Changwon Seo

Biexciton Emission from Edges and Grain Boundaries of Triangular WS2 Monolayers

Monolayer tungsten disulfides (WS2) constitute a high quantum yield two-dimensional (2D) system, and can be synthesized on a large area using chemical vapor deposition (CVD), suggesting promising nanophotonics applications. However, spatially nonuniform photoluminescence (PL) intensities and peak wavelengths observed in single WS2 grains have puzzled researchers, with the origins of variation in relative contributions of excitons, trions, and biexcitons to the PL emission not well understood. Here, we present nanoscale PL and Raman spectroscopy images of triangular CVD-grown WS2 monolayers of different sizes, with these images obtained under different temperatures and values of excitation power. Intense PL emissions were observed around the edges of individual WS2 grains and the grain boundaries between partly merged WS2 grains. The predominant origin of the main PL emission from these regions changed from neutral excitons to trions and biexcitons with increasing laser excitation power, with biexcitons completely dominating the PL emission for the high-power condition. The intense PL emission and the preferential formation of biexcitons in the edges and grain boundaries of monolayer WS2 were attributed to larger population of charge carriers caused by the excessive incorporation of growth promoters during the CVD, suggesting positive roles of excessive carriers in the PL efficiency of TMD monolayers. Our comprehensive nanoscale spectroscopic investigation sheds light on the dynamic competition between exciton complexes occurring in monolayer WS2, suggesting a rich variety of ways to engineer new nanophotonic functions using 2D transition metal dichalcogenide monolayers.

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.

Gate-Tunable Spin Exchange Interactions and Inversion of Magnetoresistance in Single Ferromagnetic ZnO Nanowires

Electrical control of ferromagnetism in semiconductor nanostructures offers the promise of nonvolatile functionality in future semiconductor spintronics. Here, we demonstrate a dramatic gate-induced change of ferromagnetism in ZnO nanowire (NW) field-effect transistors (FETs). Ferromagnetism in our ZnO NWs arose from oxygen vacancies, which constitute deep levels hosting unpaired electron spins. The magnetic transition temperature of the studied ZnO NWs was estimated to be well above room temperature. The in situ UV confocal photoluminescence (PL) study confirmed oxygen vacancy mediated ferromagnetism in the studied ZnO NW FET devices. Both the estimated carrier concentration and temperature-dependent conductivity reveal the studied ZnO NWs are at the crossover of the metal-insulator transition. In particular, gate-induced modulation of the carrier concentration in the ZnO NW FET significantly alters carrier-mediated exchange interactions, which causes even inversion of magnetoresistance (MR) from negative to positive values. Upon sweeping the gate bias from -40 to +50 V, the MRs estimated at 2 K and 2 T were changed from -11.3% to +4.1%. Detailed analysis on the gate-dependent MR behavior clearly showed enhanced spin splitting energy with increasing carrier concentration. Gate-voltage-dependent PL spectra of an individual NW device confirmed the localization of oxygen vacancy-induced spins, indicating that gate-tunable indirect exchange coupling between localized magnetic moments played an important role in the remarkable change of the MR.

Heterogeneous modulation of exciton emission in triangular WS2 monolayers by chemical treatment

Chemical treatments were recently shown to be very effective in enhancing the exciton emission of monolayer transition metal dichalcogenides (1L-TMDs) by suppressing the exciton quenching caused by structural defects. However, the effects of these chemical treatments varied greatly depending on the synthesis method and the type of 1L-TMD; therefore, the exact origin of the emission enhancement is still elusive. Here we report the spatially heterogeneous effects of bis(trifluoromethane)sulfonimide (TFSI) and benzyl viologen (BV) treatment on the optical properties of triangular 1L-WS2 grown by chemical vapor deposition (CVD). Nanoscale photoluminescence (PL) and Raman spectral maps showed that TFSI had a minimal effect on the inner region of the triangular WS2 grain, whereas the PL of the edge region was enhanced up to 25 times; further, BV reduced the PL, also more strikingly in the edge region. Systematic variation of the spectral weights among neutral excitons, trions, and bi-excitons indicated that p-doping and n-doping with TFSI and BV, respectively, occurred in both the inner and edge regions; however, the PL enhancement was attributed mainly to the reduction of structural defects caused by TFSI treatment. Our observation of the spatially heterogeneous effects of chemical treatment suggests that the inner and edge regions of CVD-grown 1L-WS2 are populated with different types of structural defects and helps in clarifying the mechanism by which chemical treatment enhances the optical properties of 1L-TMDs.

