Defect Passivation of 2D Semiconductors by Fixating Chemisorbed Oxygen Molecules via h-BN Encapsulations.

Hexagonal boron nitride (h-BN) is a key ingredient for various 2D van der Waals heterostructure devices, but the exact role of h-BN encapsulation in relation to the internal defects of 2D semiconductors remains unclear. Here, it is reported that h-BN encapsulation greatly removes the defect-related gap states by stabilizing the chemisorbed oxygen molecules onto the defects of monolayer WS2 crystals. Electron energy loss spectroscopy (EELS) combined with theoretical analysis clearly confirms that the oxygen molecules are chemisorbed onto the defects of WS2 crystals and are fixated by h-BN encapsulation, with excluding a possibility of oxygen molecules trapped in bubbles or wrinkles formed at the interface between WS2 and h-BN. Optical spectroscopic studies show that h-BN encapsulation prevents the desorption of oxygen molecules over various excitation and ambient conditions, resulting in a greatly lowered and stabilized free electron density in monolayer WS2 crystals. This suppresses the exciton annihilation processes by two orders of magnitude compared to that of bare WS2. Furthermore, the valley polarization becomes robust against the various excitation and ambient conditions in the h-BN encapsulated WS2 crystals.

Reversible Transition of Semiconducting PtSe2 and Metallic PtTe2 for Scalable All-2D Edge-Contacted FETs.

Two-dimensional (2D) transition metal dichalcogenide (TMD) layers are highly promising as field-effect transistor (FET) channels in the atomic-scale limit. However, accomplishing this superiority in scaled-up FETs remains challenging due to their van der Waals (vdW) bonding nature with respect to conventional metal electrodes. Herein, we report a scalable approach to fabricate centimeter-scale all-2D FET arrays of platinum diselenide (PtSe2) with in-plane platinum ditelluride (PtTe2) edge contacts, mitigating the aforementioned challenges. We realized a reversible transition between semiconducting PtSe2 and metallic PtTe2 via a low-temperature anion exchange reaction compatible with the back-end-of-line (BEOL) processes. All-2D PtSe2 FETs seamlessly edge-contacted with transited metallic PtTe2 exhibited significant performance improvements compared to those with surface-contacted gold electrodes, e.g., an increase of carrier mobility and on/off ratio by over an order of magnitude, achieving a maximum hole mobility of ∼50.30 cm2 V-1 s-1 at room temperature. This study opens up new opportunities toward atomically thin 2D-TMD-based circuitries with extraordinary functionalities.

In situ synthesis of hierarchically-assembled three-dimensional ZnS nanostructures and 3D printed visualization.

Nanomaterials have gained enormous interest in improving the performance of energy harvest systems, biomedical devices, and high-strength composites. Many studies were performed fabricating more elaborate and heterogeneous nanostructures then the structures were characterized using TEM tomographic images, upgrading the fabrication technique. Despite the effort, intricate fabrication process, agglomeration characteristic, and non-uniform output were still limited to presenting the 3D panoramic views straightforwardly. Here we suggested in situ synthesis method to prepare complex and hierarchically-assembled nanostructures that consisted of ZnS nanowire core and nanoparticles under Ag2S catalyst. We demonstrated that the vaporized Zn and S were solidified in different shapes of nanostructures with the temperatures solely. To our knowledge, this is the first demonstration of synthesizing heterogeneous nanostructures, consisting of a nanowire from the vapor-liquid-solid and then nanoparticles from the vapor-solid grown mechanism by in situ temperature control. The obtained hierarchically-assembled ZnS nanostructures were characterized by various TEM technologies, verifying the crystal growth mechanism. Lastly, electron tomography and 3D printing enabled the nanoscale structures to visualize with centimeter scales. The 3D printing from randomly fabricated nanomaterials is rarely performed to date. The collaborating work could offer a better opportunity to fabricate advanced and sophisticated nanostructures.

Large-area vertically aligned 2D MoS2layers on TEMPO-cellulose nanofibers for biodegradable transient gas sensors.

