ترغب بنشر مسار تعليمي؟ اضغط هنا

Structure determination of a brownmillerite Ca2Co2O5 thin film by Precession Electron Diffraction

188   0   0.0 ( 0 )
 نشر من قبل W. Prellier
 تاريخ النشر 2009
  مجال البحث فيزياء
والبحث باللغة English




اسأل ChatGPT حول البحث

Calcium cobaltite thin films with a ratio Ca/Co=1 were grown on (101)-NdGaO3 substrate by the pulsed laser deposition technique. The structure of the deposited metastable phase is solved using a precession electron diffraction 3D dataset recorded from a cross-sectional sample. It is shown that an ordered oxygen-deficient Ca2Co2O5+d perovskite of the brownmillerite-type with lattice parameters a= 0.546nm, b=1.488nm and c=0.546nm (SG: Ibm2) has been stabilized using the substrate induced strain. The structure and microstructure of this metastable cobaltite is further discussed and compared to related bulk materials based on our transmission electron microscopy investigations



قيم البحث

اقرأ أيضاً

The equilibrium structure and functional properties exhibited by brownmillerite oxides, a family of perovskite-derived structures with alternating layers of $B$O$_6$ octahedra and $B$O$_4$ tetrahedra, viz., ordered arrangements of oxygen vacancies, i s dependent on a variety of competing crystal-chemistry factors. We use electronic structure calculations to disentangle the complex interactions in two ferrates, Sr$_2$Fe$_2$O$_5$ and Ca$_2$Fe$_2$O$_5$, relating the stability of the equilibrium (strain-free) and thin film structures to both previously identified and newly herein proposed descriptors. We show that cation size and intralayer separation of the tetrahedral chains provide key contributions to the preferred ground state. We show the bulk ground state structure is retained in the ferrates over a range of strain values; however, a change in the orientation of the tetrahedral chains, i.e., a perpendicular orientation of the vacancies relative to the substrate, is stabilized in the compressive region. The structure stability under strain is largely governed by maximizing the intraplane separation of the `dipoles generated from rotations of the FeO$_4$ tetrahedra. Lastly, we find that the electronic band gap is strongly influenced by strain, manifesting as an unanticipated asymmetric-vacancy alignment dependent response. This atomistic understanding establishes a practical route for the design of novel functional electronic materials in thin film geometries.
The rich phase diagram of bulk Pr$_{1-x}$Ca$_{x}$MnO$_3$ resulting in a high tunability of physical properties gave rise to various studies related to fundamental research as well as prospective applications of the material. Importantly, as a consequ ence of strong correlation effects, electronic and lattice degrees of freedom are vigorously coupled. Hence, it is debatable whether such bulk phase diagrams can be transferred to inherently strained epitaxial thin films. In this paper, the structural orthorhombic to pseudo-cubic transition for $x=0.1$ is studied in ion-beam sputtered thin films and point out differences to the respective bulk system by employing in-situ heating nano-beam electron diffraction to follow the temperature dependence of lattice constants. In addition, it is demonstrated that controlling the environment during heating, i.e. preventing oxygen loss, is crucial in order to avoid irreversible structural changes, which is expected to be a general problem of compounds containing volatile elements under non-equilibrium conditions.
The nitrogen substitution into the oxygen sites of several oxide materials leads to a reduction of the band gap to the visible light energy range, which makes these oxynitride semiconductors potential photocatalysts for efficient solar water splittin g. Oxynitrides typically show a different crystal structure compare to the pristine oxide material. Since the band gap is correlated to both the chemical composition and the crystal structure, it is not trivial to distinguish what modifications of the electronic structure induced by the nitrogen substitution are related to compositional and/or structural effects. Here, X-ray emission and absorption spectroscopy is used to investigate the electronic structures of orthorhombic perovskite LaTiOxNy thin films in comparison with films of the pristine oxide LaTiOx with similar orthorhombic structure and cationic oxidation state. Experiment and theory show the expected upward shift in energy of the valence band maximum that reduces the band gap as a consequence of the nitrogen incorporation. But this study also shows that the conduction band minimum, typically considered almost unaffected by the nitrogen substitution, undergoes a significant downward shift in energy. For a rational design of oxynitride photocatalysts the observed changes of both the unoccupied and occupied electronic states have to be taken into account to justify the total band gap narrowing induced by the nitrogen incorporation.
237 - W. Sinkler , L. D. Marks 2009
Precession Electron Diffraction (PED) offers a number of advantages for crystal structure analysis and solving unknown structures using electron diffraction. The current article uses many-beam simulations of PED intensities, in combination with model structures, to arrive at a better understanding of how PED differs from standard unprecessed electron diffraction. It is shown that precession reduces the chaotic oscillatory behavior of electron diffraction intensities as a function of thickness. An additional characteristic of PED which is revealed by simulations is reduced sensitivity to structure factor phases. This is shown to be a general feature of dynami-cal intensities collected under conditions in which patterns with multiple incident beam orienta-tions are averaged together. A new and significantly faster method is demonstrated for dynami-cal calculations of PED intensities, based on using information contained in off-central columns of the scattering matrix.
Ca2Co2O5 in the brownmillerite form was synthesized using a high-pressure optical-image floating zone furnace, and single crystals with dimensions up to 1.4x0.8x0.5 mm3 were obtained. At room temperature, Ca2Co2O5 crystallizes as a fully ordered brow nmillerite variant in the orthorhombic space group Pcmb (No. 57) with unit cell parameters a=5.28960(10) {AA}, b=14.9240(2) {AA}, and c=10.9547(2) {AA}. With decreasing temperature, it undergoes a re-entrant sequence of first-order structural phase transitions (Pcmb to P2/c11 to P121/m1 to Pcmb) that is unprecedented among brownmillerites, broadening the family of space groups available to these materials and challenging current approaches for sorting the myriad variants of brownmillerite structures. Magnetic susceptibility data indicate antiferromagnetic ordering in Ca2Co2O5 occurs near 240 K, corroborated by neutron powder diffraction. Below 140 K, the specimen exhibits a weak ferromagnetic component directed primarily along the b axis that shows a pronounced thermal and magnetic history dependence.
التعليقات
جاري جلب التعليقات جاري جلب التعليقات
سجل دخول لتتمكن من متابعة معايير البحث التي قمت باختيارها
mircosoft-partner

هل ترغب بارسال اشعارات عن اخر التحديثات في شمرا-اكاديميا