Effects of annealing on copper substrate surface morphology and graphene growth by chemical vapor deposition

Understanding the mechanism of graphene synthesis by chemical vapor deposition and the effect of process parameters is critical for production of high-quality graphene. In the present work, we investigated the effect of H₂ concentration during annealing on evolution of Cu surface morphology, and on deposited graphene characteristics. Our results revealed that H₂ had a smoothening effect on Cu surface as its surface roughness was reduced significantly at high H₂ concentration along with the formation of surface facets, dents and nanometer-sized particles. Furthermore, H₂ content influenced the graphene morphology and its quality. A low H₂ concentration (0% and 2.5%) during annealing promoted uniform and good quality bilayer graphene. In contrast, a high concentration of H₂ (20% and 50%) resulted in multilayer, non-uniform and defective graphene. Interestingly, the annealed Cu surface morphology differed considerably from that obtained after deposition of graphene, indicating that graphene deposition has its own impact on Cu surface.     

Multi-layer graphene obtained by high temperature carbon implantation into nickel films

We present a study of carbon implantation in a stacked layered substrate made of Ni(200 nm)/SiO₂(300 nm)/Si(1 0 0). The carbon atoms have energy of 20 keV. Simultaneous or subsequent heat treatment is performed in the 450–600 °C range. The carbon dose was set to be 4 equivalent graphene monolayers (EGM). Most of the carbon implanted diffuses directly to the surface, forming multi-layer graphene (MLG). A progressive structuration of these graphitic fragments occurs with the increase of the implantation temperature. However, this structuration is more pronounced if the thermal treatment is performed in situ following the carbon implantation at room temperature. The mean MLG thickness, corresponding to around 4–5 EGM, was measured by angular X-ray Photoemission Spectroscopy. Moreover, the overall carbon concentration inside and at the limits of the nickel films, determined by nuclear reaction analysis (NRA), is in the 7–10 EGM range. This concentration depends on the temperature but it exceeds surprisingly the expected carbon concentration. This discrepancy shows that some carbon is incorporated along the different steps. NRA analyses of the preparation confirm this point. To obtain large film, the presented results stress the interest to better understand the full system carbon–nickel in the preparation of MLG at each step of the process.     

Fabrication of graphitic layers in diamond using FIB implantation and high pressure high temperature annealing

We have used high pressure high temperature annealing (HPHT) for graphitisation of implanted layers in diamond created by 30 keV Ga⁺ focused ion beam. Electron microscopy has been used to investigate the implanted layers. It has been revealed that, unlike annealing at vacuum pressure, the graphitization during HPHT annealing occurred through epitaxial growth of graphite (002) planes parallel to (111) diamond planes. High quality of graphite was confirmed by high resolution electron microscopy and electron energy loss spectroscopy.     

The nature of high surface energy sites in graphene and graphite

Variations in the adsorption enthalpies of acetone to few-layer graphene and graphite nanopowders were analyzed as a function of surface coverage. The adsorption enthalpies were measured by inverse gas chromatography at low monolayer coverage levels (0.1–20%). The adsorption enthalpies increased from −13 kcal/mol at the lowest coverage to −7.5 kcal/mol. We fitted the measured adsorption enthalpies as a function of coverage using a two-state model and estimated the number of high-energy sites on both materials. The graphite powder had seven times more high-energy sites than the few-layer graphene, which explains why the adsorption enthalpies for graphite increased more slowly with increasing coverage. We also performed a theoretical study based on density functional theory calculations using a functional that accounts for dispersive interactions to elucidate the nature of the high-energy adsorption sites. The calculated adsorption enthalpies ranged from −16 to −1 kcal/mol while the adsorption enthalpy to a plain graphite surface was −9 kcal/mol. The high-energy adsorption sites were localized on surface steps and edge-cavities. The adsorption enthalpies at very low coverage therefore corresponded to adsorption on steps and edge cavities, while those measured at coverage levels of ∼4% or more reflected adsorption to the flat surface.     

