Synthesis of Multilayer Graphene Films on Copper by Modified Chemical Vapor Deposition

In this paper, large-area uniform multilayer graphene films were synthesized on copper in one growth route by modified low pressure chemical vapor deposition (LPCVD) method by introducing an assembly into the conventional LPCVD method. Scanning electronic microscopy, optical microscopy, Raman spectroscopy, ellipsometry, and transmission electron microscopy were used to characterize the graphene films. The results showed that the graphene films were multilayer. And there are about six layers with good continuity and uniformity. Meanwhile, the growth mechanism was illustrated by a growth model based on the analysis of the effects of the introduced assembly on the generation of the activated carbon atoms and on the catalysis of Cu molecules.     

Structure and magnetic properties of mono- and bi-layer graphene films on ultraprecision figured 4H-SiC(0001) surfaces

Monolayer and bilayer graphene films with a few hundred nm domain size were grown on ultraprecision figured 4H-SiC(0001) on-axis and 8 degrees -off surfaces by annealing in ultra-high vacuum. Using X-ray photoelectron spectroscopy (XPS), atomic force microscopy, reflection high-energy electron diffraction, low-energy electron diffraction (LEED), Raman spectroscopy, and scanning tunneling microscopy, we investigated the structure, number of graphene layers, and chemical bonding of the graphene surfaces. Moreover, the magnetic property of the monolayer graphene was studied using in-situ surface magneto-optic Kerr effect at 40 K. LEED spots intensity distribution and XPS spectra for monolayer and bilayer graphene films could become an obvious and accurate fingerprint for the determination of graphene film thickness on SiC surface.     

Synthesis and characterization of large-area graphene and graphite films on commercial Cu-Ni alloy foils

Controlling the thickness and uniformity during growth of multilayer graphene is an important goal. Here we report the synthesis of large-area monolayer and multilayer, particularly bilayer, graphene films on Cu-Ni alloy foils by chemical vapor deposition with methane and hydrogen gas as precursors. The dependence of the initial stages of graphene growth rate on the substrate grain orientation was observed for the first time by electron backscattered diffraction and scanning electron microscopy. The thickness and quality of the graphene and graphite films obtained on such Cu-Ni alloy foils could be controlled by varying the deposition temperature and cooling rate and were studied by optical microscopy, scanning electron microscopy, atomic force microscopy, and micro-Raman imaging spectroscopy. The optical and electrical properties of the graphene and graphite films were studied as a function of thickness.     

High-quality liquid phase-pulsed laser ablation graphene synthesis by flexible graphite exfoliation

This work reports a one-pot procedure of laser ablation on a graphite target in a liquid medium, based on the variation of different parameters such as target type, laser wavelength, and ablation medium,to obtain high-quality graphene nanosheets. The morphology of derived products was characterized by the field emission scanning electron microscopy(FE-SEM). Then, the morphology and structure of the optimized sample were characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD), ultraviolet-visible-near infrared(UV–vis-NIR) spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy(XPS). By controlling the laser ablation parameters, we were able to prepare micrometer-sized few-layer graphene nanosheets with mainly less than ten layers. Such synthesized graphene nanosheets were grown at the surface of a flexible graphite target, indicating many potential applications in fundamental research, electrochemical and as hydrophobic surfaces.     

Control of thickness uniformity and grain size in graphene films for transparent conductive electrodes

Large-scale and transferable graphene films grown on metal substrates by chemical vapor deposition (CVD) still hold great promise for future nanotechnology. To realize the promise, one of the key issues is to further improve the quality of graphene, e.g., uniform thickness, large grain size, and low defects. Here we grow graphene films on Cu foils by CVD at ambient pressure, and study the graphene nucleation and growth processes under different concentrations of carbon precursor. On the basis of the results, we develop a two-step ambient pressure CVD process to synthesize continuous single-layer graphene films with large grain size (up to hundreds of square micrometers). Scanning electron microscopy and Raman spectroscopy characterizations confirm the film thickness and uniformity. The transferred graphene films on cover glass slips show high electrical conductivity and high optical transmittance that make them suitable as transparent conductive electrodes. The growth mechanism of CVD graphene on Cu is also discussed, and a growth model has been proposed. Our results provide important guidance toward the synthesis of high quality uniform graphene films, and could offer a great driving force for graphene based applications.     

