Layer-by-layer growth of graphene layers on graphene substrates by chemical vapor deposition

We demonstrate a synthesis of graphene layers on graphene templates prepared by the mechanical exfoliation of graphite crystals using a developed chemical vapor deposition (CVD) apparatus that has a furnace with three temperature zones and can regulate the temperatures separately in each zone. This results in individual control over the decomposition reaction of the carbon feedstock and the growth of graphene layers by activated carbon species. CVD growth using multi-temperature zones provides wider temperature windows appropriate to grow graphene layers. We observed that graphene layers proceed by a layer-by-layer growth mode using an optical microscopy, an atomic force microscopy, and Raman spectroscopy. This result suggests that a graphene growth technique using the CVD apparatus is a potential approach for making graphene sheets with precise control of the layer numbers.     

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.     

Large physisorption strain in chemical vapor deposition of graphene on copper substrates

Graphene single layers grown by chemical vapor deposition on single crystal Cu substrates are subject to nonuniform physisorption strains that depend on the orientation of the Cu surface. The strains are revealed in Raman spectra and quantitatively interpreted by molecular dynamics (MD) simulations. An average compressive strain on the order of 0.5% is determined in graphene on Cu(111). In graphene on Cu (100), MD simulations interpret the observed highly nonuniform strains.     

石墨烯的化学气相沉积法制备

化学气相沉积(CVD)法是近年来发展起来的制备石墨烯的新方法,具有产物质量高、生长面积大等优点,逐渐成为制备高质量石墨烯的主要方法.通过简要分析石墨烯的几种主要制备方法(胶带剥离法、化学剥离法、SiC外延生长法和CVD方法)的原理和特点,重点从结构控制、质量提高以及大面积生长等方面评述了CVD法制备石墨烯及其转移技术的研究进展,并展望了未来CVD法制备石墨烯的可能发展方向,如大面积单晶石墨烯、石墨烯带和石墨烯宏观体的制备与无损转移等.     

Single- and few-layer graphene growth on stainless steel substrates by direct thermal chemical vapor deposition

Increasing interest in graphene research in basic sciences and applications emphasizes the need for an economical means of synthesizing it. We report a method for the synthesis of graphene on commercially available stainless steel foils using direct thermal chemical vapor deposition. Our method of synthesis and the use of relatively cheap precursors such as ethanol (CH(3)CH(2)OH) as a source of carbon and SS 304 as the substrate proved to be economically viable. The presence of single- and few-layer graphene was confirmed using confocal Raman microscopy/spectroscopy. X-ray photoelectron spectroscopic measurements were further used to establish the influence of various elemental species present in stainless steel on graphene growth. The role of cooling rate on surface migration of certain chemical species (oxides of Fe, Cr and Mn) that promote or hinder the growth of graphene is probed. Such analysis of the chemical species present on the surface can be promising for graphene based catalytic research.     

Polymer layers by initiated chemical vapor deposition for thin film gas barrier encapsulation

A combination of SiN_x and polymer layers, in our case poly(glycidyl methacrylate) (PGMA) is very suitable as a permeation barrier layer on sensitive electronic devices. Our experiments thus far concentrate on increasing the stability and deposition rate of the polymer layers. To reach the thermal stability needed for the deposition of SiN_x on PGMA by HWCVD, the PGMA chain length must be large. PGMA with a very high molecular weight (M_W) (78,000 Da, ~ 548 monomers) was deposited at a high deposition rate (> 60 nm/min). To mimic the reactive atomic H ambient during SiN_x deposition conditions during HWCVD, the polymer layers were exposed to an atomic hydrogen environment for 0 to 550 s. Surprisingly, the most important factor for stability under these conditions was the filament temperature which was used during PGMA deposition, rather than the expected parameters such as M_W or surface roughness. Using lower filament temperatures for PGMA deposition, the layers were much more stable in atomic H ambient.     

Direct growth of graphene on vertically standing glass by a metal-free chemical vapor deposition method

A new method to directly grow graphene on quartz glass substrate by atmospheric-pressure chemical vapor deposition (CVD) without using any catalyst was developed. The prime feature of this method is to build a vertical-glass model in the quartz tube to significantly increase the collision probability of the carbon precursors and reactive fragments between each other with the glass surface. The growth rate of high-quality graphene on glass remarkably increases compared with the conventional gas flow CVD technique. The optical transmittance and sheet resistance of the graphene glass can be readily adjusted by regulating growth time. When growth time is 35?min, the graphene glass presents an intriguing sheet resistance of about 1.48 kΩ sq^?1 at a transmittance of 93.08% and exhibits an excellent hydrophobic performance. The method is simple and scalable, and might stimulate various potential applications of transparent and conductive graphene glass in practical fields.     