Crystallographically anisotropic two-dimensional (2D) molybdenum disulfide (MoS2) with vertically aligned (VA) layers is attractive for electrochemical sensing owing to its surface-enriched dangling bonds coupled with extremely large mechanical deformability. In this study, we explored VA-2D MoS2layers integrated on cellulose nanofibers (CNFs) for detecting various volatile organic compound gases. Sensor devices employing VA-2D MoS2/CNFs exhibited excellent sensitivities for the tested gases of ethanol, methanol, ammonia, and acetone; e.g. a high response rate up to 83.39% for 100 ppm ethanol, significantly outperforming previously reported sensors employing horizontally aligned 2D MoS2layers. Furthermore, VA-2D MoS2/CNFs were identified to be completely dissolvable in buffer solutions such as phosphate-buffered saline solution and baking soda buffer solution without releasing toxic chemicals. This unusual combination of high sensitivity and excellent biodegradability inherent to VA-2D MoS2/CNFs offers unprecedented opportunities for exploring mechanically reconfigurable sensor technologies with bio-compatible transient characteristics.

Multiwavelength Optoelectronic Synapse with 2D Materials for Mixed-Color Pattern Recognition.

Neuromorphic visual systems emulating biological retina functionalities have enormous potential for in-sensor computing, with prospects of making artificial intelligence ubiquitous. Conventionally, visual information is captured by an image sensor, stored by memory units, and eventually processed by the machine learning algorithm. Here, we present an optoelectronic synapse device with multifunctional integration of all the processes required for real time object identification. Ultraviolet-visible wavelength-sensitive MoS2 FET channel with infrared sensitive PtTe2/Si gate electrode enables the device to sense, store, and process optical data for a wide range of the electromagnetic spectrum, while maintaining a low dark current. The device exhibits optical stimulation-controlled short-term and long-term potentiation, electrically driven long-term depression, synaptic weight update for multiple wavelengths of light ranging from 300 nm in ultraviolet to 2 µm in infrared. An artificial neural network developed using the extracted weight update parameters of the device can be trained to identify both single wavelength and mixed wavelength patterns. This work demonstrates a device that could potentially be used for realizing a multiwavelength neuromorphic visual system for pattern recognition and object identification.

Peel-and-Stick Integration of Atomically Thin Nonlayered PtS Semiconductors for Multidimensionally Stretchable Electronic Devices.

Various near-atom-thickness two-dimensional (2D) van der Waals (vdW) crystals with unparalleled electromechanical properties have been explored for transformative devices. Currently, the availability of 2D vdW crystals is rather limited in nature as they are only obtained from certain mother crystals with intrinsically possessed layered crystallinity and anisotropic molecular bonding. Recent efforts to transform conventionally non-vdW three-dimensional (3D) crystals into ultrathin 2D-like structures have seen rapid developments to explore device building blocks of unique form factors. Herein, we explore a "peel-and-stick" approach, where a nonlayered 3D platinum sulfide (PtS) crystal, traditionally known as a cooperate mineral material, is transformed into a freestanding 2D-like membrane for electromechanical applications. The ultrathin (∼10 nm) 3D PtS films grown on large-area (>cm2) silicon dioxide/silicon (SiO2/Si) wafers are precisely "peeled" inside water retaining desired geometries via a capillary-force-driven surface wettability control. Subsequently, they are "sticked" on strain-engineered patterned substrates presenting prominent semiconducting properties, i.e., p-type transport with an optical band gap of ∼1.24 eV. A variety of mechanically deformable strain-invariant electronic devices have been demonstrated by this peel-and-stick method, including biaxially stretchable photodetectors and respiratory sensing face masks. This study offers new opportunities of 2D-like nonlayered semiconducting crystals for emerging mechanically reconfigurable and stretchable device technologies.

Microwave-assisted thermochemical conversion of Zr-FeOOH nanorods to Zr-ZnFe2O4 nanorods for bacterial disinfection and photo-Fenton catalytic degradation of organic pollutants.

Herein, we report a CoOx-loaded Zr-doped ZnFe2O4 (CoOx/Zr-ZFO) NR photocatalyst synthesized by successive microwave and wet impregnation methods for bacterial inactivation and degradation of organic pollutants. For the first time, microwave treatment was used for Zn attachment on hydrothermally synthesized self-assembled Zr-FeOOH NRs to produce Zr-doped ZnFe2O4 (Zr-ZFO) NRs. The lowest bandgap energy (1.96 eV) enables for significant absorption in the visible light region, which helps to improve bacteria degradation inactivation efficiency. Further, various metal oxides (Cu, Ag and Co) were loaded onto the surface of photocatalysts (Zr-ZFO NRs) by a wet impregnation method. As-synthesized CoOx/Zr-ZFO-3 NRs were systematically characterized and used as photocatalysts for inactivation of E. coli and S. aureus and degradation of organic pollutants. The CoOx/Zr-ZFO-3 NR photocatalyst exhibited better inactivation efficiency (99.4 %) than other metal oxide-loaded Zr-ZFO NRs (Ag2Ox-loaded Zr-ZFO NRs (33.6 %), CuOx-loaded Zr-ZFO NRs (77.6 %)). Additionally, the optimum CoOx/Zr-ZFO-3 NR photocatalyst showed 98.3 % and 98.1 % degradation efficiencies for BPA and orange II dye, respectively, under visible light irradiation (λ ≥ 420 nm). Therefore, this work affords a novel, simple and rapid approach for the development of photocatalysts which active in visible light for bacterial disinfection and organic degradation.