Graphene films with large domain size by a two-step chemical vapor deposition process

The fundamental properties of graphene are making it an attractive material for a wide variety of applications. Various techniques have been developed to produce graphene and recently we discovered the synthesis of large area graphene by chemical vapor deposition (CVD) of methane on Cu foils. We also showed that graphene growth on Cu is a surface-mediated process and the films were polycrystalline with domains having an area of tens of square micrometers. In this paper, we report on the effect of growth parameters such as temperature, and methane flow rate and partial pressure on the growth rate, domain size, and surface coverage of graphene as determined by Raman spectroscopy, and transmission and scanning electron microscopy. On the basis of the results, we developed a two-step CVD process to synthesize graphene films with domains having an area of hundreds of square micrometers. Scanning electron microscopy and Raman spectroscopy clearly show an increase in domain size by changing the growth parameters. Transmission electron microscopy further shows that the domains are crystallographically rotated with respect to each other with a range of angles from about 13 to nearly 30°. Electrical transport measurements performed on back-gated FETs show that overall films with larger domains tend to have higher carrier mobility up to about 16,000 cm(2) V(-1) s(-1) at room temperature.     

Synthesis and layer-by-layer self-assembly of silver nanoparticles capped by mercaptosulfonic acid

Spherical silver nanoparticles capped by mercaptosulfonic acid with a diameter of about 8 nm were prepared by a simple chemical reaction. The resulting silver nanoparticles were characterized by UV–vis spectroscopy (UV–vis) and transmission electron microscopy (TEM). Using layer-by-layer (LBL) self-assembly technique, the multilayer films containing silver nanoparticles and polycation poly(dialyldimethylammonium chloride) (PDDA) were successfully fabricated. The fabrication process was monitored by UV–vis spectra and the morphology of the multilayer films was investigated by atomic force microscopy (AFM). The cyclic voltammogram (CV) measurements further confirmed that the silver nanoparticles had assembled into the multilayer films successfully. Surface-enhanced Raman spectroscopy (SERS) measurements showed that the multilayer films containing silver nanoparticles could serve as SERS-active substrate.     

Thinning of multilayer graphene to monolayer graphene in a plasma environment

We present a facile approach to transform multilayer graphene to single-layer graphene in a gradual thinning process. Our technique is based upon gradual etching of multilayer graphene in a hydrogen and nitrogen plasma environment. High resolution transmission microscopy, selected area electron diffraction and Raman spectroscopy confirm the transformation of multilayer graphene to monolayer graphene at a substrate temperature of ～ 400?°C. The shift in the position of the G-band peak shows a perfect linear dependence with substrate temperature, which indicates a controlled gradual etching process. Selected area electron diffraction also confirmed the removal of functional groups from the graphene surface due to the plasma treatment. We also show that plasma treatment can be used to engineer graphene nanomesh structures.     

Growth and characterization of diamond particles,diamond films,and CNT-diamond composite films deposited simultaneously by hot filament CVD

It is important to understand the growth of CNT-diamond composite films in order to improve the inter-link between two carbon allotropes, and, in turn, their physical properties for field emission and other applications. Isolated diamond particles, continuous diamond thin films, and thin films of carbon nanotubes (CNTs) having non-uniformly distributed diamond particles (CNT-diamond composite films) were simultaneously grown on unseeded, seeded, and catalyst pre-treated substrates, respectively, using a large-area multi-wafer-scale hot filament chemical vapor deposition. Films were deposited for four different growth durations at a given deposition condition. The changes in surface morphology and growth behavior of diamond particles with growth duration were investigated ex situ using field emission scanning electron microscopy and 2D confocal Raman depth spectral imaging, respectively. A surface morphological transition from faceted microcrystalline nature to nanocrystalline nature was observed as a function of growth duration in the case of isolated diamond particles grown on both unseeded and catalyst pre-treated substrates. However, such a morphological transition was not observed on the simultaneously grown continuous diamond thin films on seeded substrates. 2D confocal Raman depth spectral imaging of diamond particles showed that the local growth of CNTs did not affect the growth behavior of neighboring diamond particles on catalyst pre-treated substrates. These observations emphasize the importance of surface chemical reactions at the growth site in deciding sp² or sp³ carbon growth and the final grain size of the diamond films.     

Few-layer graphene direct deposition on Ni and Cu foil by cold-wall chemical vapor deposition

We report an alternative synthesis process, cold-wall thermal chemical vapor deposition (CVD), is replied to directly deposit single-layer and few-layer graphene films on Ar plasma treated Ni and Cu foils using CH4 as carbon source. Through optimizing the process parameters, large scale single-layer graphene grown on Ni foil is comparable to that grown on Cu foil. The graphene films were able to be transferred to other substrates such as SiO2/Si, flexible transparent PET and verified by optical microscopy, Raman microscopy and scanning electron microscopy. The sheet resistance and transmission of the transferred graphene films on PET substrate were also discussed.     