Enhancement of Al-N co-dopant solubility in ZnO by high temperature thermal annealing

In this paper, we have developed a method to enhance the Al-N co-dopant solubility in bulk ZnO prepared by solid state reaction method. Reactive donor Al and acceptor N were mobilized by annealing the samples at various temperatures from 650 to 850?°C with a step of 50?°C in a programmable furnace. The solubility enhancement argument was verified by the conductivity measurements which showed that the conductivity of annealed films increases as the annealing temperature increases. The activation energy was calculated by the Arrhenius plot and was found to be (0.08?eV) very close to activation energy of shallow acceptor (nitrogen). To further strengthened our argument, we have also performed XRD, FTIR, Raman Spectroscopy and SEM measurements. XRD data suggested that only ZnO phases were present and no evidence for the presence of AlN, Al₂O₃ or Zn₃N₂ phases. We have also observed weakening and peak shifting of (002) with annealing temperature that suggested the incorporation of more acceptor defects in the crystal of ZnO. FTIR results verified the presence of Zn-O bond (437?cm^?1) along with week vibration of Al-N bond at 917?cm^?1. Raman spectroscopy data consists of 2E₂, A₁ (LO) and E_2(high) modes of ZnO but sample annealed at 800?°C has additional nitrogen related mode at 507?cm^?1. SEM images demonstrated the crystalline nature of samples having smooth surface but sample annealed at 800?°C has rough surface which indicated the enhancement of acceptor defects density.     

Atomic-scale mechanical behaviors of polycrystalline graphene under biaxial loadings and high temperature

Graphene is widely utilized due to its excellent properties. Nevertheless, the failure mechanism previously acquired by uniaxial tension needs to be optimized urgently as its service conditions become more and more demanding. Here, the mechanical behaviors of polycrystalline graphene under tensile-shear biaxial strains and high temperature were investigated by molecular dynamics simulations. We proved that the shear strain dominated the failure of polycrystalline graphene when tensile and shear loading were applied simultaneously. As the temperature rises, the structural destruction of polycrystalline graphene changes from stress-dominated to temperature-dominated. Moreover, the ultimate shear stress increases with the increase of grain size, while the ultimate strain is the opposite. The polycrystalline graphene with a large grain size has better high temperature resistance. These results extend our understanding of the mechanical properties of polycrystalline graphene and guide the design of devices composed of 2D materials under extreme conditions.     

Effect of annealing temperature and graphene concentrations on photovoltaic and NIR-detector applications of PbS/rGO nanocomposites

The effect of annealing temperature on photovoltaic and near-infrared (NIR) detector applications of PbS nanoparticles (NPs) and PbS/graphene nanocomposites was investigated. The products were synthesized by a simple co-precipitation method and graphene oxide (GO) sheets were used as graphene source. Several characterization techniques were used to show transfer of the GO into reduced graphene oxide (rGO) during the synthesis process. In addition, the effect of graphene concentrations on morphology, structure, photovoltaic, and detector parameters of the samples were studied. Transmission electron microscope (TEM) images showed that, the PbS NPs were agglomerated, while, the PbS/rGO nanocomposites were dispersed completely after annealing under H₂/Ar gas atmosphere. UV–visible spectrometer showed an absorption peak for all samples in the near infrared red (NIR) region of the electromagnetic spectrum. The results indicated that, photocurrent intensity, responsivity of the samples to an NIR source, and solar-cell efficiency were affected by annealing of samples and graphene concentrations.     

The effect of high temperature annealing process on crystallization process of polypropylene,mechanical properties,and surface quality of plastic parts

This work studied the effects and action mechanism of high‐temperature annealing process parameters, such as annealing temperature, annealing duration and cooling speed, on the microstructural evolution of polypropylene (PP) on different thickness layers, the surface quality, and mechanical properties of PP plastic parts. The results show that when the PP plastic parts are annealed at slightly higher than 100°C, the resin on the surface and internal layers of plastic parts just generates the relaxation and rearrangement at the molecular level. Only at an enough high annealing temperature, the secondary crystallization and phase transformation process can be observed. The crystallinity of all annealed samples is higher than that of unannealed samples, but the crystallinity is decreased with the increase of cooling speed after annealing duration, and the annealing duration exceeding 60 min almost has no effect on the crystallinity. The microstructural change of PP on the internal layer of plastic parts is weaker than that on the surface layer. The surface hardness of the plastic parts mainly depends on the crystallinity of the surface layer, whereas the surface roughness of the plastic parts depends on not only the crystallinity, but also the space conformation of molecular chains and the residual stress. With the change of annealing process parameters, the tensile and impact strengths of plastic parts show a non‐monotonic change law. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42773.     

