ZnGeP2 and CdGeAs2 have long been recognized as promising crystals for infrared frequency generation. They exhibit the highest nonlinear optical coefficients (d36 equals 75 pm/V and 236 pm/V for ZnGeP2 and CdGeAs2, respectively) among all known compounds that possess adequate birefringence for phase matching. ZnGeP2's transparency range (0.62−13 μm) makes it the optimum material for shifting the wavelength of 2-μm pump lasers into the 3–5-μm range via optical parametric oscillation (OPO), whereas that of CdGeAs2 (2.3–18 μm) is better suited for doubling the frequency of CO2 lasers (9–11 μm) into the same range via second-harmonic generation. In both cases however, the application of these materials has been hindered by great difficulty in achieving crack-free single crystals, and by large defect-related absorption losses.
The horizontal-gradient-freeze (HGF) growth technique has been instrumental in overcoming these difficulties. “Ultralow” axial gradients (1–3°C/cm) have been used to control stoichiometry by minimizing vapor transport as well as to eliminate cracking due to anisotropic thermal expansion. (The a-axis and c-axis thermal-expansion coefficients of ZnGeP2 differ by a factor of two, whereas those of CdGeAs2 differ by a factor of 15.) In addition, oriented seeds were used to ensure monocrystalline nucleation (because even a small degree of polycrystallinity can lead to cracking even in low gradients) and growth along preferred directions to facilitate fabrication of device crystals. Finally growth was performed in a two-zone, transparent furnace in order to monitor and control the seeding-and-growth process.