Engineering functionalization and properties of graphene quantum dots (GQDs) with controllable synthesis for energy and display applications.

Graphene quantum dots (GQDs), a new type of 0D nanomaterial, are composed of a graphene lattice with sp2 bonding carbon core and characterized by their abundant edges and wide surface area. This unique structure imparts excellent electrical properties and exceptional physicochemical adsorption capabilities to GQDs. Additionally, the reduction in dimensionality of graphene leads to an open band gap in GQDs, resulting in their unique optical properties. The functional groups and dopants in GQDs are key factors that allow the modulation of these characteristics. So, controlling the functionalization level of GQDs is crucial for understanding their characteristics and further application. This review provides an overview of the properties and structure of GQDs and summarizes recent developments in research that focus on their controllable synthesis, involving functional groups and doping. Additionally, we provide a comprehensive and focused explanation of how GQDs have been advantageously applied in recent years, particularly in the fields of energy storage devices and displays.

Role of Local Conductivities in the Plasmon Reflections at the Edges and Stacking Domain Boundaries of Trilayer Graphene.

We employed infrared scattering-type scanning near-field optical microscopy (IR-sSNOM) to study surface plasmon polaritons (SPPs) in trilayer graphene (TLG). Our study reveals systematic differences in near-field IR spectra and SPP wavelengths between Bernal (ABA) and rhombohedral (ABC) TLG domains on SiO2, which can be explained by stacking-dependent intraband conductivities. We also observed that the SPP reflection profiles at ABA-ABC boundaries could be mostly accounted for by an idealized domain boundary defined by the conductivity discontinuity. However, we identified distinct shapes in the SPP profiles at the edges of the ABA and ABC TLG, which cannot be solely attributed to idealized edges with stacking-dependent conductivities. Instead, this can be explained by the presence of various edge structures with local conductivities differing from those of bulk TLGs. Our findings unveil a new structural element that can control SPP, and provide insights into the structures and electronic states of the edges of few-layer graphene.

Graphene-Based Intrinsically Stretchable 2D-Contact Electrodes for Highly Efficient Organic Light-Emitting Diodes.

Intrinsically stretchable organic light-emitting diodes (ISOLEDs) are becoming essential components of wearable electronics. However, the efficiencies of ISOLEDs have been highly inferior compared with their rigid counterparts, which is due to the lack of ideal stretchable electrode materials that can overcome the poor charge injection at 1D metallic nanowire/organic interfaces. Herein, highly efficient ISOLEDs that use graphene-based 2D-contact stretchable electrodes (TCSEs) that incorporate a graphene layer on top of embedded metallic nanowires are demonstrated. The graphene layer modifies the work function, promotes charge spreading, and impedes inward diffusion of oxygen and moisture. The work function (WF) of 3.57 eV is achieved by forming a strong interfacial dipole after deposition of a newly designed conjugated polyelectrolyte with crown ether and anionic sulfonate groups on TCSE; this is the lowest value ever reported among ISOLEDs, which overcomes the existing problem of very poor electron injection in ISOLEDs. Subsequent pressure-controlled lamination yields a highly efficient fluorescent ISOLED with an unprecedently high current efficiency of 20.3 cd A-1 , which even exceeds that of an otherwise-identical rigid counterpart. Lastly, a 3 inch five-by-five passive matrix ISOLED is demonstrated using convex stretching. This work can provide a rational protocol for designing intrinsically stretchable high-efficiency optoelectronic devices with favorable interfacial electronic structures.

Photothermally Crumpled MoS2 Film as an Omnidirectionally Stretchable Platform.

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.

Gradual Edge Contact between Mo and MoS2 Formed by Graphene-Masked Sulfurization for High-Performance Field-Effect Transistors.

Two-dimensional materials have attracted great attention for their outstanding electronic properties. In particular, molybdenum disulfide (MoS2) shows great potential as a next-generation semiconductor due to its tunable direct bandgap with a high on-off ratio and extraordinary stability. However, the performance of MoS2 synthesized by physical vapor deposition has been limited by contact resistance between an electrode and MoS2, which determines overall device characteristics. Here, in order to reduce the contact resistance, we use in situ sulfurization of Mo by H2S gas treatment masked by a patterned graphene gas barrier, so that the Mo channel area can be selectively formed, resulting in a gradual edge contact between Mo and MoS2. Compared with field-effect transistors with a top contact between the Au/Ti electrode and the MoS2 channel, a gradual edge contact between the Mo electrode and the MoS2 channel provides a considerably enhanced electrical performance.

