1：Experimental Design and Method Selection:

The study uses a graded doping strategy with thermally evaporated tetracene and lithium-doped Spiro-OMeTAD as hole transport layers in perovskite solar cells. Methods include film fabrication, optical characterization, and device testing.

2：Sample Selection and Data Sources:

Samples include perovskite films (Cs0.06FA0.79MA0.15Pb(I0.85Br0.15)3 with rubidium passivation) and devices with different HTL configurations. Data are sourced from fabricated devices and films.

3：06FA79MA15Pb(I85Br15)3 with rubidium passivation) and devices with different HTL configurations. Data are sourced from fabricated devices and films. List of Experimental Equipment and Materials:

3. List of Experimental Equipment and Materials: Equipment includes scanning electron microscope (Merlin, Hitachi S-5500), spectrophotometer (PerkinElmer LAMBDA 1050), photothermal deflection spectroscopy setup, PL quantum yield setup with Andor iDus DU490A detector, time-resolved PL system with Andor iStar DH740 camera, ultraviolet photoelectron spectroscopy system, solar simulators (Newport, Oriel), source meters (Keithley 2400, 2636), impedance analyzer (HP4294A), and thermal evaporation systems. Materials include tetracene, Spiro-OMeTAD, TiO2, gold, perovskite precursors (PbI2, FAI, MABr, PbBr2, CsI, RbI), solvents (DMF, DMSO, chlorobenzene), and Fluorinert FC-

4：Experimental Procedures and Operational Workflow:

Perovskite films are spin-coated and annealed. Tetracene is thermally evaporated. Devices are fabricated with FTO/TiO2/perovskite/HTL/Au architecture. Optical and electrical characterizations are performed, including absorption, PL, TRPL, J-V measurements, stability tests, and impedance spectroscopy.

5：Data Analysis Methods:

Data are analyzed using fitting routines for PL decays, equivalent circuits for EIS, Arrhenius fits for activation energy, and statistical analysis for device parameters.