Optical grade transformation of monolayer transition metal dichalcogenides via encapsulation annealing.

Monolayer transition metal dichalcogenides (TMDs) have emerged as highly promising candidates for optoelectronic applications due to their direct band gap and strong light-matter interactions. However, exfoliated TMDs have demonstrated optical characteristics that fall short of expectations, primarily because of significant defects and associated doping in the synthesized TMD crystals. Here, we report the improvement of optical properties in monolayer TMDs of MoS2, MoSe2, WS2, and WSe2, by hBN-encapsulation annealing. Monolayer WSe2 showed 2000% enhanced photoluminescence quantum yield (PLQY) and 1000% increased lifetime after encapsulation annealing at 1000 °C, which are attributed to dominant radiative recombination of excitons through dedoping of monolayer TMDs. Furthermore, after encapsulation annealing, the transport characteristics of monolayer WS2 changed from n-type to ambipolar, along with an enhanced hole transport, which also support dedoping of annealed TMDs. This work provides an innovative approach to elevate the optical grade of monolayer TMDs, enabling the fabrication of high-performance optoelectronic devices.

Analysis of p-Type Doping in Graphene Induced by Monolayer-Oxidized TMDs.

Doping is one of the most difficult technological challenges for realizing reliable two-dimensional (2D) material-based semiconductor devices, arising from their ultrathinness. Here, we systematically investigate the impact of different types of nonstoichiometric solid MOx (M are W or Mo) dopants obtained by oxidizing transition metal dichalcogenides (TMDs: WSe2 or MoS2) formed on graphene FETs, which results in p-type doping along with disorders. From the results obtained in this study, we were able to suggest an analytical technique to optimize the optimal UV-ozone (UVO) treatment to achieve high p-type doping concentration in graphene FETs (∼2.5 × 1013 cm-2 in this study) without generating defects, mainly by analyzing the time dependency of D and D' peaks measured by Raman spectroscopy. Furthermore, an analysis of the structure of graphene sheets using TEM indicates that WOx plays a better protective role in graphene, compared to MoOx, suggesting that WOx is more effective for preventing the degradation of graphene during UVO treatment. To enhance the practical application aspect of our work, we have fabricated a graphene photodetector by selectively doping the graphene through oxidized TMDs, creating a p-n junction, which resulted in improved photoresponsivity compared to the intrinsic graphene device. Our results offer a practical guideline for the utilization of surface charge transfer doping of graphene toward CMOS applications.

Synergetic Enhancement of Quantum Yield and Exciton Lifetime of Monolayer WS2 by Proximal Metal Plate and Negative Electric Bias.

The efficiency of light emission is a critical performance factor for monolayer transition metal dichalcogenides (1L-TMDs) for photonic applications. While various methods have been studied to compensate for lattice defects to improve the quantum yield (QY) of 1L-TMDs, exciton-exciton annihilation (EEA) is still a major nonradiative decay channel for excitons at high exciton densities. Here, we demonstrate that the combined use of a proximal Au plate and a negative electric gate bias (NEGB) for 1L-WS2 provides a dramatic enhancement of the exciton lifetime at high exciton densities with the corresponding QY enhanced by 30 times and the EEA rate constant decreased by 80 times. The suppression of EEA by NEGB is attributed to the reduction of the defect-assisted EEA process, which we also explain with our theoretical model. Our results provide a synergetic solution to cope with EEA to realize high-intensity 2D light emitters using TMDs.

Polymer-Waveguide-Integrated 2D Semiconductor Heterostructures for Optical Communications.

The demand for high-speed and low-loss interconnects in modern computer architectures is difficult to satisfy by using traditional Si-based electronics. Although optical interconnects offer a promising solution owing to their high bandwidth, low energy dissipation, and high-speed processing, integrating elements such as a light source, detector, and modulator, comprising different materials with optical waveguides, presents many challenges in an integrated platform. Two-dimensional (2D) van der Waals (vdW) semiconductors have attracted considerable attention in vertically stackable optoelectronics and advanced flexible photonics. In this study, optoelectronic components for exciton-based photonic circuits are demonstrated by integrating lithographically patterned poly(methyl methacrylate) (PMMA) waveguides on 2D vdW devices. The excitonic signals generated from the 2D materials by using laser excitation were transmitted through patterned PMMA waveguides. By introducing an external electric field and combining vdW heterostructures, an excitonic switch, phototransistor, and guided-light photovoltaic device on SiO2/Si substrates were demonstrated.

