Spectro-Microscopic Perceptions into Oxidation Behavior of Large-Scale Molybdenum Disulfide and its Photoelectrical Correlation.

Despite the encouraging properties and research of 2D MoS2 , an ongoing issue associated with the oxidative instability remains elusive for practical optoelectronic applications. Thus, in-depth understanding of the oxidation behavior of large-scale and homogeneous 2D MoS2 is imperative. Here the structural and chemical transformations of large-area MoS2 multilayers by air-annealing with altered temperature and time via combinatorial spectro-microscopic analyses (Raman spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy) are surveyed. The results gave indications pertaining to temperature- and time-dependent oxidation effects: i) heat-driven elimination of redundant residues, ii) internal strain stimulated by the formation of MoO bonds, iii) deterioration of the MoS2 crystallinity, iv) layer thinning, and v) morphological transformation from 2D MoS2 layers to particles. Photoelectrical characterization of the air-annealed MoS2 is implemented to capture the link between the oxidation behavior of MoS2 multilayers and their photoelectrical properties. The photocurrent based on MoS2 air-annealed at 200 °C is assessed to be 4.92 µA, which is 1.73 times higher than that of pristine MoS2 (2.84 µA). The diminution in the photocurrent of the photodetector based on MoS2 air-annealed above 300 °C in terms of the structural, chemical, and electrical conversions induced by the oxidation process is further discussed.

Wafer-Scale Production of Two-Dimensional Tin Monoselenide: Expandable Synthetic Platform for van der Waals Semiconductor-Based Broadband Photodetectors.

A synthetic platform for industrially applicable two-dimensional (2D) semiconductors that addresses the paramount issues associated with large-scale production, wide-range photosensitive materials, and oxidative stability has not yet been developed. In this study, we attained the 6 in. scale production of 2D SnSe semiconductors with spatial homogeneity using a rational synthetic platform based on the thermal decomposition of solution-processed single-source precursors. The long-range structural and chemical homogeneities of the 2D SnSe layers are manifested using comprehensive spectroscopic analyses. Furthermore, the capability of the SnSe-based photodetectors for broadband photodetection is distinctly verified. The photoresponsivity and detectivity of the SnSe-based photodetectors are 5.89 A W-1 and 1.8 × 1011 Jones at 532 nm, 1.2 A W-1 and 3.7 × 1010 Jones at 1064 nm, and 0.14 A W-1 and 4.3 × 109 Jones at 1550 nm, respectively. The minimum rise times for the 532 and 1064 nm lasers are 62 and 374 µs, respectively. The photoelectrical analysis of the 5 × 5 SnSe-based photodetector array reveals 100% active devices with 95.06% photocurrent uniformity. We unequivocally validated that the air and thermal stabilities of the photocurrent yielded from the SnSe-based photodetector are determined to be >30 d in air and 160 °C, respectively, which are suitable for optoelectronic applications.

Chemical Patterning of Graphene via Metal-Assisted Highly Energetic Electron Irradiation for Graphene Homojunction-Based Gas Sensors.

To gain the target functionality of graphene for gas detection, nonfocused and large-scale compatible MeV electron beam irradiation on graphene with Ag patterns is innovatively adopted in air for chemical patterning of graphene. This strategy allows the metal-assisted site-specific oxidation of graphene to realize monolithically integrated graphene-chemically patterned graphene (CPG)-graphene homojunction-based gas sensors. The size-tunable CPG patterns can be mediated by regulating the size of Ag prepatterns. The impacts of highly energetic electron irradiation (HEEI) on graphene are summarized as follows: (i) the selective p-type doping and the defect generation of graphene by the HEEI-induced oxidation, (ii) the resistance of the homojunction devices manipulated by the HEEI dose, (iii) the band gap opening of graphene as well as the lowering of the Fermi level, (iv) the work function values for pristine graphene and CPG corresponding to 4.14 and 4.88 eV, respectively, and (v) graphene-CPG-graphene homojunction for NO2 gas, revealing an 839% enhanced gas response compared with that of the pristine graphene-based gas sensor.

Fabrication of vertical van der Waals gap array using single-and multi-layer graphene.

Arrays of van der Waals gaps were manufactured by synthesizing the vertically aligned graphene layer stacked between two copper (Cu) catalytic films. The Cu-graphene-Cu laminated structure was obtained by directly synthesizing graphene on a patterned Cu film followed by depositing a second copper layer for optical measurements. The synthesis of graphene on the Cu surface was optimized by adjusting the synthesis temperatures and pre-annealing time using plasma enhanced chemical vapor deposition (PECVD). Resonant Raman spectroscopy measurements reveal that graphene can be synthesized on both bulk Cu foil and relatively thin Cu film under the same growth mechanism using PECVD. Structural and optical characterizations of the array of graphene van der Waals gaps were implemented by the transmission electron microscope and terahertz-time domain spectroscopy (THz-TDS). In THz-TDS, the measured THz amplitude transmitted through the graphene van der Waals gap slit array was constant regardless of the gap width determined by the number of graphene layers between the Cu thin films in a single slit. These results imply that the optical dielectric constant of graphene at THz frequencies in the out-of-plane direction is linearly proportional to the gap width. Our results of the manufacturing method can be adopted to investigate mechanical, electrical, and optical properties of other 2D materials such as h-BN, MoS2, and others. Furthermore, metal-graphene-metal structures with vertical orientations can be used in many electronic, optic, and optoelectronic applications.

