Dedoping of Intraband Silver Selenide Colloidal Quantum Dots through Strong Electronic Coupling at Organic/Inorganic Hybrid Interfaces.

Colloidal quantum dot (CQD) infrared (IR) photodetectors can be fabricated and operated with larger spectral tunability, fewer limitations in terms of cooling requirements and substrate lattice matching, and at a potentially lower cost than detectors based on traditional bulk materials. Silver selenide (Ag2Se) has emerged as a promising sustainable alternative to current state-of-the-art toxic semiconductors based on lead, cadmium, and mercury operating in the IR. However, an impeding gap in available absorption bandwidth for Ag2Se CQDs exists in the short-wave infrared (SWIR) region due to degenerate doping by the environment, switching the CQDs from intrinsic interband semiconductors in the near-infrared (NIR) to intraband absorbing CQDs in the mid-wave infrared (MWIR). Herein, we show that the small molecular p-type dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) can be used to extract electrons from the 1Se state of MWIR active Ag2Se CQDs to activate their intrinsic energy gap in the SWIR window. We demonstrate quenching of the MWIR Ag2Se absorbance peak, shifting of nitrile vibrational peaks characteristic of charge-neutral F4-TCNQ, as well as enhanced CQD absorption around ∼2500 nm after doping both in ambient and under air-free conditions. We elucidate the doping mechanism to be one that involves an integer charge transfer akin to doping in semiconducting polymers. These indications of charge transfer are promising milestones on the path to achieving sustainable SWIR Ag2Se CQD photodetectors.

High-performance thermoelectric silver selenide thin films cation exchanged from a copper selenide template.

Over the past decade, Ag2Se has attracted increasing attention due to its potentially excellent thermoelectric (TE) performance as an n-type semiconductor. It has been considered a promising alternative to Bi-Te alloys and other commonly used yet toxic and/or expensive TE materials. To optimize the TE performance of Ag2Se, recent research has focused on fabricating nanosized Ag2Se. However, synthesizing Ag2Se nanoparticles involves energy-intensive and time-consuming techniques with poor yield of final product. In this work, we report a low-cost, solution-processed approach that enables the formation of Ag2Se thin films from Cu2-x Se template films via cation exchange at room temperature. Our simple two-step method involves fabricating Cu2-x Se thin films by the thiol-amine dissolution of bulk Cu2Se, followed by soaking Cu2-x Se films in AgNO3 solution and annealing to form Ag2Se. We report an average power factor (PF) of 617 ± 82 µW m-1 K-2 and a corresponding ZT value of 0.35 at room temperature. We obtained a maximum PF of 825 µW m-1 K-2 and a ZT value of 0.46 at room temperature for our best-performing Ag2Se thin-film after soaking for 5 minutes. These high PFs have been achieved via full solution processing without hot-pressing.

Synthesis of luminescent core/shell α-Zn3P2/ZnS quantum dots.

Metal chalcogenide nanoparticles offer vast control over their optoelectronic properties via size, shape, composition, and morphology which has led to their use across fields including optoelectronics, energy storage, and catalysis. While cadmium and lead-based nanocrystals are prevalent in applications, concerns over their toxicity have motivated researchers to explore alternate classes of nanomaterials based on environmentally benign metals such as zinc and tin. The goal of this research is to identify material systems that offer comparable performance to existing metal chalcogenide systems from abundant, recyclable, and environmentally benign materials. With band gaps that span the visible through the infrared, II-V direct band gap semiconductors such as tetragonal zinc phosphide (α-Zn3P2) are promising candidates for optoelectronics. To date, syntheses of α-Zn3P2 nanoparticles have been hindered because of the toxicity of zinc and phosphorus precursors, surface oxidation, and defect states leading to carrier trapping and low photoluminescence quantum yield. This work reports a colloidal synthesis of quantum confined α-Zn3P2 nanoparticles from common phosphorus precursor tris(trimethylsilyl)phosphine and environmentally benign zinc carboxylates. Shelling of the nanoparticles with zinc sulfide is shown as a method of preventing oxidation and improving the optical properties of the nanoparticles. These results show a route to stabilizing α-Zn3P2 nanoparticles for optoelectronic device applications.