This PDF file includes:

• Section S1. Methods and materials characterization
• Section S2. Normalized integrated intensity based on LP factor, investigation of crystallite size, and lattice parameter
• Section S3. Hopping probability by Miller-Abrahams model
• Section S4. Optical bandgap (E_g) and Urbach energy (E_U) investigation
• Table S1. The deposition parameters used in the growth of oCVD PEDOT films.
• Table S2. The normalized integrated peak intensity of oCVD PEDOT films.
• Table S3. The XPS elemental analysis of PEDOT films.
• Table S4. The crystallite domain size in PEDOT films.
• Table S5. The a-axis and b-axis lattice parameter information of PEDOT films.
• Fig. S1. Saturation vapor pressure of monomer and oxidant at different temperatures.
• Fig. S2. Thickness and deposition rate of PEDOT films as a function of process parameters.
• Fig. S3. Effect of process parameters on the crystalline orientation of PEDOT films.
• Fig. S4. The XPS analysis of PEDOT films.
• Fig. S5. The effect of OSR on the a-axis lattice parameter of PEDOT films.
• Fig. S6. The optical absorption spectra of PEDOT films.
• Fig. S7. Urbach plot for PEDOT films.
• Fig. S8. Statistics of the PV parameters for the PSCs with different HTLs.
• Fig. S9. Statistics of HIs for the PSC devices.
• Fig. S10. Variation of PSC device performance versus the thickness of oCVD PEDOT.

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