MoS2 Synapses with Ultra-low Variability and Their Implementation in Boolean Logic.

Brain-inspired computing enabled by memristors has gained prominence over the years due to the nanoscale footprint and reduced complexity for implementing synapses and neurons. The demonstration of complex neuromorphic circuits using conventional materials systems has been limited by high cycle-to-cycle and device-to-device variability. Two-dimensional (2D) materials have been used to realize transparent, flexible, ultra-thin memristive synapses for neuromorphic computing, but with limited knowledge on the statistical variation of devices. In this work, we demonstrate ultra-low-variability synapses using chemical vapor deposited 2D MoS2 as the switching medium with Ti/Au electrodes. These devices, fabricated using a transfer-free process, exhibit ultra-low variability in SET voltage, RESET power distribution, and synaptic weight update characteristics. This ultra-low variability is enabled by the interface rendered by a Ti/Au top contact on Si-rich MoS2 layers of mixed orientation, corroborated by transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), and X-ray photoelectron spectroscopy (XPS). TEM images further confirm the stability of the device stack even after subjecting the device to 100 SET-RESET cycles. Additionally, we implement logic gates by monolithic integration of MoS2 synapses with MoS2 leaky integrate-and-fire neurons to show the viability of these devices for non-von Neumann computing.

Efficient Suppression of Charge Recombination in Self-Powered Photodetectors with Band-Aligned Transferred van der Waals Metal Electrodes.

Recombination of photogenerated electron-hole pairs dominates the photocarrier lifetime and then influences the performance of photodetectors and solar cells. In this work, we report the design and fabrication of band-aligned van der Waals-contacted photodetectors with atomically sharp and flat metal-semiconductor interfaces through transferred metal integration. A unity factor α is achieved, which is essentially independent of the wavelength of the light, from ultraviolet to near-infrared, indicating effective suppression of charge recombination by the device. The short-circuit current (0.16 µA) and open-circuit voltage (0.72 V) of the band-aligned van der Waals-contacted devices are at least 1 order of magnitude greater than those of band-aligned deposited devices and 2 orders of magnitude greater than those of non-band-aligned deposited devices. High responsivity, detectivity, and polarization sensitivity ratio of 283 mA/W, 6.89 × 1012 cm Hz1/2 W-1, and 3.05, respectively, are also obtained for the device at zero bias. Moreover, the efficient suppression of charge recombination in our air-stable self-powered photodetectors also results in a fast response speed and leads to polarization-sensitive performance.

Crystal Phase Transition Creates a Highly Active and Stable RuCX Nanosurface for Hydrogen Evolution Reaction in Alkaline Media.

Although metastable crystal structures have received much attention owing to their utilization in various fields, their phase-transition to a thermodynamic structure has attracted comparably little interest. In the case of nanoscale crystals, such an exothermic phase-transition releases high energy within a confined surface area and reconstructs surface atomic arrangement in a short time. Thus, this high-energy nanosurface may create novel crystal structures when some elements are supplied. In this work, the creation of a ruthenium carbide (RuCX , X < 1) phase on the surface of the Ru nanocrystal is discovered during phase-transition from cubic-close-packed to hexagonal-close-packed structure. When the electrocatalytic hydrogen evolution reaction (HER) is tested in alkaline media, the RuCX exhibits a much lower overpotential and good stability relative to the counterpart Ru-based catalysts and the state-of-the-art Pt/C catalyst. Density functional theory calculations predict that the local heterogeneity of the outermost RuCX surface promotes the bifunctional HER mechanism by providing catalytic sites for both H adsorption and facile water dissociation.

Efficient and additive-free synthesis of morphology variant iron oxyhydroxide nanostructures for phosphate adsorption application.

