Targeted chemical pressure yields tuneable millimetre-wave dielectric.

Epitaxial strain can unlock enhanced properties in oxide materials, but restricts substrate choice and maximum film thickness, above which lattice relaxation and property degradation occur. Here we employ a chemical alternative to epitaxial strain by providing targeted chemical pressure, distinct from random doping, to induce a ferroelectric instability with the strategic introduction of barium into today's best millimetre-wave tuneable dielectric, the epitaxially strained 50-nm-thick n = 6 (SrTiO3)nSrO Ruddlesden-Popper dielectric grown on (110) DyScO3. The defect mitigating nature of (SrTiO3)nSrO results in unprecedented low loss at frequencies up to 125 GHz. No barium-containing Ruddlesden-Popper titanates are known, but the resulting atomically engineered superlattice material, (SrTiO3)n-m(BaTiO3)mSrO, enables low-loss, tuneable dielectric properties to be achieved with lower epitaxial strain and a 200% improvement in the figure of merit at commercially relevant millimetre-wave frequencies. As tuneable dielectrics are key constituents of emerging millimetre-wave high-frequency devices in telecommunications, our findings could lead to higher performance adaptive and reconfigurable electronics at these frequencies.

Exploiting dimensionality and defect mitigation to create tunable microwave dielectrics.

The miniaturization and integration of frequency-agile microwave circuits--relevant to electronically tunable filters, antennas, resonators and phase shifters--with microelectronics offers tantalizing device possibilities, yet requires thin films whose dielectric constant at gigahertz frequencies can be tuned by applying a quasi-static electric field. Appropriate systems such as BaxSr1-xTiO3 have a paraelectric-ferroelectric transition just below ambient temperature, providing high tunability. Unfortunately, such films suffer significant losses arising from defects. Recognizing that progress is stymied by dielectric loss, we start with a system with exceptionally low loss--Srn+1TinO3n+1 phases--in which (SrO)2 crystallographic shear planes provide an alternative to the formation of point defects for accommodating non-stoichiometry. Here we report the experimental realization of a highly tunable ground state arising from the emergence of a local ferroelectric instability in biaxially strained Srn+1TinO3n+1 phases with n ≥ 3 at frequencies up to 125 GHz. In contrast to traditional methods of modifying ferroelectrics-doping or strain-in this unique system an increase in the separation between the (SrO)2 planes, which can be achieved by changing n, bolsters the local ferroelectric instability. This new control parameter, n, can be exploited to achieve a figure of merit at room temperature that rivals all known tunable microwave dielectrics.

Multicolor lasers using birefringent filters: experimental demonstration with Cr:Nd:GSGG and Cr:LiSAF.

In this study, we numerically and experimentally investigate application of birefringent filters (BRFs) as frequency selective elements in multicolor lasers. A BRF plate made out of crystalline quartz with an arbitrarily oriented optical axis has been explored. Simulation results have shown that compared to regular BRFs where the optical axis lies in the plane of the plates surface, a BRF with an optical axis pointing out of its surface enables design flexibility in filter parameters, providing access to a wider set of free spectral range and bandwidth values. As a result, multicolor operation could be obtained in many wavelength pairs using a single BRF plate. In the experiments a 3-mm thick quartz BRF with an optical axis 45° to the surface plane has been used. With Cr:Nd:GSGG as a laser medium two-color and three-color cw laser operation has been demonstrated in 11 and 3 different transition combinations, respectively. Moreover, two-color laser operation has been demonstrated in 10 different wavelength pairs in Cr:LiSAF. To our knowledge, this study is the first detailed investigation and experimental demonstration of BRFs with tilted optical axis for multicolor operation of solid-state lasers. Compared to other methods, BRFs enable a rich selection of transition pairs and also the ratio of the power in each line could be regulated by fine adjustment of the rotation angle. Implementation of tilted-axis BRFs should boost development of efficient and low-cost multicolor lasers in other gain media as well.

A strong ferroelectric ferromagnet created by means of spin-lattice coupling.

