Nanoarchitectonics of MXene Derived TiO2 /Graphene with Vertical Alignment for Achieving the Enhanced Supercapacitor Performance.

Structural engineering and hybridization of heterogeneous 2D materials can be effective for advanced supercapacitor. Furthermore, architectural design of electrodes particularly with vertical construction of structurally anisotropic graphene nanosheets, can significantly enhance the electrochemical performance. Herein, MXene-derived TiO2 nanocomposites hybridized with vertical graphene is synthesized via CO2 laser irradiation on MXene/graphene oxide nanocomposite film. Instantaneous photon energy by laser irradiation enables the formation of vertical graphene structures on nanocomposite films, presenting the controlled anisotropy in free-standing film. This vertical structure enables improved supercapacitor performance by forming an open structure, increasing the electrolyte-electrode interface, and creating efficient electron transport path. In addition, the effective oxidation of MXene nanosheets by instantaneous photon energy leads to the formation of rutile TiO2 . TiO2 nanoparticles directly generated on graphene enables the effective current path, which compensates for the low conductivity of TiO2 and enables the functioning of an effective supercapacitor by utilizing its pseudocapacitive properties. The resulting film exhibits excellent specific areal capacitance of 662.9 mF cm-2 at a current density of 5 mA cm-2 . The film also shows superb cyclic stability during 40 000 repeating cycles, maintaining high capacitance. Also, the pseudocapacitive redox reaction kinetics is evaluated, showing fast redox kinetics with potential for high-performance supercapacitor applications.

Dual Catalytic and Self-Assembled Growth of Two-Dimensional Transition Metal Dichalcogenides Through Simultaneous Predeposition Process.

The recent introduction of alkali metal halide catalysts for chemical vapor deposition (CVD) of transition metal dichalcogenides (TMDs) has enabled remarkable two-dimensional (2D) growth. However, the process development and growth mechanism require further exploration to enhance the effects of salts and understand the principles. Herein, simultaneous predeposition of a metal source (MoO3 ) and salt (NaCl) by thermal evaporation is adopted. As a result, remarkable growth behaviors such as promoted 2D growth, easy patterning, and potential diversity of target materials can be achieved. Step-by-step spectroscopy combined with morphological analyses reveals a reaction path for MoS2 growth in which NaCl reacts separately with S and MoO3 to form Na2 SO4 and Na2 Mo2 O7 intermediates, respectively. These intermediates provide a favorable environment for 2D growth, including an enhanced source supply and liquid medium. Consequently, large grains of monolayer MoS2 are formed by self-assembly, indicating the merging of small equilateral triangular grains on the liquid intermediates. This study is expected to serve as an ideal reference for understanding the principles of salt catalysis and evolution of CVD in the preparation of 2D TMDs.

Mesoporous Metal Fluoride Nanocomposite Films with Tunable Optical Properties Derived from Precursor Instability.

The precisely tailored refractive index of optical materials is the key to utilizing and manipulating light during its propagation through the matrix, thereby improving their application performances. In this paper, mesoporous metal fluoride films with engineered composition (MgF2 :LaF3 ) are demonstrated to achieve finely tunable refractive indices. These films are prepared using a precursor-derived one-step assembly approach via the simple mixing of precursor solutions (Mg(CF3 OO)2 and La(CF3 OO)3 ); then pores are formed simultaneously during solidification owing to the inherent instability of La(CF3 OO)3 . The mesoporous structures are realized through Mg(CF3 OO)2 and La(CF3 OO)3 ions, which interacted with each other based on their electrostatic forces, providing a wide range of refractive indices (from 1.37 to 1.16 at 633 nm). Furthermore, it is systematically several MgF2(1-x) -LaF3(x) layers with different compositions (x = 0.0, 0.3, and 0.5) to form the graded refractive index coating that is optically consecutive between the substrate and the air for broadband and omnidirectional antireflection. An average transmittance of ≈98.03% (400-1100 nm) is achieved with a peak transmittance of ≈99.04% (at 571 nm), and the average antireflectivity is maintained at ≈15.75% even at an incidence of light of 65° (400-850 nm).

Strategic Customization of Polymeric Nanocomposites Modified by 2D Titanium Oxide Nanosheet for High-k and Flexible Gate Dielectrics.

