Nanoscale three-dimensional fabrication based on mechanically guided assembly.

The growing demand for complex three-dimensional (3D) micro-/nanostructures has inspired the development of the corresponding manufacturing techniques. Among these techniques, 3D fabrication based on mechanically guided assembly offers the advantages of broad material compatibility, high designability, and structural reversibility under strain but is not applicable for nanoscale device printing because of the bottleneck at nanofabrication and design technique. Herein, a configuration-designable nanoscale 3D fabrication is suggested through a robust nanotransfer methodology and design of substrate's mechanical characteristics. Covalent bonding-based two-dimensional nanotransfer allowing for nanostructure printing on elastomer substrates is used to address fabrication problems, while the feasibility of configuration design through the modulation of substrate's mechanical characteristics is examined using analytical calculations and numerical simulations, allowing printing of various 3D nanostructures. The printed nanostructures exhibit strain-independent electrical properties and are therefore used to fabricate stretchable H2 and NO2 sensors with high performances stable under external strains of 30%.

An Ultralow Power Mixed Dimensional Heterojunction Transistor Based on the Charge Plasma pn Junction.

Development of a reliable doping method for 2D materials is a key issue to adopt the materials in the future microelectronic circuits and to replace the silicon, keeping the Moore's law toward the sub-10 nm channel length. Especially hole doping is highly required, because most of the transition metal dichalcogenides (TMDC) among the 2D materials are electron-doped by sulfur vacancies in their atomic structures. Here, hole doping of a TMDC, tungsten disulfide (WS2 ) using the silicon substrate as the dopant medium is demonstrated. An ultralow-power current sourcing transistor or a gated WS2 pn diode is fabricated based on a charge plasma pn heterojunction formed between the WS2 thin-film and heavily doped bulk silicon. An ultralow switchable output current down to 0.01 nA µm-1 , an off-state current of ≈1 × 10-14 A µm-1 , a static power consumption range of 1 fW µm-1 -1 pW µm-1 , and an output current ratio of 103 at 0.1 V supply voltage are achieved. The charge plasma heterojunction allows a stable (less than 3% variation) output current regardless of the gate voltage once it is turned on.

Radiative pattern of intralayer and interlayer excitons in two-dimensional WS2/WSe2 heterostructure.

Two-dimensional (2D) heterostructures (HS) formed by transition-metal dichalcogenide (TMDC) monolayers offer a unique platform for the study of intralayer and interlayer excitons as well as moiré-pattern-induced features. Particularly, the dipolar charge-transfer exciton comprising an electron and a hole, which are confined to separate layers of 2D semiconductors and Coulomb-bound across the heterojunction interface, has drawn considerable attention in the research community. On the one hand, it bears significance for optoelectronic devices, e.g. in terms of charge carrier extraction from photovoltaic devices. On the other hand, its spatially indirect nature and correspondingly high longevity among excitons as well as its out-of-plane dipole orientation render it attractive for excitonic Bose-Einstein condensation studies, which address collective coherence effects, and for photonic integration schemes with TMDCs. Here, we demonstrate the interlayer excitons' out-of-plane dipole orientation through angle-resolved spectroscopy of the HS photoluminescence at cryogenic temperatures, employing a tungsten-based TMDC HS. Within the measurable light cone, the directly-obtained radiation profile of this species clearly resembles that of an in-plane emitter which deviates from that of the intralayer bright excitons as well as the other excitonic HS features recently attributed to artificial superlattices formed by moiré patterns.

Nanogap Formation Using a Chromium Oxide Film and Its Application as a Palladium Hydrogen Switch.

