Large-scale Monolayer Research Articles

Self-Assembled Large-Scale Monolayer of Au Nanoparticles at the Air/Water Interface Used as a SERS Substrate.

Self-assembly of metal nanoparticles has attracted considerable attention because of its unique applications in technologies such as plasmonics, surface-enhanced optics, sensors, and catalysts. However, fabrication of ordered nanoparticle structures remains a significant challenge. Thus, developing an efficient approach for the assembly of large-scale Au nanoparticles films for theoretical studies and for various applications is highly desired. In this paper, a facial approach for fabricating a monolayer film of Au nanoparticles was developed successfully. Using the surfactant polyvinylpyrrolidone (PVP), a large-scale monolayer film of well-ordered, uniform-sized Au nanoparticles was fabricated at the air/water interface. The film exhibited a two-dimensional (2D) hexagonal close-packed (HCP) structure having interparticle gaps smaller than 2 nm. These gaps generated numerous uniform "hot spots" for surface-enhanced Raman scattering (SERS) activity. The as-prepared monolayer film could be transferred to a solid substrate for use as a suitable SERS substrate with high activity, high uniformity, and high stability. The low spot-to-spot and substrate-to-substrate variations of intensity (<10%), the large surface enhancement factor (∼10(6)), and the high stability (∼45 days) make the substrate suitable for SERS measurements. Transfer of the monolayer film onto a glassy carbon electrode produced an Au electrode with clean, well-defined nanostructure suitable for electrochemical SERS measurements. The adsorption process of ionic liquids on the electrode with the monolayer film is similar to that on bulk metal electrodes. The present strategy provides an effective way for self-assembly of Au nanoparticles into well-defined nanostructures that may form optimal reproducible SERS substrates for quantitative analysis. It also provides an electrode with clean, well-defined nanostructure for electrochemical investigations.

Stable electrical performance observed in large-scale monolayer WSe2(1−x)S2x with tunable band gap

Two-dimensional (2D) semiconductor materials have attracted broad interest due to their unique structures and physical properties. The stability of the 2D-material-based devices plays a key role in their practical applications. Here, we report the promising stable electrical performance in the large-scale monolayer WSe2(1−x)S2x with a tunable band gap. Photoluminescence (PL) spectroscopy was utilized to verify the tunable band gap in the as-grown monolayer with a tuning capability of 120 meV. Gated field effect transistor (FET) performance confirmed the p-type transport behavior in monolayer WSe2(1−x)S2x with a high on/off ratio (>104). Top-gated FET configuration improves the carrier mobility with two orders larger than that in the back-gated FET device. After exposure to air for three months, the device performance manifested excellent stability with no source-drain current drop observed. P-type WSe2(1−x)S2x with a tunable band gap is the ideal complement to n-type tunable monolayers in the application of pn junction-related flexible nanodevices.

A monolayer of hierarchical silver hemi-mesoparticles with tunable surface topographies for highly sensitive surface-enhanced Raman spectroscopy.

We proposed a facile green synthesis system to synthesize large-scale Ag hemi-mesoparticles monolayer on Cu foil. Ag hemi-mesoparticles have different surface morphologies on their surfaces, including ridge-like, meatball-like, and fluffy-like shapes. In the reaction, silver nitrate was reduced by copper at room temperature in dimethyl sulfoxide via the galvanic displacement reaction. The different surface morphologies of the Ag hemi-mesoparticles were adjusted by changing the reaction time, and the hemi-mesoparticle surface formed fluffy-spherical nanoprotrusions at longer reaction time. At the same time, we explored the growth mechanism of silver hemi-mesoparticles with different surface morphologies. With 4-mercaptobenzoic acid as Raman probe molecules, the fluffy-like silver hemi-mesoparticles monolayer with the best activity of surface enhanced Raman scattering (SERS), the enhancement factor is up to 7.33 × 10(7) and the detection limit can reach 10(-10)M. SERS measurements demonstrate that these Ag hemi-mesoparticles can serve as sensitive SERS substrates. At the same time, using finite element method, the distribution of the localized electromagnetic field near the particle surface was simulated to verify the enhanced mechanism. This study helps us to understand the relationship between morphology Ag hemi-mesoparicles and the properties of SERS.

