Highly Ordered Pyrolytic Graphite Surface Research Articles

Effect of Graphite Aging on Its Wetting Properties and Surface Blocking by Gaseous Nanodomains.

Early works considered basal planes of highly ordered pyrolytic graphite (HOPG) as hydrophobic, relatively inert materials with low electrocatalytic activity due to nonpolar sp2 carbon. On the contrary, a freshly prepared HOPG surface exhibits intrinsically mildly hydrophilic properties, with a low contact angle of water, which increases after exposure to an ambient atmosphere. This process, called aging, ascribed to adsorption of airborne hydrocarbons, is reportedly accompanied by strong decay of electron transfer kinetics, the mechanism of which is not yet fully understood. Examining both freshly prepared and aged basal plane HOPG immersed in water by PeakForce quantitative nanomechanical imaging, we have found that aged HOPG is occupied by ambient gaseous nanodomains, the existence of which is explained by incomplete wetting. They cover up to 60% of the immersed surface and their incidence is in direct relation with graphite aging time. In contrast with aged graphite, gaseous nanodomains were absent on the freshly stripped HOPG surface. It can be concluded that ambient gaseous nanodomains can prevent aged basal plane HOPG from contact with aqueous media and may thus affect processes at the solid-liquid interface.

Electronic Structure and Surface Chemistry of Hexagonal Boron Nitride on HOPG and Nickel Substrates.

The effect of point defects and interactions with the substrate are shown by density functional theory calculations to be of significant importance for the structure and functional properties of hexagonal boron nitride (h-BN) films on highly ordered pyrolytic graphite (HOPG) and Ni(111) substrates. The structure, surface chemistry, and electronic properties are calculated for h-BN systems with selected intrinsic, oxygen, and carbon defects and with graphene hybrid structures. The electronic structure of a pristine monolayer of h-BN is dependent on the type of substrate, as h-BN is decoupled electronically from the HOPG surface and acts as bulk-like h-BN, whereas on a Ni(111) substrate, metallic-like behavior is predicted. These different film/substrate systems therefore show different reactivities and defect chemistries. The formation energies for substitutional defects are significantly lower than for intrinsic defects regardless of the substrate, and vacancies formed during film deposition are expected to be filled by either ambient oxygen or carbon from impurities. Significantly lower formation energies for intrinsic and oxygen and carbon substitutional defects were predicted for h-BN on Ni(111). In-plane h-BCN hybrid structures were predicted to be terminated by N-C bonding. Substitutional carbon on the boron site imposes n-type semiconductivity in h-BN, and the n-type character increases significantly for h-BN on HOPG. The h-BN film surface becomes electronically decoupled from the substrate when exceeding monolayer thickness, showing that the surface electronic properties and point defect chemistry for multilayer h-BN films should be comparable to those of a freestanding h-BN layer.

Electrochemical grafting assisted modification of graphite surface by 3,4,5-trimethoxybenzenediazonium based monolayer

A conventional route to create such nanoscale electronic devices using the autonomous ordering and assembly of organic molecules on atomically well-defined surfaces has been proposed. However, these thin films are unstable in realistic environments due to weak interaction between the organic molecules and crystal surfaces. Therefore, enhancing the interfacial interaction between them is assigned as the key approach to extend the scope of application of these promising monolayer thin films. In this work, we demonstrate the formation of an organic monolayer, namely 3,4,5-trimethoxy diazonium (3,4,5-TMD), on a Highly Ordered Pyrolytic Graphite (HOPG) electrode by using the power of electrochemical method. The structural properties at the nano scale as well as the bonding nature between 3,4,5-TMD adlayer and HOPG electrode at the interface were investigated by a combination of cyclic voltammetry (CV), atomic force spectroscopy (AFM) and Raman spectroscopy. As a result, the 3,4,5-TMD molecules covalently bond to carbon atoms located at the HOPG interface for forming a monolayer with its thickness of 0.92 ± 0.02 nm. This finding opens a partway to apply the electrochemical grafting for covalent functionalization of 2D materials on HOPG and other metallic surfaces.

