Terahertz time-domain spectroscopy is employed to investigate temperature-dependent properties of bulk chalcopyrite crystals (CdGeP$_2$, ZnGeP$_2$ and CdSiP$_2$). The complex spectra provide the refraction and absorption as a function of temperature,
from which electron-phonon coupling and average phonon energies are extracted and linked to the mechanics of the A- and B-site cations. Also, AC conductivity spectra provide carrier densities and electron scattering times, the temperature dependence of which is associated with unintentional shallow dopants. Temperature dependence of the scattering time is converted into carrier mobility and modeled with microscopic transport mechanisms such as polar optical phonon, acoustic phonons, deformation potential, ionized impurity and dislocation scattering. Hence, analysis links the THz optical and electronic properties to relate microscopic carrier transport and carrier-lattice interactions.
Collinear phase-matched optical rectification is studied in ZnGeP$_{2}$ pumped with near-infrared light. The pump-intensity dependence is presented for three crystal lengths (0.3, 1.0 and 3.0 mm) to determine the effects of linear optical absorption,
nonlinear optical absorption and terahertz free-carrier absorption on the generation. Critical parameters such as the coherence length (for velocity matching), dispersion length (for linear pulse broadening) and nonlinear length (for self-phase modulation) are determined for this material. These parameters provide insight into the upper limit of pulse intensity and crystal length required to generate intense terahertz pulse without detriment to the pulse shape. It is found that for 1-mm thick ZnGeP$_{2}$(012), pumped at 1.28 micron with intensity of ~15 GW/cm2 will produce intense undistorted pulses, whereas longer crystals or larger intensities modify the pulse shape to varying degrees. Moreover, phase-matching dispersion maps are presented for the terahertz generation over a large tuning range (1.1-2.4 micron) in longer (3 mm) crystal, demonstrating the phase-matching bandwidth and phase mismatch that leads to fringing associated with multi-pulse interference. All observed results are simulated numerically showing good qualitative agreement.