Iron oxyhydroxide (FeOOH) nanostructures of different shapes were successfully synthesized on flexible textile cloth of polyester using a novel and simple technique based on hydrolysis method. The technique used herein is newly designed specifically to improve the efficiency in terms of energy, simplicity and cost involved in large scale synthesis of nanostructured thin films. Additionally, the morphology of nano-sized iron oxyhydroxide could be tuned into different shapes through variation in the type of precursors used for synthesis. The uniformity and adhesion of the depositions were also found to be excellent as examined by qualitative techniques. The as-deposited samples exhibited monoclinic and orthorhombic structures of FeOOH. A significant variation in the shape of as-deposited FeOOH nanostructures with change in precursor was observed through morphological studies, which displayed lance-shaped, rounded clusters and rod-like growth features in different cases. The nanocrystalline FeOOH can be directly applied to attract and trap phosphate from water reservoirs, thus contributing to environmental solutions. The proposed technique can also be utilized to deposit larger areas, which could be suitable for practical applications.

Scalable Van der Waals Two-Dimensional PtTe2 Layers Integrated onto Silicon for Efficient Near-to-Mid Infrared Photodetection.

In recent years, there has been increasing interest in leveraging two-dimensional (2D) van der Waals (vdW) crystals for infrared (IR) photodetection, exploiting their unusual optoelectrical properties. Some 2D vdW materials with small band gap energies such as graphene and black phosphorus have been explored as stand-alone IR responsive layers in photodetectors. However, the devices incorporating these IR-sensitive 2D layers often exhibited poor performances owing to their preparation issues such as limited scalability and air instability. Herein, we explored wafer-scale 2D platinum ditelluride (PtTe2) layers for near-to-mid IR photodetection by directly growing them onto silicon (Si) wafers. 2D PtTe2/Si heterojunctions exhibited wavelength- and intensity-dependent high photocurrents in a spectral range of ∼1-7 µm, significantly outperforming stand-alone 2D PtTe2 layers. The observed superiority is attributed to their excellent Schottky junction characteristics accompanying suppressed carrier recombination as well as optical absorbance competition between 2D PtTe2 layers and Si. The direct and scalable growth of 2D PtTe2 layers was further extended to demonstrate mechanically flexible IR photodetectors.

Mechanically rollable photodetectors enabled by centimetre-scale 2D MoS2 layer/TOCN composites.

Two-dimensional (2D) molybdenum disulfide (MoS2) layers are suitable for visible-to-near infrared photodetection owing to their tunable optical bandgaps. Also, their superior mechanical deformability enabled by an extremely small thickness and van der Waals (vdW) assembly allows them to be structured into unconventional physical forms, unattainable with any other materials. Herein, we demonstrate a new type of 2D MoS2 layer-based rollable photodetector that can be mechanically reconfigured while maintaining excellent geometry-invariant photo-responsiveness. Large-area (>a few cm2) 2D MoS2 layers grown by chemical vapor deposition (CVD) were integrated on transparent and flexible substrates composed of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibers (TOCNs) by a direct solution casting method. These composite materials in three-dimensionally rollable forms exhibited a large set of intriguing photo-responsiveness, well preserving intrinsic opto-electrical characteristics of the integrated 2D MoS2 layers; i.e., light intensity-dependent photocurrents insensitive to illumination angles as well as highly tunable photocurrents varying with the rolling number of 2D MoS2 layers, which were impossible to achieve with conventional photodetectors. This study provides a new design principle for converting 2D materials to three-dimensional (3D) objects of tailored functionalities and structures, significantly broadening their potential and versatility in futuristic devices.

Large-area 2D PtTe2/silicon vertical-junction devices with ultrafast and high-sensitivity photodetection and photovoltaic enhancement by integrating water droplets.

2D PtTe2 layers, a relatively new class of 2D crystals, have unique band structure and remarkably high electrical conductivity promising for emergent opto-electronics. This intrinsic superiority can be further leveraged toward practical device applications by merging them with mature 3D semiconductors, which has remained largely unexplored. Herein, we explored 2D/3D heterojunction devices by directly growing large-area (>cm2) 2D PtTe2 layers on Si wafers using a low-temperature CVD method and unveiled their superior opto-electrical characteristics. The devices exhibited excellent Schottky transport characteristics essential for high-performance photovoltaics and photodetection, i.e., well-balanced combination of high photodetectivity (>1013 Jones), small photo-responsiveness time (∼1 µs), high current rectification ratio (>105), and water super-hydrophobicity driven photovoltaic improvement (>300%). These performances were identified to be superior to those of previously explored 2D/3D or 2D layer-based devices with much smaller junction areas, and their underlying principles were confirmed by DFT calculations.

