Birong Luo

Low Temperature Growth of Highly Nitrogen-Doped Single Crystal Graphene Arrays by Chemical Vapor Deposition

The ability to dope graphene is highly important for modulating electrical properties of graphene. However, the current route for the synthesis of N-doped graphene by chemical vapor deposition (CVD) method mainly involves high growth temperature using ammonia gas or solid reagent melamine as nitrogen sources, leading to graphene with low doping level, polycrystalline nature, high defect density and low carrier mobility. Here, we demonstrate a self-assembly approach that allows the synthesis of single-layer, single crystal and highly nitrogen-doped graphene domain arrays by self-organization of pyridine molecules on Cu surface at temperature as low as 300 °C. These N-doped graphene domains have a dominated geometric structure of tetragonal-shape, reflecting the single crystal nature confirmed by electron-diffraction measurements. The electrical measurements of these graphene domains showed their high carrier mobility, high doping level, and reliable N-doped behavior in both air and vacuum.

Fractal etching of graphene.

An anisotropic etching mode is commonly known for perfect crystalline materials, generally leading to simple Euclidean geometric patterns. This principle has also proved to apply to the etching of the thinnest crystalline material, graphene, resulting in hexagonal holes with zigzag edge structures. Here we demonstrate for the first time that the graphene etching mode can deviate significantly from simple anisotropic etching. Using an as-grown graphene film on a liquid copper surface as a model system, we show that the etched graphene pattern can be modulated from a simple hexagonal pattern to complex fractal geometric patterns with sixfold symmetry by varying the Ar/H2 flow rate ratio. The etched fractal patterns are formed by the repeated construction of a basic identical motif, and the physical origin of the pattern formation is consistent with a diffusion-controlled process. The fractal etching mode of graphene presents an intriguing case for the fundamental study of material etching.

Two‐Stage Metal‐Catalyst‐Free Growth of High‐Quality Polycrystalline Graphene Films on Silicon Nitride Substrates

By using two-stage, metal-catalyst-free chemical vapor deposition (CVD), it is demonstrated that high-quality polycrystalline graphene films can directly grow on silicon nitride substrates. The carrier mobility can reach about 1500 cm(2) V(-1) s(-1) , which is about three times the value of those grown on SiO(2) /Si substrates, and also is better than some examples of metal-catalyzed graphene, reflecting the good quality of the graphene lattice.

Controlled Growth of Single‐Crystal Twelve‐Pointed Graphene Grains on a Liquid Cu Surface

The controlled fabrication of single-crystal twelve-pointed graphene grains is demonstrated for the first time by ambient pressure chemical vapor deposition on a liquid Cu surface. An edge-diffusion limited mechanism is proposed. The highly controllable growth of twelve-pointed graphene grains presents an intriguing case for the fundamental study of graphene growth and should exhibit wide applications in graphene-based electronics.

Layer-Stacking Growth and Electrical Transport of Hierarchical Graphene Architectures

Hierarchical graphene architectures (HGAs) that grow by stacking of layers are produced on a liquid copper surface using chemical vapor deposition. The stacking mode--for example hexagonal-hexagonal-hexagonal or hexagonal-snowflake-dendritic--can be simply controlled. Measurements of the electrical properties of HGAs indicate that hierarchical stacking of graphene may be a simple and effective way of tailoring their properties without degrading them.

