Structure and thermal expansion of Ca9Gd(VO4)7\mathrm{Ca_{9}Gd(VO_{4})_{7}}: A combined powder-diffraction and dilatometric study of a Czochralski-grown crystal

Materials of the Ca$_9$RE(VO$_4$)$_7$ (CRVO) formula (RE = rare earth) and whitlockite-related structures are considered for applications in optoelectronics, e.g., in white-light emitting diodes and lasers. In the CRVO structure, the RE atoms are known to share the site occupation with Ca atoms at two or three among four Ca sites, with partial occupancy values depending on the choice of the RE atom. In this work, the structure and quality of a Czochralski-grown crystal of this family, Ca$_9$Gd(VO$_4$)$_7$ (CGVO), are studied using X-ray diffraction methods. The room-temperature structure is refined using the powder diffraction data collected at a high-resolution synchrotron beamline ID22 (ESRF, Grenoble); for comparison purposes, a laboratory diffraction pattern was collected and analyzed, as well. The site occupancies are discussed on the basis of comparison with literature data of isostructural synthetic crystals of the CRVO series. The results confirm the previously reported site-occupation scheme and indicate a tendency of the CGVO compound to adopt a Gd-deficient composition. Moreover, the thermal expansion coefficient is determined for CGVO as a function of temperature in the 302–1023 K range using laboratory diffraction data. Additionally, for CGVO and six other single crystals of the same family, thermal expansion is studied in the 298–473 K range, using the dilatometric data. The magnitude and anisotropy of thermal expansion, being of importance for laser applications, are discussed for these materials

Tm:CaGdAlO4: spectroscopy, microchip laser and passive Q-switching by carbon nanostructures

Absorption, stimulated-emission and gain cross-sections are determined for 3 at.% Tm:CaGdAlO4. This crystal is employed in a microchip laser diode-pumped at 802 nm. In the continuous-wave (CW) regime, this laser generates 1.16 W at 1883-1893 nm with a slope efficiency of 32% with respect to the absorbed pump power. Using a special "bandpass" output coupler, vibronic CW laser operation up to 2043 nm is achieved. For passive Q-switching of the Tm:CaGdAlO4 laser-saturable absorbers (SAs) based on CVD-grown graphene and randomly-oriented arc-discharge single-walled carbon nanotubes (SWCNTs) in a PMMA film. The SWCNT-SA demonstrates superior performance. The laser produced a maximum average output power of 245 mW at 1844 nm with a slope efficiency of 8%. The latter corresponds to a pulse energy and duration of 6 μJ and 138 ns, respectively, at a repetition rate of 41 kHz. Using the graphene-SA, 2.8 μJ, 490 ns pulses are obtained at a repetition rate of 86 kHz