Fig.1 Schematic of PSCs device structure and self-assembled monolayer （SAMs） structural composition

Fig.2 The molecular structures of SAMs with different groups used in iPSCs

Fig.3 Energy level alignment of SAMs and the perovskite layer

Fig.4 （A）Molecular packing patterns of π-backbones in single crystals， corresponding to： （a） 4PACz （pristine carbazole）， （b） CbzPh （7H-benzo［c］carbazole）， and （c） CbzNaph （7H-dibenzo［c，g］carbazole）. The dihedral angles were measured through the plane defined by the central pyrrole ring and the outermost benzene ring［54］； （B） Molecular structures， calculated dipole moments and HOMO energy levels of CbzPh， CbzBF and CbzBT［55］； （C） Schematic representation of A-4PADCB as the hole-selective layer （HSL） between ITO and perovskite［56］

Fig.5 （A） Energy level diagram between different hole transport layers （HTL） and the perovskite［39］； （B） Energetic alignment of different HTL contacts and CsMAFA perovskite with reference to the vacuum level， where the red dashed lines represent the Fermi energy levels measured by UPS［52］

Fig.6 （A） Characterization of perovskite films： （a） Time-resolved photoluminescence spectra， （b） photoluminescence quantum yield ［58］； （B） Interfacial orbital distribution of TDPA-Cl and perovskite from the DFT calculation. The inset shows the orbital overlap between TDPA-Cl and perovskite［59］； （C） Schematic illustration of interaction of Cbz2S and Cbz2SMe as HSLs with the perovskite［60］； （D） Cross-sectional SEM images of 1000-h-tested iPSCs with SAMs： （a） 2PACz and （b） I-2PACz， dashed and solid arrows in （a） mark pores and delamination， respectively. SEM images of fracture surfaces （MHP side） of 1000-h-tested iPSCs with SAMs： （c） 2PACz and （d） I-2PACz. Dashed ovals in （c） mark some examples of in-grain microscopic pores［42］

Fig.7 （A） Photographs of the precursor perovskite films on Me-/MeO-/GM-4PACz substrates after annealing for different times ［61］； （B） The deviation angles of （a） 2PACz/I atom， （b） 9CPA/I atom and （c） 9CAA/I atom［62］

Fig.8 （A） （a） In situ PL spectra for FAPbI3 perovskite films deposited on MeO-2PACz and PTZ-CPA during the spin-coating process［64］； （B） Energy level diagrams of FTO/Me-4PACz/perovskite and FTO/Ph-4PACz/perovskite［65］； （C） X-ray photoelectron spectroscopy （XPS） of the C1s region with 365 nm UV light irradiation for 24 h［66］

Fig.9 （A） Contact angles with respect to perovskite precursor droplets on SAMs-modified substrates［68］； （B） Long-term stability studies of the iPSCs： （a） Damp-heat stability for the most-stable encapsulated iPSCs using ITO with MeO-2PACz and ALD ITO with DC-TMPS and MeO-2PACz； （b） MPP of the most-stable encapsulated iPSCs measured at 85 ℃ using ITO with MeO-2PACz and ALD ITO with DC-TMPS and MeO-2PACz under simulated AM1.5 G illumination （100 mW/cm2）［69］

Fig.10 （A） Top views of equilibrated molecular representations of control and mixed systems； （B） Successive steps along an AIMD trajectory showcasing the interactions between the two molecules. The interfacial structures within small circles are magnified in larger circle areas； （C） High-resolution atomic force microscope （AFM） images of the buried interfaces of 2PACz- and CA-based perovskite thin films， along with corresponding models［71］； （D） Schematic diagram of the sequential deposition process［48］

Fig.11 KPFM surface potential images of （A） single-SAMs and （B） Co-SAMs［75］； （C） A schematic illustration of the perovskite/silicon tandem solar cells（P/S-TSCs）； （D） Along with the J-V curves measured under forward and reverse scanning directions for the champion P/S-TSCs. The inset features a photograph of the P/S-TSCs［78］

Fig.12 （A） Schematic diagram of the fabrication of Co-SAMs monolayers［79］； （B） Schematic diagram of the inverted device structure and the interaction of Co-SAMs with NiO x and perovskite films［46］； （C） Schematic diagram of the lattice structure and stability tests of Sn-Pb perovskite films coated on ITO/2PACz and ITO/Co-SAMs［47］

Fig.13 （A） （a） Schematic illustration of the interaction between tin perovskite and MeO-2PACz and 6PA； （b） GIWAXS images of tin perovskite films on PEDOT：PSS and Co-SAMs substrates at an incidence angle of 0.20 （°）［80］； （B） （a） Contact angle tests of perovskite precursor solutions on ITO/SAM， ITO/SAM-4NPBA， and SAM-4NPBA/FAI substrates， with corresponding images of perovskite films after spin-coating shown below； （b） AFM topography images of ITO/SAM， ITO/SAM/FAI， ITO/SAM-4NPBA， and SAM-4NPBA/FAI substrates［81］； （C） （a） DFT calculations of Me-4PACz with and without DMPU additive strategy on ITO and glass. Interface formation energy of Me-4PACz on glass/ITO surfaces； （b） Stacking energy of Me-4PACz on glass/ITO surfaces； （c） Electrostatic potential （ESP） distribution and interaction energy between perovskite and Me-4PACz， perovskite and Me-4PACz+DMPU［82］