Observation of aligned dipoles and angular chromism of exciplexes in organic molecular heterostructures.

The dipole characteristics of Frenkel excitons and charge-transfer excitons between donor and acceptor molecules in organic heterostructures such as exciplexes are important in organic photonics and optoelectronics. For the bilayer of the organic donor 4,4',4''-tris[(3-methylphenyl)phenylamino]triphenylamine and acceptor 2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine molecules, the exciplexes form aligned dipoles perpendicular to the Frenkel excitons, as observed in back focal plane photoluminescence images. The angular chromism of exciplexes observed in the 100 meV range indicates possible delocalization and angle-sensing photonic applications. The blue shift of the peak position and increase in the linewidth of photoluminescene spectra with increasing excitation power are caused by the repulsive aligned exciplex dipole moments with a long lifetime (4.65 µs). Electroluminescence spectra of the exciplex from organic light-emitting diodes using the bilayer are blue-shifted with increasing bias, suggesting unidirectional alignment of the exciplex dipole moments. The observation of exciplex dipole moment alignments across molecular interfaces can facilitate the controlled coupling of exciton species and increase efficiency of organic light-emitting diodes.

Incommensurate Antiferromagnetic Order in Weakly Frustrated Two-Dimensional van der Waals Insulator CrPSe3.

Although magnetic order is suppressed by a strong frustration, it appears in complex forms such as a cycloid or spin density wave in weakly frustrated systems. Herein, we report a weakly magnetically frustrated two-dimensional (2D) van der Waals material CrPSe3. Polycrystalline CrPSe3 was synthesized at an optimized temperature of 700 °C to avoid the formation of any secondary phases (e.g., Cr2Se3). The antiferromagnetic transition appeared at TN ≈ 127 K with a large Curie-Weiss temperature θCW ≈ -301 K via magnetic susceptibility measurements, indicating weak frustration in CrPSe3 with a frustration factor of f (|θCW|/TN) ≈ 2.4. Evidently, the formation of a long-range incommensurate antiferromagnetic order was revealed by neutron diffraction measurements at low temperatures (below 120 K). The monoclinic crystal structure of the C2/m symmetry is preserved over the studied temperature range down to 20 K, as confirmed by Raman spectroscopy measurements. Our findings on the incommensurate antiferromagnetic order in 2D magnetic materials, not previously observed in the MPX3 family, are expected to enrich the physics of magnetism at the 2D limit, thereby opening opportunities for their practical applications in spintronics and quantum devices.

Temperature Dependence of Excitonic Auger Recombination in Excitonic-Complex-Free Monolayer WS2 by Considering Auger Broadening and Generation Efficiency.

Monolayer transition metal dichalcogenides (TMDs) have been extensively studied for their optoelectronic properties and applications. However, even at moderate exciton densities, their light-emitting capability is severely limited by Auger-type exciton-exciton annihilation (EEA). Previous work on EEA used oversimplified models in the presence of excitonic complexes, resulting in seriously underestimated values for the Auger coefficient. In this work, we transferred monolayer WS2 on a gold substrate with hBN encapsulation, where excitons persist as the main species at 3-300 K via metal proximity. We numerically solved the rate equation for excitons to accurately determine the Auger coefficient as a function of temperature by considering laser pulse width and spatially inhomogeneous exciton distribution. We found that the Auger coefficient consists of temperature-dependent and independent terms, consistent with a theoretical model for direct and exchange processes, respectively. We believe that our results provide a guide for enhancing the luminescence quantum yield of TMDs.

Far-Red Interlayer Excitons of Perovskite/Quantum-Dot Heterostructures.