In Situ Imaging and Computational Modeling Reveal That Thiophene Complexation with Co(II)porphyrin/Graphite Is Highly Cooperative

Scanning tunneling microscopy (STM) was employed to quantitively investigate in situ binding of 3-phenyl thiophene (PhTh) to Co(II)octaethyl porphyrin (CoOEP) supported on highly ordered pyrolytic graphite (HOPG) in fluid solution. To our knowledge, this is the first single-molecule level study of a complexation reaction between a metalloporphyrin and a sulfur base at the solution/solid interface and one of the few examples of thiophene coordination with a d7 transition metal. Real-time imaging experiments revealed that PhTh binds reversibly to HOPG-supported CoOEP at room temperature. The coordination process increases with increasing PhTh concentration. The nearest-neighbor analysis of STM images indicates that the complexation reaction is cooperative. Because PhTh does not bind to CoOEP in solution, the STM results strongly suggest that the presence of HOPG is crucial to observe ligand binding and cooperativity in this system. Periodic plane-wave density functional theory (DFT) computations corroborate that PhTh has low binding affinity toward CoOEP in solution but predict that the ligand can adsorb to CoOEP/HOPG through coordination with S atoms or interact through noncovalent π–π bonding with the porphyrin chromophore. Three possible structures were considered, and DFT theory was used to calculate binding energies and free energies. In solution and on the HOPG surface both a π–π configuration and a η1(S) configuration have similar computed energies. The η1(S) structure shows the largest stabilization in going from the vapor to adsorbed on HOPG. We also show that statistical analysis of nearest neighbors is more sensitive to cooperative binding than is fitting with the Temkin or Langmuir isotherm. The implication is that isotherm fitting alone is insufficient for identifying cooperative binding on surfaces.

Unoccupied Electronic States and Potential Barrier in Films of Substituted Diphenylphthalides on the Surface of Highly Ordered Pyrolytic Graphite

The results of a study of the unoccupied electronic states of ultrathin films of bis-carboxyphenyl-phthalide (DCA-DPP) and bis-methylphenyl-phthalide (DM-DPP) up to 8 nm thick are presented. The studies are carried out by total current spectroscopy (TCS) in the energy range from 5 to 20 eV above EF during thermal vacuum deposition of these organic films on the surface of highly ordered pyrolytic graphite (HOPG). The values of Evac relative to EF, i.e., the work function of electrons of the DM-DPP films at a film thickness of 5–8 nm are found to be 4.3 ± 0.1 eV. The values of the work function of electrons of the DCA‑DPP films are found to be 3.7 ± 0.1 eV. The structure of the maxima of unoccupied electronic states of DCA-DPP and DM-DPP films in the studied energy range is established. A comparison of the obtained properties of DCA-DPP and DM-DPP films with the properties of films of molecules of unsubstituted diphenylphthalide (DPP) is presented. Thus, the –CH3 substitution of the DPP molecule has almost no effect on the height of the potential barrier between the film and the HOPG surface, while –COOH substitution of the DPP molecule leads to an increase in the height of the potential barrier between the film and the HOPG substrate surface by 0.5–0.6 eV. Substitution of DPP molecules with –COOH functional groups and, thus, the formation of DCA-DPP molecules lead to a shift of two maxima of the fine structure of the total current spectra located at energies in the range from 5 to 8 eV above EF by about 1 eV towards the lower electron energies.

Multiscale modeling of damaged surface topology in a hypersonic boundary.

In this work, we used molecular dynamics (MD) to perform trajectory simulations of ice-like argon and amorphous silica aggregates on atomically smooth highly ordered pyrolytic graphite (HOPG) and a comparatively rougher quartz surface. It was found that at all incidence velocities, the quartz surface was stickier than the HOPG surface. The sticking probabilities and elastic moduli obtained from MD were then used to model surface evolution at a micron length scale using kinetic Monte Carlo (kMC) simulations. Rules were derived to control the number of sites available for the process execution in kMC to accurately model erosion of HOPG by atomic oxygen (AO) attack and ice-nucleation on surfaces. It was observed that the effect of defects was to increase the material erosion rate, while that of aggregate nucleation was to lower it. Similarly, simulations were performed to study the effects of AO attack and N2 adsorption-desorption on surface evolution and it was found that N2 adsorption-desorption limits the surface available for erosion by AO attack.

