RESUMO
III-V colloidal quantum dots (CQDs) are of interest in infrared photodetection, and recent developments in CQDs synthesis and surface engineering have improved performance. Here this work investigates photodetector stability, finding that the diffusion of zinc ions from charge transport layers (CTLs) into the CQDs active layer increases trap density therein, leading to rapid and irreversible performance loss during operation. In an effort to prevent this, this work introduces organic blocking layers between the CQDs and ZnO layers; but these negatively impact device performance. The device is then, allowing to use a C60:BCP as top electron-transport layer (ETL) for good morphology and process compatibility, and selecting NiOX as the bottom hole-transport layer (HTL). The first round of NiOX -based devices show efficient light response but suffer from high leakage current and a low open-circuit voltage (Voc) due to pinholes. This work introduces poly[bis(4-phenyl) (2,4,6-trimethylphenyl)amine] (PTAA) with NiOX NC to form a hybrid HTL, an addition that reduces pinhole formation, interfacial trap density, and bimolecular recombination, enhancing carrier harvesting. The photodetectors achieve 53% external quantum efficiency (EQE) at 970 nm at 1 V applied bias, and they maintain 95% of initial performance after 19 h of continuous illuminated operation. The photodetectors retain over 80% of performance after 80 days of shelf storage.
RESUMO
Addition of aqueous hydrohalic acids during the synthesis of colloidal quantum dots (QDs) is widely employed to achieve high-quality QDs. However, this reliance on the use of aqueous solutions is incompatible with oxygen- and water-sensitive precursors such as those used in the synthesis of Te-alloyed ZnSe QDs. Herein, it is shown that this incompatibility leads to phase segregation into Te-rich and Te-poor regions, causing spectral broadening and luminescence peak shifting under high laser irradiation and applied electrical bias. Here, a synthetic strategy to produce anhydrous-HF in situ by using benzenecarbonyl fluoride (BF) as a chemical additive is reported. Through in situ 19 F NMR spectroscopy, it is found that BF reacts with surfactants in tandem, ultimately producing intermediary F···H···trioctylamine adducts. These act as a pseudo-HF source that releases anhydrous HF. The controlled release of HF during nucleation and growth steps homogenizes Te distribution in ZnSeTe lattice, leading to spectrally stable blue-emitting QDs under increasing laser flux from ≈3 µW to ≈12 mW and applied bias from 2.6 to 10 V. Single-dot photoluminescence (PL) spectroscopy and analyses of the absorption, PL and transient absorption spectra together with density functional theory point to the role of anhydrous HF as a Te homogenizer.