Direct Synthesis of a Self-Assembled WSe2 /MoS2 Heterostructure Array and its Optoelectrical Properties.

Functional van der Waals heterojunctions of transition metal dichalcogenides are emerging as a potential candidate for the basis of next-generation logic devices and optoelectronics. However, the complexity of synthesis processes so far has delayed the successful integration of the heterostructure device array within a large scale, which is necessary for practical applications. Here, a direct synthesis method is introduced to fabricate an array of self-assembled WSe2 /MoS2 heterostructures through facile solution-based directional precipitation. By manipulating the internal convection flow (i.e., Marangoni flow) of the solution, the WSe2 wires are selectively stacked over the MoS2 wires at a specific angle, which enables the formation of parallel- and cross-aligned heterostructures. The realized WSe2 /MoS2 -based p-n heterojunction shows not only high rectification (ideality factor: 1.18) but also promising optoelectrical properties with a high responsivity of 5.39 A W-1 and response speed of 16 µs. As a feasible application, a WSe2 /MoS2 -based photodiode array (10 × 10) is demonstrated, which proves that the photosensing system can detect the position and intensity of an external light source. The solution-based growth of hierarchical structures with various alignments could offer a method for the further development of large-area electronic and optoelectronic applications.

Atomic-Level Customization of 4 in. Transition Metal Dichalcogenide Multilayer Alloys for Industrial Applications.

Despite many encouraging properties of transition metal dichalcogenides (TMDs), a central challenge in the realm of industrial applications based on TMD materials is to connect the large-scale synthesis and reproducible production of highly crystalline TMD materials. Here, the primary aim is to resolve simultaneously the two inversely related issues through the synthesis of MoS2(1- x ) Se2 x ternary alloys with customizable bichalcogen atomic (S and Se) ratio via atomic-level substitution combined with a solution-based large-area compatible approach. The relative concentration of bichalcogen atoms in the 2D alloy can be effectively modulated by altering the selenization temperature, resulting in 4 in. scale production of MoS1.62 Se0.38 , MoS1.37 Se0.63 , MoS1.15 Se0.85 , and MoS0.46 Se1.54 alloys, as well as MoS2 and MoSe2 . Comprehensive spectroscopic evaluations for vertical and lateral homogeneity in terms of heteroatom distribution in the large-scale 2D TMD alloys are implemented. Se-stimulated strain effects and a detailed mechanism for the Se substitution in the MoS2 crystal are further explored. Finally, the capability of the 2D alloy for industrial application in nanophotonic devices and hydrogen evolution reaction (HER) catalysts is validated. Substantial enhancements in the optoelectronic and HER performances of the 2D ternary alloy compared with those of its binary counterparts, including pure-phase MoS2 and MoSe2 , are unambiguously achieved.

High energy electron beam stimulated nanowelding of silver nanowire networks encapsulated with graphene for flexible and transparent electrodes.

Low-dimensional nanostructures and their complementary hybridization techniques are in the vanguard of technological advances for applications in transparent and flexible nanoelectronics due to the intriguing electrical properties related to their atomic structure. In this study, we demonstrated that welding of Ag nanowires (NWs) encapsulated in graphene was stimulated by flux-optimized, high-energy electron beam irradiation (HEBI) under ambient conditions. This methodology can inhibit the oxidation of Ag NWs which is induced by the inevitably generated reactive ozone as well as improve of their electrical conductivity. We have systematically explored the effects of HEBI on Ag NWs and graphene. The optimized flux for HEBI welding of the Ag NWs with graphene was 150 kGy, which decreased the sheet resistance of the graphene/Ag NWs to 12 Ohm/sq. Following encapsulation with graphene, the initial chemical states of the Ag NWs were well-preserved after flux-tuned HEBI, whereas graphene underwent local HEBI-induced defect generation near the junction area. We further employed resonant Raman spectroscopy to follow the structural evolution of the sacrificial graphene in the hybrid film after HEBI. Notably, the sheet resistance of the welded Ag NWs encapsulated with graphene after HEBI was well-maintained even after 85 days.

A facile synthetic route to tungsten diselenide using a new precursor containing a long alkyl chain cation for multifunctional electronic and optoelectronic applications.