Effect of high temperature annealing on scratch behavior of acrylonitrile styrene acrylate copolymers

The scratch behavior of butyl-acrylate rubber-modified styrene-acrylonitrile (ASA) upon high temperature annealing is investigated following the ASTM D7027/ISO 19252 linearly increasing normal load test methodology. The critical normal loads at the onset of the major deformation transitions along the scratch path, such as groove formation, scratch visibility, microcrack formation, and plowing, are reported and quantitatively analyzed. It is found that the scratch resistance improves with high temperature annealing, i.e., 30 °C above T_g, as compared to annealing below or around T_g. Microscopic investigation suggests that the increase in scratch resistance is related to the changes in surface morphology of the polymer. It is concluded that performing high temperature annealing enhances the scratch performance without compromising ASA bulk properties. Implication of the present study for improving scratch resistance of polymers is discussed.     

Flexible conductive graphene paper obtained by direct and gentle annealing of graphene oxide paper

We report the fabrication of flexible conductive graphene paper through a direct and gentle annealing process of graphene oxide paper. Thermal treatments at 700 °C under argon or hydrogen atmosphere directly applied to parent graphene oxide paper lead to a significant removal of disruptive oxygen-containing functional groups, and to a considerable recovery of the sp² network structure. Detailed comparison of chemical and combined chemical–thermal treatments by scanning electronic microscopy (SEM), Raman, X-photoelectron spectroscopy (XPS) and conductivity measurements underline the high efficiency of the direct annealing process. The resulting highly reduced graphene oxide paper exhibits electrical conductivities as high as 8100 S/m representing an increase of five orders of magnitude with respect to the parent graphene oxide paper, which significantly outperforms the results of chemical treatments. Moreover, our direct and gentle thermal reduction allows maintaining the structural integrity and mechanical flexibility of the parent graphene oxide paper thus overcoming problems of brittleness typically encountered in annealing processes. Our approach sets the base for an easy, cost-effective and environmentally friendly fabrication route for flexible conducting graphene paper of great application potential as flexible electrodes in various fields of technology.     

Interdiffusion between silica thin films and soda-lime glass substrate during annealing at high temperature

We study the diffusive interaction between soda-lime glass substrates and sputtered aluminum-doped silica thin films at 650°C, the temperature of commercial soda-lime glass shaping or tempering. A first rapid migration of alkali ions from substrate to thin film has been described in a companion paper (J Am Ceram Soc. 2018;101:1516). Using the same samples as (J Am Ceram Soc. 2018;101:1516), we focus here on later interactions, when the layer is consumed by the substrate resulting from diffusive interactions. Using Secondary Ion Mass Spectroscopy profilometry, we show that the interdiffusion rate increases with the aluminum doping content of the layer. We show that the alkali uptake of silica layers accelerates diffusive exchanges with the substrate, consistently with a decrease of viscosity of the layer. Diffusion profiles of silicon are well reproduced when solving the diffusion equation for a diffusivity having an exponential dependence with silicon concentration. The diffusivity of aluminum is shown to be 10 times slower than the diffusion of silicon. Specific exchanges of the two network formers with network modifiers are deduced from the composition-space trajectories, providing evidence for multicomponent diffusive couplings between species.     

Tuning doping and strain in graphene by microwave-induced annealing

We propose microwave-induced annealing as a rapid, simple, and effective method of controlling surface doping and strain in graphene. Raman spectroscopy was used to confirm that heavy and uniform p-type (1.2 × 10¹³ cm⁻²) doping can be achieved within only 5 min without unintended defects by placing graphene onto a substrate with a sufficiently high dielectric constant and exposing graphene and its substrate to microwave irradiation. Further, we showed that ripples are formed in suspended graphene when it is exposed to microwave irradiation. Silicon has a sufficiently high dielectric constant (11.9) and graphene is commonly deposited on silicon-based substrates, so our proposed microwave-induced annealing technique can be used for the rapid manipulation of the properties of graphene at low cost.     

Oxidation behavior of graphene nanoplatelet reinforced tantalum carbide composites in high temperature plasma flow

Graphene nanoplatelets (GNP) reinforced tantalum carbide (TaC) composites are exposed to a high temperature plasma flow in order to evaluate the effects of GNP on the oxidation behavior of TaC at conditions approaching those of hypersonic flight environments. The addition of GNP is found to suppress the formation of the oxide layer by up to 60%. The high thermal conductivity of GNPs dissipates heat throughout the sample thereby reducing thermal gradients and reducing the intensity of heating at the surface exposed to plasma. In addition, GNPs enhance oxidation resistance by providing toughening which suppresses crack formation and bursting that accelerates oxidation. Scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HR-TEM) reveal that GNPs have the ability to survive the intense high temperature of the plasma. GNPs are believed to seal oxide grain boundaries and hinder the further influx of oxygen. GNPs also provide nano sized carbon needed to induce the localized reduction of Ta₂O₅ to TaC. Micro computed X-ray tomography (MicroCT) validates that the above mechanisms protect the underlying unoxidized material from the structural damage caused by thermal shocks and high shear forces, by reducing thermal gradients and providing toughness.     

