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Graphene quantum dots (GQDs) are carbon-based zero-dimensional materials that have received considerable scientific interest due to their exceptional optical, electrical, and optoelectrical properties. Their unique electronic band structures, influenced by quantum confinement and edge effects, differentiate the physical and optical characteristics of GQDs from other carbon nanostructures. Additionally, GQDs can be synthesized using various top-down and bottom-up approaches, distinguishing them from other carbon nanomaterials. This review discusses recent advancements in GQD research, focusing on their synthesis and functionalization for potential applications. Particularly, various methods for synthesizing functionalized GQDs using different doping routes are comprehensively reviewed. Based on previous reports, current challenges and future directions for GQDs research are discussed in detail herein.
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Self-assembled alkane layers are introduced between graphene layers to physically block nanometer size defects in graphene and lateral gas pathways between graphene layers. A well-defined hexatriacontane (HTC) monolayer on graphene could cover nanometer-size defects because of the flexible nature and strong intermolecular van der Waals interactions of alkane, despite the roughness of graphene. In addition, HTC multilayers between graphene layers greatly improve their adhesion. This indicates that HTC multilayers between graphene layers can effectively block the lateral pathway between graphene layers by filling open space with close-packed self-assembled alkanes. By these mechanisms, alternately stacked composites of graphene and self-assembled alkane layers greatly increase the gas-barrier property to a water vapor transmission rate (WVTR) as low as 1.2 × 10-3 g/(m2 day), whereas stacked graphene layers generally show a WVTR < 0.5 g/(m2 day). Furthermore, the self-assembled alkane layers have superior crystallinity and wide bandgap, so they have little effect on the transmittance.
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Large-scale 2D single-crystalline copper nanoplates (Cu NPLs) are synthesized by a simple hydrothermal method. The combination of a mild reductant, stabilizer, and shape modifier allows the dimensional control of the Cu nanocrystals from 1D nanowires (NWs) to 2D nanoplates. High-resolution transmission electron microscopy (HR-TEM) reveals that the prepared Cu NPLs have a single-crystalline structure. From the X-ray photoelectron spectroscopy (XPS) analysis, it is found that iodine plays an important role in the modification of the copper nanocrystals through the formation of an adlayer on the basal plane of the nanoplates. Cu NPLs with an average edge length of 10 µm are successfully synthesized, and these Cu NPLs are the largest copper 2D crystals synthesized by a solution-based process so far. The application of the metallic 2D crystals as a semitransparent electrode proves their feasibility as a conductive filler, exhibiting very low sheet resistance (0.4 Ω â«-1 ) compared to Cu NWs and a transmittance near 75%. The efficient charge transport is due to the increased contact area between each Cu NPL, i.e., so-called plane contact (2D electrical contact). In addition, this type of contact enhances the current-carrying capability of the Cu NPL electrodes, implying that the large-size Cu NPLs are promising conductive fillers for printable electrode applications.
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A network structure consisting of nanomaterials with a stable structural support and charge path on a large area is desirable for various electronic and optoelectronic devices. Generally, network structures have been fabricated via two main strategies: (1) assembly of pre-grown nanostructures onto a desired substrate and (2) direct growth of nanomaterials onto a desired substrate. In this study, we utilized the surface defects of graphene to form a nano-network of ZnO via atomic layer deposition (ALD). The surface of pure and structurally perfect graphene is chemically inert. However, various types of point and line defects, including vacancies/adatoms, grain boundaries, and ripples in graphene are generated by growth, chemical or physical treatments. The defective sites enhance the chemical reactivity with foreign atoms. ZnO nanoparticles formed by ALD were predominantly deposited at the line defects and agglomerated with increasing ALD cycles. Due to the formation of the ZnO nano-network, the photocurrent between two electrodes was clearly changed under UV irradiation as a result of the charge transport between ZnO and graphene. The line patterned ZnO/graphene (ZnO/G) nano-network devices exhibit sensitivities greater than ten times those of non-patterned structures. We also confirmed the superior operation of a fabricated flexible photodetector based on the line patterned ZnO/G nano-network.