Organic polymer-based dielectrics with intrinsic mechanical flexibility and good processability are excellent candidates for the dielectric layer of flexible electronics. These polymer films can become even more rigid and electrically robust when modified through cross-linking processes. Moreover, the composites formed by dispersing nanoscale inorganic fillers in a polymer matrix can exhibit further improved polarization property. However, these strategies can be challenging as homogeneous dispersion of nanomaterials in the matrix is difficult to achieve; thus, degradation of electrically insulating properties of nanocomposite layers is often observed. Here, a high-k, pinhole-free, and flexible poly(vinyl alcohol) (PVA)-based nanocomposite dielectric is presented, incorporating 2D TiO2 nanosheets (NSs) for the first time. Despite the attractive dielectric constant, exceptional flexibility, and electrically insulating property of PVA-TiO2 nanocomposites, only few studies on these materials have been reported. The organic/inorganic nanosheet hybrid layer, which reaches an unprecedentedly high dielectric constant of 43.8 (more than four times higher than that of cross-linked PVA), also exhibits an outstanding leakage current density as low as 10-9 A cm-2 . Furthermore, the repeated bending tests for nanocomposite capacitors reveal their capability of operating without any deterioration of their performances even after 1000 iterations of bending cycles at a bending radius of 3 mm.

Attachable piezoelectric nanogenerators using collision-induced strain of vertically grown hollow MoS2 nanoflakes.

Piezoelectric materials convert external mechanical force into electrical energy, due to the breaking of the centrosymmetry of the atomic structure. Piezoelectricity-based nano-generators (PNGs) based on two-dimensional transition metal dichalcogenides (TMDs) can generate electrical energy stably by the piezoelectric effect at their nanoscale thickness. However, the commercialization of TMD-based PNGs is limited by their poor piezoelectric performance and microscale energy harvesting. Here, we present the first centimeter-scale PNGs based on molybdenum disulfide (MoS2) nanosheets with vertically grown hollow MoS2 nanoflakes (v-MoS2 NFs) obtained by chemical vapor deposition for energy harvesting from human motions. The collision of v-MoS2 NFs with a preferred odd-atomic-layer number and their 2H antiparallel phase leads to efficient electrical energy generation during the bending movement. Further, basal MoS2 films with v-MoS2 NFs are transferred onto flexible substrates via conventional polymer-assisted methods for the fabrication of attachable and wearable piezoelectric power generators.

Improved impedance characteristics of all-water-processable triple-stacked hole-selective layers in solution-processed OLEDs.

We herein report an investigation of the device performance capabilities and impedance characteristics of solution-processed organic light-emitting devices (OLEDs) with all-water-processable triple-stacked hole-selective layers (HSLs) on an indium-tin-oxide (ITO) anode, fabricated using a simple coating technique. Highly smooth and homogeneous triple-stacked layers were deposited via horizontal-dip- (H-dip-) coating using aqueous dispersions of graphene oxide (GO), molybdenum oxide (MoO3), and poly(ethylenedioxy thiophene):poly(styrene sulfonate) ( PEDOT: PSS). From the triple-stacked GO/MoO3/ PEDOT: PSS HSLs used as hole-injection layers (HILs) in the OLEDs, which outperform a conventional single HIL of PEDOT: PSS, it was found that OLEDs with triple-stacked HILs exhibited characteristic impedance properties, including low parallel resistance with trap-free space-charge-limited conductivity. Furthermore, it was shown that the relaxation frequency of a sample OLED with triple-stacked GO/MoO3/ PEDOT: PSS HILs was much higher than that of a reference device with a single PEDOT: PSS HIL. These impedance behaviors indicate that carrier (hole) injection in the sample OLED is more efficient than that in any of the other devices tested here. The results presented here clarify that the triple-stacked GO/MoO3/ PEDOT: PSS layers can act as efficient HILs on an ITO anode, representing a remarkable advance in relation to the mass production of high-performance solution-processable OLEDs.

Tunable functionalization of graphene nanosheets for graphene-organic hybrid photodetectors.