Direct Top‐Down Fabrication of Large‐Area Graphene Arrays by an In Situ Etching Method

D. Geng, H. Wang, Dr. B. Luo, J. Xu, Prof. G. Yu Beijing National Laboratory for Molecular Sciences Institute of Chemistry Chinese Academy of Sciences Beijing 100190 , PR China E-mail: yugui@iccas.ac.cn D. Geng, H. Wang, J. Xu University of Chinese Academy of Sciences Beijing 10049 , PR China Y. Wan, Prof. Z. Xu Applied Mechanics Laboratory, Department of Engineering Mechanics and Center for Nano and Micro Mechanics Tsinghua University Beijing 100084 , PR China

Quality assessment of graphene: Continuity, uniformity, and accuracy of mobility measurements

With the increasing availability of large-area graphene, the ability to rapidly and accurately assess the quality of the electrical properties has become critically important. For practical applications, spatial variability in carrier density and carrier mobility must be controlled and minimized. We present a simple framework for assessing the quality and homogeneity of large-area graphene devices. The field effect in both exfoliated graphene devices encapsulated in hexagonal boron nitride and chemical vapor-deposited (CVD) devices was measured in dual current–voltage configurations and used to derive a single, gate-dependent effective shape factor, β, for each device. β is a sensitive indicator of spatial homogeneity that can be obtained from samples of arbitrary shape. All 50 devices investigated in this study show a variation (up to tenfold) in β as a function of the gate bias. Finite element simulations suggest that spatial doping inhomogeneity, rather than mobility inhomogeneity, is the primary cause of the gate dependence of β, and that measurable variations of β can be caused by doping variations as small as 1010 cm−2. Our results suggest that local variations in the position of the Dirac point alter the current flow and thus the effective sample shape as a function of the gate bias. We also found that such variations lead to systematic errors in carrier mobility calculations, which can be revealed by inspecting the corresponding β factor.

Chemical vapor deposition of bilayer graphene with layer-resolved growth through dynamic pressure control

In this work, a dynamic pressure atmosphere is constructed through cutting off the gas outlet in the chemical vapor deposition process, in which the total pressure of the system uniformly varies with a gradient and the associated growth environment changes. Through modulating the variation rate of system pressure, the layer-resolved growth of graphene from single-layer graphene grains to bilayer graphene patches and then ultimately larger-area bilayer graphene films has been realized. Based on the analysis results obtained, it is shown that the self-limiting effect of single-layer graphene on Cu foil can be broken by the accumulation of feedstock (CH4/H2) during this dynamic process to enable the continued growth of bilayer graphene. The electrical transport studies demonstrate that devices made of the as-grown bilayer graphene exhibit obvious tunability of the band gap, showing the typical characteristics of AB stacked bilayer graphene.

Probing the Gas-Phase Dynamics of Graphene Chemical Vapour Deposition using in-situ UV Absorption Spectroscopy

The processes governing multilayer nucleation in the chemical vapour deposition (CVD) of graphene are important for obtaining high-quality monolayer sheets, but remain poorly understood. Here we show that higher-order carbon species in the gas-phase play a major role in multilayer nucleation, through the use of in-situ ultraviolet (UV) absorption spectroscopy. These species are the volatilized products of reactions between hydrogen and carbon contaminants that have backstreamed into the reaction chamber from downstream system components. Consequently, we observe a dramatic suppression of multilayer nucleation when backstreaming is suppressed. These results point to an important and previously undescribed mechanism for multilayer nucleation, wherein higher-order gas-phase carbon species play an integral role. Our work highlights the importance of gas-phase dynamics in understanding the overall mechanism of graphene growth.

Raman spectral indicators of catalyst decoupling for transfer of CVD grown 2D materials

Through a combination of monitoring the Raman spectral characteristics of 2D materials grown on copper catalyst layers, and wafer scale automated detection of the fraction of transferred material, we reproducibly achieve transfers with over 97.5% monolayer hexagonal boron nitride and 99.7% monolayer graphene coverage, for up to 300 mm diameter wafers. We find a strong correlation between the transfer coverage obtained for graphene and the emergence of a lower wavenumber 2D− peak component, with the concurrent disappearance of the higher wavenumber 2D+ peak component during oxidation of the catalyst surface. The 2D peak characteristics can therefore act as an unambiguous predictor of the success of the transfer. The combined monitoring and transfer process presented here is highly scalable and amenable for roll-to-roll processing.