Developing high response hydrogen sensors manufacturable in a large scale is desirable in hydrogen industry. In this study, a chromium oxidation-based nanogap formation process was developed to fabricate a hydrogen switch with suspended palladium and gold films having a tens of nanometer-sized gap. The nanogap was formed by using oxidized chromium as a self-alignment shadow mask. The hydrogen switch operates by the principle of volume expansion of palladium upon exposure to the hydrogen gas and the current reading by closing of a nanogap formed between suspended palladium and gold films. Further improvement of the sensor performance was achieved by optimizing the design parameters such as suspended film lengths and thicknesses. The fabricated palladium nanogap hydrogen sensor showed an ultrahigh sensitivity of ΔI/I0 > 108 with a fast response time (22 s) to 4% hydrogen. The complementary metal-oxide-semiconductor-compatible fabrication of the hydrogen switch is easily scalable with low manufacturing cost.

Improving the Optical Quality of MoSe2 and WS2 Monolayers with Complete h-BN Encapsulation by High-Temperature Annealing.

We improved the optical quality and stability of an exfoliated monolayer (ML) MoSe2 and chemical vapor deposition (CVD)-grown WS2 MLs by encapsulating and sealing them with both top and bottom few-layer h-BN, as tested by subsequent high-temperature annealing up to 873 K and photoluminescence (PL) measurements. These transition-metal dichalcogenide (TMD) MLs remained stable up to this maximum temperature, as seen visually. After the heating/cooling cycle, the integrated photoluminescence (PL) intensity at 300 K in the MoSe2 ML was ∼4 times larger than that before heating and that from exciton and trion PL in the analogous WS2 ML sample was ∼14 times and ∼2.5 times larger at 77 K and the exciton peak was ∼9.5 times larger at 300 K. This is attributed to the reduction of impurities, the lateral expulsion of contamination leading to clean and atomically flat surfaces, and the sealing provided by the h-BN layers that prevents the diffusion of molecules such as trace O2 and H2O to the TMD ML. Stability and optical performance are much improved compared to that in earlier work using top h-BN only, in which the WS2 ML PL intensity decreased even for an optimal gas environment. This complete encapsulation is particularly promising for CVD-grown TMD MLs because they have relatively more charge and other impurities than do exfoliated MLs. These results open a new route for improving the optical properties of TMD MLs and their performance and applications both at room and higher temperatures.

Effectiveness of high curvature segmentation on the curved flexible surface plasmon resonance.

In this report, we explore a segmentation-based approach for the calculation of surface plasmon resonance (SPR) on the curved surface with high curvature by modeling it as a contiguous array of finite segments. The approach would significantly facilitate the calculation with good accuracy because of the inherent nature that transfer matrix analysis can be used. Using the segmentation model, resonance characteristics at SPR were obtained as the curvature radius was varied. For validation of the segmentation, resonance wavelength (λSPR), reflectance at resonance (RSPR), and resonance width (δλSPR) were compared with the finite element method in the parallel and perpendicular light incidence. It was found that the results from the segmentation were in excellent agreement, λSPR in particular, while RSPR and δλSPR under parallel incidence showed disparity between the two models due to the short segmentation. Resonance of curved surface on the rigid and flexible substrate was compared and the overall trend was found to be almost identical. The segmentation is expected to provide a simple, fast, and efficient way for studying plasmonic devices with high curvature in flexible and wearable applications.

Stabilization of Chemical-Vapor-Deposition-Grown WS2 Monolayers at Elevated Temperature with Hexagonal Boron Nitride Encapsulation.

Chemical vapor deposition (CVD)-grown flakes of high-quality monolayers of WS2 can be stabilized at elevated temperatures by encapsulation with several layer hexagonal boron nitride (h-BN), but to different degrees in the presence of ambient air, flowing N2, and flowing forming gas (95% N2, 5% H2). The best passivation of WS2 at elevated temperature occurs for h-BN-covered samples with flowing N2 (after heating to 873 K), as judged by optical microscopy and photoluminescence (PL) intensity after a heating/cooling cycle. Stability is worse for uncovered samples, but best with flowing forming gas. PL from trions, in addition to that from excitons, is seen for covered WS2 only for forming gas, during cooling below ∼323 K; the trion has an estimated binding energy of ∼28 meV. It might occur because of doping level changes caused by charge defect generation by H2 molecules diffusing between the h-BN and the SiO2/Si substrate. The decomposition of uncovered WS2 flakes in air suggests a dissociation and chemisorption energy barrier of O2 on the WS2 surface of ∼1.6 eV. Fitting the high-temperature PL intensities in air gives a binding energy of a free exciton of ∼229 meV.