Facile Synthesis of N-Doped Graphene Quantum Dots as Novel Transfection Agents for mRNA and pDNA.

In the wake of the coronavirus disease 2019 (COVID-19) pandemic, global pharmaceutical companies have developed vaccines for the severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2). Some have adopted lipid nanoparticles (LNPs) or viral vectors to deliver the genes associated with the spike protein of SARS-CoV-2 for vaccination. This strategy of vaccination by delivering genes to express viral proteins has been successfully applied to the mRNA vaccines for COVID-19, and is also applicable to gene therapy. However, conventional transfection agents such as LNPs and viral vectors are not yet sufficient to satisfy the levels of safety, stability, and efficiency required for the clinical applications of gene therapy. In this study, we synthesized N-doped graphene quantum dots (NGQDs) for the transfection of various genes, including messenger ribonucleic acids (mRNAs) and plasmid deoxyribonucleic acids (pDNAs). The positively charged NGQDs successfully formed electrostatic complexes with negatively charged mRNAs and pDNAs, and resulted in the efficient delivery and transfection of the genes into target cells. The transfection efficiency of NGQDs is found to be comparable to that of commercially available LNPs. Considering their outstanding stability even at room temperature as well as their low toxicity, NGQDs are expected to be novel universal gene delivery platforms that can outperform LNPs and viral vectors.

Structure-controllable growth of nitrogenated graphene quantum dots via solvent catalysis for selective C-N bond activation.

Photophysical and photochemical properties of graphene quantum dots (GQDs) strongly depend on their morphological and chemical features. However, systematic and uniform manipulation of the chemical structures of GQDs remains challenging due to the difficulty in simultaneous control of competitive reactions, i.e., growth and doping, and the complicated post-purification processes. Here, we report an efficient and scalable production of chemically tailored N-doped GQDs (NGs) with high uniformity and crystallinity via a simple one-step solvent catalytic reaction for the thermolytic self-assembly of molecular precursors. We find that the graphitization of N-containing precursors during the formation of NGs can be modulated by intermolecular interaction with solvent molecules, the mechanism of wh ich is evidenced by theoretical calculations and various spectroscopic analyses. Given with the excellent visible-light photoresponse and photocatalytic activity of NGs, it is expected that the proposed approach will promote the practical utilization of GQDs for various applications in the near future.

Photoinitiated Polymerization of Hydrogels by Graphene Quantum Dots.

As a smart stimulus-responsive material, hydrogel has been investigated extensively in many research fields. However, its mechanical brittleness and low strength have mattered, and conventional photoinitiators used during the polymerization steps exhibit high toxicity, which limits the use of hydrogels in the field of biomedical applications. Here, we address the dual functions of graphene quantum dots (GQDs), one to trigger the synthesis of hydrogel as photoinitiators and the other to improve the mechanical strength of the as-synthesized hydrogel. GQDs embedded in the network effectively generated radicals when exposed to sunlight, leading to the initiation of polymerization, and also played a significant role in improving the mechanical strength of the crosslinked chains. Thus, we expect that the resulting hydrogel incorporated with GQDs would enable a wide range of applications that require biocompatibility as well as higher mechanical strength, including novel hydrogel contact lenses and bioscaffolds for tissue engineering.

Effects of Photochemical Oxidation of the Carbonaceous Additives on Li-S Cell Performance.

We introduce a simple and easy way to functionalize the surface of various carbonaceous materials through the ultraviolet light/ozone (UV/O3) plasma where we utilize the zero-, one-, and two-dimensional carbon frameworks. In a general manner, the lamps of a UV/O3 generator create two different wavelengths (λ = 185 and 254 nm); the shorter wavelength (λ = 185 nm) dissociates the oxygen (O2) in air and the longer wavelength (λ = 254 nm) dissociates the O3 and creates the reactive and monoatomic oxygen radical, which tends to incorporate onto the defects of the carbons. By tailoring the association and dissociation of the oxygen with various forms, carbon black, carbon nanofibers, and graphite flakes, chosen as representative models for the zero-, one-, and two-dimensional carbon frameworks, their structure can be oxidized, respectively, which is known as photochemical oxidation. Various carbons have their own distinctive morphology and electron transport properties, which are applicable for the lithium-sulfur (Li-S) cell. We, here, report on the improvement of electrochemical performance of the lithium/sulfur cell through such an efficient functionalization approach.