Ferroelectric ferromagnets are exceedingly rare, fundamentally interesting multiferroic materials that could give rise to new technologies in which the low power and high speed of field-effect electronics are combined with the permanence and routability of voltage-controlled ferromagnetism. Furthermore, the properties of the few compounds that simultaneously exhibit these phenomena are insignificant in comparison with those of useful ferroelectrics or ferromagnets: their spontaneous polarizations or magnetizations are smaller by a factor of 1,000 or more. The same holds for magnetic- or electric-field-induced multiferroics. Owing to the weak properties of single-phase multiferroics, composite and multilayer approaches involving strain-coupled piezoelectric and magnetostrictive components are the closest to application today. Recently, however, a new route to ferroelectric ferromagnets was proposed by which magnetically ordered insulators that are neither ferroelectric nor ferromagnetic are transformed into ferroelectric ferromagnets using a single control parameter, strain. The system targeted, EuTiO(3), was predicted to exhibit strong ferromagnetism (spontaneous magnetization, approximately 7 Bohr magnetons per Eu) and strong ferroelectricity (spontaneous polarization, approximately 10 microC cm(-2)) simultaneously under large biaxial compressive strain. These values are orders of magnitude higher than those of any known ferroelectric ferromagnet and rival the best materials that are solely ferroelectric or ferromagnetic. Hindered by the absence of an appropriate substrate to provide the desired compression we turned to tensile strain. Here we show both experimentally and theoretically the emergence of a multiferroic state under biaxial tension with the unexpected benefit that even lower strains are required, thereby allowing thicker high-quality crystalline films. This realization of a strong ferromagnetic ferroelectric points the way to high-temperature manifestations of this spin-lattice coupling mechanism. Our work demonstrates that a single experimental parameter, strain, simultaneously controls multiple order parameters and is a viable alternative tuning parameter to composition for creating multiferroics.

Extremely slow Li ion dynamics in monoclinic Li2TiO3--probing macroscopic jump diffusion via 7Li NMR stimulated echoes.

A thorough understanding of ion dynamics in solids, which is a vital topic in modern materials and energy research, requires the investigation of diffusion properties on a preferably large dynamic range by complementary techniques. Here, a polycrystalline sample of Li(2)TiO(3) was used as a model substance to study Li motion by both (7)Li spin-alignment echo (SAE) nuclear magnetic resonance (NMR) and ac-conductivity measurements. Although the two methods do probe Li dynamics in quite different ways, good agreement was found so that the Li diffusion parameters, such as jump rates and the activation energy, could be precisely determined over a dynamic range of approximately eleven decades. For example, Li solid-state diffusion coefficients D(σ) deduced from impedance spectroscopy range from 10(-23) m(2) s(-1) to 10(-12) m(2) s(-1) (240-835 K). These values are in perfect agreement with the coefficients D(SAE) deduced from SAE NMR spectroscopy. As an example, D(SAE) = 2 × 10(-17) m(2) s(-1) at 433 K and the corresponding activation energy determined by NMR amounts to 0.77(2) eV (400-600 K). At room temperature D(σ) takes a value of 3 × 10(-21) m(2) s(-1).

Low-cost, broadly tunable (375-433 nm & 746-887 nm) Cr:LiCAF laser pumped by one single-spatial-mode diode.

We describe a low-cost, compact, and efficient Cr(3+):LiCaAlF(6) (Cr:LiCAF) laser that is broadly tunable in the near infrared (746-887 nm) and blue/ultraviolet (375-433 nm) regions of the optical spectrum. The pump source is a 660 nm single-mode-diode with 145 mW of output power. A melt-grown Cr:LiCAF crystal with an extremely high figure of merit above 2000 was used as the gain medium. This enabled the construction of a high-Q-cavity with continuous wave (cw) lasing thresholds as low as 3 mW, slope efficiencies as high as 54%, and output powers up to 63 mW. The stored intracavity power levels were above 30 W. By placing a beta-barium-borate crystal at a second intracavity focus, we could obtain tunable cw blue/ultraviolet radiation with output powers up to 3.5 mW around 400 nm. When mode-locked using a saturable Bragg reflector around 800 nm, the Cr:LiCAF laser produced 95 fs pulses with average powers of 33 mW and peak powers of 3.58 kW at a repetition rate of 85.5 MHz. Extracavity second harmonic generation enables generation of femtosecond pulses around 400 nm. These results demonstrate the possibility to grow Cr:LiCAF crystals with passive losses below 0.15% per cm, which enables construction of low-cost and complexity systems that are pumped only with one low-power single-mode-diode.

Mechanosynthesized nanocrystalline BaLiF(3): The impact of grain boundaries and structural disorder on ionic transport.

