounced once the samples are fully oxygenated and thus strongly hole doped. All as-grown and thus slightly oxygen-deficient LMO films are ferromagnetic insulators with saturation moments in excess of 2.5 μB per Mn ion, their transport and optical properties can be understood in terms of trapped ferromagnetic polarons. Upon oxygen annealing, the most La-deficient films develop a metallic response with an even larger ferromagnetic saturation moment of 3.8 μB per Mn ion. In contrast, in the oxygenated Mn-deficient films, the ferromagnetic order is strongly suppressed to less than 0.5 μB per Mn ion, and the transport remains insulatorlike. We compare our results with the ones that were previously obtained on bulk samples and present an interpretation in terms of the much stronger disruption of the electronic and magnetic structure by the Mn vacancies as compared to the La vacancies. We also discuss the implications for the growth of LMO thin films with well-defined physical properties that are a prerequisite for the study of interface effects in multilayers.

Negative ions: The overlooked species in thin film growth by pulsed laser deposition

Plasma plume species from a ceramic La0.4Ca0.6MnO3 target were studied by plasma mass spectrometry as a function of laser fluence, background gas, and deposition pressure to understand the interplay between plasma composition and oxide thin film growth by pulsed laser deposition. The plume composition reveals a significant contribution of up to 24% of negative ions, most notably using a N2O background. The significance of negative ions for thin film growth is shown for La0.4Ca0.6MnO3 films grown in different background conditions where the best structural properties coincide with the largest amount of negative plasma species.

Dealloying of Platinum-Aluminum Thin Films: Dynamics of Pattern Formation

The application of focused ion beam (FIB) nanotomography and Rutherford backscattering spectroscopy (RBS) to dealloyed platinum-aluminum thin films allows for an in-depth analysis of the dominating physical mechanisms of nanoporosity formation during the dealloying process. The porosity formation due to the dissolution of the less noble aluminum in the alloy is treated as result of a reaction-diffusion system. The RBS and FIB analysis yields that the porosity evolution has to be regarded as superposition of two independent processes, a linearly propagating diffusion front with a uniform speed and a slower dissolution process in regions which have already been passed by the diffusion front. The experimentally observed front evolution is captured by the Fisher-Kolmogorov-Petrovskii-Piskounov (FKPP). The slower dissolution is represented by a zero-order rate law which causes a gradual porosity in the thin film.

Optical Properties of Nitrogen-Substituted Strontium Titanate Thin Films Prepared by Pulsed Laser Deposition

Perovskite-type N‑substituted SrTiO3 thin films with a preferential (001) orientation were grown by pulsed laser deposition on (001)-oriented MgO and LaAlO3 substrates. Application of N2 or ammonia using a synchronized reactive gas pulse produces SrTiO3-x:Nx films with a nitrogen content of up to 4.1 at.% if prepared with the NH3 gas pulse at a substrate temperature of 720 °C. Incorporating nitrogen in SrTiO3 results in an optical absorption at 370‑460 nm associated with localized N(2p) orbitals. The estimated energy of these levels is ≈2.7 eV below the conduction band. In addition, the optical absorption increases gradually with increasing nitrogen content.

Structure, microstructure, and high-temperature transport properties of La1−xCaxMnO3−δ thin films and polycrystalline bulk materials

Single-phase samples of La1−xCaxMnO3−δ (LCMO), x≈0.3, prepared by pulsed reactive crossed beam laser ablation on SrTiO3 (STO) substrates, and soft chemistry synthesized powders were studied by various methods. The precise study of the crystal structure and microstructures by a combination of electron diffraction and high-resolution electron microscopy revealed a monoclinic distortion of the GdFeO3-type structure, P21/c space group, in both types of materials, i.e., the thin films and powder compound. The analysis of the LCMO/STO interface showed nonhomogeneous stress states and a composition that results in a different superstructure from the usual detected structure. The temperature-dependent thermoelectric power in the case of thin films presented an anomalous behavior compared to those from the powder compound. A structural transition at high temperature (T≈750 K) influences the thermopower behavior as well as the thermal conductivity values.

Stoichiometric control of the density of states in PbS colloidal quantum dot solids

Electronic structure engineering is achieved in colloidal quantum dot solids by surface-based stoichiometry adjustment. Colloidal quantum dots, and nanostructured semiconductors in general, carry the promise of overcoming the limitations of classical materials in chemical and physical properties and in processability. However, sufficient control of electronic properties, such as carrier concentration and carrier mobility, has not been achieved until now, limiting their application. In bulk semiconductors, modifications of electronic properties are obtained by alloying or doping, an approach that is not viable for structures in which the surface is dominant. The electronic properties of PbS colloidal quantum dot films are fine-tuned by adjusting their stoichiometry, using the large surface area of the nanoscale building blocks. We achieve an improvement of more than two orders of magnitude in the hole mobility, from below 10−3 to above 0.1 cm2/V⋅s, by substituting the iodide ligands with sulfide while keeping the electron mobility stable (~1 cm2/V⋅s). This approach is not possible in bulk semiconductors, and the developed method will likely contribute to the improvement of solar cell efficiencies through better carrier extraction and to the realization of complex (opto)electronic devices.