Minimization of Intrinsic Impurity Concentration in ZnGeP₂ Single Crystals via Directional Recrystallization

Zinc germanium phosphide (ZnGeP₂) is an important nonlinear crystal for mid-infrared conversion, but its performance is limited by residual absorption and intrinsic impurity phases. In this study, polycrystalline ZnGeP₂ was synthesized by a modified two-temperature method, purified by inclined directional recrystallization for up to three cycles, and then grown into single crystals by the vertical Bridgman method. The resulting material was examined by shadow-projection imaging, transmission spectroscopy in the 650-2500 nm range, absorption measurements at 2.097 µm, laser-induced damage threshold (LIDT) testing, and powder X-ray diffraction. Repeated purification improved optical homogeneity and near-infrared transparency, while the absorption coefficient at 2.097 µm decreased from 0.45 to 0.30 cm^-1 after three purification cycles. Semi-quantitative PXRD analysis showed progressive suppression of intrinsic impurity phosphides, with phase purity increasing from 86.31% after the first cycle to 95.995% after the second and reaching 100% after the third within the detection limit of the method. However, the LIDT decreased with increasing purification number, indicating a trade-off between lower optical losses and damage resistance. These results demonstrate that inclined directional recrystallization is an effective pre-growth purification route for ZnGeP₂ and that the optimal number of purification cycles should be selected according to the intended application.