Chemical Patterning of Graphene via Metal-Assisted Highly Energetic Electron Irradiation for Graphene Homojunction-Based Gas Sensors.

To gain the target functionality of graphene for gas detection, nonfocused and large-scale compatible MeV electron beam irradiation on graphene with Ag patterns is innovatively adopted in air for chemical patterning of graphene. This strategy allows the metal-assisted site-specific oxidation of graphene to realize monolithically integrated graphene-chemically patterned graphene (CPG)-graphene homojunction-based gas sensors. The size-tunable CPG patterns can be mediated by regulating the size of Ag prepatterns. The impacts of highly energetic electron irradiation (HEEI) on graphene are summarized as follows: (i) the selective p-type doping and the defect generation of graphene by the HEEI-induced oxidation, (ii) the resistance of the homojunction devices manipulated by the HEEI dose, (iii) the band gap opening of graphene as well as the lowering of the Fermi level, (iv) the work function values for pristine graphene and CPG corresponding to 4.14 and 4.88 eV, respectively, and (v) graphene-CPG-graphene homojunction for NO2 gas, revealing an 839% enhanced gas response compared with that of the pristine graphene-based gas sensor.

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.

Complementary Dual-Channel Gas Sensor Devices Based on a Role-Allocated ZnO/Graphene Hybrid Heterostructure.

Here, we present a new approach to dual-channel gas sensors on the basis of a role-allocated graphene/ZnO heterostructure, formed by the complementary hybridization of graphene and a ZnO thin film. The method enables cyclic and reproducible gas response as well as high gas response. The role allocation of graphene and ZnO was verified by studying the electrical transport properties of the heterostructure. The results indicated that the ZnO top layer and graphene bottom layer act as a gas adsorption layer and a carrier conducting layer, respectively. The charge interactions of the heterostructures were systematically explored by monitoring changes in transfer characteristics at room temperature and elevated temperature ( T = 250 °C) after introducing 20 ppm NO2. These results can be understood in terms of the dual-channel effect of the graphene/ZnO heterostructures. Remarkably, an abrupt and reliable gas response under periodic NO2 gas injection was unambiguously achieved by the heterostructure-based gas sensors and as ∼30 times higher than those of a graphene-based gas sensor. These proposed heterostructures represent a fundamental building block of a complementary hybrid gas sensor with highly sensitive and reproducible gas response.

Highly efficient and flexible photodetector based on MoS2-ZnO heterostructures.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) such as molybdenum disulfide (MoS2) and tungsten diselenide (WSe2), have recently attracted attention for their applicability as building blocks for fabricating advanced functional materials. In this study, a high quality hybrid material based on 2D TMD nanosheets and ZnO nanopatches was demonstrated. An organic promoter layer was employed for the large-scale growth of the TMD sheet, and atomic layer deposition (ALD) was utilized for the growth of ZnO nanopatches. Photodetectors based on 2D TMD nanosheets and ZnO nanopatches were successfully fabricated and investigated, which showed a high photoresponsivity of 2.7 A/W. Our novel approach is a promising and effective method for the fabrication of photodetectors with a new structure for application in TMD-based transparent and flexible optoelectronic devices.

Highly sensitive and wearable gas sensors consisting of chemically functionalized graphene oxide assembled on cotton yarn.

Highly sensitive and wearable chemical sensors for the detection of toxic gas molecules are given significant attention for a variety of applications in human health care and environmental safety. Herein, we demonstrated fiber-type gas sensors based on graphene oxide functionalized with organic molecules such as heptafluorobutylamine (HFBA), 1-(2-methoxyphenyl)piperazine (MPP), and 4-(2-keto-1-benzimidazolinyl)piperidine (KBIP) by assembling functionalized graphene oxide (FGO) on a single yarn fabric. These gas sensors of FGO on yarn exhibited extraordinarily higher sensitivity upon exposure to gas molecules than chemically reduced graphene oxide due to many active functional groups on the GO surface. Furthermore, the mechanical stability and chemical durability of the resulting gas sensors are well-maintained. Based on these results, we expected that our sensors with high sensitive and wearability will provide a good premise for wearable chemical sensors-based multidisciplinary applications.

Correction: Highly sensitive and wearable gas sensors consisting of chemically functionalized graphene oxide assembled on cotton yarn.

[This corrects the article DOI: 10.1039/C8RA01184B.].

Strain-Gradient Effect in Gas Sensors Based on Three-Dimensional Hollow Molybdenum Disulfide Nanoflakes.

A novel three-dimensional transition metal dichalcogenide (TMD) structure consisting of seamless hollow nanoflakes on two-dimensional basal layers was synthesized by a one-step chemical vapor deposition method. Here, we demonstrate that the as-grown nanoflakes are formed on an organic promoter layer which served as a positive template and are swollen at the grain boundaries by the bubbling effect. TMD nanosheets with hollow nanoflakes are successfully applied as chemical sensors, and it was found that their gas adsorption property is strongly related to the internal strain gradient resulting from the variation in the lattice parameter. This result is consistent with the theoretical prediction in previous studies. Our chemical vapor deposition-based approach is an efficient way to generate TMD-based nanostructures over a large surface area for various practical applications such as chemical sensors.

