On relationship of atomic structure, nano-sized inhomogeneities and second-order optical non-linearity of K2O-TiO2-P2O5 glasses

Glasses at early stages of phase separation, while remaining amorphous, are shown to possess or not to possess second-order optical nonlinearity (SON) depending on specific features of their short-range/medium range order and nanoinhomogeneous structure characterized with IR and Raman spectroscopy, X-ray diffraction, small-angle X-ray and neutron scattering and second harmonic generation (SHG). In the present work it is demonstrated by the example of potassium titanium phosphate glasses of composition near KTiOPO4 stoichiometry. Formation of nanoinhomogeneities, structure of which is similar to the structural motif of some non-linear optical (NLO) crystal, favors SON. Heat treatment of such glasses at temperatures near glass-transition temperature Tg stimulates remarkable SON enhancement keeping transparency and amorphous state. While temperature is increasing SHG grows up to values, comparable with those of NLO crystals with rise of Bragg reflections in the X-ray diffraction pattern of the glass and decrease of its transparency. Revealing correlations between structural peculiarities of glasses and their SON argues preference of description of short- and medium-range order in glasses with composition close to boundaries of glass-forming regions from the position of quasi-crystallite models.