Direct synthesis of large-area Al-doped graphene by chemical vapor deposition:Advancing the substitutionally doped graphene family

Graphene doping continues to gather momentum because it enables graphene properties to be tuned,thereby affording new properties to,improve the performance of,and expand the application potential of graphene.Graphene can be chemically doped using various methods such as surface functionalization,hybrid composites(e.g.,nanoparticle decoration),and substitution doping,wherein C atoms are replaced by foreign ones in the graphene lattice.Theoretical works have predicted that graphene could be substitutionally doped by aluminum(Al)atoms,which could hold promise for exciting applications,including hydrogen storage and evolution,and supercapacitors.Other theoretical predictions suggest that Al substitutionally doped graphene(AIG)could serve as a material for gas sensors and the catalytic decomposition of undesirable materials.However,fabricating Al substitutionally doped graphene has proven challenging until now.Herein,we demonstrate how controlled-flow chemical vapor deposition(CVD)implementing a simple solid precursor can yield high-quality and large-area monolayer AIG,and this synthesis is unequivocally confirmed using various characterization methods including local electron energy-loss spectroscopy(EELS).Detailed high-resolution transmission electron microscopy(HRTEM)shows numerous bonding configurations between the Al atoms and the graphene lattice,some of which are not theoretically predicted.Furthermore,the produced AIG shows a CO₂ capturability superior to those of other substitutionally doped graphenes.     

Comprehensive study of graphene grown by chemical vapor deposition

Graphene was grown on Cu foil by chemical vapor deposition with CH₄ as carbon source, and then was transferred onto various substrates for device applications. The structural and optical properties of graphene were investigated, comprehensively. Raman spectra indicate as-grown and transferred graphene films are homogenous monolayer graphene. Optical microscopy and scanning electron microscopy images reveal wrinkle-free and smooth surface of transferred graphene, confirming the high quality of graphene. In addition, the transferred graphene on glass exhibits excellent transmittances in the visible region (89.3 % at ~500 nm). Therefore, the results present the controllable approaches to achieve as-grown and transferred high quality graphene for the fabrication of multiple nanoelectronic devices.     

Investigation of crystallographic properties of thin germanium crystals grown on silicon substrates by chemical vapor deposition

The quality of germanium crystals deposited from the gas phase by chemical vapor deposition using pyrolytic decomposition of GeH₄ in a helium atmosphere at various growth temperatures on silicon substrates was determined.X-ray diffraction and rocking curve measurements proved to be very useful in determining the degree of preferred orientation of the germanium deposit, since they distinguish clearly between the reflections of the thin germanium deposited layer and those of the thick silicon substrate. Therefore they permit fairly accurate calculations. Laue measurements, in this case, proved to be unsatisfactory because of inadequately low resolution. The results show that a preferred orientation of germanium crystallites in the layer of up to 99.9% was reached.     

Piezoresistive properties of nanocrystalline silicon thin films deposited on plastic substrates by hot-wire chemical vapor deposition

The piezoresistive property of n-type and p-type nanocrystalline silicon thin films deposited on plastic (PEN) at a substrate temperature of 150 °C by hot-wire chemical vapor deposition, is studied. The crystalline fraction decreased from 80% to 65% in p-type and from 84% to 62% in n-type films, as the dopant gas-to-silane flow rate ratio was increased from 0.18% to 3-3.5%. N-type films have negative gauge factor (− 11 to − 16) and p-type films have positive gauge factor (9 to 25). In n-type films the higher gauge factors (in absolute value) were obtained by increasing the doping level whereas in p-type films higher gauge factors were obtained by increasing the crystalline fraction.     

