Nitrogen-doped graphene films from chemical vapor deposition of pyridine: influence of process parameters on the electrical and optical properties.
ABSTRACT: Graphene films were produced by chemical vapor deposition (CVD) of pyridine on copper substrates. Pyridine-CVD is expected to lead to doped graphene by the insertion of nitrogen atoms in the growing sp(2) carbon lattice, possibly improving the properties of graphene as a transparent conductive film. We here report on the influence that the CVD parameters (i.e., temperature and gas flow) have on the morphology, transmittance, and electrical conductivity of the graphene films grown with pyridine. A temperature range between 930 and 1070 °C was explored and the results were compared to those of pristine graphene grown by ethanol-CVD under the same process conditions. The films were characterized by atomic force microscopy, Raman and X-ray photoemission spectroscopy. The optical transmittance and electrical conductivity of the films were measured to evaluate their performance as transparent conductive electrodes. Graphene films grown by pyridine reached an electrical conductivity of 14.3 × 10(5) S/m. Such a high conductivity seems to be associated with the electronic doping induced by substitutional nitrogen atoms. In particular, at 930 °C the nitrogen/carbon ratio of pyridine-grown graphene reaches 3%, and its electrical conductivity is 40% higher than that of pristine graphene grown from ethanol-CVD.
Project description:There is significant interest in synthesizing large-area graphene films at low temperatures by chemical vapor deposition (CVD) for nanoelectronic and flexible device applications. However, to date, low-temperature CVD methods have suffered from lower surface coverage because micro-sized graphene flakes are produced. Here, we demonstrate a modified CVD technique for the production of large-area, continuous monolayer graphene films from benzene on Cu at 100-300?°C at ambient pressure. In this method, we extended the graphene growth step in the absence of residual oxidizing species by introducing pumping and purging cycles prior to growth. This led to continuous monolayer graphene films with full surface coverage and excellent quality, which were comparable to those achieved with high-temperature CVD; for example, the surface coverage, transmittance, and carrier mobilities of the graphene grown at 300?°C were 100%, 97.6%, and 1,900-2,500?cm(2) V(-1) s(-1), respectively. In addition, the growth temperature was substantially reduced to as low as 100?°C, which is the lowest temperature reported to date for pristine graphene produced by CVD. Our modified CVD method is expected to allow the direct growth of graphene in device manufacturing processes for practical applications while keeping underlying devices intact.
Project description:Graphene has been received a considerable amount of attention as a transparent conducting electrode (TCE) which may be able to replace indium tin oxide (ITO) to overcome the significant weakness of the poor flexibility of ITO. Given that graphene is the thinnest 2-dimensional (2D) material known, it shows extremely high flexibility, and its lateral periodic honeycomb structure of sp(2)-bonded carbon atoms enables ~2.3% of incident light absorption per layer. However, there is a trade-off between the electrical resistance and the optical transmittance, and the fixed absorption rate in graphene limits is use when fabricating devices. Therefore, a more efficient method which continuously controls the optical and electrical properties of graphene is needed. Here, we introduce a method which controls the optical transmittance and the electrical resistance of graphene through various thicknesses of the top Cu layers with a Cu/Ni metal catalyst structure used to fabricate a planar mesh pattern of single and multi-layer graphene. We exhibit a continuous transmittance change from 85% (MLG) to 97.6% (SLG) at an incident light wavelength of 550?nm on graphene samples simultaneously grown in a CVD quartz tube. We also investigate the relationships between the sheet resistances.
Project description:The synthesis of rebar graphene on Cu substrates is described using functionalized boron nitride nanotubes (BNNTs) that were annealed or subjected to chemical vapor deposition (CVD) growth of graphene. Characterization shows that the BNNTs partially unzip and form a reinforcing bar (rebar) network within the graphene layer that enhances the mechanical strength through covalent bonds. The rebar graphene is transferrable to other substrates without polymer assistance. The optical transmittance and conductivity of the hybrid rebar graphene film was tested, and a field effect transistor was fabricated to explore its electrical properties. This method of synthesizing 2D hybrid graphene/BN structures should enable the hybridization of various 1D nanotube and 2D layered structures with enhanced mechanical properties.
Project description:Large-area high-quality graphene was synthesized on different types of copper foils preannealed under positive pressure H2 atmosphere between 1 and 2 standard atmospheres. The prepared graphene showed good electrical conductivity, transmittance, and uniformity. The sheet resistance values of the grown monolayer graphene film were all about 500 ?/?, and the transmittance was as high as 97.24%. The carrier mobility of the monolayer graphene film was around 2000-3000 cm2/(V s). Furthermore, the monolayer coverage could be more than 95.00% controlled by adjusting the process parameters. The properties of the four layer-superposed graphene film nearly reached that of the commercialized indium tin oxide (ITO) glasses, which showed that the prepared graphene could be well applied to the transparent conductive electrode. The obtained graphene film has been used to construct Si/graphene solar cells without an antireflection film, which showed energy conversion efficiency among 4.99-5.62%.