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A highly efficient solution-processible charge trapping medium is a prerequisite to developing high-performance organic nano-floating gate memory (NFGM) devices. Although several candidates for the charge trapping layer have been proposed for organic memory, a method for significantly increasing the density of stored charges in nanoscale layers remains a considerable challenge. Here, solution-processible graphene quantum dots (GQDs) were prepared by a modified thermal plasma jet method; the GQDs were mostly composed of carbon without any serious oxidation, which was confirmed by x-ray photoelectron spectroscopy. These GQDs have multiple energy levels because of their size distribution, and they can be effectively utilized as charge trapping media for organic NFGM applications. The NFGM device exhibited excellent reversible switching characteristics, with an on/off current ratio greater than 10(6), a stable retention time of 10(4) s and reliable cycling endurance over 100 cycles. In particular, we estimated that the GQDs layer trapped â¼7.2 × 10(12) cm(-2) charges per unit area, which is a much higher density than those of other solution-processible nanomaterials, suggesting that the GQDs layer holds promise as a highly efficient nanoscale charge trapping material.
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Highly reactive radicals or chemicals are generated on the surfaces of oxide semiconductors via reactions between photo-induced charges and ambient gas molecules. These radicals or chemicals have been utilized in heterogeneous photosynthesis and photocatalysis. In this study, we demonstrated that the photocatalytic reactions on the surface of ZnO promoted the oxidation and decomposition of graphene. Raman spectra were used to analyze the evolution of the G and 2D peaks. The oxidation of graphene on a ZnO substrate by UV radiation was faster than that in the absence of ZnO. During oxidation, the resistivity and the transmittance of graphene also increased. The XPS results showed that functional groups related to the oxidation of graphene were formed during the photocatalytic reactions. This simple and clean approach will be also effective for selective surface modification by enhancing the surface chemical reactions that pattern graphene via oxidation.
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Assembling solution-processed van der Waals (vdW) materials into thin films holds great promise for constructing large-scale, high-performance thin-film electronics, especially at low temperatures. While transition metal dichalcogenide thin films assembled in solution have shown potential as channel materials, fully solution-processed vdW electronics have not been achieved due to the absence of suitable dielectric materials and high-temperature processing. In this work, we report on all-solution-processedvdW thin-film transistors (TFTs) comprising molybdenum disulfides (MoS2) as the channel and Dion-Jacobson-phase perovskite oxides as the high-permittivity dielectric. The constituent layers are prepared as colloidal solutions through electrochemical exfoliation of bulk crystals, followed by sequential assembly into a semiconductor/dielectric heterostructure for TFT construction. Notably, all fabrication processes are carried out at temperatures below 250 °C. The fabricated MoS2 TFTs exhibit excellent device characteristics, including high mobility (>10 cm2 V-1 s-1) and an on/off ratio exceeding 106. Additionally, the use of a high-k dielectric allows for operation at low voltage (â¼5 V) and leakage current (â¼10-11 A), enabling low power consumption. Our demonstration of the low-temperature fabrication of high-performance TFTs presents a cost-effective and scalable approach for heterointegrated thin-film electronics.
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Semi-infinite single-atom-thick graphene is an ideal reinforcing material that can simultaneously improve the mechanical, electrical, and thermal properties of matrix. Here, we present a float-stacking strategy to accurately align the monolayer graphene reinforcement in polymer matrix. We float graphene-poly(methylmethacrylate) (PMMA) membrane (GPM) at the water-air interface, and wind-up layer-by-layer by roller. During the stacking process, the inherent water meniscus continuously induces web tension of the GPM, suppressing wrinkle and folding generation. Moreover, rolling-up and hot-rolling mill process above the glass transition temperature of PMMA induces conformal contact between each layer. This allows for pre-tension of the composite, maximizing its reinforcing efficiency. The number and spacing of the embedded graphene fillers are precisely controlled. Notably, we accurately align 100 layers of monolayer graphene in a PMMA matrix with the same intervals to achieve a specific strength of about 118.5 MPa g-1 cm3, which is higher than that of lightweight Al alloy, and a thermal conductivity of about 4.00 W m-1 K-1, which is increased by about 2,000 %, compared to the PMMA film.
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We report on mode-locking of a Cr:YAG laser at 1516 nm using a monolayer graphene-based saturable absorber of transmission type generating 91 fs pulses with a Fourier product of 0.38 at an average output power exceeding 100 mW. Stable single-pulse mode-locked operation without any sign of Q-switching instabilities or multiple pulses is achieved.