Nanoslot metasurface design and characterization for enhanced organic light-emitting diodes.

We investigate bottom-emitting organic light-emitting diodes (B-OLEDs) integrated with metasurface (MS) to analyze the effect of the structural parameters on the output performance. The performance of the MS-integrated B-OLED (MIB-OLED) is evaluated by out-coupling efficiency (OCE) and reflection of the ambient light, while attention is paid mainly to dielectric capping and metal structure of MS that may influence excitation of surface plasmon (SP). The results suggest that layer thicknesses affect the performance by as much as 10% for the OCE and up to 32% for reflectance. The OCE is in general weakly affected by the structural parameters of MS. In contrast, the reflectance characteristics are found to be dominated by localized SP that is largely determined by the length and the width of a unit slot of MS. An optimization factor introduced to evaluate the performance based on out-coupling power to the radiation mode and reflectance of MIB-OLEDs confirms that integration with MS improves performance by 16% over conventional planar structure. In particular, MIB-OLED is found to enhance OCE by 51% with Lambertian-like pattern. Enhanced performance is experimentally confirmed. The findings provide insights on how to optimize the MS structure to produce MIB-OLEDs with enhanced out-coupled power and contrast ratio.

Chemo-Mechanically Operating Palladium-Polymer Nanograting Film for a Self-Powered H2 Gas Sensor.

This study proposes a reliable and self-powered hydrogen (H2) gas sensor composed of a chemo-mechanically operating nanostructured film and photovoltaic cell. Specifically, the nanostructured film has a configuration in which an asymmetrically coated palladium (Pd) film is coated on a periodic polyurethane acrylate (PUA) nanograting. The asymmetric Pd nanostructures, optimized by a finite element method simulation, swell upon reacting with H2 and thereby bend the PUA nanograting, changing the amount of transmitted light and the current output of the photovoltaic cell. Since the degree of warping is determined by the concentration of H2 gas, a wide concentration range of H2 (0.1-4.0%) can be detected by measuring the self-generated electrical current of the photovoltaic cell without external power. The normalized output current changes are ∼1.5%, ∼2.8%, ∼3.5%, ∼5.0%, ∼21.5%, and 25.3% when the concentrations of H2 gas are 0.1%, 0.5%, 1.0%, 1.6%, 2%, and 4%, respectively. Moreover, because Pd is highly chemically reactive to H2 and also because there is no electrical current applied through Pd, the proposed sensor can avoid device failure due to the breakage of the Pd sensing material, resulting in high reliability, and can show high selectivity against various gases such as carbon monoxide, hydrogen sulfide, nitrogen dioxide, and water vapor. Finally, using only ambient visible light, the sensor was modularized to produce an alarm in the presence of H2 gas, verifying a potential always-on H2 gas monitoring application.

Surface Plasmon Localization-Based Super-resolved Raman Microscopy.

We investigate label-free measurement of molecular distribution by super-resolved Raman microscopy using surface plasmon (SP) localization. Localized SP was formed with plasmonic nanopost arrays (PNAs) for measurement of the molecular distribution in HeLa cells. Compared with conventional Raman microscopy on gold thin films, PNAs induce a localized near-field, which allows for the enhancement of the peak signal-to-noise ratio by as much as 4.5 dB in the Raman shifts. Super-resolved distributions of aromatic amino acids and lipids (C-C stretching and C-H2 twist mode) as targets in HeLa cells were obtained after image reconstruction. Results show almost 4-fold improvement on average in the lateral precision over conventional diffraction-limited Raman microscopy images. Combined with axial imaging in an evanescent field, the results suggest an improvement in optical resolution due to superlocalized light volume by more than an order of magnitude over that of conventional diffraction-limited Raman microscopy.