Interlayer excitons (IXs) at the interface of heterostructures (HSs) with a staggered band alignment are fascinating quantum quasi-particles with light-emitting and long-lifetime characteristics. In this study, the energy band alignments (EBAs) of the HS of MAPbI3 perovskite thin sheets with CdSe-ZnS core-shell quantum dot (QD) layers are modulated by using different diameters of the QDs. Far-red IX emission is observed at 1.42 eV from the HS of MAPbI3 /CdSe-ZnS-QD (λem  = 645 nm) with type-II EBA owing to charge transfer. The lifetime of the far-red IXs is estimated to be 5.68 µs, which is considerably longer than that (0.715 ns) of the intralayer excitons from CdSe-ZnS-QD. With increasing incident excitation power, the PL peak and its intensity of IXs are blue-shifted and linearly increased, respectively, indicating a strong dipole alignment of far-red IXs at the heterojunction. Back focal plane imaging suggests that the directions of dipole moments of the IXs are relatively out-of-plane compared to those of the intralayer excitons (MAPbI3 and CdSe-ZnS-QD). Notably, the abnormal behavior of the optical characteristics is observed near the phase transition temperature (90 K) of MAPbI3 . MAPbI3 /CdSe-ZnS-QD HS photodetectors show the increase in photocurrent and detectivity compared to MAPbI3 at IX excitation.

Effect of morphological variation in three-dimensional multiwall carbon nanotubes as the host cathode material for high-performance rechargeable lithium-sulfur batteries.

Lithium-sulfur batteries (LSBs) demonstrate potential as next-generation energy storage systems due to the high theoretical capacity and energy density of the sulfur cathode (1672 mAh g-1 and 2600 W h kg-1, respectively) in addition to the low-cost, natural abundance, and environmentally benign characteristics of sulfur. However, the insulating nature of sulfur requires an efficient conductive and porous host material such as three-dimensional carbon nanotubes (3D CNTs). Identifying parameters that provide high conduction pathways and short diffusion lengths for Li-ions within the CNT structure is essential for a highly efficient CNT-S cathode in a LSB. Herein, the effect of morphological variation in 3D CNTs as a sulfur host material is studied, and parameters that affect the performance of a CNT-S cathode in LSB are investigated. Four different 3D CNTs are synthesized via the chemical vapor deposition (CVD) technique that vary in specific surface area (SSA), CNT diameter, pore sizes, and porosity. The superior 3D CNT-S (CNT-S-50) cathode, which possessed high surface area and porosity as compared to the rest of the 3D CNT-S cathodes, with ∼38 wt% (6.27 mg cm-2) sulfur loading, demonstrated an areal and specific discharge capacity of 8.70 mAh cm-2 and 1387 mAh g-1 at 0.1C, respectively. Results from this work demonstrate that the combination of high surface area and porosity are two crucial parameters in 3D CNTs as an efficient sulfur host material for LSB cathodes.

Kinetic-Controlled Crystallization of α-FAPbI3 Inducing Preferred Crystallographic Orientation Enhances Photovoltaic Performance.

Crystallization kinetic controls the crystallographic orientation, inducing anisotropic properties of the materials. As a result, preferential orientation with advanced optoelectronic properties can enhance the photovoltaic devices' performance. Although incorporation of additives is one of the most studied methods to stabilize the photoactive α-phase of formamidinium lead tri-iodide (α-FAPbI3 ), no studies focus on how the additives affect the crystallization kinetics. Along with the role of methylammonium chloride (MACl) as a "stabilizer" in the formation of α-FAPbI3 , herein, the additional role as a "controller" in the crystallization kinetics is pointed out. With microscopic observations, for example, electron backscatter diffraction and selected area electron diffraction, it is examined that higher concentration of MACl induces slower crystallization kinetics, resulting in larger grain size and [100] preferred orientation. Optoelectronic properties of [100] preferentially oriented grains with less non-radiative recombination, a longer lifetime of charge carriers, and lower photocurrent deviations in between each grain induce higher short-circuit current density (Jsc ) and fill factor. Resulting MACl40 mol% attains the highest power conversion efficiency (PCE) of 24.1%. The results provide observations of a direct correlation between the crystallographic orientation and device performance as it highlights the importance of crystallization kinetics resulting in desirable microstructures for device engineering.

Inductive Effect of Lewis Acidic Dopants on the Band Levels of Perovskite for a Photocatalytic Reaction.

