Zero‐Dimensional Organic Copper(I) Iodide Hybrid with High Anti‐Water Stability for Blue‐Light‐Excitable Solid‐State Lighting

Abstract

The discovery of rare‐earth free luminescent materials with blue‐light‐excitable characteristic is of great importance for solid‐sate lighting applications. Herein, a Cu(I)‐based 0D luminescent hybrid (1,3‐dppH2)2Cu4I8∙H2O is synthesized by a facile solution method, and it shows the orange‐red emission peaking at 625 nm upon 460 nm excitation. The structure‐related luminescence mechanism has been elaborated by experimental and theoretical investigations. Moreover, the emission intensity remains unchanged even after continuous water treatment for 60 days due to the improved structural stability originating from intermolecular π–π interaction between organic cations. A warm white light‐emitting diode (LED) device with the color rendering index of 91.4% has been fabricated by combining the 440 nm LED chip, green‐emitting Lu3Al5O12:Ce3+, and (1,3‐dppH2)2Cu4I8∙H2O. This work provides a new design route towards 0D cuprous halide materials and will initiate more exploration of their intrinsic luminescence mechanism.

Boosting Blue Emission of Organic Cations in a Sn(IV)-Based Perovskite by Constructing Intermolecular Interactions

“…Because of the acknowledged Perdew−Burke−Ernzerhof (PBE) band gap error, the band gap is slightly lower than the experimental value (2.75 eV). 44 Notably, the dispersion of the valence band maximum (VBM) and conduction band minimum (CBM) of this compound is relatively small in all directions, indicating a strong quantum confinement effect in (C 9 H 8 N) 2 SnCl 6 . As shown in Figure 4b, the VBM is mainly contributed by the orbitals of organic cation C 9 H 8 N + , with a small contribution from the Cl 3p orbital, while its CBM is entirely contributed by the orbitals of the organic cation.…”

“…As shown in Figure a, (C 9 H 8 N) 2 SnCl 6 possesses an indirect band gap of 2.38 eV. Because of the acknowledged Perdew–Burke–Ernzerhof (PBE) band gap error, the band gap is slightly lower than the experimental value (2.75 eV) . Notably, the dispersion of the valence band maximum (VBM) and conduction band minimum (CBM) of this compound is relatively small in all directions, indicating a strong quantum confinement effect in (C 9 H 8 N) 2 SnCl 6 .…”

Blue Light-Excitable Broadband Yellow Emission in a Zero-Dimensional Hybrid Bismuth Halide with Type-II Band Alignment

“…4 % ) , 1 4 (C 12 H 28 N) 2 SbCl 5 (yellow, 96.8%), 16 and (C 13 H 19 N 4 )-PbMn 0.69 Sn 0.31 Br 8 (white, 73%). 17 However, these broadband light-emitting materials have a large band gap (>3 eV), predominately determined by the inorganic moiety in general, and thus are difficult to be excited by visible light, 18 which greatly limits their application in optoelectronic devices. Accordingly, how to achieve visible light-excitable broadband light emissions in organic−inorganic hybrid systems by composition engineering is a key scientific issue in the current stage.…”

“…Solution-processable organic–inorganic hybrid metal halides have shown tremendous potential in many fields, such as light-emitting diodes (LED), displays, scintillators, sensors, and so on, due to their high defect tolerance, tunable band gap, high absorption coefficients, and high photoluminescence (PL) quantum yield (PLQY). − The size and steric effects of organic cations enable the three-dimensional (3D) perovskite lattice to be successively sliced along the crystallographic a , b , and c directions to obtain two-dimensional (2D) sheets, one-dimensional (1D) chains, and zero-dimensional (0D) isolated octahedral units, respectively. − 0D hybrid systems in contrast to 3D/2D/1D ones show an increased exciton binding energy and wide band gap because of the strong quantum/dielectric confinement , and also possess the softest lattices with the exciton only centralized at a distorted polyhedral cluster, allowing for the ultrabroadband and large Stokes-shifted PL properties related to self-trapped exciton (STE) states. , The past decade has witnessed rapid advances in 0D hybrid metal halides with highly efficient broadband emissions, − for instance, (MePPh 3 ) 2 SbCl 5 (orange, 99.4%), (C 12 H 28 N) 2 SbCl 5 (yellow, 96.8%), and (C 13 H 19 N 4 )­PbMn 0.69 Sn 0.31 Br 8 (white, 73%) . However, these broadband light-emitting materials have a large band gap (>3 eV), predominately determined by the inorganic moiety in general, and thus are difficult to be excited by visible light, which greatly limits their application in optoelectronic devices. Accordingly, how to achieve visible light-excitable broadband light emissions in organic–inorganic hybrid systems by composition engineering is a key scientific issue in the current stage.…”

Growth of SnX2 (X = Br, I) Single Crystals with Self-Trapped Exciton Emission

“…White light-emitting diodes (WLEDs) have irreplaceable advantages in solid-state lighting technology and are cost-effective solid-state lighting sources. , From the initial rare-earth-doped phosphors to lead halide perovskite nanocrystals, transition-metal complexes, organic polymer emitters, and organic–inorganic hybrid perovskites have been developed as luminescent materials. The dimension of material has also changed from three-dimensional (3D) to zero-dimensional (0D), among which luminescent 0D metal halides have attracted the interest of scholars due to their optical properties, low-dimensional structure, and better stability. − Most organic metal halides are 0D materials. Organic metal halides are structurally diverse and possess rich optoelectronic properties due to the variability of organic cations. − The choice of central metal ions is relatively less, such as Pb, Sn, In, Sb, Bi, and Mn.…”