Two-Dimensional Excitonic Photoluminescence in Graphene on a Cu Surface.

Despite having outstanding electrical properties, graphene is unsuitable for optical devices because of its zero band gap. Here, we report two-dimensional excitonic photoluminescence (PL) from graphene grown on a Cu(111) surface, which shows an unexpected and remarkably sharp strong emission near 3.16 eV (full width at half-maximum ≤3 meV) and multiple emissions around 3.18 eV. As temperature increases, these emissions blue shift, displaying the characteristic negative thermal coefficient of graphene. The observed PL originates from the significantly suppressed dispersion of excited electrons in graphene caused by hybridization of graphene π and Cu d orbitals of the first and second Cu layers at a shifted saddle point 0.525(M+K) of the Brillouin zone. This finding provides a pathway to engineering optoelectronic graphene devices, while maintaining the outstanding electrical properties of graphene.

Indirect Bandgap Puddles in Monolayer MoS2 by Substrate-Induced Local Strain.

An unusually large bandgap modulation of 1.23-2.65 eV in monolayer MoS2 on a SiO2 /Si substrate is found due to the inherent local bending strain induced by the surface roughness of the substrate, reaching the direct-to-indirect bandgap transition. Approximately 80% of the surface area reveals an indirect bandgap, which is confirmed further by the degraded photoluminescence compared to that from suspended MoS2 .

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.

Electrical Double Layer Capacitance in a Graphene-embedded Al2O3 Gate Dielectric.

Graphene heterostructures are of considerable interest as a new class of electronic devices with exceptional performance in a broad range of applications has been realized. Here, we propose a graphene-embedded Al2O3 gate dielectric with a relatively high dielectric constant of 15.5, which is about 2 times that of Al2O3, having a low leakage current with insertion of tri-layer graphene. In this system, the enhanced capacitance of the hybrid structure can be understood by the formation of a space charge layer at the graphene/Al2O3 interface. The electrical properties of the interface can be further explained by the electrical double layer (EDL) model dominated by the diffuse layer.

Epitaxial growth of a single-crystal hybridized boron nitride and graphene layer on a wide-band gap semiconductor.

Vertical and lateral heterogeneous structures of two-dimensional (2D) materials have paved the way for pioneering studies on the physics and applications of 2D materials. A hybridized hexagonal boron nitride (h-BN) and graphene lateral structure, a heterogeneous 2D structure, has been fabricated on single-crystal metals or metal foils by chemical vapor deposition (CVD). However, once fabricated on metals, the h-BN/graphene lateral structures require an additional transfer process for device applications, as reported for CVD graphene grown on metal foils. Here, we demonstrate that a single-crystal h-BN/graphene lateral structure can be epitaxially grown on a wide-gap semiconductor, SiC(0001). First, a single-crystal h-BN layer with the same orientation as bulk SiC was grown on a Si-terminated SiC substrate at 850 °C using borazine molecules. Second, when heated above 1150 °C in vacuum, the h-BN layer was partially removed and, subsequently, replaced with graphene domains. Interestingly, these graphene domains possess the same orientation as the h-BN layer, resulting in a single-crystal h-BN/graphene lateral structure on a whole sample area. For temperatures above 1600 °C, the single-crystal h-BN layer was completely replaced by the single-crystal graphene layer. The crystalline structure, electronic band structure, and atomic structure of the h-BN/graphene lateral structure were studied by using low energy electron diffraction, angle-resolved photoemission spectroscopy, and scanning tunneling microscopy, respectively. The h-BN/graphene lateral structure fabricated on a wide-gap semiconductor substrate can be directly applied to devices without a further transfer process, as reported for epitaxial graphene on a SiC substrate.

Direct momentum-resolved observation of one-dimensional confinement of externally doped electrons within a single subnanometer-scale wire.

Cutting-edge research in the band engineering of nanowires at the ultimate fine scale is related to the minimum scale of nanowire-based devices. The fundamental issue at the subnanometer scale is whether angle-resolved photoemission spectroscopy (ARPES) can be used to directly measure the momentum-resolved electronic structure of a single wire because of the difficulty associated with assembling single wire into an ordered array for such measurements. Here, we demonstrated that the one-dimensional (1D) confinement of electrons, which are transferred from external dopants, within a single subnanometer-scale wire (subnanowire) could be directly measured using ARPES. Convincing evidence of 1D electron confinement was obtained using two different gold subnanowires with characteristic single metallic bands that were alternately and spontaneously ordered on a stepped silicon template, Si(553). Noble metal atoms were adsorbed at room temperature onto the gold subnanowires while the overall structure of the wires was maintained. Only one type of gold subnanowire could be controlled using external noble metal dopants without transforming the metallic band of the other type of gold subnanowires. This result was confirmed by scanning tunnelling microscopy experiments and first-principles calculations. The selective control clearly showed that externally doped electrons could be confined within a single gold subnanowire. This experimental evidence was used to further investigate the effects of the disorder induced by external dopants on a single subnanowire using ARPES.