Deposition of thermal and hot-wire chemical vapor deposition copper thin films on patterned substrates

In this work we study the hot-wire chemical vapor deposition (HWCVD) of copper films on blanket and patterned substrates at high filament temperatures. A vertical chemical vapor deposition reactor was used in which the chemical reactions were assisted by a tungsten filament heated at 650 degrees C. Hexafluoroacetylacetonate Cu(I) trimethylvinylsilane (CupraSelect) vapors were used, directly injected into the reactor with the aid of a liquid injection system using N2 as carrier gas. Copper thin films grown also by thermal and hot-wire CVD. The substrates used were oxidized silicon wafers on which trenches with dimensions of the order of 500 nm were formed and subsequently covered with LPCVD W. HWCVD copper thin films grown at filament temperature of 650 degrees C showed higher growth rates compared to the thermally ones. They also exhibited higher resistivities than thermal and HWCVD films grown at lower filament temperatures. Thermally grown Cu films have very uniform deposition leading to full coverage of the patterned substrates while the HWCVD films exhibited a tendency to vertical growth, thereby creating gaps and incomplete step coverage.     

Influence of substrates on the formation of the TiSi nanowire by atmosphere pressure chemical vapor deposition

TiSi nanowires were deposited on both Si(111) and glass substrates by using SiH4, TiCl4 and N2 as the Si, Ti precursors and diluted gas respectively through atmosphere pressure chemical vapor deposition (APCVD) method. Effects of the substrates on formation of the nanowires were investigated. The results show that the nanowires can be formed on both Si(111) and glass substrates at ratio of SiH4/TiCl4 of 4. However, the quantities of the TiSi nanowires that formed with glass substrate are less than that with Si(111) substrate. The nanowires formed with glass substrate has length of 2-3 microm and diameters of 15-25 nm while that is 4-5 microm and 25-35 nm respectively with Si(111) substrate. Great quantities of the titanium silicide nanowires with relative higher contents of the C54 TiSi2 crystalline phase underneath can be obtained through improving the deposition conditions.     

Graphite formation on Ni film by chemical vapor deposition

Thin film formation of graphite by chemical vapor deposition using 2-methyl-1,2′-naphthyl ketone as a starting material was carried out on Ni film substrates. On Ni films directly deposited on quartz glass, the graphite films were obtained when the Ni film thickness was above 1 000 Å and above 5 000 Å at 700 °C and 1 000 °C, respectively. Depositions on thinner Ni film substrates comprise amorphous carbon (a-C) or graphite tubes which was owing to the thermal coagulation of the Ni film into droplets. On the other hand, graphite film was obtained on the Ni film with thickness 10 Å when a-C was inserted between the Ni film and the quartz glass. The coagulation of the Ni film is considered to be avoided by inserting a-C layer.     

Gas sensing properties of graphene synthesized by chemical vapor deposition

The gas sensing properties of graphene synthesized by a chemical vapor deposition (CVD) method are investigated. Synthesis of graphene is carried out on a copper substrate using a methane and hydrogen gas mixture by a CVD process at the atmospheric pressure. The graphene films are transferred to different substrates after wet etching of the copper substrates. The Raman spectra reveal that the graphene films made on SiO₂/Si substrates are of high quality. The reflectance spectra of graphene were measured in UV/Visible region of the spectrum. Theoretically calculated reflectance spectra based on Fresnel's approach indicates that the CVD graphene has a single layer. The gas sensing properties of graphene were tested for different reducing gasses as a function of measurement temperature and gas concentration. It is found that the gas sensing characteristics such as response time, recovery time, and sensitivity depend on the target gas, gas concentration, test temperature, and the ambient gas composition. The cross sensitivity of few combinations of reducing gasses such as, NH₃, CH_4, and H₂ was also investigated.     

Shear modulus of monolayer graphene prepared by chemical vapor deposition

We report shear modulus (G) and internal friction (Q(-1)) measurements of large-area monolayer graphene films grown by chemical vapor deposition on copper foil and transferred onto high-Q silicon mechanical oscillators. The shear modulus, extracted from a resonance frequency shift at 0.4 K where the apparatus is most sensitive, averages 280 GPa. This is five times larger than those of the multilayered graphene-based films measured previously. The internal friction is unmeasurable within the sensitivity of our experiment and thus bounded above by Q(-1) ≤ 3 × 10(-5), which is orders-of-magnitude smaller than that of multilayered graphene-based films. Neither annealing nor interface modification has a measurable effect on G or Q(-1). Our results on G are consistent with recent theoretical evaluations and simulations carried out in this work, showing that the shear restoring force transitions from interlayer to intralayer interactions as the film thickness approaches one monolayer.     

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.