A variety of defect-sensitive techniques have been employed to detect, identify, and quantify the residual impurities and native defects in high-purity (undoped) 6H-SiC crystals grown by halide chemical-vapor deposition technique. The incorporation efficiencies of N and B are determined by the site-competition effect. Most notably, material with low residual N levels (∼1014 cm-3) can be produced. In addition, the nitrogen concentrations obtained from Hall-effect measurements and low-temperature photoluminescence are systematically lower than those determined from secondary-ion-mass spectrometry. The difference is ascribed to nitrogen forming complexes with native defects. The energy level of this complex is approximately 0.27 eV below the conduction band. Four major electron traps with activation energies of 0.4, 0.5, 0.65, and 1 eV and five hole traps with activation energies of 0.3, 0.4, 0.55, 0.65, and 0.85 eV were observed by deep-level transient spectroscopy. The concentration of all traps decreased strongly with increasing C/Si ratio during growth. Increasing the C/Si flow ratio also led to increased resistivity of the crystals and change of conductivity from conductive n type to high-resistivity p type. The Fermi level in p-type material is pinned either to highly compensated shallow B acceptors or to deep B-related center at 0.6 eV above the valence band. Electron paramagnetic resonance shows the presence of positively charged carbon vacancies in such high-resistivity material.