Chemical vapor deposition of graphene on copper from methane, ethane and propane: evidence for bilayer selectivity

To study the effects of hydrocarbon precursor gases, graphene is grown by chemical vapor deposition from methane, ethane, and propane on copper foils. The larger molecules are found to more readily produce bilayer and multilayer graphene, due to a higher carbon concentration and different decomposition processes. Single- and bilayer graphene can be grown with good selectivity in a simple, single-precursor process by varying the pressure of ethane from 250 to 1000 mTorr. The bilayer graphene is AB-stacked as shown by selected area electron diffraction analysis. Additionally propane is found to only produce a combination of single- to few-layer and turbostratic graphene. The percent coverage is investgated using Raman spectroscopy and optical, scanning electron, and transmission electron microscopies. The data are used to discuss a possible mechanism for the second-layer growth of graphene involving the different cracking pathways of the hydrocarbons.     

Effect of interface on mid-infrared photothermal response of MoS2 thin film grown by pulsed laser deposition

This study reports on the mid-infrared (mid-IR) photothermal response of multilayer MoS2 thin films grown on crystalline (p-type silicon and c-axisoriented single crystal sapphire) and amorphous (Si/SiO2 and Si/SiN) substrates by pulsed laser deposition (PLD).The photothermal response of the MoS2 films is measured as the changes in the resistance of the MoS2 films when irradiated with a mid-IR (7 to 8.2 μm) source.We show that enhancing the temperature coefficient of resistance (TCR) of the MoS2 thin films is possible by controlling the film-substrate interface through a proper choice of substrate and growth conditions.The thin films grown by PLD are characterized using X-ray diffraction,Raman,atomic force microscopy,X-ray photoelectron microscopy,and transmission electron microscopy.The high-resolution transmission electron microscopy (HRTEM) images show that the MoS2 films grow on sapphire substrates in a layer-by-layer manner with misfit dislocations.The layer growth morphology is disrupted when the films are grown on substrates with a diamond cubic structure (e.g.,silicon) because of twin growth formation.The growth morphology on amorphous substrates,such as Si/SiO2 or Si/SiN,is very different.The PLD-grown MoS2 films on silicon show higher TCR (-2.9％ K-1 at 296 K),higher mid-IR sensitivity (△R/R =5.2％),and higher responsivity (8.7 V·W-1) compared to both the PLD-grown films on other substrates and the mechanically exfoliated MoS2 flakes transferred to different substrates.     

Graphene epitaxy by chemical vapor deposition on SiC

We demonstrate the growth of high quality graphene layers by chemical vapor deposition (CVD) on insulating and conductive SiC substrates. This method provides key advantages over the well-developed epitaxial graphene growth by Si sublimation that has been known for decades. (1) CVD growth is much less sensitive to SiC surface defects resulting in high electron mobilities of ～1800 cm(2)/(V s) and enables the controlled synthesis of a determined number of graphene layers with a defined doping level. The high quality of graphene is evidenced by a unique combination of angle-resolved photoemission spectroscopy, Raman spectroscopy, transport measurements, scanning tunneling microscopy and ellipsometry. Our measurements indicate that CVD grown graphene is under less compressive strain than its epitaxial counterpart and confirms the existence of an electronic energy band gap. These features are essential for future applications of graphene electronics based on wafer scale graphene growth.     

Surface-enhanced Raman spectroscopy of the growth of ultra-thin organosilicon plasma polymers on nanoporous Ag/SiO2-bilayer films

A new method for the synthesis of thin bilayer films as surface-enhanced Raman spectroscopy (SERS) active substrates was developed which is based on the combination of plasma polymerization, plasma calcination and Ag-film deposition by means of physical vapor deposition. The surface morphology of prepared substrates was characterized by field emission scanning electron microscopy, atomic force microscopy and electrochemical impedance spectroscopy. These substrates lead to high surface enhancement factors proven by the spectroscopic analysis of adsorbed Trans-1,2 bis-(4-pyridyl) ethylene molecules. By this preparation technique, SERS-active films can be deposited on any substrate. The new SERS substrates were successfully applied to study the growth of ultra-thin hexamethyldisiloxane plasma polymer films. The Raman intensity of the CH-stretching vibration was studied as a function of the film thickness. The surface enhancement decreased sharply at about 20 nm. The resulting increase in the intensity of Raman peaks for thin adsorbed plasma polymer films was observed to be a combination of the electromagnetic enhancement mechanism and the high surface area increase of the rough Ag-surface.     