The effects of substitutional Fe-doping on magnetism in MoS2and WS2monolayers.

Doping of two-dimensional (2D) semiconductors has been intensively studied toward modulating their electrical, optical, and magnetic properties. While ferromagnetic 2D semiconductors hold promise for future spintronics and valleytronics, the origin of ferromagnetism in 2D materials remains unclear. Here, we show that substitutional Fe-doping of MoS2and WS2monolayers induce different magnetic properties. The Fe-doped monolayers are directly synthesized via chemical vapor deposition. In both cases, Fe substitutional doping is successfully achieved, as confirmed using scanning transmission electron microscopy. While both Fe:MoS2and Fe:WS2show PL quenching and n-type doping, Fe dopants in WS2monolayers are found to assume deep-level trap states, in contrast to the case of Fe:MoS2, where the states are found to be shallow. Usingµm- and mm-precision local NV-magnetometry and superconducting quantum interference device, we discover that, unlike MoS2monolayers, WS2monolayers do not show a magnetic phase transition to ferromagnetism upon Fe-doping. The absence of ferromagnetism in Fe:WS2is corroborated using density functional theory calculations.

Buffered Oxide Etchant Post-Treatment of a Silicon Nanofilm for Low-Cost and Performance-Enhanced Chemical Sensors.

The high surface-to-volume ratio of nanostructured materials is the key factor for excellent performance when applied to chemical sensors. In order to achieve this by a facile and low-cost fabrication strategy, buffered oxide etchant (BOE) treatment of a silicon (Si)-based sensor was proposed. An n+-n--n+ Si nanofilm structure was treated with a BOE, and palladium nanoparticles (PdNPs) were coated on the n-type Si channel surface via short-time electron beam evaporation to enable a highly sensitive and selective sensing of hydrogen (H2) gas. The BOE treatment effect on lightly doped n-type Si was investigated, and the surface morphology of the etched Si was analyzed. Furthermore, the H2 sensing characterization of PdNP-decorated Si devices with various BOE treatment times was systematically evaluated at room temperature. The results revealed that the surface of n-type Si is roughened by BOE treatment, which can further enhance the H2-sensing performance of Pd-decorated Si. The elaborate study on the BOE-post-treated Si H2 sensor showed that the performance enhancement was stable. The BOE treatment strategy was also applied to the nanopatterned Si sensors, which induced a clear performance enhancement for the H2 sensing.

Low-temperature large-area fabrication of ZnO nanowires on flexible plastic substrates by solution-processible metal-seeded hydrothermal growth.

We have developed the low-temperature conformal ZnO nanowire fabrication on flexible plastic substrates by utilizing the solution-processible metal seed-assisted hydrothermal ZnO crystallization. Structural evolution of ZnO nanowires controlled by major parameters involving growth temperature, growth time, and seed coating condition, has been systematically investigated towards uniform and large-area growth of conformal ZnO nanowires. Direct ZnO nanowire growth on flexible plastics without undergoing the high-temperature seed sintering has been realized by developing the low-temperature Ag-seeded hydrothermal ZnO nanowire growth. The nanoporous Ag layer favorable for ZnO crystal nucleation and continued nanowire growth can be reduced from the Ag ion solution coating at the temperature as low as 130 °C. This tactfully enables the selective hydrothermal growth of ZnO nanowires on the Ag patterns on flexible plastics. Such an all-solution-processible low-temperature fabrication protocol may provide an essential and practical solution to develop many diverse applications including wearable and transparent electronics, sensors, and photocatalytic devices. As one example, we demonstrate that a transparent UV sensor can be devised based on the ZNW growth on the Ag micromesh electrode.

