Substitutional disorder and the ground state spectroscopy of gallogermanate crystals

Electron spin resonance (ESR) spectra at X-band microwave frequencies are reported for dopant ions in (CGGO), (SGGO), (LGGO) and (LGS). The ESR measurements identify two distinct sites for in CGGO and SGGO and a single site in LGGO and LGS characterized by spin S = 3/2 for ions in the ground state. In CGGO a sharp line ESR spectrum, fitted to an axially symmetric spin Hamiltonian with , and , is assigned to substituents at trigonally distorted octahedral sites with a regular array of and ions in second-nearest-neighbour sites. A second spectrum of broader lines, due to ions in orthorhombically distorted sites associated with random occupation of the second-nearest-neighbour sites by and ions, has slightly different spin Hamiltonian parameters; , and . In this spectrum the principal axis is rotated by about from the c-axis towards the a-axis. In SGGO there are also ESR spectra from ions in trigonal and orthorhombic symmetry sites with almost identical spin Hamiltonian parameters. The ground state splittings of the trigonal centres measured optically by fluorescence line narrowing gives for both crystals. In contrast, only the trigonal centres are identified in LGGO and LGS, their ESR spectra being very similar to those of the trigonal centres in CGGO and SGGO. These results are discussed in terms of the substitutional disorder in these crystals and the nature of the site environment of substituents. The spectra correspond to ions in strong and weak crystal field sites, respectively, in agreement with earlier optical studies.