The mechanosynthesis of highly pure nanocrystalline BaLiF(3) is reported. The product with mean crystallite diameter of about 30 nm was prepared by joint high-energy ball-milling of the two binary fluorides LiF and BaF(2) at ambient temperature. Compared to coarse-grained BaLiF(3) with µm-sized crystallites, which is available via conventional solid-state synthesis at much higher temperatures, the mechanosynthesized product exhibits a drastic increase of ionic conductivity by several orders of magnitude. This is presumably due to structural disorder introduced during milling and to the presence of a large volume fraction of interfacial regions in the nanocrystalline form of BaLiF(3) providing fast diffusion pathways for the charge carriers. Starting from mechanosynthesized nanocrystalline BaLiF(3) it is possible to tune the transport parameters in a well defined way by subsequent annealing. Changes of the electrical response of mechanosynthesized BaLiF(3) during annealing are studied in situ by impedance spectroscopy. The results are compared with those of a structurally well-ordered single crystal which clearly shows extrinsic and intrinsic regions of ionic conduction.

The electronic structure and the formation of polarons in Mo-doped BiVO4 measured by angle-resolved photoemission spectroscopy.

We experimentally investigated the electronic structure of Mo-doped BiVO4 high-quality single-crystals with synchrotron radiation-excited angle-resolved photoelectron spectroscopy (ARPES). By photon-energy dependent ARPES, we measured the bulk-derived valence band dispersion along the direction normal to the (010) cleavage plane, while the dispersion along the in-plane directions is obtained by angle-dependent measurements at fixed photon energy. Our data show that the valence band has a width of about 4.75 eV and is composed of many peaks, the two most intense have energies in good agreement with the theoretically calculated ones. A non-dispersive feature is observed in the fundamental gap, which we attribute to quasiparticle excitations coupling electrons and phonons, i.e. polarons. The determination of the polaron peak binding energy and bulk band gap allows to fix the value of the theoretical mixing parameter necessary in hybrid Hartree-Fock calculations to reproduce the experimental data. The attribution of the in-gap peak to polarons is strengthened by our discussion in the context of experimental transport data and ab initio theory.

Redetermination of terbium scandate, revealing a defect-type perovskite derivative.

The crystal structure of terbium(III) scandate(III), with ideal formula TbScO(3), has been reported previously on the basis of powder diffraction data [Liferovich & Mitchell (2004 ▶). J. Solid State Chem.177, 2188-2197]. The current data were obtained from single crystals grown by the Czochralski method and show an improvement in the precision of the geometric parameters. Moreover, inductively coupled plasma optical emission spectrometry studies resulted in a nonstoichiometric composition of the title compound. Site-occupancy refinements based on diffraction data support the idea of a Tb deficiency on the A site (inducing O defects on the O2 position). The crystallochemical formula of the investigated sample thus may be written as (A)(□(0.04)Tb(0.96))(B)ScO(2.94). In the title compound, Tb occupies the eightfold-coordinated sites (site symmetry m) and Sc the centres of corner-sharing [ScO(6)] octa-hedra (site symmetry ). The mean bond lengths and site distortions fit well into the data of the remaining lanthanoid scandates in the series from DyScO(3) to NdScO(3). A linear structural evolution with the size of the lanthanoid from DyScO(3) to NdScO(3) can be predicted.

Dispersion analysis of arbitrarily cut orthorhombic crystals.

We developed a measurement and evaluation scheme to perform dispersion analysis on arbitrarily cut orthorhombic crystals based on the schemes developed for triclinic and uniaxial crystals. As byproduct of dispersion analysis the orientations of the crystal axes are found. In contrast to the spectra of arbitrarily cut uniaxial crystals, where the fit routine has to separate two independent principal spectra, the spectra of arbitrarily cut orthorhombic crystals are a combination of three independent spectra and the evaluation scheme gets more complex. Dispersion analysis is exemplary performed on two different crystals, which show different spectral features and different levels of difficulties to evaluate. Neodymium gallate (NdGaO3) has broad overlapping reflections bands while topaz (Al2SiO4 [F, OH]2) has a quite high total number of infrared active bands.

Generalized dispersion analysis of arbitrarily cut monoclinic crystals.

Dispersion analysis is applicable to arbitrarily cut monoclinic crystals of unknown orientation in order to find the symmetry axis. By this it is possible to differentiate between the transition moments oriented parallel and normal to the b-axis and to determine the dielectric tensor functions of those two principal directions. Dispersion analysis of arbitrarily cut monoclinic crystals is based on an extension of the evaluation scheme developed for arbitrarily cut orthorhombic crystals. We present dispersion analysis of monoclinic crystals exemplarily on spodumene (LiAl(SiO3)2) and yttrium orthosilicate (Y2SiO5).

