Controllable chemical vapor deposition of large area uniform nanocrystalline graphene directly on silicon dioxide

Metal-catalyst-free chemical vapor deposition (CVD) of large area uniform nanocrystalline graphene on oxidized silicon substrates is demonstrated. The material grows slowly, allowing for thickness control down to monolayer graphene. The as-grown thin films are continuous with no observable pinholes, and are smooth and uniform across whole wafers, as inspected by optical-, scanning electron-, and atomic force microscopy. The sp 2 hybridized carbon structure is confirmed by Raman spectroscopy. Room temperature electrical measurements show ohmic behavior (sheet resistance similar to exfoliated graphene) and up to 13 of electric-field effect. The Hall mobility is ∼40 cm 2/Vs, which is an order of magnitude higher than previously reported values for nanocrystalline graphene. Transmission electron microscopy, Raman spectroscopy, and transport measurements indicate a graphene crystalline domain size ∼10 nm. The absence of transfer to another substrate allows avoidance of wrinkles, holes, and etching residues which are usually detrimental to device performance. This work provides a broader perspective of graphene CVD and shows a viable route toward applications involving transparent electrodes. © 2012 American Institute of Physics.

Topologically invariant reaction coordinates for simulating multistate chemical reactions.

Evaluating free energy profiles of chemical reactions in complex environments such as solvents and enzymes requires extensive sampling, which is usually performed by potential of mean force (PMF) techniques. The reliability of the sampling depends not only on the applied PMF method but also the reaction coordinate space within the dynamics is biased. In contrast to simple geometrical collective variables that depend only on the positions of the atomic coordinates of the reactants, the E(gap) reaction coordinate (the energy difference obtained by evaluating a suitable force field using reactant and product state topologies) has the unique property that it is able to take environmental effects into account leading to better convergence, a more faithful description of the transition state ensemble and therefore more accurate free energy profiles. However, E(gap) requires predefined topologies and is therefore inapplicable for multistate reactions, in which the barrier between the chemically equivalent topologies is comparable to the reaction activation barrier, because undesired "side reactions" occur. In this article, we introduce a new energy-based collective variable by generalizing the E(gap) reaction coordinate such that it becomes invariant to equivalent topologies and show that it yields more well behaved free energy profiles than simpler geometrical reaction coordinates.

Tests of an adaptive QM/MM calculation on free energy profiles of chemical reactions in solution.

We present reaction free energy calculations using the adaptive buffered force mixing quantum mechanics/molecular mechanics (bf-QM/MM) method. The bf-QM/MM method combines nonadaptive electrostatic embedding QM/MM calculations with extended and reduced QM regions to calculate accurate forces on all atoms, which can be used in free energy calculation methods that require only the forces and not the energy. We calculate the free energy profiles of two reactions in aqueous solution: the nucleophilic substitution reaction of methyl chloride with a chloride anion and the deprotonation reaction of the tyrosine side chain. We validate the bf-QM/MM method against a full QM simulation, and show that it correctly reproduces both geometrical properties and free energy profiles of the QM model, while the electrostatic embedding QM/MM method using a static QM region comprising only the solute is unable to do so. The bf-QM/MM method is not explicitly dependent on the details of the QM and MM methods, so long as it is possible to compute QM forces in a small region and MM forces in the rest of the system, as in a conventional QM/MM calculation. It is simple, with only a few parameters needed to control the QM calculation sizes, and allows (but does not require) a varying and adapting QM region which is necessary for simulating solutions.

Controlled amine functionality in self-assembled monolayers via the hidden amine route: chemical and electronic tunability.

A synthetic strategy for fabricating a dense amine functionalized self-assembled monolayer (SAM) on hydroxylated surfaces is presented. The assembly steps are monitored by X-ray photoelectron spectroscopy, Fourier transform infrared- attenuated total reflection, atomic force microscopy, variable angle spectroscopic ellipsometry, UV-vis surface spectroscopy, contact angle wettability, and contact potential difference measurements. The method applies alkylbromide-trichlorosilane for the fabrication of the SAM followed by surface transformation of the bromine moiety to amine by a two-step procedure: S(N)2 reaction that introduces the hidden amine, phthalimide, followed by the removal of the protecting group and exposing the free amine. The use of phthalimide moiety in the process enabled monitoring the substitution reaction rate on the surface (by absorption spectroscopy) and showed first-order kinetics. The simplicity of the process, nonharsh reagents, and short reaction time allow the use of such SAMs in molecular nanoelectronics applications, where complete control of the used SAM is needed. The different molecular dipole of each step of the process, which is verified by DFT calculations, supports the use of these SAMs as means to tune the electronic properties of semiconductors and for better synergism between SAMs and standard microelectronics processes and devices.

SiO2 coating of silver nanoparticles by photoinduced chemical vapor deposition.

Gas-phase silver nanoparticles were coated with silicon dioxide (SiO2) by photoinduced chemical vapor deposition (photo-CVD). Silver nanoparticles, produced by inert gas condensation, and a SiO2 precursor, tetraethylorthosilicate (TEOS), were exposed to vacuum ultraviolet (VUV) radiation at atmospheric pressure and varying temperatures. The VUV photons dissociate the TEOS precursor, initiating a chemical reaction that forms SiO2 coatings on the particle surfaces. Coating thicknesses were measured for a variety of operation parameters using tandem differential mobility analysis and transmission electron microscopy. The chemical composition of the particle coatings was analyzed using energy dispersive x-ray spectrometry and Fourier transform infrared spectroscopy. The highest purity films were produced at 300-400 degrees C with low flow rates of additional oxygen. The photo-CVD coating technique was shown to effectively coat nanoparticles and limit core particle agglomeration at concentrations up to 10(7) particles cm(-3).