Copper-based chalcogenides that comprise abundant, low-cost, and environmental friendly elements are excellent materials for a number of energy conversion applications, including photovoltaics, photocatalysis, and thermoelectrics (TE). In such applications, the use of solution-processed nanocrystal (NC) to produce thin films or bulk nanomaterials has associated several potential advantages, such as high material yield and throughput, and composition control with unmatched spatial resolution and cost. Here we report on the production of Cu3SbSe4 (CASe) NCs with tuned amounts of Sn and Bi dopants. After proper ligand removal, as monitored by nuclear magnetic resonance and infrared spectroscopies, these NCs were used to produce dense CASe bulk nanomaterials for solid state TE energy conversion. By adjusting the amount of extrinsic dopants, dimensionless TE figures of merit (ZT) up to 1.26 at 673 K were reached. Such high ZT values are related to an optimized carrier concentration by Sn doping, a minimized lattice thermal conductivity due to efficient phonon scattering at point defects and grain boundaries, and to an increase of the Seebeck coefficient obtained by a modification of the electronic band structure with the Bi doping. Nanomaterials were further employed to fabricate ring-shaped TE generators to be coupled to hot pipes and which provided 20 mV and 1 mW per TE element when exposed to a 160 °C temperature gradient. The simple design and good thermal contact associated with the ring geometry and the potential low cost of the material solution processing may allow the fabrication of TE generators with short payback times.Peer ReviewedPostprint (author's final draft
Materials exhibiting reversible changes in optical properties upon light irradiation have shown great potential in diverse optoelectronic areas. In particular, the modulation of photochromic behavior on demand for such materials is of fundamental importance, but it remains a formidable challenge. Here, we report a facile and effective strategy to engineer controllable photochromic properties by varying the counterions in a series of zinc complexes consisting of a spirolactam-based photochromic ligand. Colorability and coloration rate can be finely tuned by conveniently changing their counterions. Through utilization of the reversible feature of the metal-ligand coordination bond between Zn2+ and the spirolactam-based ligand, dynamic manipulation of photochromic behavior was achieved. Furthermore, we demonstrated the practical applications of the tunable photochromic properties for these complexes by creating photochromic films and developing multilevel security printing. These findings show opportunities for the development of smart materials with dynamically controllable responsive behavior in advanced optoelectronic applications.
Materials exhibiting reversible changes of their photoluminescence properties upon exposure to heat have an immense potential in various advanced photonic applications. Particularly, the control over an on‐demand response of thermochromic luminescent materials (TLMs) similar to a chameleon is of great importance. However, it is still difficult and challenging to achieve it. Therefore, this paper reports a simple and effective way to construct TLMs, which involves the incorporation of the metal–ligand complexes into polyethylene glycol (PEG). Ratiometric or off–on response modes of these TLMs can be tuned by incorporating metal complexes based on either Zn2+ or Co2+ into PEG and by taking advantage of reversible metal–ligand coordination, dissociation, or excited‐state conformation changes of the resulting materials. Moreover, by choosing PEG matrices with different molecular weights, the thermochromic transition temperatures of these TLMs can be tuned. It is also demonstrated that the controllable response behavior of these chameleon‐like TLMs can be used in applications related to real‐life anti‐counterfeiting and security printing. This work opens novel opportunities for the development of smart materials with controllable responses useful for advanced photonic applications.
Single molecules with dual persistent luminescence are very rarely explored, in spite of their emerging use in frontier optoelectronic applications. Here, a pure organic phosphor of tris(4‐chlorophenyl)phosphine oxide (CPO) possessing a large energy gap between the lowest excited triplet (T1) and higher excited triplet (T2) states is reported, which can emit dual persistent room‐temperature phosphorescence (RTP) from low‐ and high‐lying triplet excited states. The femtosecond transient absorption experiments and theoretical calculations reveal that the excitons to the T1 and T2 states are populated through different pathways. As a result, the distribution of the triplet excitons can be efficiently manipulated by using different excitation energy, and tunable afterglow colors from green to yellow can be achieved. Furthermore, the CPO molecule is successfully applied in the fabrication of high‐level anti‐counterfeiting tags and flexible 3D objects with curling properties. From these initial discoveries, it is expected that triphenylphosphine derivatives, with their rich chemistry of core‐substitution, can provide infinite opportunities in the expansion of organic molecules with high‐lying persistent RTP.
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