Band-edge modulation of halide perovskites as photoabsorbers plays significant roles in the application of photovoltaic and photochemical systems. Here, Lewis acidity of dopants (M) as the new descriptor of engineering the band-edge position of the perovskite is investigated in the gradiently doped perovskite along the core-to-surface (CsPbBr3-CsPb1-xMxBr3). Reducing M-bromide bond strength with an increase in hardness of acidic M increases the electron ability of basic Br, thus strengthening the Pb-Br orbital coupling in M-Pb-Br, noted as the inductive effect of dopants. Especially, the highly hard Lewis acidic Mg localized in the outer position of the perovskite induces the increase of work function and then shifts band edge upward along the core-to-surface of the perovskite. Thus, charge separation driven by the dopant-induced internal electric field induces the slow annihilation of the excited holes, improving the slow aromatic Csp3-H dissociation in the photocatalytic oxidation process by ∼211% (491.39 µmol g-1 h-1) enhancements, compared with undoped nanocrystals.

Exciton-dominant photoluminescence of MoS2 by a functionalized substrate.

Transition metal dichalcogenides (TMDs) have been considered as promising candidates for transparent and flexible optoelectronic devices owing to their large exciton binding energy and strong light-matter interaction. However, monolayer (1L) TMDs exhibited different intensities and spectra of photoluminescence (PL), and the characteristics of their electronic devices also differed in each study. This has been explained in terms of various defects in TMDs, such as vacancies and grain boundaries, and their surroundings, such as dielectric screening and charged impurities, which lead to non-radiative recombination of trions, low quantum yield (QY), and unexpected doping. However, it should be noted that the surface conditions of the substrate are also a critical factor in determining the properties of TMDs located on the substrate. Here, we demonstrate that the optical and electrical properties of 1L MoS2 are strongly influenced by the functionalized substrate. The PL of 1L MoS2 placed on the oxygen plasma-treated SiO2 substrate was highly p-doped owing to the functional groups of -OH on SiO2, resulting in a strong enhancement of PL by approximately 20 times. The PL QY of 1L MoS2 on plasma-treated SiO2 substrate increased by one order of magnitude. Surprisingly, the observed PL spectra show the suppression of non-radiative recombination by trions, thus the exciton-dominant PL led to a prolonged lifetime of MoS2 on the plasma-treated substrate. The MoS2 field-effect transistors fabricated on plasma-treated SiO2 also exhibited a large hysteresis in the transfer curve owing to charge trapping of the functional groups. Our study demonstrates that the functional groups on the substrate strongly affect the characteristics of 1L MoS2, which provides clues as to why MoS2 exfoliated on various substrates always exhibited different properties in previous studies.

Gas-Phase Alkali Metal-Assisted MOCVD Growth of 2D Transition Metal Dichalcogenides for Large-Scale Precise Nucleation Control.

Advances in large-area and high-quality 2D transition metal dichalcogenides (TMDCs) growth are essential for semiconductor applications. Here, the gas-phase alkali metal-assisted metal-organic chemical vapor deposition (GAA-MOCVD) of 2D TMDCs is reported. It is determined that sodium propionate (SP) is an ideal gas-phase alkali-metal additive for nucleation control in the MOCVD of 2D TMDCs. The grain size of MoS2 in the GAA-MOCVD process is larger than that in the conventional MOCVD process. This method can be applied to the growth of various TMDCs (MoS2 , MoSe2 , WSe2 , and WSe2 ) and the generation of large-scale continuous films. Furthermore, the growth behaviors of MoS2 under different SP and oxygen injection time conditions are systematically investigated to determine the effects of SP and oxygen on nucleation control in the GAA-MOCVD process. It is found that the combination of SP and oxygen increases the grain size and nucleation suppression of MoS2 . Thus, the GAA-MOCVD with a precise and controllable supply of a gas-phase alkali metal and oxygen allows achievement of optimum growth conditions that maximizes the grain size of MoS2 . It is expected that GAA-MOCVD can provide a way for batch fabrication of large-scale atomically thin electronic devices based on 2D semiconductors.

Boosting quantum yields in two-dimensional semiconductors via proximal metal plates.