Bulk Single Crystal-Like Structural and Magnetic Characteristics of Epitaxial Spinel Ferrite Thin Films with Elimination of Antiphase Boundaries.

Spinel ferrite NiFe2 O4 thin films have been grown on three isostructural substrates, MgAl2 O4 , MgGa2 O4 , and CoGa2 O4 using pulsed laser deposition. These substrates have lattice mismatches of 3.1%, 0.8%, and 0.2%, respectively, with NiFe2 O4 . As expected, the films grown on MgAl2 O4 substrate show the presence of the antiphase boundary defects. However, no antiphase boundaries (APBs) are observed for films grown on near-lattice-matched substrates MgGa2 O4 and CoGa2 O4 . This demonstrates that by using isostructural and lattice-matched substrates, the formation of APBs can be avoided in NiFe2 O4 thin films. Consequently, static and dynamic magnetic properties comparable with the bulk can be realized. Initial results indicate similar improvements in film quality and magnetic properties due to the elimination of APBs in other members of the spinel ferrite family, such as Fe3 O4 and CoFe2 O4 , which have similar crystallographic structure and lattice constants as NiFe2 O4 .

Adsorption-controlled growth of BiFeO3 by MBE and integration with wide band gap semiconductors.

BiFeO3 thin films have been deposited on (001) SrTiO3, (101) DyScO3, (011) DyScO3, (0001) AlGaN/GaN, and (0001) 6H-SiC single crystal substrates by reactive molecular beam epitaxy in an adsorption-controlled growth regime. This is achieved by supplying a bismuth over-pressure and utilizing the differential vapor pressures between bismuth oxides and BiFeO3 to control stoichiometry in accordance with thermodynamic calculations. Four-circle x-ray diffraction and transmission electron microscopy reveal phase-pure, epitaxial films with rocking curve full width at half maximum values as narrow as 7.2 arc seconds (0.002 degrees). Epitaxial growth of (0001)-oriented BiFeO3 thin films on (0001) GaN, including AlGaN HEMT structures, and (0001) SiC has been realized using intervening epitaxial (111) SrTiO3 / (100) TiO2 buffer layers. The epitaxial BiFeO3 thin films have 2 in-plane orientations: [1120] BiFeO3 || [1120] GaN (SiC) plus a twin variant related by a 180 degrees in-plane rotation. This epitaxial integration of the ferroelectric with the highest known polarization, BiFeO3, with high bandgap semiconductors is an important step toward novel field-effect devices.

Terawatt diode-pumped Yb:CaF2 laser.

We present what we believe to be the first terawatt diode-pumped laser employing single-crystalline Yb:CaF(2) as the amplifying medium. A maximum pulse energy of 420 mJ at a repetition rate of 1 Hz was achieved by seeding with a stretched femtosecond pulse 2 ns in duration, preamplified to 40 mJ. After recompression, a pulse energy of 197 mJ and a duration of 192 fs were obtained, corresponding to a peak power of 1 TW. Furthermore, nanosecond pulses containing an energy of up to 905 mJ were generated without optical damage.

High-peak-power tunable laser operation of Yb:SrF2.

Growth, spectroscopic properties, and laser performance of Yb:SrF(2) crystals have been investigated. In spatial multimode operation of a diode-pumped Yb:SrF(2) laser a slope efficiency of 46% was measured. 180W output power with high beam quality at a pulse duration of 1.5ms was achieved by installing a mode cleaning aperture. A maximum average output power of 270mW and a tuning range of 73nm was observed.

(3 + 1)-dimensional structure refinement of the fresnoite framework-structure type compound Ba(2)TiGe(2)O(8).

The incommensurately modulated structure of the fresnoite framework-structure type compound Ba(2)TiGe(2)O(8) has been solved using a (3 + 1)-dimensional superspace approach. The structure is orthorhombic and adopts the superspace group Cmm2(0,beta,1/2)s00 with beta approximately 0.635 at room temperature. The refinement was based on neutron powder diffraction data obtained from a powdered single crystal grown by Czochralski pulling. The modulation parameters that were obtained support the idea that frozen-in rigid-unit modes cause the modulation. The modulation is mainly manifested by positional displacements of O atoms. Barium ions are either eightfold, ninefold or tenfold coordinated in the one-dimensional modulated structure. A significant improvement of the bond-valence sum for both barium positions is achieved by the introduction of the positional modulation. This finding strongly suggests that underbonded barium positions are critically involved in provoking the incommensurate modulation in Ba(2)TiGe(2)O(8).