Enhanced Thermopower of Saturated Molecules by Noncovalent Anchor-Induced Electron Doping of Single-Layer Graphene Electrode.

Enhancing thermopower is a key goal in organic and molecular thermoelectrics. Herein, it is shown that introducing noncovalent contact with a single-layer graphene (SLG) electrode improves the thermopower of saturated molecules as compared to the traditional gold-thiolate covalent contact. Thermoelectric junction measurements with a liquid-metal technique reveal that the value of Seebeck coefficient in large-area junctions based on n-alkylamine self-assembled monolayers (SAMs) on SLG is increased up to fivefold compared to the analogous junction based on n-alkanethiolate SAMs on gold. Experiments with Raman spectroscopy and field-effect transistor analysis indicate that such enhancements benefit from the creation of new in-gap states and electron doping through noncovalent interaction between the amine anchor and the SLG electrode, which leads to a reduced energy offset between the Fermi level and the transport channel. This work demonstrates that control of interfacial bonding nature in molecular junctions improves the Seebeck effect in saturated molecules.

Graphene Quantum Dots from Carbonized Coffee Bean Wastes for Biomedical Applications.

Recent studies concerning graphene quantum dots (GQDs) focus extensively on their application in biomedicine, exploiting their modifiable optical properties and ability to complex with various molecules via π-π or covalent interactions. Among these nascent findings, the potential therapeutic efficacy of GQDs was reported against Parkinson's disease, which has to date remained incurable. Herein, we present an environmentally friendly approach for synthesizing GQDs through a waste-to-treasure method, specifically from coffee waste to nanodrug. Consistent with the previous findings with carbon fiber-derived GQDs, the inhibitory effects of coffee bean-derived GQDs demonstrated similar effectiveness against abnormal α-synuclein fibrillation and the protection of neurons from relevant subcellular damages. The fact that a GQDs-based nanodrug can be prepared from a non-reusable yet edible source illustrates a potential approach to convert such waste materials into novel therapeutic agents with minimal psychological rejection by patients.

Chemically Robust Indium Tin Oxide/Graphene Anode for Efficient Perovskite Light-Emitting Diodes.

Graphene is an optimal material to be employed as an ionic diffusion barrier because of its outstanding impermeability and chemical robustness. Indium tin oxide (ITO) is often used in perovskite light-emitting diodes (PeLEDs), and it can release indium easily upon exposure to the acidic hole-injection layer so that luminescence can be quenched significantly. Here, we exploit the outstanding impermeability of graphene and use it as a chemical barrier to block the etching that can occur in ITO exposed to an acidic hole-injection layer in PeLEDs. This barrier reduced the luminescence quenching that these metallic species can cause, so the photoluminescence lifetime of perovskite film was substantially higher in devices with ITO and graphene layer (87.9 ns) than in devices that had only an ITO anode (22.1 ns). Luminous current efficiency was also higher in PeLEDs with a graphene barrier (16.4 cd/A) than in those without graphene (9.02 cd/A). Our work demonstrates that graphene can be used as a barrier to reduce the degradation of transparent electrodes by chemical etching in optoelectronic devices.

Graphene Quantum Dots Alleviate Impaired Functions in Niemann-Pick Disease Type C in Vivo.

While the neuropathological characteristics of Niemann-Pick disease type C (NPC) result in a fatal diagnosis, the development of clinically available therapeutic agent remains a challenge. Here we propose graphene quantum dots (GQDs) as a potential candidate for the impaired functions in NPC in vivo. In addition to the previous findings that GQDs exhibit negligible long-term toxicity and are capable of penetrating the blood-brain barrier, GQD treatment reduces the aggregation of cholesterol in the lysosome through expressed physical interactions. GQDs also promote autophagy and restore defective autophagic flux, which, in turn, decreases the atypical accumulation of autophagic vacuoles. More importantly, the injection of GQDs inhibits the loss of Purkinje cells in the cerebellum while also demonstrating reduced activation of microglia. The ability of GQDs to alleviate impaired functions in NPC proves the promise and potential of the use of GQDs toward resolving NPC and other related disorders.

