Understanding of the Electrochemical Behavior of Lithium at Bilayer-Patched Epitaxial Graphene/4H-SiC.

Novel two-dimensional materials (2DMs) with balanced electrical conductivity and lithium (Li) storage capacity are desirable for next-generation rechargeable batteries as they may serve as high-performance anodes, improving output battery characteristics. Gaining an advanced understanding of the electrochemical behavior of lithium at the electrode surface and the changes in interior structure of 2DM-based electrodes caused by lithiation is a key component in the long-term process of the implementation of new electrodes into to a realistic device. Here, we showcase the advantages of bilayer-patched epitaxial graphene on 4H-SiC (0001) as a possible anode material in lithium-ion batteries. The presence of bilayer graphene patches is beneficial for the overall lithiation process because it results in enhanced quantum capacitance of the electrode and provides extra intercalation paths. By performing cyclic voltammetry and chronoamperometry measurements, we shed light on the redox behavior of lithium at the bilayer-patched epitaxial graphene electrode and find that the early-stage growth of lithium is governed by the instantaneous nucleation mechanism. The results also demonstrate the fast lithium-ion transport (~4.7-5.6 × 10-7 cm2∙s-1) to the bilayer-patched epitaxial graphene electrode. Raman measurements complemented by in-depth statistical analysis and density functional theory calculations enable us to comprehend the lithiation effect on the properties of bilayer-patched epitaxial graphene and ascribe the lithium intercalation-induced Raman G peak splitting to the disparity between graphene layers. The current results are helpful for further advancement of the design of graphene-based electrodes with targeted performance.

Understanding Graphene Response to Neutral and Charged Lead Species: Theory and Experiment.

Deep understanding of binding of toxic Lead (Pb) species on the surface of two-dimensional materials is a required prerequisite for the development of next-generation sensors that can provide fast and real-time detection of critically low concentrations. Here we report atomistic insights into the Lead behavior on epitaxial graphene (Gr) on silicon carbide substrates by thorough complementary study of voltammetry, electrical characterization, Raman spectroscopy, and Density Functional Theory (DFT). It is verified that the epitaxial graphene exhibits quasi-reversible anode reactions in aqueous solutions, providing a well-defined redox peak for Pb species and good linearity over a concentration range from 1 nM to 1 µM. The conductometric approach offers another way to investigate Lead adsorption, which is based on the formations of stable charge-transfer complexes affecting the p-type conductivity of epitaxial graphene. Our results suggest the adsorption ability of the epitaxial graphene towards divalent Lead ions is concentration-dependent and tends to saturate at higher concentrations. To elucidate the mechanisms responsible for Pb adsorption, we performed DFT calculations and estimated the solvent-mediated interaction between Lead species in different oxidative forms and graphene. Our results provide central information regarding the energetics and structure of Pb-graphene interacting complexes that underlay the adsorption mechanisms of neutral and divalent Lead species. Such a holistic understanding favors design and synthesis of new sensitive materials for water quality monitoring.

Uniform doping of graphene close to the Dirac point by polymer-assisted assembly of molecular dopants.

Tuning the charge carrier density of two-dimensional (2D) materials by incorporating dopants into the crystal lattice is a challenging task. An attractive alternative is the surface transfer doping by adsorption of molecules on 2D crystals, which can lead to ordered molecular arrays. However, such systems, demonstrated in ultra-high vacuum conditions (UHV), are often unstable in ambient conditions. Here we show that air-stable doping of epitaxial graphene on SiC-achieved by spin-coating deposition of 2,3,5,6-tetrafluoro-tetracyano-quino-dimethane (F4TCNQ) incorporated in poly(methyl-methacrylate)-proceeds via the spontaneous accumulation of dopants at the graphene-polymer interface and by the formation of a charge-transfer complex that yields low-disorder, charge-neutral, large-area graphene with carrier mobilities ~70 000 cm2 V-1 s-1 at cryogenic temperatures. The assembly of dopants on 2D materials assisted by a polymer matrix, demonstrated by spin-coating wafer-scale substrates in ambient conditions, opens up a scalable technological route toward expanding the functionality of 2D materials.

Lead (Pb) interfacing with epitaxial graphene.