Graphene-organic hybrid thin films are promising candidates for use as advanced transparent electrodes and high-performance photodetectors. In this work, we fabricated hybrid thin film structures consisting of graphene and either tetraphenyl-porphyrin (H2TPP) or metalloporphyrins such as aluminum (III) tetraphenyl-porphyrin (Al(III)TPP) and zinc tetraphenyl-porphyrin (ZnTPP). The optical and electrical characteristics of ultrathin photodetectors based on the graphene-organic hybrid layers were subsequently evaluated. A hybrid deposition system capable of both thermal evaporation and vapor phase metalation was employed to synthesize the tunable metalloporphyrin-based thin films. As a proof of concept, we successfully fabricated various graphene-based photodetectors via the simple and efficient vapor-phase metalation of porphyrin. This work may facilitate the development of new architectures for flexible graphene-organic devices.

Tuning the Electrical Properties of Graphene via Nitrogen Plasma-Assisted Chemical Modification.

The control in electrical properties of graphene is essentially required in order to realize graphenebased nanoelectronics. In this study, N-doped graphene was successfully obtained via nitrogen plasma treatment. Graphene was synthesized on copper foil using thermal chemical vapor deposition. After N2 plasma treatment, the G-band of the graphene was blueshifted and the intensity ratio of 2D- to G-bands decreased with increasing the plasma power. Pyrrolic-N bonding configuration induced by N2 plasma treatment was studied by X-ray photoelectron spectroscopy. Remarkably, electrical characterization including Hall measurement and I-V characteristics of the N-doped graphene exhibit semiconducting behavior as well as the n-type doping effect.

Fabrication of graphene-based flexible devices utilizing a soft lithographic patterning method.

There has been considerable interest in soft lithographic patterning processing of large scale graphene sheets due to the low cost and simplicity of the patterning process along with the exceptional electrical or physical properties of graphene. These properties include an extremely high carrier mobility and excellent mechanical strength. Recently, a study has reported that single layer graphene grown via chemical vapor deposition (CVD) was patterned and transferred to a target surface by controlling the surface energy of the polydimethylsiloxane (PDMS) stamp. However, applications are limited because of the challenge of CVD-graphene functionalization for devices such as chemical or bio-sensors. In addition, graphene-based layers patterned with a micron scale width on the surface of biocompatible silk fibroin thin films, which are not suitable for conventional CMOS processes such as the patterning or etching of substrates, have yet to be reported. Herein, we developed a soft lithographic patterning process via surface energy modification for advanced graphene-based flexible devices such as transistors or chemical sensors. Using this approach, the surface of a relief-patterned elastomeric stamp was functionalized with hydrophilic dimethylsulfoxide molecules to enhance the surface energy of the stamp and to remove the graphene-based layer from the initial substrate and transfer it to a target surface. As a proof of concept using this soft lithographic patterning technique, we demonstrated a simple and efficient chemical sensor consisting of reduced graphene oxide and a metallic nanoparticle composite. A flexible graphene-based device on a biocompatible silk fibroin substrate, which is attachable to an arbitrary target surface, was also successfully fabricated. Briefly, a soft lithographic patterning process via surface energy modification was developed for advanced graphene-based flexible devices such as transistors or chemical sensors and attachable devices on a biocompatible silk fibroin substrate. Significantly, this soft lithographic patterning technique enables us to demonstrate a simple and efficient chemical sensor based on reduced graphene oxide (rGO), a metallic nanoparticle composite, and an attachable graphene-based device on a silk fibroin thin film.

Edge-Rich 3D Structuring of Metal Chalcogenide/Graphene with Vertical Nanosheets for Efficient Photocatalytic Hydrogen Production.

Constructing pertinent nanoarchitecture with abundant exposed active sites is a valid strategy for boosting photocatalytic hydrogen generation. However, the controllable approach of an ideal architecture comprising vertically standing transition metal chalcogenides (TMDs) nanosheets on a 3D graphene network remains challenging despite the potential for efficient photocatalytic hydrogen production. In this study, we fabricated edge-rich 3D structuring photocatalysts involving vertically grown TMDs nanosheets on a 3D porous graphene framework (referred to as 3D Gr). 2D TMDs (MoS2 and WS2)/3D Gr heterostructures were produced by location-specific photon-pen writing and metal-organic chemical vapor deposition for maximum edge site exposure enabling efficient photocatalytic reactivity. Vertically aligned 2D Mo(W)S2/3D Gr heterostructures exhibited distinctly boosted hydrogen production because of the 3D Gr caused by synergetic impacts associated with the large specific surface area and improved density of exposed active sites in vertically standing Mo(W)S2. The heterostructure involving graphene and TMDs corroborates an optimum charge transport pathway to rapidly separate the photogenerated electron-hole pairs, allowing more electrons to contribute to the photocatalytic hydrogen generation reaction. Consequently, the size-tailored heterostructure showed a superior hydrogen generation rate of 6.51 mmol g-1 h-1 for MoS2/3D graphene and 7.26 mmol g-1 h-1 for WS2/3D graphene, respectively, which were 3.59 and 3.76 times greater than that of MoS2 and WS2 samples. This study offers a promising path for the potential of 3D structuring of vertical TMDs/graphene heterostructure with edge-rich nanosheets for photocatalytic applications.