Oscillatory barrier-assisted Langmuir–Blodgett deposition of large-scale quantum dot monolayers

Depositing continuous, large-scale quantum dot films with low pinhole density is an inevitable but nontrivial step for studying their properties for applications in catalysis, electronic devices, and optoelectronics. This rising interest in high-quality quantum dot films has provided research impetus to improve the deposition technique. We show that by incorporating oscillatory barriers in the commonly used Langmuir–Blodgett method, large-scale monolayers of quantum dots with full coverage up to several millimeters have been achieved. With assistance of perturbation provided by the oscillatory barriers, the film has been shown to relax towards thermal equilibrium, and this physical process has been supported by molecular dynamics simulation. In addition, time evolution of dilatational moduli has been shown to give a clear indication of the film morphology and its stability.

Ultraclean and large-area monolayer hexagonal boron nitride on Cu foil using chemical vapor deposition

Atomically thin hexagonal boron nitride (h-BN) has been demonstrated to be an excellent dielectric layer as well as an ideal van der Waals epitaxial substrate for fabrication of two-dimensional (2D) atomic layers and their vertical heterostructures. Although many groups have obtained large-scale monolayer h-BN through low pressure chemical vapor deposition (LPCVD), it is still a challenge to grow clean monolayers without the reduction of domain size. Here we report the synthesis of large-area (4 × 2 cm2) high quality monolayer h-BN with an ultraclean and unbroken surface on copper foil by using LPCVD. A detailed investigation of the key factors affecting growth and transfer of the monolayer was carried out in order to eliminate the adverse effects of impurity particles. Furthermore, an optimized transfer approach allowed the nondestructive and clean transfer of the monolayer from copper foil onto an arbitrary substrate, including a flexible substrate, under mild conditions. Atomic force microscopy indicated that the root-mean-square (RMS) roughness of the monolayer h-BN on SiO2 was less than 0.269 nm for areas with fewer wrinkles. Selective area electron diffraction analysis of the h-BN revealed a pattern of hexagonal diffraction spots, which unambiguously demonstrated its highly crystalline character. Our work paves the way toward the use of ultraclean and large-area monolayer h-BN as the dielectric layer in the fabrication of high performance electronic and optoelectronic devices for novel 2D atomic layer materials.

Effect of Refractive Index of Substrate on Fabrication and Optical Properties of Hybrid Au-Ag Triangular Nanoparticle Arrays

In this study, the nanosphere lithography (NSL) method was used to fabricate hybrid Au-Ag triangular periodic nanoparticle arrays. The Au-Ag triangular periodic arrays were grown on different substrates, and the effect of the refractive index of substrates on fabrication and optical properties was systematically investigated. At first, the optical spectrum was simulated by the discrete dipole approximation (DDA) numerical method as a function of refractive indexes of substrates and mediums. Simulation results showed that as the substrates had the refractive indexes of 1.43 (quartz) and 1.68 (SF5 glass), the nanoparticle arrays would have better refractive index sensitivity (RIS) and figure of merit (FOM). Simulation results also showed that the peak wavelength of the extinction spectra had a red shift when the medium’s refractive index n increased. The experimental results also demonstrated that when refractive indexes of substrates were 1.43 and 1.68, the nanoparticle arrays and substrate had better adhesive ability. Meanwhile, we found the nanoparticles formed a large-scale monolayer array with the hexagonally close-packed structure. Finally, the hybrid Au-Ag triangular nanoparticle arrays were fabricated on quartz and SF5 glass substrates and their experiment extinction spectra were compared with the simulated results.