Single source precursors for coating and subsequent thermal decomposition processes enable a large-scale, low-cost synthesis of two-dimensional transition metal dichalcogenides (TMDs). However, practical applications based on two-dimensional TMDs have been limited by the lack of applicable single source precursors for the synthesis of p-type TMDs including layered tungsten diselenide (WSe2). We firstly demonstrate the simple and facile synthesis of WSe2 layers using a newly developed precursor that allows improved dispersibility and lower decomposition temperature. We study the thermal decomposition mechanism of three types of (Cat+)2[WSe4] precursors to assess the most suitable precursor for the synthesis of WSe2 layers. The resulting chemical and structural exploration of solution-processed WSe2 layers suggests that the (CTA)2[WSe4] may be a promising precursor because it resulted in the formation of high-crystalline WSe2. In addition, this study verifies the capability of WSe2 layers for multifunctional applications in optoelectronic and electronic devices. The photocurrent of WSe2-based photodetectors shows an abrupt switching behavior under periodic illumination of visible or IR light. The extracted photoresponsivity values for WSe2-based photodetectors recorded at 0.5 V correspond to 26.3 mA W-1 for visible light and 5.4 mA W-1 for IR light. The WSe2-based field effect transistors exhibit unipolar p-channel transistor behavior with a carrier mobility of 0.45 cm2 V-1 s-1 and an on-off ratio of ∼10.

Highly efficient and flexible photodetector based on MoS2-ZnO heterostructures.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) such as molybdenum disulfide (MoS2) and tungsten diselenide (WSe2), have recently attracted attention for their applicability as building blocks for fabricating advanced functional materials. In this study, a high quality hybrid material based on 2D TMD nanosheets and ZnO nanopatches was demonstrated. An organic promoter layer was employed for the large-scale growth of the TMD sheet, and atomic layer deposition (ALD) was utilized for the growth of ZnO nanopatches. Photodetectors based on 2D TMD nanosheets and ZnO nanopatches were successfully fabricated and investigated, which showed a high photoresponsivity of 2.7 A/W. Our novel approach is a promising and effective method for the fabrication of photodetectors with a new structure for application in TMD-based transparent and flexible optoelectronic devices.

Roll-to-Roll Production of Layer-Controlled Molybdenum Disulfide: A Platform for 2D Semiconductor-Based Industrial Applications.

A facile methodology for the large-scale production of layer-controlled MoS2 layers on an inexpensive substrate involving a simple coating of single source precursor with subsequent roll-to-roll-based thermal decomposition is developed. The resulting 50 cm long MoS2 layers synthesized on Ni foils possess excellent long-range uniformity and optimum stoichiometry. Moreover, this methodology is promising because it enables simple control of the number of MoS2 layers by simply adjusting the concentration of (NH4 )2 MoS4 . Additionally, the capability of the MoS2 for practical applications in electronic/optoelectronic devices and catalysts for hydrogen evolution reaction is verified. The MoS2 -based field effect transistors exhibit unipolar n-channel transistor behavior with electron mobility of 0.6 cm2 V-1 s-1 and an on-off ratio of ≈10³. The MoS2 -based visible-light photodetectors are fabricated in order to evaluate their photoelectrical properties, obtaining an 100% yield for active devices with significant photocurrents and extracted photoresponsivity of ≈22 mA W-1 . Moreover, the MoS2 layers on Ni foils exhibit applicable catalytic activity with observed overpotential of ≈165 mV and a Tafel slope of 133 mV dec-1 . Based on these results, it is envisaged that the cost-effective methodology will trigger actual industrial applications, as well as novel research related to 2D semiconductor-based multifaceted applications.

Dimensional-Hybrid Structures of 2D Materials with ZnO Nanostructures via pH-Mediated Hydrothermal Growth for Flexible UV Photodetectors.

Complementary combination of heterostructures is a crucial factor for the development of 2D materials-based optoelectronic devices. Herein, an appropriate solution for fabricating complementary dimensional-hybrid nanostructures comprising structurally tailored ZnO nanostructures and 2D materials such as graphene and MoS2 is suggested. Structural features of ZnO nanostructures hydrothermally grown on graphene and MoS2 are deliberately manipulated by adjusting the pH value of the growing solution, which will result in the formation of ZnO nanowires, nanostars, and nanoflowers. The detailed growth mechanism is further explored for the structurally tailored ZnO nanostructures on the 2D materials. Furthermore, a UV photodetector based on the dimensional-hybrid nanostructures is fabricated, which demonstrates their excellent photocurrent and mechanical durability. This can be understood by the existence of oxygen vacancies and oxygen-vacancies-induced band narrowing in the ZnO nanostructures, which is a decisive factor for determining their photoelectrical properties in the hybrid system.

Wafer-Scale, Homogeneous MoS2 Layers on Plastic Substrates for Flexible Visible-Light Photodetectors.

An appropriate solution is suggested for synthesizing wafer-scale, continuous, and stoichiometric MoS2 layers with spatial homogeneity at the low temperature of 450 °C. It is also demonstrated that the MoS2 -based visible-light photodetector arrays are both fabricated on 4 inch SiO2 /Si wafer and polyimide films, revealing 100% active devices with a narrow photocurrent distribution and excellent mechanical durability.