1：Experimental Design and Method Selection:

The study uses steady-state and time-resolved photoluminescence (PL) measurements to investigate interfacial charge-transfer (CT) states in pentacene (PEN) and C60 heterostructures. The design aims to identify interface-specific features by comparing heterostacks with unitary films. Theoretical models from literature are referenced for CT state predictions.

2：Sample Selection and Data Sources:

Samples include highly ordered, crystalline thin films of PEN and C60 grown on natively oxidized Si(100), NaCl(100), and sapphire substrates under ultrahigh-vacuum conditions using organic molecular beam deposition (OMBD). Unitary films and heterostacks (e.g., PEN on C60 and vice versa) are prepared to avoid Diels-Alder adduct formation by growing at room temperature or below.

3：List of Experimental Equipment and Materials:

Equipment includes a closed-cycle cryostat for cooling to 15 K, a tungsten-halogen lamp for absorption measurements, a Ti:sapphire laser oscillator (100-fs pulses, 78 MHz repetition rate) for excitation, a streak camera setup with reflective optics, Si-CCD camera, InGaAs photodetector array, spectrographs, quartz crystal microbalance (QCM) for rate monitoring, X-ray diffraction for structural characterization, and AFM for morphology. Materials are PEN (Sigma Aldrich, purity ≥99.9%) and C60 (Sigma Aldrich, purity ≥99.5%).

4：9%) and C60 (Sigma Aldrich, purity ≥5%). Experimental Procedures and Operational Workflow:

4. Experimental Procedures and Operational Workflow: Films are grown with controlled deposition rates (6 ?/min for PEN, 2 ?/min for C60). Absorption measurements are performed in transmission geometry. PL measurements are conducted at 10 K using excitation energies of 1.5 eV, 3.0 eV, and 4.5 eV. Time-resolved PL is acquired with a streak camera for visible range and InGaAs detector for NIR range. Data analysis involves spectral fitting and lifetime extraction.

5：0). Absorption measurements are performed in transmission geometry. PL measurements are conducted at 10 K using excitation energies of 5 eV, 0 eV, and 5 eV. Time-resolved PL is acquired with a streak camera for visible range and InGaAs detector for NIR range. Data analysis involves spectral fitting and lifetime extraction. Data Analysis Methods:

5. Data Analysis Methods: PL spectra are analyzed to identify CT emission peaks using Gaussian fitting. Exciton lifetimes are extracted from transients fitted mono-exponentially. Theoretical calculations and literature values are used to interpret energy levels and transfer processes.