Photostimulated Pyrothermoelectric Coupling in Two-Dimensional Tin Monoselenide Enabling Zero-Biased Multimodal Transducers.

Despite the advancement of the Internet of Things (IoT) and portable devices, the development of zero-biased sensing systems for the dual detection of light and gases remains a challenge. As an emerging technology, direct energy conversion driven by intriguing physical properties of two-dimensional (2D) materials can be realized in nanodevices or a zero-biased integrated system. In this study, we unprecedentedly attempted to exploit the photostimulated pyrothermoelectric coupling of two-dimensional SnSe for use in zero-biased multimodal transducers for the dual detection of light and gases. We synthesized homogeneous, large-area 6 in SnSe multilayers via a rational synthetic route based on the thermal decomposition of a solution-processed single-source precursor. Zero-biased SnSe transducers for the dual monitoring of light and gases were realized by exploiting the synergistic coupling of the photostimulated pyroelectric and thermoelectric effects of SnSe. The extracted photoresponsivity at 532 nm and NO2 gas responsivity of the SnSe-based transducers corresponded to 1.07 × 10-6 A/W and 13263.6% at 0 V, respectively. To bring universal applicability of the zero-biased SnSe transducers, the wide operation bandwidth photoelectrical properties (visible to NIR) and dynamic current responses toward two NO2/NH3 gases were systematically evaluated.

Artificial Q-Grader: Machine Learning-Enabled Intelligent Olfactory and Gustatory Sensing System.

Portable and personalized artificial intelligence (AI)-driven sensors mimicking human olfactory and gustatory systems have immense potential for the large-scale deployment and autonomous monitoring systems of Internet of Things (IoT) devices. In this study, an artificial Q-grader comprising surface-engineered zinc oxide (ZnO) thin films is developed as the artificial nose, tongue, and AI-based statistical data analysis as the artificial brain for identifying both aroma and flavor chemicals in coffee beans. A poly(vinylidene fluoride-co-hexafluoropropylene)/ZnO thin film transistor (TFT)-based liquid sensor is the artificial tongue, and an Au, Ag, or Pd nanoparticles/ZnO nanohybrid gas sensor is the artificial nose. In order to classify the flavor of coffee beans (acetic acid (sourness), ethyl butyrate and 2-furanmethanol (sweetness), caffeine (bitterness)) and the origin of coffee beans (Papua New Guinea, Brazil, Ethiopia, and Colombia-decaffeine), rational combination of TFT transfer and dynamic response curves capture the liquids and gases-dependent electrical transport behavior and principal component analysis (PCA)-assisted machine learning (ML) is implemented. A PCA-assisted ML model distinguished the four target flavors with >92% prediction accuracy. ML-based regression model predicts the flavor chemical concentrations with >99% accuracy. Also, the classification model successfully distinguished four different types of coffee-bean with 100% accuracy.

Preharvest Methyl Jasmonate Treatment Affects the Mineral Profile, Metabolites, and Antioxidant Capacity of Radish Microgreens Produced without Substrate.

This study investigated the impact of Methyl Jasmonate (MeJA) application on the nutritional content and yield of five different colored radish microgreens. Microgreens were produced without substrate and subjected to 0.5 mM and 1.0 mM MeJA treatments on the 7th day, three days before harvest. The parameters measured included yield, dry matter, minerals, amino acids, secondary metabolites such as chlorophylls (Chls), anthocyanins, flavonoids, phenolics, glucosinolates (GSLs), vitamin C, and antioxidant capacity. MeJA at 1.0 mM generally improved yield and dry weight across cultivars, and all microgreens exhibited rich mineral and amino acid composition, with the influence of cultivar being more significant than MeJA treatment. However, MeJA enhanced all cultivars' anthocyanins, GSLs, phenolics, flavonoids, and antioxidant activities. Generally, as the antioxidant capacity is the primary factor influencing the nutritional quality of microgreens, MeJA-treated microgreens, especially with selected superior cultivars such as 'Asia purple' and 'Koregon red', could offer a potential for cultivation of value-added, eco-friendly microgreens with substrate-free cultivation.

