4f and 5d levels of Ce3+ in D2 eightfold oxygen coordination

The effects on the 4f and 5d levels of Ce3+ of its first coordination shell geometry in Ce-doped oxides with a D2 8-fold site, like garnets, are studied with embedded cluster, wave function based ab initio methods. The only deformations of a CeO8 cube that are found to shift the lowest 4f-5d transition to the red are the symmetric Ce-O bond compression and the tetragonal symmetric bond bending. These results are analyzed in terms of centroid and ligand field stabilization energy differences. The splittings of the upper 5d levels and of the 4f levels are also discussed.Comment: 17 pages, 5 igure

Fast microwave-assisted synthesis of Li-stuffed garnets and insights into Li diffusion from muon spin spectroscopy

Lithium-stuffed garnets attract huge attention due to their outstanding potential as solid-state electrolytes for lithium batteries. However, there exists a persistent challenge in the reliable synthesis of these complex functional oxides together with a lack of complete understanding of the lithium-ion diffusion mechanisms in these important materials. Addressing these issues is critical to realizing the application of garnet materials as electrolytes in all solid-state lithium-ion batteries. In this work, a cubic phase garnet of nominal composition Li6.5Al0.25La2.92Zr2O12 is synthesized through a microwave-assisted solid-state route for the first time, reducing considerably the reaction times and heating temperatures. Lithium-ion diffusion behavior is investigated by electrochemical impedance spectroscopy (EIS) and state-of-art muon spin relaxation (μSR) spectroscopy, displaying activation energies of 0.55 ± 0.03 eV and 0.19 ± 0.01 eV respectively. This difference arises from the high inter-grain resistance, which contributes to the total resistance in EIS measurements. In contrast, μSR acts as a local probe providing insights on the order of the lattice, giving an estimated value of 4.62 × 10−11 cm2 s−1 for the lithium diffusion coefficient. These results demonstrate the potential of this lithium-stuffed garnet as a solid-state electrolyte for all-solid state lithium-ion batteries, an area of growing interest in the energy storage community

Structure and ionic conductivity in lithium garnets

Garnets are capable of accommodating an excess of lithium cations beyond that normally found in this prototypical structure. This excess lithium is found in a mixture of coordination environments with considerable positional and occupational disorder and leads to ionic conductivity of up to 4×10-4 S cm-1 at room temperature. This high value for total conductivity, combined with excellent thermal and (electro)chemical resistance makes these candidate materials for operation in all solid-state batteries. This review looks at garnets with a wide range of stoichiometries and lithium concentrations and the impact of complex lithium distributions and crystallographic order/disorder transitions on the transport properties of these materials

Comparison of the Magnetic properties of Mn3Fe2Si3O12 as a crystalline garnet and as a glass

The crystalline garnet Mn3Fe2Si3O12 and an amorphous phase of the same nominal composition are synthesized at high pressure. The magnetic properties of the two forms are reported. Both phases order antiferromagnetically. The crystalline phase exhibits a Curie-Weiss theta of -47.2 K, with a sharp ordering transition at 12 K. The glassy phase exhibits a larger antiferromagnetic Curie-Weiss theta, of -83.0 K, with a broad ordering transition observed at 2.5 K. Both phases can be classified as magnetically frustrated, although the amorphous phase shows a much higher degree of frustration. The amorphous phase exhibits spin-glass behavior and is determined to have an actual composition of Mn3Fe2Si3O13.Comment: 14 pages, 7 figures, 2 table

Optimized magneto-optical isolator designs inspired by seedlayer-free terbium iron garnets with opposite chirality

Simulations demonstrate that undoped yttrium iron garnet (YIG) seedlayers cause reduced Faraday rotation in silicon-on-insulator (SOI) waveguides with Ce-doped YIG claddings. Undoped seedlayers are required for the crystallization of the magneto-optical Ce:YIG claddings, but they diminish the interaction of the Ce:YIG with the guided modes. Therefore new magneto-optical garnets, terbium iron garnet (TIG) and bismuth-doped TIG (Bi:TIG), are introduced that can be integrated directly on Si and quartz substrates without seedlayers. The Faraday rotations of TIG and Bi:TIG films at 1550nm were measured to be +500 and -500°/cm, respectively. Simulations show that these new garnets have the potential to significantly mitigate the negative impact of the seedlayers under Ce:YIG claddings. The successful growth of TIG and Bi:TIG on low-index fused quartz inspired novel garnet-core waveguide isolator designs, simulated using finite difference time domain (FDTD) methods. These designs use alternating segments of positive and negative Faraday rotation for push-pull quasi phase matching in order to overcome birefringence in waveguides with rectangular cross-sections

Nonreciprocal Bloch Oscillations in Magneto-Optic Waveguide Arrays

We show that nonreciprocal optical Bloch-like oscillations can emerge in transversely magnetized waveguide arrays in the presence of an effective index step between the waveguides. Normal modes of the system are shown to acquire different wavenumbers in opposite propagation directions. Significant differences in phase coherence and decoherence between these normal modes are presented and discussed. Non-reciprocity is established by imposing unequal vertical refractive index gradients at the substrate/core, and core/cover interfaces in the presence of transverse magnetization.Comment: 12 pages, 2 figure