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Construction of lead halide perovskite nanocrystals (LHP NCs) heterostructures is essential to obtain highly stable photoluminescence and expand their applications. Herein, a novel self-assembly strategy combining with a solvent-free thermal-assisted synthesis and a water-triggered reaction is developed to subsequently grow BaWO4/CsPbX3/CsPb2X5 (X = Cl, Br, I) heterostructures at low nucleation temperature with high crystallinity. The as-obtained ternary BaWO4/CsPbX3/CsPb2X5 (X = Cl, Br, I) heterostructures exhibit remarkably enhanced panchromatic emission and ultrastable luminescence ascribing to the low-defect growth based on lattice matching. Stable white light-emitting diodes (WLEDs) have been constructed with a high correlated color temperature (CCT) of 7225 K and luminous efficiency of 74.4 lm·W−1. Ln3+-doped BaWO4/CsPbX3/CsPb2X5 (Ln3+ = Eu3+, Tb3+, Dy3+, Sm3+, Yb3+/Er3+) nanocomposites are further designed with excitation-dependent photoluminescence and thermochromic properties, making them excellent candidates for high-level anti-counterfeiting and encryption. This work offers a green and universal approach in assembling CsPbX3 (X = Cl, Br, I) on lattice-matched tungstate with adjustable panchromatic emission for versatile optical applications.

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