Synthesis of graphene and carbon nanotubes hybrid nanostructures and their electrical properties.

The gapless semimetallic nature of graphene-based nanoelectronics is a major hurdle for the advancement of graphene-based field-effect transistors. Here graphene-carbon nanotubes hybrid nanostructures (Gr-CNTs HNSs) were formed by synthesizing single-walled carbon nanotubes (SWCNTs) with a bandgap on monolayer graphene by thermal chemical vapor deposition. We systematically established optimum conditions for the synthesis of Gr-CNTs HNSs by adjusting catalytic layer formation. The structural features of Gr-CNTs HNSs were investigated by scanning electron icroscopy and Raman spectroscopy. The surface morphologies and chemical states of the catlytic films used to optimize Gr-CNTs HNSs synthesis were explored by atomic force microscopy and X-ray photoelectron spectroscopy. In this process, graphene played a role as a barrier to prevent Fe nanoparticles from interdiffusing into Al2O3 layer. Based on these studies, we determined the catalytic structure (Fe/Graphene/Al2O3/SiO2) optimal for growing high-density SWCNTs on monolayer graphene. Electrical transport measurements revealed that Gr-CNTs HNSs exhibited p-type semiconducting behavior with combined properties of graphene and CNTs.

Radish microgreens produced without substrate in a vertical multi-layered growing unit are rich in nutritional metabolites.

Growing microgreens on trays without substrate in a vertical multilayered growing unit offers several advantages over traditional agriculture methods. This study investigated the yield performance and nutritional quality of five selections of radish microgreens grown in sprouting trays, without a substrate using only water, in an indoor multilayer cultivation system using artificial light. Various parameters were measured, including fresh weight, dry matter, chlorophyll, minerals, amino acids, phenolics, flavonoids, anthocyanins, vitamin C, glucosinolates, and antioxidant activity with four different in vitro assays. After ten days, the biomass had increased by 6-10 times, and the dry matter varied from 4.75-7.65%. The highest yield was obtained from 'Asia red', while the lowest was from 'Koregon red'. However, 'Koregon red' and 'Asia red' had the highest dry matter. 'Asia red' was found to have the highest levels of both Chls and vitamin C compared to the other cultivars, while 'Koregon red' exhibited the highest levels of total phenolics and flavonoids. Although variations in the levels of individual glucosinolates were observed, there were no significant differences in the total content of glucosinolates among the five cultivars. 'Asia purple' had the highest anthocyanin content, while 'Asia green 2' had the lowest. The K, Mg, and Na concentrations were significantly highest in 'Asia green 2', and the highest Ca was recorded in 'Asia purple'. Overall, 'Asia purple' and 'Koregon red' were the best cultivars in terms of nutritional quality among the tested radish microgreens. These cultivars exhibited high levels of dry weight, total phenolics, flavonoids, anthocyanins, essential and total amino acids, and antioxidant activities. Moreover, the implementation of this vertical cultivation method for microgreens, which relies solely on water and seeds known for their tall shoots during the sprouting could hold promise as a sustainable approach. This method can effectively be utilized for cultivar screening and fulfilling the nutritional and functional needs of the population while minimizing the environmental impacts associated with traditional agriculture practices.

One-Dimensional π-d Conjugated Coordination Polymer Intercalated MXene Compound for High-Performance Supercapacitor Electrode.