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Implementing a heterostructure by vertically stacking two-dimensional semiconductors is necessary for responding to various requirements in the future of semiconductor technology. However, the chemical-vapor deposition method, which is an existing two-dimensional (2D) material-processing method, inevitably causes heat damage to surrounding materials essential for functionality because of its high synthesis temperature. Therefore, the heterojunction of a 2D material that directly synthesized MoS2 on graphene using a laser-based photothermal reaction at room temperature was studied. The key to the photothermal-reaction mechanism is the difference in the photothermal absorption coefficients of the materials. The device in which graphene and MoS2 were vertically stacked using a laser-based photothermal reaction demonstrated its potential application as a photodetector that responds to light and its stability against cycling. The laser-based photothermal-reaction method for 2D materials will be further applied to various fields, such as transparent display electrodes, photodetectors, and solar cells, in the future.
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We demonstrate low-temperature growth and direct transfer of graphene-graphitic carbon films (G-GC) onto plastic substrates without the use of supporting materials. In this approach, G-GC films were synthesized on copper layers by using inductively coupled plasma enhanced chemical vapor deposition, enabling the growth of few-layer graphene (G) on top of Cu and the additional growth of graphitic carbon (GC) films above the graphene layer at temperatures as low as 300 °C. The patterned G-GC films are not easily damaged or detached from the polymer substrates during the wet etching and transfer process because of the van der Waals forces and π-π interactions between the films and the substrates. Raman spectroscopy reveals the two-dimensional hexagonal lattice of carbon atoms and the crystallinity of the G-GC films. The optical transparency and sheet resistance of the G-GC films are controlled by modulating the film thickness. Strain sensors are successfully fabricated on plastic substrates, and their resistance modulation at different strains is investigated.
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It is known that low-field mobility of graphene depends largely on the substrate material on which it is transferred. We measured Drude optical conductivity of graphene on various substrates and determined the carrier density and carrier scattering rate. The carrier density varies widely depending on the substrate material. However the scattering rate is almost constant, approximately 100 cm(-1), for 5 different substrates. We calculate carrier mobility of graphene using the two quantities, i.e., carrier density and scattering rate, to find that it agrees with the mobility measured from dc transport experiment. We conclude that substrate-depent mobility of graphene originates from different carrier density but not from the scattering rate.
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We demonstrate injection, transport, and detection of spins in spin valve arrays patterned in both copper based chemical vapor deposition (Cu-CVD) synthesized wafer scale single layer and bilayer graphene. We observe spin relaxation times comparable to those reported for exfoliated graphene samples demonstrating that chemical vapor deposition specific structural differences such as nanoripples do not limit spin transport in the present samples. Our observations make Cu-CVD graphene a promising material of choice for large scale spintronic applications.
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Cobre/química , Grafite/química , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
We demonstrate high-performance, flexible, transparent heaters based on large-scale graphene films synthesized by chemical vapor deposition on Cu foils. After multiple transfers and chemical doping processes, the graphene films show sheet resistance as low as â¼43 Ohm/sq with â¼89% optical transmittance, which are ideal as low-voltage transparent heaters. Time-dependent temperature profiles and heat distribution analyses show that the performance of graphene-based heaters is superior to that of conventional transparent heaters based on indium tin oxide. In addition, we confirmed that mechanical strain as high as â¼4% did not substantially affect heater performance. Therefore, graphene-based, flexible, transparent heaters are expected to find uses in a broad range of applications, including automobile defogging/deicing systems and heatable smart windows.
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We successfully develop a self-powered image array (IA) composed of 16 touch-free sensors (TFSs) fabricated with semiconductor InN nanowires (NWs) as a response medium. Without using a power supply, the InN-NW TFS can detect the position of a human hand 30 cm away from the device surface. It also distinguishes different materials such as polyimide, Al foil, printing paper, latex, and polyvinyl chloride in non-contact mode at a distance of 1 cm. The self-powered TFS-IA clearly distinguishes square-shaped transparent polydimethylsiloxane film attached to the back of a human hand positioned 5 cm from the device, indicating the possibility for detecting changes in the surface texture of human skin, such as skin burns or skin cancer. The performance of the self-powered TFS and TFS-IA is attributed to high electrostatic induction of InN NWs by external triboelectricity resulting from the simple movement of the target object, which differs markedly from conventional sensors designed to detect variations in the temperature or light essentially using a power supply.
