Emission Wavelength Tuning via Competing Lattice Expansion and Octahedral Tilting for Efficient Red Perovskite Light-Emitting Diodes

The band-edge electronic structure of lead halide perovskites (ABX₃) is composed of the orbitals of B and X components and can be tuned through the composition and structure of the BX₆ octahedron. Although A-site cations do not directly contribute to near-edge states, the bandgap of 3D metal halide perovskites can be affected by A-cations through BX₆ octahedron tilting or lattice size variation. Here, as confirmed by the Rietveld refinement results of X-ray diffraction characterization, the competition between lattice expansion and octahedral tilting is identified for the first time in emission wavelength tuning when introducing a large A-site cation (C₂H₅NH₃⁺, EA⁺) into 1-naphthylmethylammonium iodide-passivated CsPbI₃ system. The former dominates spectral redshift, while the latter leads to a blueshift of emission peak, which broadens the way to tune the emission wavelength. In addition, excess cations can also passivate the perovskites, leading to a photoluminescence (PL) quantum yield as high as 61%, increased average PL lifetime of 74.7 ns, and a high radiative and non-radiative recombination ratio of 15.7. Eventually, spectral-stable deep-red perovskite light-emitting diode with a maximum external quantum efficiency of 17.5% is realized, which is one of the highest efficiencies without using any light outcoupling and anti-solvent techniques.