Graphene substrate for inducing neurite outgrowth

A few recent studies demonstrated that graphene may have cytocompatibility with several cell types. However, when assessing cell behavior on graphene, there has been no precise control over the quality of graphene, number of graphene layers, and substrate surface coverage by graphene. In this study, using well-controlled monolayer graphene film substrates we tested the cytocompatibility of graphene for human neuroblastoma (SH-SY5Y) cell culture. A large-scale monolayer graphene film grown on Cu foils by chemical vapor deposition (CVD) could be successfully transferred onto glass substrates by wet transfer technique. We observed that graphene substrate could induce enhanced neurite outgrowth, both in neurite length and number, compared with control glass substrate. Interestingly, the positive stimulatory effect by graphene was achieved even in the absence of soluble neurogenic factor, retinoic acid (RA). Key genes relevant to cell neurogenesis, e.g., neurofilament light chain (NFL), were also upregulated on graphene. Inhibitor studies suggested that the graphene stimulation of cellular neurogenesis may be achieved through focal adhesion kinase (FAK) and p38 mitogen-activated protein kinase (MAPK) cascades. Our data indicate that graphene may be exploited as a platform for neural regenerative medicine, and the suggested molecular mechanism may provide an insight into the graphene control of neural cells.

Oriented colloidal-crystal thin films of polystyrene spheres via spin coating

We developed a simple and inexpensive synthesis of a large-scale close-packed monolayer of polystyrene sphere arrays, which have a variety of applications. The influence of three step spin speeds, spinning time, solution quantity and relative humidity is studied in order to achieve a large area close-packed monolayer. A relatively high surface coverage and uniform monolayer of PS spheres in the range of 85%–90% are achieved by appropriate control of the preparative parameters. Also the effect of the oxygen plasma etching process on the reduction of PS spheres has been studied. We conclude that it can be useful in industrial applications, because of the fabrication speed, surface coverage, control over PS spheres and cost of the process.

Atomistic mechanisms for bilayer growth of graphene on metal substrates

Epitaxial growth on metal substrates has been shown to be the most powerful approach in producing large-scale high-quality monolayer graphene, yet it remains a major challenge to realize uniform bilayer graphene growth. Here we carry out a comparative study of the atomistic mechanisms for bilayer graphene growth on the (111) surfaces of Cu and Ni, using multiscale approaches combining first-principles calculations and rate-equation analysis. We first show that the relatively weak graphene-Cu interaction enhances the lateral diffusion and effective nucleation of C atoms underneath the graphene island, thereby making it more feasible to grow bilayer graphene on Cu. In contrast, the stronger graphene-Ni interaction suppresses the lateral mobility and dimerization of C atoms underneath the graphene, making it unlikely to achieve controlled growth of bilayer graphene on Ni. We then determine the critical graphene size beyond which nucleation of the second layer will take place. Intriguingly, the critical size exhibits an effective inverse Ehrlich-Schwoebel barrier effect, becoming smaller for faster C migration from the Cu surface to the graphene-Cu interface sites across the graphene edge. Lastly, these findings allow us to propose a novel alternating growth scheme to realize mass production of bilayer graphene.

Monolayer MoS2 heterojunction solar cells.

We realized photovoltaic operation in large-scale MoS2 monolayers by the formation of a type-II heterojunction with p-Si. The MoS2 monolayer introduces a built-in electric field near the interface between MoS2 and p-Si to help photogenerated carrier separation. Such a heterojunction photovoltaic device achieves a power conversion efficiency of 5.23%, which is the highest efficiency among all monolayer transition-metal dichalcogenide-based solar cells. The demonstrated results of monolayer MoS2/Si-based solar cells hold the promise for integration of 2D materials with commercially available Si-based electronics in highly efficient devices.

High quality and large-scale manually operated monolayer graphene pasters

Graphene is a well-known material with various potential applications. Here we report the manufacture of high-quality and large-scale monolayer graphene pasters via polyvinyl butyral (PVB). These pasters have good self-supporting properties and overcome the drawback of weak mechanical strength of PMMA. Manual manipulations to monolayer graphene become realizable via graphene pasters. Graphene pasters can be quickly diverted onto any substrate with sufficient contact and greatly minimize the challenges in graphene transfer, measurements, and other applications. The improved transfer process via graphene pasters protects the integrity of monolayer graphene and introduces few cracks or tears into graphene. Large-scale monolayer graphene films diverted onto SiO2/Si by using graphene pasters maintain low resistivity and low Dirac point, while also exhibiting a higher magnetoresistance than traditional results. High magnetoresistance up to 600% and signs of saturation at high magnetic fields can be seen. Obvious negative magnetoresistance at low magnetic fields due to weak localization also can be observed. Graphene pasters can be used in many different domains and will promote future studies and applications of graphene.