Here, we report the electrochemical deposition of lead (Pb) as a model metal on epitaxial graphene fabricated on silicon carbide (Gr/SiC). The kinetics of electrodeposition and morphological characteristics of the deposits were evaluated by complementary electrochemical, physical and computational methods. The use of Gr/SiC as an electrode allowed the tracking of lead-associated redox conversions. The analysis of current transients passed during the deposition revealed an instantaneous nucleation mechanism controlled by convergent mass transport on the nuclei locally randomly distributed on epitaxial graphene. This key observation of the deposit topology was confirmed by low values of the experimentally-estimated apparent diffusion coefficient, Raman spectroscopy and scanning electron microscopy (SEM) studies. First principles calculations showed that the nucleation of Pb clusters on the graphene surface leads to weakening of the interaction strength of the metal-graphene complex, and only spatially separated Pb adatoms adsorbed on bridge and/or edge-plane sites can affect the vibrational properties of graphene. We expect that the lead adatoms can merge in large metallic clusters only at defect sites that reinforce the metal-graphene interactions. Our findings provide valuable insights into both heavy metal ion electrochemical analysis and metal electroplating on graphene interfaces that are important for designing effective detectors of toxic heavy metals.

On the interaction of toxic Heavy Metals (Cd, Hg, Pb) with graphene quantum dots and infinite graphene.

The promise of graphene and its derivatives as next generation sensors for real-time detection of toxic heavy metals (HM) requires a clear understanding of behavior of these metals on the graphene surface and response of the graphene to adsorption events. Our calculations herein were focused on the investigation of the interaction between three HMs, namely Cd, Hg and Pb, with graphene quantum dots (GQDs). We determine binding energies and heights of both neutral and charged HM ions on these GQDs. The results show that the adsorption energy of donor-like physisorbed neutral Pb atoms is larger than that of either Cd or Hg. In contrast to the donor-like behavior of elemental HMs, the chemisorbed charged HM species act as typical acceptors. The energy barriers to migration of the neutral adatoms on GQDs are also estimated. In addition, we show how the substitution of a carbon atom by a HM adatom changes the geometric structure of GQDs and hence their electronic and vibrational properties. UV-visible absorption spectra of HM-adsorbed GQDs vary with the size and shape of the GQD. Based on our results, we suggest a route towards the development of a graphene-based sensing platform for the optical detection of toxic HMs.

Monolayer graphene/SiC Schottky barrier diodes with improved barrier height uniformity as a sensing platform for the detection of heavy metals.

A vertical diode structure comprising homogeneous monolayer epitaxial graphene on silicon carbide is fabricated by thermal decomposition of a Si-face 4H-SiC wafer in argon atmosphere. Current-voltage characteristics of the graphene/SiC Schottky junction were analyzed by applying the thermionic-emission theory. Extracted values of the Schottky barrier height and the ideality factor are found to be 0.4879 ± 0.013 eV and 1.01803 ± 0.0049, respectively. Deviations of these parameters from average values are smaller than those of previously observed literature data, thereby implying uniformity of the Schottky barrier height over the whole diode area, a stable rectifying behaviour and a good quality of ohmic palladium-graphene contacts. Keeping in mind the strong sensitivity of graphene to analytes we propose the possibility to use the graphene/SiC Schottky diode as a sensing platform for the recognition of toxic heavy metals. Using density functional theory (DFT) calculations we gain insight into the nature of the interaction of cadmium, mercury and lead with graphene as well as estimate the work function and the Schottky barrier height of the graphene/SiC structure before and after applying heavy metals to the sensing material. A shift of the I-V characteristics of the graphene/SiC-based sensor has been proposed as an indicator of presence of the heavy metals. Since the calculations suggested the strongest charge transfer between Pb and graphene, the proposed sensing platform was characterized by good selectivity towards lead atoms and slight interferences from cadmium and mercury. The dependence of the sensitivity parameters on the concentration of Cd, Hg and Pb is studied and discussed.

On the differing sensitivity to chemical gating of single and double layer epitaxial graphene explored using scanning Kelvin probe microscopy.

Using environmental scanning Kelvin probe microscopy, we show that the position of the Fermi level of single layer graphene is more sensitive to chemical gating than that of double layer graphene. We calculate that the difference in sensitivity to chemical gating is not entirely due to the difference in band structure of 1 and 2 layer graphene. The findings are important for gas sensing where the sensitivity of the electronic properties to gas adsorption is monitored and suggest that single layer graphene could make a more sensitive gas sensor than double layer graphene. We propose that the difference in surface potential between adsorbate-free single and double layer graphene, measured using scanning kelvin probe microscopy, can be used as a noninvasive method of estimating substrate-induced doping in epitaxial graphene.