Self-Powered Gas Sensor Based on a Photovoltaic Cell and a Colorimetric Film with Hierarchical Micro/Nanostructures.

We report a new type of self-powered gas sensors based on the combination of a colorimetric film with hierarchical micro/nanostructures and organic photovoltaic cells. The transmittance of the colorimetric film with micro/nanostructures coated with N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) changes by reacting with NO2 gas, and it is measured as a current output of the photovoltaic cell. For this purpose, materials for the organic photovoltaic cells were carefully chosen to match the working wavelength of the TMPD. Micropost arrays and nanowires increase the surface area for the gas reaction and thus improve the transmittance changes by NO2 gas (6.7% change for the plain film vs 27.7% change for the film with hierarchical micro/nanostructures to 20 ppm of NO2). Accordingly, the colorimetric device with the hierarchical structures showed a response of ΔI/I0 = 0.27-20 ppm of NO2, which is a 71% improvement compared to that of the plain sensing film. Furthermore, it showed a high selectivity against other gases such as H2S and CO with almost negligible responses. Since the current output change of the photovoltaic cell is utilized as a sensor signal, no extra electrical power is required for the operation of gas sensors. We also integrated the sensor device with an electrical module and demonstrated a self-powered gas alarm system.

Enabling room temperature ferromagnetism in monolayer MoS2 via in situ iron-doping.

Two-dimensional semiconductors, including transition metal dichalcogenides, are of interest in electronics and photonics but remain nonmagnetic in their intrinsic form. Previous efforts to form two-dimensional dilute magnetic semiconductors utilized extrinsic doping techniques or bulk crystal growth, detrimentally affecting uniformity, scalability, or Curie temperature. Here, we demonstrate an in situ substitutional doping of Fe atoms into MoS2 monolayers in the chemical vapor deposition growth. The iron atoms substitute molybdenum sites in MoS2 crystals, as confirmed by transmission electron microscopy and Raman signatures. We uncover an Fe-related spectral transition of Fe:MoS2 monolayers that appears at 2.28 eV above the pristine bandgap and displays pronounced ferromagnetic hysteresis. The microscopic origin is further corroborated by density functional theory calculations of dipole-allowed transitions in Fe:MoS2. Using spatially integrating magnetization measurements and spatially resolving nitrogen-vacancy center magnetometry, we show that Fe:MoS2 monolayers remain magnetized even at ambient conditions, manifesting ferromagnetism at room temperature.

Microporous Elastomer Filter Coated with Metal Organic Frameworks for Improved Selectivity and Stability of Metal Oxide Gas Sensors.

Despite various advantages and usefulness of semiconductor metal oxide gas sensors, low selectivity and humidity interference have limited their practical applications. In order to resolve these issues, we propose a new concept of a selective gas filtering structure that increases the gas selectivity and decreases the moisture interference of metal oxide gas sensors by coating metal organic frameworks (MOFs) on a microporous elastomer scaffold. Cu(BTC) with an excellent selective adsorption capacity for carbon monoxide (CO) compared to hydrogen (H2) and MIL-160 with an excellent moisture adsorption capacity were uniformly coated on the microporous polydimethylsiloxane (PDMS) structure through a squeeze coating method, resulting in a high content of MOFs with a large effective surface area. A Cu(BTC)-coated microporous PDMS filter showed an excellent adsorption efficiency (62.4%) for CO, thereby dramatically improving the selectivity of H2/CO by up to 2.6 times. In addition, an MIL-160 coated microporous PDMS filter showed a high moisture adsorption efficiency (76.2%).

Nanotransfer Printing on Textile Substrate with Water-Soluble Polymer Nanotemplate.