Highly efficient field emission from large-scale and uniform monolayer graphene sheet supported on patterned ZnO nanorod arrays

A graphene/patterned ZnO (G/PZO) nanorod array composite was successfully fabricated by using the colloidal nanosphere monolayer templating strategy. Compared with graphene/compact ZnO (G/CZO) nanorod arrays, the G/PZO nanorod array composite exhibited a highly efficient and stable field emission with a low turn-on field. The field emission had a strong dependence on the density and the inter-distance of the emitters. By changing the diameter of polystyrene (PS) colloidal nanospheres, optimal emitter inter-distance was obtained. Graphene supported on ZnO nanorod arrays, patterned by an 886 nm PS colloidal nanosphere monolayer, displayed the best field emission with a turn-on electric field of only 6.4 V μm−1 and the field enhancement factor β was 1158. The K point in the Fowler–Nordheim plot demonstrated the electron tunneling mechanism took place in this composite material. The cyclic experiment showed that the field emission of the G/PZO nanorod array composite was of high stability.

Full-Layer Controlled Synthesis and Transfer of Large-Scale Monolayer Graphene for Nitrogen Dioxide and Ammonia Sensing

The controlled synthesis of large-scale monolayer graphene to be used in the development of cost-effective, mass-produced, and easy-to-use gas sensors for the real time monitoring of toxic gases is an important issue. In this study, scalable monolayer graphene was controllably synthesized by chemical vapor deposition on a copper substrate, and effectively transferred on a silica (insulator) substrate for gas sensing. A high-quality graphene layer was obtained by changing the growth conditions. Raman measurements indicated that large-area (1 × 1 cm2) monolayer graphene dominated the transferred films. Gas sensing characterizations demonstrated that monolayer graphene can effectively detect NO2 and NH3 within the temperature range of 100°C to 200°C. [Supplementary materials are available for this article. Go to the publisher's online edition of Analytical Letters for the following free supplemental resource(s): Additional figures.]

Alumina-coated Ag nanocrystal monolayers as surfaceenhanced Raman spectroscopy platforms for the direct spectroscopic detection of water splitting reaction intermediates

A novel Ag-alumina hybrid surface-enhanced Raman spectroscopy (SERS) platform has been designed for the spectroscopic detection of surface reactions in the steady state. Single crystalline and faceted silver (Ag) nanoparticles with strong light scattering were prepared in large quantity, which enables their reproducible self-assembly into large scale monolayers of Raman sensor arrays by the Langmuir-Blodgett technique. The close packed sensor film contains high density of sub-nm gaps between sharp edges of Ag nanoparticles, which created large local electromagnetic fields that serve as “hot spots” for SERS enhancement. The SERS substrate was then coated with a thin layer of alumina by atomic layer deposition to prevent charge transfer between Ag and the reaction system. The photocatalytic water splitting reaction on a monolayer of anatase TiO2 nanoplates decorated with Pt co-catalyst nanoparticles was employed as a model reaction system. Reaction intermediates of water photo-oxidation were observed at the TiO2/solution interface under UV irradiation. The surface-enhanced Raman vibrations corresponding to peroxo, hydroperoxo and hydroxo surface intermediate species were observed on the TiO2 surface, suggesting that the photo-oxidation of water on these anatase TiO2 nanosheets may be initiated by a nucleophilic attack mechanism.

From Boron Cluster to Two-Dimensional Boron Sheet on Cu(111) Surface: Growth Mechanism and Hole Formation

As attractive analogue of graphene, boron monolayers have been theoretically predicted. However, due to electron deficiency of boron atom, synthesizing boron monolayer is very challenging in experiments. Using first-principles calculations, we explore stability and growth mechanism of various boron sheets on Cu(111) substrate. The monotonic decrease of formation energy of boron cluster BN with increasing cluster size and low diffusion barrier for a single B atom on Cu(111) surface ensure continuous growth of two-dimensional (2D) boron cluster. During growth process, hexagonal holes can easily arise at the edge of a 2D triangular boron cluster and then diffuse entad. Hence, large-scale boron monolayer with mixed hexagonal-triangular geometry can be obtained via either depositing boron atoms directly on Cu(111) surface or soft landing of small planar BN clusters. Our theoretical predictions would stimulate further experiments of synthesizing boron sheets on metal substrates and thus enrich the variety of 2D monolayer materials.