Vertically Aligned 2D MoS2 Layers with Strain-Engineered Serpentine Patterns for High-Performance Stretchable Gas Sensors: Experimental and Theoretical Demonstration.

Two-dimensional (2D) molybdenum disulfide (MoS2) with vertically aligned (VA) layers exhibits significantly enriched surface-exposed edge sites with an abundance of dangling bonds owing to its intrinsic crystallographic anisotropy. Such structural variation renders the material with exceptionally high chemical reactivity and chemisorption ability, making it particularly attractive for high-performance electrochemical sensing. This superior property can be further promoted as far as it is integrated on mechanically stretchable substrates well retaining its surface-exposed defective edges, projecting opportunities for a wide range of applications utilizing its structural uniqueness and mechanical flexibility. In this work, we explored VA-2D MoS2 layers configured in laterally stretchable forms for multifunctional nitrogen dioxide (NO2) gas sensors. Large-area (>cm2) VA-2D MoS2 layers grown by a chemical vapor deposition (CVD) method were directly integrated onto a variety of flexible substrates with serpentine patterns judiciously designed to accommodate a large degree of tensile strain. These uniquely structured VA-2D MoS2 layers were demonstrated to be highly sensitive to NO2 gas of controlled concentration preserving their intrinsic structural and chemical integrity, e.g., significant current response ratios of ∼160-380% upon the introduction of NO2 at a level of 5-30 ppm. Remarkably, they exhibited such a high sensitivity even under lateral stretching up to 40% strain, significantly outperforming previously reported 2D MoS2 layer-based NO2 gas sensors of any structural forms. Underlying principles for the experimentally observed superiority were theoretically unveiled by density functional theory (DFT) calculation and finite element method (FEM) analysis. The intrinsic high sensitivity and large stretchability of VA-2D MoS2 layers confirmed in this study are believed to be applicable in sensing diverse gas species, greatly broadening their versatility in stretchable and wearable technologies.

High-performance flexible asymmetric supercapacitor based on rGO anode and WO3/WS2 core/shell nanowire cathode.

Flexible smart electronics require their energy storage device to be flexible in nature. Developing high-performance flexible energy storage devices require direct integration of electrode active materials on current collectors to satisfy the high electronic/ionic conductivity and long-term durability requirements. Herein, we develop a flexible all-solid-state asymmetric supercapacitor comprised of reduced graphene oxide (rGO) and core/shell tungsten trioxide/tungsten disulfide (WO3/WS2) nanowire based electrodes. The electrodes synthesized via electrochemical deposition and chemical vapor deposition avoided the necessity to use non-conductive binders and offered excellent cyclic stability. The structural integrity provided by the rGO and WO3/WS2 electrodes facilitated excellent electrochemical stability with capacitance retention of 90% and 100% after 10 000 charge-discharge cycles, respectively. An all-solid-state device provides a voltage window of 1.5 V and more than 70% capacitance retention after 10 000 charge-discharge cycles. Providing 97% capacitance retention upon mechanical bending reveals its potential to be used as an energy storage devices in flexible electronics.

Wafer-Scale Two-Dimensional MoS2 Layers Integrated on Cellulose Substrates Toward Environmentally Friendly Transient Electronic Devices.

We explored the feasibility of wafer-scale two-dimensional (2D) molybdenum disulfide (MoS2) layers toward futuristic environmentally friendly electronics that adopt biodegradable substrates. Large-area (> a few cm2) 2D MoS2 layers grown on silicon dioxide/silicon (SiO2/Si) wafers were delaminated and integrated onto a variety of cellulose-based substrates of various components and shapes in a controlled manner; examples of the substrates include planar papers, cylindrical natural rubbers, and 2,2,6,6-tetramethylpiperidine-1-oxyl-oxidized cellulose nanofibers. The integrated 2D layers were confirmed to well preserve their intrinsic structural and chemical integrity even on such exotic substrates. Proof-of-concept devices employing large-area 2D MoS2 layers/cellulose substrates were demonstrated for a variety of applications, including photodetectors, pressure sensors, and field-effect transistors. Furthermore, we demonstrated the complete "dissolution" of the integrated 2D MoS2 layers in a buffer solution composed of baking soda and deionized water, confirming their environmentally friendly transient characteristics. Moreover, the approaches to delaminate and integrate them do not demand any chemicals except for water, and their original substrates can be recycled for subsequent growths, ensuring excellent chemical benignity and process sustainability.

Wafer-scale 2D PtTe2 layers for high-efficiency mechanically flexible electro-thermal smart window applications.

