Intrinsic “Vacancy Point Defect” Induced Electrochemiluminescence from Coreless Supertetrahedral Chalcogenide Nanocluster

Abstract

A deep understanding of distinct functional differences of various defects in semiconductor materials is conducive to effectively control and rationally tune defect-induced functionalities. However, such research goals remain a substantial challenge due to great difficulties in identifying the defect types and distinguishing their own roles, especially when various defects coexist in bulk or nanoscale material. Hereby, we subtly selected a molecular-type semiconductor material as structural mode composed of supertetrahedral chalcogenide Cd-In-S nanoclusters (NCs) with intrinsic vacancy point defect at the core site and antisite point defects at the surface of supertetrahedron and successfully established the correlation of those point defects with their own electrochemiluminescence (ECL) behaviors. The multichannel ECL properties were recorded, and the corresponding reaction mechanisms were also proposed. The predominant radiation recombination path of ECL emission peak at 585 nm was significantly distinguished from asymmetrically broad PL emission with a peak at 490 nm. In addition, the ECL performance of the coreless supertetrahedral chalcogenide nanocluster can be modulated by atomically precise doping of monomanganese ion at the core vacant site. A relatively high ECL efficiency of 2.1% was also gained. Actually, this is the first investigation of ECL behavior of semiconductor materials based on supertetrahedral chalcogenide nanocluster in aqueous solution. Current research may open up a new avenue to probe the roles of various different defects with defined composition and position in the NC. The versatile and bright ECL properties of Cd-In-S NC combined with tunable ECL potential and ECL peak suggest that the new kind of NC-based ECL material may hold great promising for its potential applications in electrochemical analysis, sensing, and imaging.

Near-infrared aggregation-induced enhanced electrochemiluminescence from tetraphenylethylene nanocrystals: a new generation of ECL emitters

“…In consequence, we chose the anode ECL signal of the TPE NCs for further study. Moreover, the [Ru(bpy) 3 ] 2+ /TPA system was selected as the standard to calculate the relative ECL efficiency of the TPE NCs/TPA system (the detailed formula is shown in the ESI†) and it was found to be 1.35%, which was higher than those of polyaniline-[Ru(bpy) 2 PIC] 2+ (1.0%)29 and Mn@CdInS films (0.8%) 30…”

Polymer Electrochemiluminescence Featuring Thermally Activated Delayed Fluorescence

“…To testify such viewpoint, co‐reactant ECL of fluorescent polymer F8BT/TPrA couple [4] was also characterized in parallel (Figure S17). The relative ECL efficiencies (Φ ECL ) of the PCzAPT10‐modifed GCE/40 mM TPrA couple and the F8BT‐modified GCE/40 mM TPrA couple were measured according to the routine procedures, [1j,6,16] in which the Ru(bpy) 3 2+ /TPrA couple (0.1 mM Ru(bpy) 3 2+ , 40 mM TPrA, 0.1 M TBAP in ACN) was used as the standard (Φ ECL‐0 =100 %) [1j] . As shown in Table 1, Φ ECL of F8BT/TPrA couple (Φ ECL‐1 ) was 44 %, while the Φ ECL of PCzAPT10/TPrA couple (Φ ECL‐2 ) was as high as 194 %.…”

Electrogenerated chemiluminescence detection of single entities

“…In addition, the development of novel ECL reagent systems may greatly improve the intensity and the imaging resolution. In recent years, nanocrystals and clusters, 113,114 aggregation-induced ECL polymers [115][116][117][118] or near-infrared materials, 119,120 with high ECL efficiency, stability, and biocompatibility have been reported, which are expected to replace the conventionally used Ru(bpy) 3…”