Monolayer transition metal dichalcogenides (1L-TMDs) have tremendous potential as atomically thin, direct bandgap semiconductors that can be used as convenient building blocks for quantum photonic devices. However, the short exciton lifetime due to the defect traps and the strong exciton-exciton interaction in TMDs has significantly limited the efficiency of exciton emission from this class of materials. Here, we show that exciton-exciton interaction in 1L-WS2 can be effectively screened using an ultra-flat Au film substrate separated by multilayers of hexagonal boron nitride. Under this geometry, induced dipolar exciton-exciton interaction becomes quadrupole-quadrupole interaction because of effective image dipoles formed within the metal. The suppressed exciton-exciton interaction leads to a significantly improved quantum yield by an order of magnitude, which is also accompanied by a reduction in the exciton-exciton annihilation (EEA) rate, as confirmed by time-resolved optical measurements. A theoretical model accounting for the screening of the dipole-dipole interaction is in a good agreement with the dependence of EEA on exciton densities. Our results suggest that fundamental EEA processes in the TMD can be engineered through proximal metallic screening, which represents a practical approach towards high-efficiency 2D light emitters.

Spin-Selective Hole-Exciton Coupling in a V-Doped WSe2 Ferromagnetic Semiconductor at Room Temperature.

While valley polarization with strong Zeeman splitting is the most prominent characteristic of two-dimensional (2D) transition metal dichalcogenide (TMD) semiconductors under magnetic fields, enhancement of the Zeeman splitting has been demonstrated by incorporating magnetic dopants into the host materials. Unlike Fe, Mn, and Co, V is a distinctive dopant for ferromagnetic semiconducting properties at room temperature with large Zeeman shifting of band edges. Nevertheless, little known is the excitons interacting with spin-polarized carriers in V-doped TMDs. Here, we report anomalous circularly polarized photoluminescence (CPL) in a V-doped WSe2 monolayer at room temperature. Excitons couple to V-induced spin-polarized holes to generate spin-selective positive trions, leading to differences in the populations of neutral excitons and trions between left and right CPL. Using transient absorption spectroscopy, we elucidate the origin of excitons and trions that are inherently distinct for defect-mediated and impurity-mediated trions. Ferromagnetic characteristics are further confirmed by the significant Zeeman splitting of nanodiamonds deposited on the V-doped WSe2 monolayer.

Charge-Transfer Effect and Enhanced Photoresponsivity of WS2- and MoSe2-Based Field Effect Transistors with π-Conjugated Polyelectrolyte.

The characteristics of field effect transistors (FETs) fabricated using two-dimensional (2D) transition-metal dichalcogenides (TMDCs) can be modulated by surface treatment of the active layers. In this study, an ionic π-conjugated polyelectrolyte, poly(9,9-bis(4'-sulfonatobutyl)fluorene-alt-1,4-phenylene) potassium (FPS-K), was used for the surface treatment of MoSe2 and WS2 FETs. The photoluminescence (PL) intensities of monolayer (1L)-MoSe2 and 1L-WS2 clearly decreased, and the PL peaks were red-shifted after FPS-K treatment, suggesting a charge-transfer effect. In addition, the n-channel current of both the MoSe2 and WS2 FETs increased and the threshold voltage (Vth) shifted negatively after FPS-K treatment owing to the charge-transfer effect. The photoresponsivity of the MoSe2 FET under light irradiation (λex = 455 nm) increased considerably, from 5300 A W-1 to approximately 10 000 A W-1, after FPS-K treatment, and similar behavior was observed in the WS2 FET. The results can be explained in terms of the increase in electron concentration due to photogating. The external quantum efficiency and photodetectivity of both FETs were also enhanced by the charge-transfer effect resulting from surface treatment with FPS-K containing mobile cations (K+) and fixed anions (SO3-), as well as by the photogating effect. The variation in charge-carrier density due to the photogating and charge-transfer effects is estimated to be approximately 2 × 1012 cm-2. The results suggest that π-conjugated polyelectrolytes such as FPS-K can be a promising candidate for the passivation of TMDC-based FETs and obtaining enhanced photoresponsivity.

Doping-Mediated Lattice Engineering of Monolayer ReS2 for Modulating In-Plane Anisotropy of Optical and Transport Properties.

ReS2 exhibits strong anisotropic optical and electrical responses originating from the asymmetric lattice. Here, we show that the anisotropy of monolayer (1L) ReS2 in optical scattering and electrical transport can be practically erased by lattice engineering via lithium (Li) treatment. Scanning transmission electron microscopy revealed that significant strain is induced in the lattice of Li-treated 1L-ReS2, due to high-density electron doping and the resultant formation of continuous tiling of nanodomains with randomly rotating orientations of 60°, which produced a nearly isotropic response of polarized Raman scattering and absorption of Li-treated 1L-ReS2. With Li treatment, the in-plane conductance of 1L-ReS2 increased by an order of magnitude, and its angle dependence became negligible. Our result that the asymmetric phase was converted into the isotropic phase by electron injection could significantly expand the optoelectronic applications of polymorphic two-dimensional transition metal dichalcogenides.