The growing interest in wearable devices has drawn increased attention to smart textiles, and various transfer methods have therefore been introduced to realize the desired functions using textiles as substrates. However, the existing transfer techniques are not suited for the production of sophisticated nanoscale patterns on textiles, as textile roughness and difficulty of precise pattern size control hinder miniaturization, deteriorate device performance, and complicate the use of optical phenomena such as surface plasmon resonance. To address these limitations, we have developed a method based on simple dissolution of a water-soluble nanopatterned polymer film for the facile transfer of nanostructures of on-film-deposited functional materials onto textile substrates. The above method tolerates a variety of functional materials, e.g., metals and SiO2, and nano/microscale structures, e.g., nanoscale lines, dots, holes, and mesh patterns with a minimum pattern width of 50 nm. The proposed technique is employed to fabricate a palladium nanoscale line array (utilized as a highly sensitive and selective hydrogen sensor) and is shown to be suitable for the production of security patterns on textiles, as it allows the printing of complex nanostructure patterns with electrical and optical functionalities.

Half-Pipe Palladium Nanotube-Based Hydrogen Sensor Using a Suspended Nanofiber Scaffold.

A half-pipe palladium nanotube network (H-PdNTN) structure was developed for high-performance hydrogen (H2) sensor applications. To fabricate the sensor, suspended poly(vinyl alcohol) (PVA) nanofiber bundles were electrospun on a conductive substrate, followed by a palladium (Pd) deposition on top of the PVA nanofiber bundles. Then, Pd-deposited PVA nanofibers were transferred to a host substrate, and the PVA nanofiber templates were selectively removed. Various material analyses confirmed that the PVA nanofibers were successfully dissolved leaving a half-pipe-shaped Pd nanotube network. The fabricated Pd nanotube-based sensors were tested for H2 responses with different gas concentrations. The 4 nm thick sensor showed the highest response (Δ R/ R0) to H2 gas. Platinum (Pt) decoration of the sensor showed an improved response speed compared to that of the pristine sensor via the catalytic function of Pt. Additionally, the sensor exhibited good H2 selectivity against other interfering gases. The H-PdNTN H2 sensor provides a facile and cost-effective way to fabricate high-performance H2 sensors.

Effective optical properties of nanoparticle-mediated surface plasmon resonance sensors.

We investigate effective medium properties of nanoparticles (NPs) in surface plasmon (SP) resonance detection. Attention was paid to the effective medium characteristics with respect to the particle distribution in equally spaced, aggregated, and intermediate models, although effects of other parameters such as size, material, and concentration were also explored. The results suggest that the distribution may cause significant measurement deviation by as much as 20% for gold NPs and less than 5% for silica. Particle concentration showed complicated dependence in the effective medium. Different mechanisms were observed to govern effective medium properties of dielectric and metal NPs, SP mode transition and multiple scattering for silica NPs. In contrast, metal damping dominated resonance characteristics for gold NPs. The results are expected to provide fresh insights on how to apply an effective medium and interpret measured data in SP resonance sensors and beyond.

Theoretical comparison of the excitation efficiency of waveguide and surface plasmon modes between quantum-mechanical and electromagnetic optical models of organic light-emitting diodes.

We theoretically compare the excitation efficiency of waveguide and surface plasmon modes between quantum-mechanical and classical electromagnetic optical models of organic light-emitting diodes (OLEDs). A sophisticated optical model combining the two approaches is required to obtain an accurate calculation result and a comprehensive understanding of the micro-cavity effect in OLEDs. In the quantum-mechanical approach based on the Fermi's golden rule, the mode expansion method is used to calculate the excitation efficiency. In the classical electromagnetic approach, the spectral power density calculated by the point dipole model is fitted by the summation of the Lorentzian line shape functions, which provide the excitation probability of each waveguide and surface plasmon modes. The mode coupling efficiencies on the basis of the two approaches are calculated in a bottom-emitting OLED when the position of a dipole emitter is varied. By comparing the calculation results, we confirm the equivalence of two approaches and obtain the better optical interpretation to the calculated excitation efficiency of waveguide and surface plasmon modes. The ratio of mode excitation efficiencies calculated by two approaches agrees well with each other except the contribution of the near-field absorption component.