RESUMEN
2D conjugated metal-organic frameworks (c-MOFs) have emerged as promising materials for (opto)electronic applications due to their excellent charge transport properties originating from the unique layered-stacked structures with extended in-plane conjugation. The further advancement of MOF-based (opto)electronics necessitates the development of novel 2D c-MOF thin films with high quality. Cu-HHHATN (HHHATN: hexahydroxyl-hexaazatrinaphthylene) is a recently reported 2D c-MOF featuring high in-plane conjugation, strong interlayer π-π stacking, and multiple coordination sites, while the production of its thin-film form has not yet been reported. Herein, large-area Cu-HHHATN thin films with preferential orientation, high uniformity, and smooth surfaces are realized by using a convenient layer-by-layer growth method. Flexible photodetectors are fabricated, showing broadband photoresponse ranging from UV to short-wave infrared (370 to 1450 nm). The relatively long relaxation time of photocurrent, which arises from the trapping of photocarriers, renders the device's synaptic plasticity similar to that of biological synapses, promising its use in neuromorphic visual systems. This work demonstrates the great potential of Cu-HHHATN thin films in flexible optoelectronic devices for various applications.
RESUMEN
Cu3 (HHTT)2 (HHTT: 2,3,7,8,12,13-hexahydroxytetraazanaphthotetraphene) is a novel 2D conjugated metal-organic framework (2D c-MOF) with efficient in-plane d-π conjugations and strong interlayer π-π interactions while the growth of Cu3 (HHTT)2 thin films has never been reported until now. Here, the successful fabrication of highly oriented wafer-scale Cu3 (HHTT)2 thin films with a layer-by-layer growth method on various substrates is presented. Its semiconducting behavior and carrier transport mechanisms are clarified through temperature and frequency-dependent conductivity measurements. Flexible photodetectors based on Cu3 (HHTT)2 thin films exhibit reliable photoresponses at room temperature in a wavelength region from UV to mid-IR, which is much broader than those of solution-processed broadband photodetectors reported previously. Moreover, the photodetectors can show a typical synaptic behavior and excellent data recognition accuracy in artificial neural networks. This work opens a window for the exploration of high-performance and multifunctional optoelectronic devices based on 2D c-MOFs.
RESUMEN
Two new A-D-A small-molecule donors (C8T-BDTDP and C8ST-BDTDP) are prepared from benzodithiophene (BDT)-linked dimeric porphyrin (DP), which differ in side chains of BDT linkers with 4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene (C8T-BDT) for the former and 4,8-bis{5-[(2-ethylhexyl)thio]-2-thienyl}benzo[1,2-b:4,5-b']dithiophene (C8ST-BDT) for the latter. Both dimeric porphyrin donors show strongly UV-visible to near-infrared absorption. Compared to C8T-BDTDP, C8ST-BDTDP with an alkylthiothienyl-substituted BDT linker exhibits more intense absorption bands in the film and a lower highest occupied molecular orbital energy level. The blend film of the electron acceptor 6TIC with the respective dimeric porphyrin donor displays a broad photon response from 400 to 900 nm, unfortunately, with an absorption valley at ca. 600 nm. The device based on C8ST-BDTDP/6TIC demonstrates a promising power conversion efficiency (PCE) of 10.39% with a high short-circuit current density (JSC) of 19.53 mA cm-2, whereas the device based on C8T-BDTDP/6TIC shows a slightly lower PCE of 8.73% with a JSC of 17.75 mA cm-2. The better performance for C8ST-BDTDP/6TIC is mainly attributed to efficient charge dissociation and transportation because of the smooth surface morphology and highly ordered crystalline packing.
RESUMEN
Diketopyrrolopyrrole-ethynylene-bridged porphyrin dimers are capped with electron-deficient 3-ethylrhodanine (A2) via a π-bridge of phenylene ethynylene, affording two new acceptor-donor-acceptor structural porphyrin dimers (DPP-2TTP and DPP-2TP) with strong absorption in ranges of 400-550 nm (Soret bands) and 700-900 nm (Q bands). Their intrinsic absorption deficiency between the Soret and Q bands could be perfectly compensated by a wide-bandgap small molecule DR3TBDTTF (D*) with absorption at 500-700 nm. Impressively, the optimal ternary device based on the blend films of DPP-2TPP, DR3TBDTTF (20 wt %), and PC71BM shows a PCE of 11.15%, whereas the binary devices based on DPP-2TTP/PC71BM and DPP-2TP/PC71BM blend films exhibit PCEs of 9.30 and 8.23%, respectively. The high compatibility of the low bandgap porphyrin dimers with the wide-bandgap small molecule provides a new threesome with PC71BM for highly efficient panchromatic ternary organic solar cells.
