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Laser-heated pedestal growth of cerium doped calcium scandate crystal fibers

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 Added by Detlef Klimm
 Publication date 2012
  fields Physics
and research's language is English




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Ce3+ doped oxide materials are promising for optical emission in the green spectral range. The growth of CaSc2O4:Ce3+ single crystals is reported here for the first time. Laser heated pedestal growth (LHPG) proved to be suitable for this refractive material, if performed in nitrogen of 99.999% purity. If the oxygen content of the growth atmosphere is substantially larger, Ce4+ is formed, which shows no useful optical emission. If the oxygen content is substantially lower, severe evaporation of calcium impedes stable crystal growth. Thermodynamic equilibrium calculations allowed to describe evaporation of species and cerium dopant charging under different growth conditions. The evaporation could be investigated by quadrupole mass spectrometry of emanating gases and by chemical analysis of fibers with ICP-OES. The congruent melting point was confirmed by DTA at 2110 degrees centigrade. Photoluminescence spectrometry of fibers revealed the dependence of optical emission in the green spectral range on growth conditions.



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We have developed the laser-diode-heated floating zone (LDFZ) method, in order to improve the broad and inhomogeneous light focusing in the conventional lamp-heated floating zone method, which often causes difficulties in the crystal growth especially for the incongruently melting materials. We have simulated the light focusing properties of the LDFZ method to make irradiated light homogeneous and restricted mostly to the molten zone. We have designed and assembled an LDFZ furnace, and have demonstrated how it works through actual crystal growth. The method is applicable to various kinds of materials, and enables stable and reproducible crystal growth even for the incongruently melting materials. We have succeeded in the crystal growth of representative incongruently melting materials such as BiFeO3 and (La,Ba)2CuO4, which are difficult to grow by the conventional method. Tolerance to the decentering of the sample and highly efficient heating are also established in the LDFZ method.
Boron-doped single crystal diamond films were grown homoepitaxially on synthetic (100) Type Ib diamond substrates using microwave plasma assisted chemical vapor deposition. A modification in surface morphology of the film with increasing boron concentration in the plasma has been observed using atomic force microscopy. Use of nitrogen during boron doping has been found to improve the surface morphology and the growth rate of films but it lowers the electrical conductivity of the film. The Raman spectra indicated a zone center optical phonon mode along with a few additional bands at the lower wavenumber regions. The change in the peak profile of the zone center optical phonon mode and its downshift were observed with the increasing boron content in the film. However, shrinkage and upshift of Raman line was observed in the film that was grown in presence of nitrogen along with diborane in process gas.
We have evaluated the performance of a Ce-doped fused-silica fiber as wavelength shifter coupled to a CeF$_{3}$ crystal using electron beams at CERN. The pulse shape and collection efficiency were measured using irradiated (100 kGy) and un-irradiated fibers. In addition, we evaluated the light yield of various Ce-doped fibers and explored the possibility of using them in the future, including for precision timing applications in a high-luminosity collider environment.
The d.c. magnetization and magnetic relaxation studies of the calcium doped samples, Y0.95Ca0.05BaCo2O5.5 and YBa0.95Ca0.05Co2O5.5, show the existence of a magnetic glass like behaviour in the family of cobaltites for the first time. Our investigations reveal glass-like arrest of kinetics at low temperature which prevents the system from reaching its magnetic ground state. We show that the low temperature state of these calcium doped phases, which consists of coexisting antiferromagnetic and ferro (or ferri) magnetic phase fractions, can be tuned in a number of ways. Our observations establish that the low temperature state of this oxide is not in thermal equilibrium. The glassy state is formed with the assistance of an external magnetic field, which makes it distinctly different from the more well known metastable state, the spin glass state. The cooling field can tune the fractions of the coexisting phases, and the glass-like state formed at low temperature can also be devitrified by warming the sample. The role of Ca doping in the appearance of these phenomena is discussed in terms of phase separation, involving Co3+ disproportionation into Co4+ ferromagnetic clusters and Co2+ antiferromagnetic clusters.
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Experimental studies established that calcium undergoes several counterintuitive transitions under pressure: fcc rightarrow bcc rightarrow simple cubic rightarrow Ca-IV rightarrow Ca-V, and becomes a good superconductor in the simple cubic and higher-pressure phases. Here, using ab initio evolutionary simulations, we explore the behavior of Ca under pressure and find a number of new phases. Our structural sequence differs from the traditional picture for Ca, but is similar to that for Sr. The {beta}-tin (I41/amd) structure, rather than simple cubic, is predicted to be the theoretical ground state at 0 K and 33-71 GPa. This structure can be represented as a large distortion of the simple cubic structure, just as the higher-pressure phases stable between 71 and 134 GPa. The structure of Ca-V, stable above 134 GPa, is a complex host-guest structure. According to our calculations, the predicted phases are superconductors with Tc increasing under pressure and reaching ~20 K at 120 GPa, in good agreement with experiment.
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