Gold nanoparticle-mediated non-covalent functionalization of graphene for field-effect transistors.

Since its discovery, graphene has attracted much attention due to its unique electrical transport properties that can be applied to high-performance field-effect transistors (FETs). However, mounting chemical functionalities onto graphene inevitably involves the breaking of sp2 bonds, resulting in the degradation of the mechanical and electrical properties compared to pristine graphene. Here, we report a new strategy to chemically functionalize graphene for use in FETs without affecting the electrical performance. The key idea is to control the Fermi level of the graphene using the consecutive treatment of gold nanoparticles (AuNPs) and thiol-SAM (self-assembled monolayer) molecules, inducing positive and negative doping effects, respectively, by flipping the electric dipoles between AuNPs and SAMs. Based on this method, we demonstrate a Dirac voltage switcher on a graphene FET using heavy metal ions on functionalized graphene, where the carboxyl functional groups of the mediating SAMs efficiently form complexes with the metal ions and, as a result, the Dirac voltage can be positively shifted by different charge doping on graphene. We believe that the nanoparticle-mediated SAM functionalization of graphene can pave the way to developing high-performance chemical, environmental, and biological sensors that fully utilize the pristine properties of graphene.

Tailored Graphene Micropatterns by Wafer-Scale Direct Transfer for Flexible Chemical Sensor Platform.

2D materials, such as graphene, exhibit great potential as functional materials for numerous novel applications due to their excellent properties. The grafting of conventional micropatterning techniques on new types of electronic devices is required to fully utilize the unique nature of graphene. However, the conventional lithography and polymer-supported transfer methods often induce the contamination and damage of the graphene surface due to polymer residues and harsh wet-transfer conditions. Herein, a novel strategy to obtain micropatterned graphene on polymer substrates using a direct curing process is demonstrated. Employing this method, entirely flexible, transparent, well-defined self-activated graphene sensor arrays, capable of gas discrimination without external heating, are fabricated on 4 in. wafer-scale substrates. Finite element method simulations show the potential of this patterning technique to maximize the performance of the sensor devices when the active channels of the 2D material are suspended and nanoscaled. This study contributes considerably to the development of flexible functional electronic devices based on 2D materials.

Layer-Selective Synthesis of MoS2 and WS2 Structures under Ambient Conditions for Customized Electronics.

Transition metal dichalcogenides (TMDs) have attracted significant interest as one of the key materials in future electronics such as logic devices, optoelectrical devices, and wearable electronics. However, a complicated synthesis method and multistep processes for device fabrication pose major hurdles for their practical applications. Here, we introduce a direct and rapid method for layer-selective synthesis of MoS2 and WS2 structures in wafer-scale using a pulsed laser annealing system (λ = 1.06 µm, pulse duration ∼100 ps) in ambient conditions. The precursor layer of each TMD, which has at least 3 orders of magnitude higher absorption coefficient than those of neighboring layers, rigorously absorbed the incoming energy of the laser pulse and rapidly pyrolyzed in a few nanoseconds, enabling the generation of a MoS2 or WS2 layer without damaging the adjacent layers of SiO2 or polymer substrate. Through experimental and theoretical studies, we establish the underlying principles of selective synthesis and optimize the laser annealing conditions, such as laser wavelength, output power, and scribing speed, under ambient condition. As a result, individual homostructures of patterned MoS2 and WS2 layers were directly synthesized on a 4 in. wafer. Moreover, a consecutive synthesis of the second layer on top of the first synthesized layer realized a vertically stacked WS2/MoS2 heterojunction structure, which can be treated as a cornerstone of electronic devices. As a proof of concept, we demonstrated the behavior of a MoS2-based field-effect transistor, a skin-attachable motion sensor, and a MoS2/WS2-based heterojunction diode in this study. The ultrafast and selective synthesis of the TMDs suggests an approach to the large-area/mass production of functional heterostructure-based electronics.

