1：Experimental Design and Method Selection:

The study used vapor transport (VT) method to synthesize monolayer WS2 with varying defect densities by altering deposition parameters. Photoluminescence (PL) and Raman spectroscopy were employed to analyze optical properties, with theoretical models like density functional theory (DFT) for calculations.

2：Sample Selection and Data Sources:

Four samples (T1-T4) of monolayer WS2 were prepared on Si/SiO2 substrates with different defect densities, characterized using optical microscopy, atomic force microscopy (AFM), and Auger electron spectroscopy.

3：List of Experimental Equipment and Materials:

Equipment includes tube furnace for synthesis, optical microscope (MV3000, NOVEL), Raman spectrometers (iHR320 Horiba, Labram Horiba, Renishaw invia), CCD detector (Syncerity Horiba), AFM (Innova Bruker), and nano-Auger electron spectroscopy. Materials include WS2 powder (Aladdin,

4：9%), Si/SiO2 substrates, Ar/H2 gas. Experimental Procedures and Operational Workflow:

WS2 monolayers were grown via VT method with specific temperature, pressure, and gas flow conditions. Samples were characterized at room and low temperatures (down to 80K) using PL and Raman measurements with various laser wavelengths. Data were collected and analyzed for excitonic energies and Raman intensities.

5：Data Analysis Methods:

PL spectra were deconvoluted using Gaussian functions for exciton types; Raman intensities were analyzed based on resonance conditions. Statistical fitting was done for power dependence and temperature effects.