Efficacy of reduced-size short tandem repeat PCR analysis for degraded DNA samples.

BACKGROUND: Short tandem repeats (STR) typing is an essential analysis method for human identification in forensic field. When DNAs obtained from the field as evidences are severely degraded or in too small amounts, STR analysis often shows allele drop-out. OBJECTIVE: To improve STR analysis for degraded DNA or trace DNA, reduced-size STR (rSTR) polymerase chain reaction (PCR) system was devised by selecting relatively large-size STR loci. METHODS: The rSTR PCR system consisted of 8 loci (amelogenin, SE33, CSF1PO, D7S820, D13S317, D2S1338, TPOX, and FGA). The size of PCR product was reduced by designing new primers in the flanking region. The efficiency of this system was verified against existing kits through concordance study, sensitivity study, efficiency study, and casework sample study. RESULTS: The size of PCR product in the rSTR PCR system was reduced to be less than 322 bp. The amplicon of each locus was reduced by about 100 bp on average. Results of this rSTR PCR system were confirmed using 146 Korean samples and other commercial kits. The rSTR PCR system was capable of analyzing DNA samples with a minimum amount of DNA of 16 pg and a degradation index of 4.215. CONCLUSION: The rSTR PCR system was more effective than other PCR kits for obtaining genetic profiles from a small amount of DNA or degraded DNA. The combination of this new system and other commercial kits is more effective than existing systems. This combination is expected to be helpful for the identification of unidentified bodies and skeletal samples.

Massively parallel sequencing of 25 short tandem repeat loci including the SE33 marker in Koreans.

BACKGROUND: Massively parallel sequencing (MPS) technology has recently been introduced in research, clinical diagnostics, and forensics. MPS enables determination of the genotypes of multiple short tandem repeat (STR) markers and to determine nucleotide sequence variations, additionally. OBJECTIVE: To improve STR analysis and a paternity index, a new, smaller-sized STR panel was designed that includes the SE33 locus. METHODS: This study performed MPS using an STR panel including the SE33 marker in 101 Koreans. The concordance study was conducted by comparing the data obtained from the MPS assay with the results of a capillary electrophoresis (CE)-based method. RESULTS: In this study, an in-house MPS panel is designed that incorporates the 20 Combined DNA Index System (CODIS) loci and the Penta D, Penta E, and SE33 markers for enhanced discriminatory ability. The data obtained via MPS analysis were compared with CE data to confirm concordance. Fifty previously unreported alleles were detected through the MPS analysis. Three new SNP variations in the flanking region were also identified. Statistical analysis demonstrated that the SE33 marker was most effectively determined the match probability (PM) and typical paternity index (TPI). In the sensitivity study, concentrations as low as 80 pg could be used to obtain full and concordant profiles. CONCLUSIONS: We designed a new, smaller-sized STR panel that includes the SE33 locus to improve STR analysis and the paternity index. Various new alleles were identified in SE33, indicating a high degree of polymorphism. The panel is expected to provide valid data for discrimination of unidentified bodies.

Switchable, Tunable, and Directable Exciton Funneling in Periodically Wrinkled WS2.

The extreme elastic strain of monolayer transition metal dichalcogenides provides an ideal platform to achieve efficient exciton funneling via local strain modulation; however, studies conducted thus far have focused on the use of substrates with fixed strain profiles. We prepared 1L-WS2 on a flexible substrate such that the formation of topographic wrinkles could be switched on or off, and the depth or the direction of the wrinkle could be modified by external strain, thereby providing full control of the periodic undulation of the band gap profile of 1L-WS2 in the range 0-57 meV. Nanoscale photoluminescence (PL) imaging unambiguously evinced that the photoexcited excitons of 1L-WS2 were accumulated at the top regions of the wrinkles with less band gap than the valley region. Our results of broad tunability of the two-dimensional (2D) exciton funneling suggest a promising route to control exciton drift for enhanced optoelectronic performances and future 2D exciton devices.