MXenes possess the characteristics required for high-performance supercapacitors, such as high metallic conductivity and electrochemical activity, but their full potential remains unrealized owing to their tendency to self-restack when fabricated into an electrode. Designing an MXene interlayer with an effective intercalant has, therefore, become an important criterion to alleviate the restacking issue while also synergistically interact with MXene to further improve its electrochemical activity. This study reports the intercalation of 1D π-d conjugated coordination polymer (Ni-BTA) within the Ti3 C2 Tx nanosheet for the fabrication of a highly efficient supercapacitor electrode. Ni-BTA, which consists of a nickel center and 1,2,4,5-benzenetetramine (BTA) organic chain, is uniformly intercalated by direct synthesis on the abundant oxygen terminals on the Ti3 C2 Tx nanosheet surface. The intercalated Ni-BTA acts as an effective charge carrier transportation pathway through its 1D stretched delocalized π-d electrons while participating in pseudocapacitive activity with the Ni centers. As a result, the Ni-BTA/MXene film exhibits excellent rate performance and a gravimetric specific capacitance of 264.4 F g-1 at 5 mV s-1 . This magnitude is retained up to 94.6% after 10 000 cycles. The present study provides insights into the design of MXene interlayers for the fabrication of highly robust and stable supercapacitors.

Shape-Configurable MXene-Based Thermoacoustic Loudspeakers with Tunable Sound Directivity.

Film-type shape-configurable speakers with tunable sound directivity are in high demand for wearable electronics. Flexible, thin thermoacoustic (TA) loudspeakers-which are free from bulky vibrating diaphragms-show promise in this regard. However, configuring thin TA loudspeakers into arbitrary shapes is challenging because of their low sound pressure level (SPL) under mechanical deformations and low conformability to other surfaces. By carefully controlling the heat capacity per unit area and thermal effusivity of an MXene conductor and substrates, respectively, it fabricates an ultrathin MXene-based TA loudspeaker exhibiting high SPL output (74.5 dB at 15 kHz) and stable sound performance for 14 days. Loudspeakers with the parylene substrate, whose thickness is less than the thermal penetration depth, generated bidirectional and deformation-independent sound in bent, twisted, cylindrical, and stretched-kirigami configurations. Furthermore, it constructs parabolic and spherical versions of ultrathin, large-area (20 cm × 20 cm) MXene-based TA loudspeakers, which display sound-focusing and 3D omnidirectional-sound-generating attributes, respectively.

Method for synthesis of tetrabenzoporphyrin precursor for use in organic electronic devices.

We developed a new synthetic method for bicyclo[2.2.2]octadiene (BCOD)-fused porphyrin (1), a tetrabenzoporphyrin (TBP, 2) precursor that is well-known as a good material for use in organic electronic devices. The newly developed method synthesizes the BCOD-fused pyrrole intermediate (which is the most important intermediate in synthesizing BCOD-fused porphyrin) in a simpler and easier manner than other existing methods, and thus, the new method can efficiently synthesize the TBP precursor.

Direct growth of oxide nanowires on CuOx thin film.

Oxide nanowires were directly grown on a CuO(x) thin film deposited by plasma-enhanced atomic layer deposition without additional metal catalysts. Oxide nanowires would exhibit metal-catalyst-free growth on the CuO(x) thin film with oxide materials diffused on the top. Through a focused ion beam and transmission electron microscopy, we could verify that SnO(2) and ZnO nanowires were grown as single-crystalline structures just above the CuO(x) thin film. Bottom-gate structural SnO(2) and ZnO nanowire transistors exhibited mobilities of 135.2 and 237.6 cm(2) V(-1) s(-1), respectively. We anticipate that a variety of large-area and high-density oxide nanowires can be grown at low cost by using the CuO(x) thin film.

Effect of nitrogen plasma on the surface of indium oxide nanowires.

The change in the atomic nitrogen concentration on a semiconducting nanowire's surface and the consequent changes in the electrical characteristics of a nanowire transistor were investigated by exposing In(2)O(3) nanowires to nitrogen (N(2)) plasma. After plasma was applied at N(2) flow rates of 20, 40, and 70 sccm with a fixed source power of 50 W, the In(2)O(3) nanowire transistor exhibited changes in the threshold voltage (V(th)), subthreshold slope (SS), and on-current (I(on)). In particular, after treatment at an N(2) flow rate of 40 sccm, V(th) shifted positively by ~2.3 V, the SS improved by ~0.24 V/dec, and I(on) increased by ~0.8 µA on average. The changes are attributed to the combination of nitrogen ions produced by the plasma with oxygen vacancies or indium interstitials on the nanowires. Optimization of the plasma treatment conditions is expected to yield desirable device characteristics by a simple, nondestructive process.