Self‐Aligned Single‐Crystal Graphene Grains

The precisely controllable growth of self‐aligned single‐crystal graphene grains on liquid Cu surface by ambient pressure chemical vapor deposition is reported. Large scale monolayer graphene arrays are modulated by varying growth conditions such as flow rate of carbon source, growth temperature, and growth time. Further, bilayer graphene grains are also controllably prepared under optimized growth conditions. The self‐alignment mechanism of graphene is also studied and a growth model is proposed to explain that process involving surface tension of liquid phase. In all, the growth mechanism of graphene arrays is firstly probed and the grown graphene arrays show reasonable mobility and high current density, posing great potential for graphene‐based electronics.

PH Sensor Based on Chemical-Vapor-Deposition-Synthesized Graphene Transistor Array

We have successfully fabricated a pH-sensor array based on chemical-vapor-deposition (CVD)-synthesized graphene. As large-scale monolayer graphene is synthesized by this method, the size and the position of graphene can be controlled. Therefore, after transferring graphene onto SiO2/Si substrates, a graphene field-effect transistor (FET) array was produced. The sensing characteristics of the CVD-synthesized graphene-based device were investigated using three buffer solutions with different pH values (pHs 4.0, 6.8, and 9.3). The electrical measurements reveal that for most of the graphene FETs in the array, a similar stepwise increment in drain current was observed upon the introduction of each buffer solution with increasing pH value sequence. This will lead to the realization of the fabrication of multiplex hand-held chemical and biological sensors based on CVD-synthesized graphene.

Graphene–Ferroelectric Hybrid Structure for Flexible Transparent Electrodes

Graphene has exceptional optical, mechanical, and electrical properties, making it an emerging material for novel optoelectronics, photonics, and flexible transparent electrode applications. However, the relatively high sheet resistance of graphene is a major constraint for many of these applications. Here we propose a new approach to achieve low sheet resistance in large-scale CVD monolayer graphene using nonvolatile ferroelectric polymer gating. In this hybrid structure, large-scale graphene is heavily doped up to 3 × 10(13) cm(-2) by nonvolatile ferroelectric dipoles, yielding a low sheet resistance of 120 Ω/□ at ambient conditions. The graphene-ferroelectric transparent conductors (GFeTCs) exhibit more than 95% transmittance from the visible to the near-infrared range owing to the highly transparent nature of the ferroelectric polymer. Together with its excellent mechanical flexibility, chemical inertness, and the simple fabrication process of ferroelectric polymers, the proposed GFeTCs represent a new route toward large-scale graphene-based transparent electrodes and optoelectronics.

Rapid Assembly of Colloidal Monolayer for the Synthesis of Surface Anisotropic Particles

A facile and efficient technique for synthesizing rapid and large-scale colloidal monolayer is introduced to obtain surface anisotropic particles. Silica particles grafted with long alkyl chains are rapidly organized into monolayer assemblies by implementing water-film climbing and convective particle assembly on glass slides. Assembled particles are modified into surface-anisotropic particles utilizing physical vapor deposition with a magnetically active material. The magnetic hemisphere enables separation of modified and unmodified surface-anisotropic particles. The proposed methodology can lead to a large-scale production opportunity for surface-anisotropic particles.

Formation and magnetic properties of a large-scale FePt nanoparticle monolayer on silicon substrate

A large-scale FePt nanocube monolayer was fabricated on silicon substrate by a simple spin-coating method. After sputtering a B4C thin film on the particle monolayer, these films were annealed at elevated temperature. Transmission electron microscope and magnetic property characterizations demonstrate that FePt nanocubes are well separated under high-temperature annealing and yield the magnetically attractive L10 phase without any indication of sintering under the protection of a B4C layer. Moreover, it is observed that the texture of the nanocube monolayer is lost in the high-temperature annealing. The magnetic properties with Hc=2200 Oe along the film normal and Hc=1700 Oe along the film plane are obtained for the Fe46Pt54 /B4C thin film.