2D/3D perovskite heterostructure solar cells with orientation controlled 2D perovskite were realized. The obliquely and horizontally oriented Dion-Jacobson (DJ) 2D perovskites were fabricated by templated growth onto (200)/(112)-oriented MAPbI3 and (110)-oriented MAPbI2Br, respectively. The obliquely oriented 2D perovskite exhibited the excellent carrier transport properties, while the horizontally oriented 2D perovskite inhibited the carrier transport and drastically deteriorated the solar cell performances. In addition, the 2D/3D heterostructure solar cell with obliquely oriented DJ 2D perovskite demonstrated the enhanced stability. The excellent carrier transport properties of orientation-controlled 2D perovskite would contribute to the 2D/3D heterostructure solar cells with high stability and performance.

We demonstrate the formation of a well-organized thin film of twodimensional (2D) layered (C 18 H 37 NH 3 ) 2 PbI 4 hybrid perovskite by immersing octadecyl amine (ODA) Langmuir−Blodgett (LB) films in an aqueous solution of PbI 2 /HI. The immersed films exhibit a sharp absorption band at 486 nm (2.55 eV), which is assigned to the excitonic absorption. The film exhibits a bright green emission under ultraviolet light at room temperature. The photoluminescence spectrum has a distinct peak at 497 nm (2.49 eV) and is a mirror image of the absorption spectrum. Xray diffraction (XRD) analyses reveal that the film has a bilayer-like structure with a dspacing of 6.4 nm, which is equal to that of a (C 18 H 37 NH 3 ) 2 PbI 4 perovskite single crystal with a quantum well (QW) structure. Only intense peaks of the (0 0 l) (l = 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, and 24) reflections are observed in the out-of-plane XRD pattern, indicating that the c axis is vertically oriented with respect to the substrate surface, and the orientational order is remarkably high. Fourier transform infrared spectroscopy reveals that the ODA molecules are protonated in the PbI 2 /HI solution. These results suggest that the nitrogen atoms of the ODA molecules in the film are protonated in the PbI 2 /HI solution, and then, inorganic layers of the PbI 6 octahedra are intercalated in the alkyl ammonium film to neutralize the positive charge and form a QW structure. Fluorescence microscopy observation reveals that the 2D layered (C 18 H 37 NH 3 ) 2 PbI 4 film has a relatively uniform surface, reflecting the well-organized layered structure of the base material (ODA LB film). Because the intercalation process can be applied to various metal cations and halogen anions, we believe that the proposed technique will aid in the development of highly efficient 2D layered organic−inorganic hybrid perovskite materials.