A Family of Highly Efficient CuI-Based Lighting Phosphors Prepared by a Systematic, Bottom-up Synthetic Approach

Abstract

Copper(I) iodide (CuI)-based inorganic-organic hybrid materials in the general chemical formula of CuI(L) are well-known for their structural diversity and strong photoluminescence and are therefore considered promising candidates for a number of optical applications. In this work, we demonstrate a systematic, bottom-up precursor approach to developing a series of CuI(L) network structures built on CuI rhomboid dimers. These compounds combine strong luminescence due to the CuI inorganic modules and significantly enhanced thermal stability as a result of connecting individual building units into robust, extended networks. Examination of their optical properties reveals that these materials not only exhibit exceptionally high photoluminescence performance (with internal quantum yield up to 95%) but also that their emission energy and color are systematically tunable through modification of the organic component. Results from density functional theory calculations provide convincing correlations between these materials' crystal structures and chemical compositions and their optophysical properties. The advantages of cost-effective, solution-processable, easily scalable and fully controllable synthesis as well as high quantum efficiency with improved thermal stability, make this phosphor family a promising candidate for alternative, RE-free phosphors in general lighting and illumination. This solution-based precursor approach creates a new blueprint for the rational design and controlled synthesis of inorganic-organic hybrid materials.

Structural variation from linear, layer to 3D framework: Syntheses, structures and luminescence

“…On the basis of the potential applications of Zn (II) and Cd (II)‐based MOCPs as the luminescent sensors and probes, herein, the luminescent properties of these ten complexes, the free L1 and L2 ligands, as well as the two arenensulfonic acids were carried out in the solid state at room temperature. As shown in Figure S10, the free L1, L2 ligands, 1,5‐H 2 NDS and p ‐HTS molecules exhibit emission maximum at 470, 460, 407 and 419 nm upon excitation at 385, 395, 353 and 321 nm, respectively, in which these values for L1, L2 and 1,5‐H 2 NDS are identical to the reported values in previous work…”

Highly Luminescent Inks: Aggregation‐Induced Emission of Copper–Iodine Hybrid Clusters

“…According to reported density functional theory (DFT) calculations,the band gap of the Cu-I hybrids can be tuned by different ligands. [14] To expand the light emission colors of Cu-I hybrid nanoparticle inks,t he ligand exchange strategy was conducted on as-fabricated Cu 4 I 4 (P-(m-Tol) 3 ) 4 nanoparticles.B efore conducting the ligand exchange of Cu 4 I 4 (P-(m-Tol) 3 ) 4 nanoparticles,p reliminary experiments on ligand exchanges of Cu 4 I 4 (P-(m-Tol) 3 ) 4 bulk powders were carried out. Three ligands including 3-chloro-pyridine (3-Cl-py), pyrazine (pz), and 4,4'-bipyridine (4,4'-bpy) have been chosen to prepare different hybrid compounds.T he PL spectra and PXRD patterns ( Figure S14 and S15) of the products indicated the successful exchange of azo-heterocyclic ligands with the P-(m-Tol) 3 ligands,w hich implied the possibility to apply the same strategy to Cu 4 I 4 (P-(m-Tol) 3 ) 4 nanoparticles to expand light emission colors of AIE inks.As shown in Figure 3a,b ya dding the target ligands into the aqueous Cu 4 I 4 (P-(m-Tol) 3 ) 4 nanoparticle inks,t he color emission of the inks under UV light (365 nm) irradiation immediately changed and the emission intensity gradually became stronger with prolonged stirring time.A fter continuously stirring for several hours,t he powder samples were collected by centrifugation.…”

“…have synthesized aseries of Cu-I cluster-based highly luminescent hybrids via facile solution routes further promoting the potentials of these hybrid materials as solid state phosphors. [14] Whereas,t hese Cu-I hybrid cluster-based photoluminescent materials were usually synthesized as insoluble powders,i nw hich the AIE phenomenon has not been observed, let alone the fabrication of uniform highly luminescent AIE nanoparticle inks based on the Cu-I hybrid clusters.Herein, we report the AIE phenomenon and the synthesis of low-cost luminescent nanoparticles via af acile selfassembly of Cu-I hybrid clusters for the first time.D uring the past years,m ost of reported Cu-I hybrid luminescent materials have faced the problem of poor solubility,w hich makes it hard to obtain the molecularly dissolved state.T o obtain highly soluble Cu-I hybrid clusters,wefirst developed al igand exchange process to synthesize an ew Cu-I hybrid which is highly soluble in common organic solvents (Figure 1a). On the basis of the excellent solubility and stability of the as-synthesized Cu-I hybrid clusters in organic solvent, we adopted the microemulsion method to confine the Cu-I hybrid clusters in small-sized droplets to investigate the AIE phenomenon induced by the organic solvent evaporation and fabricate highly luminescent AIE inks (Figure 1b-d).In our proposed strategy,the choice of highly luminescent 0D-Cu 4 I 4 (py) 4 hybrid clusters as initial building blocks is based on their higher stability in comparison to other Cu x I xbased cluster species.…”

“…have synthesized aseries of Cu-I cluster-based highly luminescent hybrids via facile solution routes further promoting the potentials of these hybrid materials as solid state phosphors. [14] Whereas,t hese Cu-I hybrid cluster-based photoluminescent materials were usually synthesized as insoluble powders,i nw hich the AIE phenomenon has not been observed, let alone the fabrication of uniform highly luminescent AIE nanoparticle inks based on the Cu-I hybrid clusters.…”

A novel nonenzymatic biosensor for evaluation of oxidative stress based on nanocomposites of graphene blended with CuI

“…Especially, cuprous compounds have been widely applied to electrochemical catalysis such as Cu 2 O [45,48,49] and Cu 2 S [50,51]. Whereas, another kind of cuprous compounds, i.e., CuI has extensively being used as an analytical reagent, resin modifier, agent of artificial rainfall and anode tube cover, which also has photoluminescence [52] and catalytic activity. Recently, CuI has been used to catalyze the coupling reaction because of its stability in air and good activity with or without the assistance of supporting ligands [53], such as catalyzed Coupling Reaction of (Hetero) Aryl chlorides and amines [54] and catalyzed cycloaddition reaction of azide [55].…”