Graphene quantum dots as anti-inflammatory therapy for colitis.

While graphene and its derivatives have been suggested as a potential nanomedicine in several biomimetic models, their specific roles in immunological disorders still remain elusive. Graphene quantum dots (GQDs) may be suitable for treating intestinal bowel diseases (IBDs) because of their low toxicity in vivo and ease of clearance. Here, GQDs are intraperitoneally injected to dextran sulfate sodium (DSS)-induced chronic and acute colitis model, and its efficacy has been confirmed. In particular, GQDs effectively prevent tissue degeneration and ameliorate intestinal inflammation by inhibiting TH1/TH17 polarization. Moreover, GQDs switch the polarization of macrophages from classically activated M1 to M2 and enhance intestinal infiltration of regulatory T cells (Tregs). Therefore, GQDs effectively attenuate excessive inflammation by regulating immune cells, indicating that they can be used as promising alternative therapeutic agents for the treatment of autoimmune disorders, including IBDs.

Multifunctional reduced graphene oxide-CVD graphene core-shell fibers.

The insufficient electrical conductivity and mechanical stretchability of conventional graphene fibers based on reduced graphene oxide liquid crystals (rGO-LCs) has limited their applications to numerous textile devices. Here, we report a simple method to fabricate multifunctional fibers with mechanically strong rGO cores and highly conductive CVD graphene shells (rGO@Gr fibers), which show an outstanding electrical conductivity as high as ∼137 S cm-1 and a failure strain value of 21%, which are believed to be the highest values among polymer-free graphene fibers. We also demonstrate the use of the rGO@Gr fibers for high power density supercapacitors with enhanced mechanical stability and durability, which would enable their practical applications in various smart wearable devices in the future.

Au decoration of a graphene microchannel for self-activated chemoresistive flexible gas sensors with substantially enhanced response to hydrogen.

Graphene is one of the most promising materials for high-performance gas sensors due to its unique properties such as high sensitivity at room temperature, transparency, and flexibility. However, the low selectivity and irreversible behavior of graphene-based gas sensors are major problems. Here, we present unprecedented room temperature hydrogen detection by Au nanoclusters supported on self-activated graphene. Compared to pristine graphene sensors, the Au-decorated graphene sensors exhibit highly improved gas-sensing properties upon exposure to various gases. In particular, an unexpected substantial enhancement in H2 detection is found, which has never been reported for Au decoration on any type of chemoresistive material. Density functional theory calculations reveal that Au nanoclusters on graphene contribute to the adsorption of H atoms, whereas the surfaces of Au and graphene do not bind with H atoms individually. The discovery of such a new functionality in the existing material platform holds the key to diverse research areas based on metal nanocluster/graphene heterostructures.

Threshold Voltage Control of Multilayered MoS2 Field-Effect Transistors via Octadecyltrichlorosilane and their Applications to Active Matrixed Quantum Dot Displays Driven by Enhancement-Mode Logic Gates.

In recent past, for next-generation device opportunities such as sub-10 nm channel field-effect transistors (FETs), tunneling FETs, and high-end display backplanes, tremendous research on multilayered molybdenum disulfide (MoS2 ) among transition metal dichalcogenides has been actively performed. However, nonavailability on a matured threshold voltage control scheme, like a substitutional doping in Si technology, has been plagued for the prosperity of 2D materials in electronics. Herein, an adjustment scheme for threshold voltage of MoS2 FETs by using self-assembled monolayer treatment via octadecyltrichlorosilane is proposed and demonstrated to show MoS2 FETs in an enhancement mode with preservation of electrical parameters such as field-effect mobility, subthreshold swing, and current on-off ratio. Furthermore, the mechanisms for threshold voltage adjustment are systematically studied by using atomic force microscopy, Raman, temperature-dependent electrical characterization, etc. For validation of effects of threshold voltage engineering on MoS2 FETs, full swing inverters, comprising enhancement mode drivers and depletion mode loads are perfectly demonstrated with a maximum gain of 18.2 and a noise margin of ≈45% of 1/2 VDD . More impressively, quantum dot light-emitting diodes, driven by enhancement mode MoS2 FETs, stably demonstrate 120 cd m-2 at the gate-to-source voltage of 5 V, exhibiting promising opportunities for future display application.