Monolayer transition-metal dichalcogenides (TMDCs) in the 2H-phase are semiconductors promising for opto-valleytronic and opto-spintronic applications because of their strong spin-valley coupling. Here we report detailed studies of opto-valleytronic properties of heterogeneous domains in CVD-grown monolayer WS₂ single crystals. By illuminating WS₂ with off-resonance circularly-polarized light and measuring the resulting spatially resolved circularly-polarized emission (P_circ), we find significantly large circular polarization (P_(circ) up to 60% and 45% for α- and β-domains, respectively) already at 300 K, which increases to nearly 90% in the α-domains at 80 K. Studies of spatially resolved photoluminescence (PL) spectroscopy, Raman spectroscopy, x-ray photoelectron spectroscopy (XPS), Kelvin-probe force microscopy (KPFM) and conductive atomic force microscopy (CAFM) reveal direct correlation among the PL intensity, defect densities and chemical potential, with the α-domains showing lower defect densities and a smaller work function by 0.13 eV than the β-domains. This work function difference indicates the occurrence of type-two band alignments between the α- and β-domains. We adapt a classical model to explain how electronically active defects may serve as non-radiative recombination centers, and find good agreement between experiments and the model. Scanning tunneling microscopic/spectroscopic (STM/STS) studies provide further evidences for tungsten vacancies (WVs) being the primary defects responsible for the suppressed PL and circular polarization in WS₂. These results therefore suggest a pathway to control the opto-valleytronic properties of TMDCs via defect engineering