Two-dimensional (2D) transition metal dichalcogenide (TMD) layers have gained increasing attention for a variety of emerging electrical, thermal, and optical applications. Recently developed metallic 2D TMD layers have been projected to exhibit unique attributes unattainable in their semiconducting counterparts; e.g., much higher electrical and thermal conductivities coupled with mechanical flexibility. In this work, we explored 2D platinum ditelluride (2D PtTe2) layers - a relatively new class of metallic 2D TMDs - by studying their previously unexplored electro-thermal properties for unconventional window applications. We prepared wafer-scale 2D PtTe2 layer-coated optically transparent and mechanically flexible willow glasses via a thermally-assisted tellurization of Pt films at a low temperature of 400 °C. The 2D PtTe2 layer-coated windows exhibited a thickness-dependent optical transparency and electrical conductivity of >106 S m-1 - higher than most of the previously explored 2D TMDs. Upon the application of electrical bias, these windows displayed a significant increase in temperature driven by Joule heating as confirmed by the infrared (IR) imaging characterization. Such superior electro-thermal conversion efficiencies inherent to 2D PtTe2 layers were utilized to demonstrate various applications, including thermochromic displays and electrically-driven defogging windows accompanying mechanical flexibility. Comparisons of these performances confirm the superiority of the wafer-scale 2D PtTe2 layers over other nanomaterials explored for such applications.

Automated Assembly of Wafer-Scale 2D TMD Heterostructures of Arbitrary Layer Orientation and Stacking Sequence Using Water Dissoluble Salt Substrates.

We report a novel strategy to assemble wafer-scale two-dimensional (2D) transition metal dichalcogenide (TMD) layers of well-defined components and orientations. We directly grew a variety of 2D TMD layers on "water-dissoluble" single-crystalline salt wafers and precisely delaminated them inside water in a chemically benign manner. This manufacturing strategy enables the automated integration of vertically aligned 2D TMD layers as well as 2D/2D heterolayers of arbitrary stacking orders on exotic substrates insensitive to their kind and shape. Furthermore, the original salt wafers can be recycled for additional growths, confirming high process sustainability and scalability. The generality and versatility of this approach have been demonstrated by developing proof-of-concept "all 2D" devices for diverse yet unconventional applications. This study is believed to shed a light on leveraging opportunities of 2D TMD layers toward achieving large-area mechanically reconfigurable devices of various form factors at the industrially demanded scale.

Thickness-Independent Semiconducting-to-Metallic Conversion in Wafer-Scale Two-Dimensional PtSe2 Layers by Plasma-Driven Chalcogen Defect Engineering.

Platinum diselenide (PtSe2) is an emerging class of two-dimensional (2D) transition-metal dichalcogenide (TMD) crystals recently gaining substantial interest, owing to its extraordinary properties absent in conventional 2D TMD layers. Most interestingly, it exhibits a thickness-dependent semiconducting-to-metallic transition, i.e., thick 2D PtSe2 layers, which are intrinsically metallic, become semiconducting with their thickness reduced below a certain point. Realizing both semiconducting and metallic phases within identical 2D PtSe2 layers in a spatially well-controlled manner offers unprecedented opportunities toward atomically thin tailored electronic junctions, unattainable with conventional materials. In this study, beyond this thickness-dependent intrinsic semiconducting-to-metallic transition of 2D PtSe2 layers, we demonstrate that controlled plasma irradiation can "externally" achieve such tunable carrier transports. We grew wafer-scale very thin (a few nm) 2D PtSe2 layers by a chemical vapor deposition (CVD) method and confirmed their intrinsic semiconducting properties. We then irradiated the material with argon (Ar) plasma, which was intended to make it more semiconducting by thickness reduction. Surprisingly, we discovered a reversed transition of semiconducting to metallic, which is opposite to the prediction concerning their intrinsic thickness-dependent carrier transports. Through extensive structural and chemical characterization, we identified that the plasma irradiation introduces a large concentration of near-atomic defects and selenium (Se) vacancies in initially stoichiometric 2D PtSe2 layers. Furthermore, we performed density functional theory (DFT) calculations and clarified that the band-gap energy of such defective 2D PtSe2 layers gradually decreases with increasing defect concentration and dimensions, accompanying a large number of midgap energy states. This corroborative experimental and theoretical study decisively verifies the fundamental mechanism for this externally controlled semiconducting-to-metallic transition in large-area CVD-grown 2D PtSe2 layers, greatly broadening their versatility for futuristic electronics.