Comparison of graphene films grown on 6H-SiC and 4H-SiC substrates

Abstract

Atomic force microscopy, Kelvin-probe microscopy and Raman spectroscopy have been used to examine graphene films grown by thermal decomposition of the Si face of semi-insulating substrates of 6H-SiC and 4H-SiC polytypes in the atmosphere of argon. It was demonstrated that the quality of graphene grown on substrates of various polytypes at identical technological growth regimes is about the same. A conclusion was made that the differences in crystal structure between 6H-SiC and 4H-SiC does not lead to significant dissimilarities in the mechanism of sublimation of silicon carbide components from the surface of a crystal and in that of graphene crystallization.     

Cyclic voltammetry and impedance studies of undoped diamond films

The undoped, polycrystalline diamond films were deposited on tungsten wire substrates by hot filament chemical vapor deposition (HF CVD), using a precursor gas mixture of methanol with excess of hydrogen. The morphology and quality of the as-deposited films were monitored by scanning electron microscopy (SEM) and Raman spectroscopy. The surface morphology analyzed by SEM resembles a continuous and well faceted diamond film. Raman results showed essential differences in qualities of diamond films grown at different hydrocarbon concentrations. The electrochemical properties of diamond electrodes were examined with cyclic voltammetry (CV) and the electrochemical impedance spectroscopy (EIS). The CV experiments revealed a large chemical window (>～4.3 V) of undoped diamond. Analysis of the ferrocyanide-ferricyanide couple at a diamond electrode suggests some extent of electrochemical quasi-reversibility, but the rates of charge transfer across the diamond substrate interface vary with diamond quality.     

Wafer scale homogeneous bilayer graphene films by chemical vapor deposition

The discovery of electric field induced band gap opening in bilayer graphene opens a new door for making semiconducting graphene without aggressive size scaling or using expensive substrates. However, bilayer graphene samples have been limited to μm(2) size scale thus far, and synthesis of wafer scale bilayer graphene poses a tremendous challenge. Here we report homogeneous bilayer graphene films over at least a 2 in. × 2 in. area, synthesized by chemical vapor deposition on copper foil and subsequently transferred to arbitrary substrates. The bilayer nature of graphene film is verified by Raman spectroscopy, atomic force microscopy, and transmission electron microscopy. Importantly, spatially resolved Raman spectroscopy confirms a bilayer coverage of over 99%. The homogeneity of the film is further supported by electrical transport measurements on dual-gate bilayer graphene transistors, in which a band gap opening is observed in 98% of the devices.     

表面波激发等离子体合成类金刚石薄膜的实验研究

用表面波等离子体装置进行了类金刚石薄膜的合成实验,研究了微波功率、基底负偏压和气体组成等条件对成膜的影响.用拉曼光谱和扫描电子显微镜对薄膜结构和表面形貌进行了分析,得出在100Pa的工作气压下,使用CH4放电,大功率和高偏压有利于生成质量较好的薄膜.     

Synthesis and characterization of electrochemically-reduced graphene

Graphene has superior electrical conductivity than graphite and other allotropes of carbon because of its high surface area and chemical tolerance. Electrochemically processed graphene sheets were obtained through the reduction of graphene oxide from hydrazine hydrate. The prepared samples were heated to different temperatures such as 673 and 873 K. X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), transmission electron microscopy (TEM), Raman spectra and conductivity measurements were made for as-prepared and heat-treated graphene samples. XRD pattern of graphene shows a sharp and intensive peak centred at a diffraction angle (2θ) of 26·350. FTIR spectra of as-prepared and heated graphene were used to confirm the oxidation of graphite. TEM results indicated that the defect density and number of layers of graphene sheets were varied with heating temperature. The hexagonal sheet morphology and purity of as-prepared and heat treated samples were confirmed by SEM–EDX and Raman spectroscopy. The conductivity measurements revealed that the conductivity of graphene was decreased with an increase in heating temperature. The present study explains that graphene with enhanced functional properties can be achieved from the as-prepared sample.     

CVD金刚石形核的研究

在钢渗铬层和硅片上进行了化学气相沉积金刚石膜,发现在渗铬层上形成的金刚石膜以球形金刚石为主;用高倍扫描电子显微镜分析显示,渗铬层上的球形金刚石是由大量二次晶核长大的微晶金刚石和非晶碳组成.