Efficient Energy Transfer (EnT) in Pyrene- and Porphyrin-Based Mixed-Ligand Metal–Organic Frameworks

Designing and synthesizing the ordered light-harvesting systems, possessing complementary absorption and energy-transfer process between the chromophores, are essential steps to accomplish successful mimicking of the natural photosynthetic systems. Metal–organic frameworks (MOFs) can be considered as an ideal system to achieve this due to their highly ordered structure, superior synthetic versatility, and tailorable functionality. Herein, we have synthesized the new light-harvesting mixed-ligand MOFs (MLMs, MLM-1–3) via solvothermal reactions between a Zr₆ cluster and a mixture of appropriate ratio of 1,3,6,8-tetrakis­(<i>p</i>-benzoic acid)­pyrene and [5,10,15,20-tetrakis­(4-carboxy-phenyl)­porphyrinato]-Zn­(II) ligands. The identical symmetry and connectivity of the two ligands of the MLMs was the key parameter of successful synthesis as a single MOF form, and the ample overlap between the emission spectrum of pyrene and the absorption spectrum of porphyrin provided the ideal platform to design an efficient-energy transfer (EnT) process within the MLMs. We obtained the nanoscale maps of the fluorescence intensities and lifetimes of microsize MLM grains for unambiguous visualization of EnT phenomena occurring between two ligands in MLMs. Moreover, due to complementary absorption and energy transfer between the two ligands in the MLMs, our MLMs performed as superior photoinduced singlet-oxygen generators, verifying the enhanced light-harvesting properties of the pyrene- and porphyrin-based MLMs

Impeding Exciton–Exciton Annihilation in Monolayer WS₂ by Laser Irradiation

Monolayer (1L) transition metal dichalcogenides (TMDs) are two-dimensional direct-bandgap semiconductors with promising applications of quantum light emitters. Recent studies have shown that intrinsically low quantum yields (QYs) of 1L-TMDs can be greatly improved by chemical treatments. However, nonradiative exciton–exciton annihilation (EEA) appears to significantly limit light emission of 1L-TMDs at a nominal density of photoexcited excitons due to strong Coulomb interaction. Here we show that the EEA rate constant (γ) can be reduced by laser irradiation treatment in mechanically exfoliated monolayer tungsten disulfide (1L-WS₂), causing significantly improved light emission at the saturating optical pumping level. Time-resolved photoluminescence (PL) measurements showed that γ reduced from 0.66 ± 0.15 cm²/s to 0.20 ± 0.05 cm²/s simply using our laser irradiation. The laser-irradiated region exhibited lower PL response at low excitation levels, however at the high excitation level displayed 3× higher PL intensity and QY than the region without laser treatment. The shorter PL lifetime and lower PL response at low excitation levels suggested that laser irradiation increased the density of sulfur vacancies of 1L-WS₂, but we attribute these induced defects, adsorbed by oxygen in air, to the origin for reduced EEA by hindering exciton diffusion. Our laser irradiation was likewise effective for reducing EEA and increasing PL of chemically treated 1L-WS₂ with a high QY, exhibiting the general applicability of our method. Our results suggest that exciton–exciton interaction in 1L-TMDs may be conveniently controlled by the laser treatment, which may lead to unsaturated exciton emission at high excitation levels

Simultaneous Hosting of Positive and Negative Trions and the Enhanced Direct Band Emission in MoSe₂/MoS₂ Heterostacked Multilayers

Heterostacking of layered transition-metal dichalcogenide (LTMD) monolayers (1Ls) offers a convenient way of designing two-dimensional exciton systems. Here we demonstrate the simultaneous hosting of positive trions and negative trions in heterobilayers made by vertically stacking 1L MoSe₂ and 1L MoS₂. The charge transfer occurring between the 1Ls of MoSe₂ and MoS₂ converted the polarity of trions in 1L MoSe₂ from negative to positive, resulting in the presence of positive trions in the 1L MoSe₂ and negative trions in the 1L MoS₂ of the same heterostacked bilayer. Significantly enhanced MoSe₂ photoluminescence (PL) in the heterostacked bilayers compared to the PL of 1L MoSe₂ alone suggests that, unlike other previously reported heterostacked bilayers, direct band transition of 1L MoSe₂ in heterobilayer was enhanced after the vertical heterostacking. Moreover, by inserting hexagonal BN monolayers between 1L MoSe₂ and 1L MoS₂, we were able to adjust the charge transfer to maximize the MoSe₂ PL of the heteromultilayers and have achieved a 9-fold increase of the PL emission. The enhanced optical properties of our heterostacked LTMDs suggest the exciting possibility of designing LTMD structures that exploit the superior optical properties of 1L LTMDs

Simple Chemical Treatment to n‑Dope Transition-Metal Dichalcogenides and Enhance the Optical and Electrical Characteristics

The optical and electrical properties of monolayer transition-metal dichalcogenides (1L-TMDs) are critically influenced by two dimensionally confined exciton complexes. Although extensive studies on controlling the optical properties of 1L-TMDs through external doping or defect engineering have been carried out, the effects of excess charges, defects, and the populations of exciton complexes on the light emission of 1L-TMDs are not yet fully understood. Here, we present a simple chemical treatment method for n-dope 1L-TMDs, which also enhances their optical and electrical properties. We show that dipping 1Ls of MoS₂, WS₂, and WSe₂, whether exfoliated or grown by chemical vapor deposition, into methanol for several hours can increase the electron density and also can reduce the defects, resulting in the enhancement of their photoluminescence, light absorption, and the carrier mobility. This methanol treatment was effective for both n- and p-type 1L-TMDs, suggesting that the surface restructuring around structural defects by methanol is responsible for the enhancement of optical and electrical characteristics. Our results have revealed a simple process for external doping that can enhance both the optical and electrical properties of 1L-TMDs and help us understand how the exciton emission in 1L-TMDs can be modulated by chemical treatments