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.

Optically active charge transfer in hybrids of Alq3 nanoparticles and MoS2 monolayer

Organic/inorganic hybrid structures have been widely studied because of their enhanced physical and chemical properties. Monolayers of transition metal dichalcogenides (1L-TMDs) and organic nanoparticles can provide a hybridization configuration between zero- and two-dimensional systems with the advantages of convenient preparation and strong interface interaction. Here, we present such a hybrid system made by dispersing π-conjugated organic (tris (8-hydroxyquinoline) aluminum(III)) (Alq3) nanoparticles (NPs) on 1L-MoS2. Hybrids of Alq3 NP/1L-MoS2 exhibited a two-fold increase in the photoluminescence of Alq3 NPs on 1L-MoS2 and the n-doping effect of 1L-MoS2, and these spectral and electronic modifications were attributed to the charge transfer between Alq3 NPs and 1L-MoS2. Our results suggested that a hybrid of organic NPs/1L-TMD can offer a convenient platform to study the interface interactions between organic and inorganic nano objects and to engineer optoelectronic devices with enhanced performance.

Sensitive optical bio-sensing of p-type WSe2 hybridized with fluorescent dye attached DNA by doping and de-doping effects

Layered transition metal dichalcogenides, such as MoS2, WSe2 and WS2, are exciting two-dimensional (2D) materials because they possess tunable optical and electrical properties that depend on the number of layers. In this study, the nanoscale photoluminescence (PL) characteristics of the p-type WSe2 monolayer, and WSe2 layers hybridized with the fluorescent dye Cy3 attached to probe-DNA (Cy3/p-DNA), have been investigated as a function of the concentration of Cy3/DNA by using high-resolution laser confocal microscopy. With increasing concentration of Cy3/p-DNA, the measured PL intensity decreases and its peak is red-shifted, suggesting that the WSe2 layer has been p-type doped with Cy3/p-DNA. Then, the PL intensity of the WSe2/Cy3/p-DNA hybrid system increases and the peak is blue-shifted through hybridization with relatively small amounts of target-DNA (t-DNA) (50-100 nM). This effect originates from charge and energy transfer from the Cy3/DNA to the WSe2. For t-DNA detection, our systems using p-type WSe2 have the merit in terms of the increase of PL intensity. The p-type WSe2 monolayers can be a promising nanoscale 2D material for sensitive optical bio-sensing based on the doping and de-doping responses to biomaterials.

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(p-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.

Enhanced Luminescence and Photocurrent of Organic Microrod/ZnO Nanoparticle Hybrid System: Nanoscale Optical and Electrical Characteristics

We studied the enhanced photoluminescence (PL) and photocurrent (PC) of 1,4-bis(3,5-bis(trifluoromethyl)styryl)-2,5-dibromobenzene (TSDB) microrods decorated with ZnO nanoparticles (NPs). Chemically synthesized crystalline ZnO NPs with an average size of 40 nm were functionalized with (3-aminopropyl)trimethoxysilane to result in the chemical bonding of the NPs onto the surface of the TSDB microrods. We observed a 2-fold PL enhancement in the ZnO/TSDB hybrid microrods compared with the PL of the pure TSDB microrods. In addition, PC measurement carried out on the TSDB and ZnO/TSDB hybrid microrods at two different excitation wavelengths of 355 nm and 405 nm showed the significant enhancement of the PC from the hybrid system, where the resonant excitation of the laser (355 nm) corresponding to the absorption of both ZnO and TSDB caused ∼3 times enhancement of the PC from the ZnO/TSDB hybrid microrods.