氧化石墨烯/磺化聚苯并咪唑高温质子交换膜的制备和表征

通过共混法和原位聚合法成功制备氧化石墨烯（GO）/磺化聚苯并咪唑（SPBI）质子交换复合膜。用FTIR及TEM表征了复合膜的结构,并测试了复合膜的热稳定性、力学性能、尺寸稳定性、含水率、酸掺杂率、氧化稳定性及质子电导率,重点考察不同制备方法、GO的加入对GO/SPBI质子交换复合膜结构和性能的影响。实验结果表明,GO在Y-GO/SPBI-1%复合膜中呈薄片状并良好分散。添加GO后复合膜的力学性能大幅提高,拉伸强度相较于Nafion 117膜（26.65MPa）提高了2.5倍。Y-GO/SPBI-1%复合膜热稳定性稍高于G-GO/SPBI-1%复合膜。Y-GO/SPBI-1%复合膜拥有与SPBI膜相当的含水率,比G-GO/SPBI-1%复合膜的含水率提高了51.36%,表明原位聚合法制备的膜具有良好的保水能力。原位聚合法制备的复合膜具有更高的酸掺杂率和更低的酸溶胀度,提高了膜的尺寸稳定性。Y-GO/SPBI-1%质子交换复合膜在相对湿度40%、160℃下具有最高的质子电导率0.113S/cm。GO上的含氧官能团有助于复合膜中质子的跳跃,原位聚合法使GO更均匀地分散在SPBI基质中,对复合膜质子电导率的提高起到关键作用。     

Dramatic change of water-cluster accessibility of highly pure double-walled carbon nanotubes with high temperature annealing

Highly pure double-walled carbon nanotubes (DWCNTs) synthesized by a catalytic chemical vapour deposition method have a well-ordered bundle structure giving explicit diffraction peaks by synchrotron X-ray diffraction measurement. The changes of nanopore structural properties and water adsorptivity of DWCNTs with high-temperature heat treatment were investigated using molecular probe adsorption methods. It was founded that their nanoporosities and apparent hydrophilicities decreased with thermal annealing. However, a specific surface area of 275 m(2) g(-1) and the residual microporosity of more than 60% even after heat treatment at 2673 K suggest their unique applications.     

Synthesis of sulfur-doped p-type graphene by annealing with hydrogen sulfide

Doping is an important method to modulate the electronic properties of graphene. Among various types of doped graphene, sulfur-doped graphene is expected to have a wider band gap due to the electron-withdrawing character of sulfur. However, it is difficult to dope graphene with S because S atom is much larger than C atom. In this paper, S-doped graphene is synthesized by a simple method with hydrogen sulfide annealing. It is confirmed by high-resolution transmission electron microscopy diffraction and Raman spectra that S-doping in graphene is surface adsorption doping forming carbon–sulfur compound crystal domains. We are also noted that the doping intensity is affected by annealing time indicating the doping process is controllable. Electrical measurements show that sulfur plays an acceptor role in S-doped graphene leading to a p-type behavior, and after sulfur-doping, graphene exhibits higher resistance and larger on/off ratio.     

Measurements and correlations for gas liquid surface tension at high pressure and high temperature

Surface tension of water/nitrogen and water–phenol/nitrogen systems was successfully measured by the hanging drop method in a wide domain of temperature (from 100 to 300°C) and pressure (from 4 to 30MPa), conditions little explored in litterature. Results show that surface tension of water–phenol mixtures decreases as phenol mass fraction increases. This decrease is observed under saturated and unsaturated conditions and is more pronounced at low temperatures and does not seem to depend on pressure. The effect of saturation on surface tension in the water/nitrogen system has been correlated with water vapor pressure by using experimental points with a great accuracy. For the water–phenol/nitrogen system, experimental data obtained with different mass fraction of phenol were correlated using Macleod‐Sugden equation for mixtures. © 2018 American Institute of Chemical Engineers © 2018 American Institute of Chemical Engineers AIChE J, 64: 4110–4117, 2018