Novel fabrication of flexible graphene-based chemical sensors with heaters using soft lithographic patterning method.

We have fabricated graphene-based chemical sensors with flexible heaters for the highly sensitive detection of specific gases. We believe that increasing the temperature of the graphene surface significantly enhanced the electrical signal change of the graphene-based channel, and reduced the recovery time needed to obtain a normal state of equilibrium. In addition, a simple and efficient soft lithographic patterning process was developed via surface energy modification for advanced, graphene-based flexible devices, such as gas sensors. As a proof of concept, we demonstrated the high sensitivity of NO2 gas sensors based on graphene nanosheets. These devices were fabricated using a simple soft-lithographic patterning method, where flexible graphene heaters adjacent to the channel of sensing graphene were utilized to control graphene temperature.

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.

Immobilization of carbon nanotubes on functionalized graphene film grown by chemical vapor deposition and characterization of the hybrid material.

We report the surface functionalization of graphene films grown by chemical vapor deposition and fabrication of a hybrid material combining multi-walled carbon nanotubes and graphene (CNT-G). Amine-terminated self-assembled monolayers were prepared on graphene by the UV-modification of oxidized groups introduced onto the film surface. Amine-termination led to effective interaction with functionalized CNTs to assemble a CNT-G hybrid through covalent bonding. Characterization clearly showed no defects of the graphene film after the immobilization reaction with CNT. In addition, the hybrid graphene material revealed a distinctive CNT-G structure and p-n type electrical properties. The introduction of functional groups on the graphene film surface and fabrication of CNT-G hybrids with the present technique could provide an efficient, novel route to device fabrication.

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.

Opening and reversible control of a wide energy gap in uniform monolayer graphene.

For graphene to be used in semiconductor applications, a 'wide energy gap' of at least 0.5 eV at the Dirac energy must be opened without the introduction of atomic defects. However, such a wide energy gap has not been realized in graphene, except in the cases of narrow, chemically terminated graphene nanostructures with inevitable edge defects. Here, we demonstrated that a wide energy gap of 0.74 eV, which is larger than that of germanium, could be opened in uniform monolayer graphene without the introduction of atomic defects into graphene. The wide energy gap was opened through the adsorption of self-assembled twisted sodium nanostrips. Furthermore, the energy gap was reversibly controllable through the alternate adsorption of sodium and oxygen. The opening of such a wide energy gap with minimal degradation of mobility could improve the applicability of graphene in semiconductor devices, which would result in a major advancement in graphene technology.

Immobilization of iron oxide nanoclusters on surface functionalized silicon substrate and their catalytic behavior to synthesize multi-walled carbon nanotubes.

Multi-walled carbon nanotubes (MWCNTs) were grown using iron oxide nanoclusters (Nc) assisted by self-assembled monolayer (SAM) on substrate. The amine-terminated SAM fabricated on silicon substrate (APTMS/SI) was carried out by UV-treatment and immersed into the FeCI3/HCI aqueous solution. Then, Nc were immobilized onto oxidized SAM silicon substrate (SAMs/Si) through electrostatic interaction between cationic Nc and anionic SAMs/Si. The characterization results clearly show that the well-graphitized MWCNTs were synthesized by using functionalized silicon substrate (Nc/SAMs/Si) as a template having appropriate density of catalyst. These consequences show that SAM containing template is important to achieve the effective layer of catalyst to synthesize MWCNTs in chemical vapor deposition (CVD).

Rotated domains in chemical vapor deposition-grown monolayer graphene on Cu(111): an angle-resolved photoemission study.

Copper is considered to be the most promising substrate for the growth of high-quality and large area graphene by chemical vapor deposition (CVD), in particular, on the (111) facet. Because the interactions between graphene and Cu substrates influence the orientation, quality, and properties of the synthesized graphene, we studied the interactions using angle-resolved photoemission spectroscopy. The evolution of both the Shockley surface state of the Cu(111) and the π band of the graphene was measured from the initial stage of CVD growth to the formation of a monolayer. Graphene growth was initiated along the Cu(111) lattice, where the Dirac band crossed the Fermi energy (EF) at the K point without hybridization with the d-band of Cu. Then two rotated domains were additionally grown as the area covered with graphene became wider. The Dirac energy was about -0.4 eV and the energy of the Shockley surface state of Cu(111) shifted toward the EF by ~0.15 eV upon graphene formation. These results indicate weak interactions between graphene and Cu, and that the electron transfer is limited to that between the Shockley surface state of Cu(111) and the π band of graphene. This weak interaction and slight lattice mismatch between graphene and Cu resulted in the growth of rotated graphene domains (9.6° and 8.4°), which showed no significant differences in the Dirac band with respect to different orientations. These rotated graphene domains resulted in grain boundaries which would hinder a large-sized single monolayer growth on Cu substrates.