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Nanofios , Humanos , Fontes de Energia Elétrica , SemicondutoresRESUMO
Electronic fibres have been considered one of the desired device platforms due to their dimensional compatibility with fabrics by weaving with yarns. However, a precise connecting process between each electronic fibre is essential to configure the desired electronic circuits or systems. Here, we present an integrated electronic fibre platform by fabricating electronic devices onto a one-dimensional microfibre substrate. Electronic components such as transistors, inverters, ring oscillators, and thermocouples are integrated together onto the outer surface of a fibre substrate with precise semiconductor and electrode patterns. Our results show that electronic components can be integrated on a single fibre with reliable operation. We evaluate the electronic properties of the chip on the fibre as a multifunctional electronic textile platform by testing their switching and data processing, as well as sensing or transducing units for detecting optical/thermal signals. The demonstration of the electronic fibre suggests significant proof of concepts for the realization of high performance with wearable electronic textile systems.
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Molybdenum disulfide (MoS2 ) is considered a fascinating material for next-generation semiconducting applications due to its outstanding mechanical stability and direct transition characteristics comparable to silicon. However, its application to stretchable platforms still is a challenging issue in wearable logic devices and sensors with noble form-factors required for future industry. Here, an omnidirectionally stretchable MoS2 platform with laser-induced strained structures is demonstrated. The laser patterning induces the pyrolysis of MoS2 precursors as well as the weak adhesion between Si and SiO2 layers. The photothermal expansion of the Si layer results in the crumpling of SiO2 and MoS2 layers and the field-effect transistors with the crumpled MoS2 are found to be suitable for strain sensor applications. The electrical performance of the crumpled MoS2 depends on the degree of stretching, showing the stable omnidirectional stretchability up to 8% with approximately four times higher saturation current than its initial state. This platform is expected to be applied to future electronic devices, sensors, and so on.
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High-quality monolayer graphene as large as 1.2×1.2 cm2 was synthesized by chemical vapor deposition and used as a transmitting saturable absorber for efficient passive mode-locking of a femtosecond bulk solid-state laser. The monolayer graphene mode-locked Cr:forsterite laser was tunable around 1.25 µm and delivered sub-100 fs pulses with output powers up to 230 mW. The nonlinear optical characteristics of the monolayer graphene saturable absorber and the mode-locked operation were then compared with the case of the bilayer graphene saturable absorber.
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We developed means to produce wafer scale, high-quality graphene films as large as 3 in. wafer size on Ni and Cu films under ambient pressure and transfer them onto arbitrary substrates through instantaneous etching of metal layers. We also demonstrated the applications of the large-area graphene films for the batch fabrication of field-effect transistor (FET) arrays and stretchable strain gauges showing extraordinary performances. Transistors showed the hole and electron mobilities of the device of 1100 +/- 70 and 550 +/- 50 cm(2)/(V s) at drain bias of -0.75 V, respectively. The piezo-resistance gauge factor of strain sensor was approximately 6.1. These methods represent a significant step toward the realization of graphene devices in wafer scale as well as application in optoelectronics, flexible and stretchable electronics.
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Cobre/química , Nanotecnologia/métodos , Níquel/química , Catálise , Dimetilpolisiloxanos/química , Eletrônica , Desenho de Equipamento , Grafite/química , Teste de Materiais , Nanoestruturas/química , Óptica e Fotônica , Polímeros/química , PressãoRESUMO
Doping is an effective method for controlling the electrical properties and work function of graphene which can improve the power conversion efficiency of graphene-based Schottky junction solar cells (SJSCs). However, in previous approaches, the stability of chemical doping decreased over time due to the decomposition of dopants on the surface of graphene under ambient conditions. Here, we report an efficient and strong p-doping by simple sandwich doping on both the top and bottom surfaces of graphene. We confirmed that the work function of sandwich-doped graphene increased by 0.61 eV and its sheet resistance decreased by 305.8 Ω/sq, compared to those of the pristine graphene. Therefore, the graphene-silicon SJSCs that used sandwich-doped graphene had a power conversion efficiency of 10.02%, which was 334% higher than that (2.998%) of SJSCs that used pristine graphene. The sandwich-doped graphene-based silicon SJSCs had excellent long-term stability over 45 days without additional encapsulation.