Project description:Indium tin oxide (ITO) still remains as the main candidate for high-performance optoelectronic devices, but there is a vital requirement in the development of sol-gel based synthesizing techniques with regards to green environment and higher conductivity. Graphene/ITO transparent bi-film was synthesized by a two-step process: 10 wt. % tin-doped ITO thin films were produced by an environmentally friendly aqueous sol-gel spin coating technique with economical salts of In(NO3)3.H2O and SnCl4, without using organic additives, on surface free energy enhanced (from 53.826 to 97.698 mJm-2) glass substrate by oxygen plasma treatment, which facilitated void-free continuous ITO film due to high surface wetting. The chemical vapor deposited monolayer graphene was transferred onto the synthesized ITO to enhance its electrical properties and it was capable of reducing sheet resistance over 12% while preserving the bi-film surface smoother. The ITO films contain the In2O3 phase only and exhibit the polycrystalline nature of cubic structure with 14.35?±?0.5?nm crystallite size. The graphene/ITO bi-film exhibits reproducible optical transparency with 88.66% transmittance at 550?nm wavelength, and electrical conductivity with sheet resistance of 117 ?/sq which is much lower than that of individual sol-gel derived ITO film.
Project description:Direct growth of graphene films on dielectric substrates (quartz and silica) is reported, by means of remote electron cyclotron resonance plasma assisted chemical vapor deposition r-(ECR-CVD) at low temperature (650°C). Using a two step deposition process- nucleation and growth- by changing the partial pressure of the gas precursors at constant temperature, mostly monolayer continuous films, with grain sizes up to 500 nm are grown, exhibiting transmittance larger than 92% and sheet resistance as low as 900 ?·sq-1. The grain size and nucleation density of the resulting graphene sheets can be controlled varying the deposition time and pressure. In additon, first-principles DFT-based calculations have been carried out in order to rationalize the oxygen reduction in the quartz surface experimentally observed. This method is easily scalable and avoids damaging and expensive transfer steps of graphene films, improving compatibility with current fabrication technologies.
Project description:Mass production of high-quality graphene with low cost is the footstone for its widespread practical applications. We present herein a self-limited growth approach for producing graphene powders by a small-methane-flow chemical vapour deposition process on naturally abundant and industrially widely used diatomite (biosilica) substrates. Distinct from the chemically exfoliated graphene, thus-produced biomorphic graphene is highly crystallized with atomic layer-thickness controllability, structural designability and less noncarbon impurities. In particular, the individual graphene microarchitectures preserve a three-dimensional naturally curved surface morphology of original diatom frustules, effectively overcoming the interlayer stacking and hence giving excellent dispersion performance in fabricating solution-processible electrodes. The graphene films derived from as-made graphene powders, compatible with either rod-coating, or inkjet and roll-to-roll printing techniques, exhibit much higher electrical conductivity (?110,700?S?m(-1) at 80% transmittance) than previously reported solution-based counterparts. This work thus puts forward a practical route for low-cost mass production of various powdery two-dimensional materials.
Project description:Large-area freestanding graphene films are facilely fabricated by reducing graphene oxide films on recyclable Cu foils in H2-containing atmosphere at high temperature. Cu might act as efficient catalysts for considerably improved reduction of graphene oxide according to the SEM, EDS, XRD, XPS, Raman and TGA results. Comparing to the graphene films with ~30 ?m thickness reduced without Cu substrate at 900?°C, the thermal conductivity and electrical conductivity of graphene films reduced on Cu foils are enhanced about 140% to 902 Wm(-1)K(-1) and 3.6 × 10(4) S/m, respectively. Moreover, the graphene films demonstrate superior thermal conductivity of ~1219 Wm(-1)K(-1) as decreasing the thickness of films to ~10 ?m. The graphene films also exhibit excellent mechanical properties and flexibility.
Project description:Inverted perovskite solar cells incorporating RF sputtered NiO thin films as a hole transport layer and window layer are demonstrated. The electrical and optical properties of the NiO thin films are engineered using varied sputtering conditions. The localized states within bandgap owing to its crystal disorder and nonstoichiometric features affect the transmittance and the optical bandgap of the NiO thin films which in turn influences the Jsc of the perovskite solar cells. In addition, the electrical properties of the NiO thin films can be also varied during sputtering condition affecting the concentration of nickel vacancies and the resulting hole concentration. The conductivity largely originates from the hole concentration relating to the density of states in the NiO thin films which influence the fill factor (FF) of the solar cells. The solar cells fabricated with the NiO thin films made at 4?Pa of deposition pressure show highest performance owing to excellent transmittance and wider bandgap along with moderate conductivity. With further optimization, the perovskite solar cells exhibit ~20?mA/cm2 of Jsc and a 12.4% PCE (11.3% of averaged PCE).
Project description:Tailoring and assembling graphene into functional macrostructures with well-defined configuration are key for many promising applications. We report on a graphene-based woven fabric (GWF) prepared by interlacing two sets of graphene micron-ribbons where the ribbons pass each other essentially at right angles. By using a woven copper mesh as the template, the GWF grown from chemical vapour deposition retains the network configuration of the copper mesh. Embedded into polymer matrices, it has significant flexibility and strength gains compared with CVD grown graphene films. The GWFs display both good dimensional stability in both the warp and the weft directions and the combination of film transparency and conductivity could be optimized by tuning the ribbon packing density. The GWF creates a platform to integrate a large variety of applications, e.g., composites, strain sensors and solar cells, by taking advantages of the special structure and properties of graphene.