Ambient-pressure atomic force microscope with variable pressure from ultra-high vacuum up to one bar.

We present the design and performance of an ambient-pressure atomic force microscope (AP-AFM) that allows AFM measurements using the laser deflection technique in a highly controlled environment from ultra-high vacuum (UHV) up to 1 bar with various gases. While the UHV of the AP-AFM system is obtained by a combination of turbo-molecular and ion pumps, for the higher-pressure studies, the ambient-pressure chamber is isolated from the pumps and high-purity gases are dosed via a leak valve from a gas manifold. The AP-AFM system, therefore, provides versatile AFM techniques, including the measurement of topography, friction and local conductance mapping, and force spectroscopy in a highly controlled environment with pressures ranging from UHV up to atmospheric pressure. Atomically resolved stick-slip images and force spectroscopy of highly ordered pyrolytic graphite (HOPG) at variable pressure conditions are presented to demonstrate the performance of the AP-AFM system. Force spectroscopy results of vacuum-cleaved HOPG, followed by exposure to lab air, oxygen, and methane show that adhesion between the AFM tip and the HOPG depends significantly on the exposed gas and pressure. Our results show that the deposition of airborne hydrocarbon impurities at ambient conditions leads to a significant change in adhesion force, implying that the wettability of the HOPG surface depends on the environment and the pressure.

Microcontact Printing Patterning of an HOPG Surface by an Inverse Electron Demand Diels-Alder Reaction.

The chemical modification of an sp2 hybridized carbon surface in a controllable manner is very challenging but also crucial for many applications. An inverse electron demand Diels-Alder (IEDDA) reaction using microcontact printing technique is introduced to spatially control the modification of a highly ordered pyrolytic graphite (HOPG) surface under ambient conditions. The covalent modification was characterized by Raman spectroscopy, XPS, and SECM. Tetrazine derivatives can effectively react with an HOPG surface and with microcontact printing methods resulting in spatially patterned surfaces being produced with micrometer-scale resolution.

Electrostatic Deposition of Large-Surface Graphene.

This work describes a method for electrostatic deposition of graphene over a large area using controlled electrostatic exfoliation from a Highly Ordered Pyrolytic Graphite (HOPG) block. Deposition over 130 × 130 µm2 with 96% coverage is achieved, which contrasts with sporadic micro-scale depositions of graphene with little control from previous works on electrostatic deposition. The deposition results are studied by Raman micro-spectroscopy and hyperspectral analysis using large fields of view to allow for the characterization of the whole deposition area. Results confirm that laser pre-patterning of the HOPG block prior to cleaving generates anchor points favoring a more homogeneous and defect-free HOPG surface, yielding larger and more uniform graphene depositions. We also demonstrate that a second patterning of the HOPG block just before exfoliation can yield features with precisely controlled geometries.

Controlling the Molecular Direction of Dinuclear Ruthenium Complexes on HOPG Surface through Noncovalent Bonding.

We synthesized three types of binuclear Ru complexes (1-3) that contain pyrene anchors for the adsorption of 1-3 onto nanocarbon materials via noncovalent π-π interactions, in order to investigate their adsorption onto and their desorption from highly ordered pyrolytic graphite (HOPG). The adsorption saturation for 1 (6.22 pmol/cm2), 2 (2.83 pmol/cm2), and 3 (3.53 pmol/cm2) on HOPG was obtained from Langmuir isotherms. The desorption rate from HOPG electrodes decreased in the order 3 (2.4 × 10-5 s-1) > 2 (1.4 × 10-5 s-1) ≫ 1 (1.8 × 10-6 s-1). These results indicate that the number of pyrene anchors and their position of substitution in such complexes strongly affect the desorption behavior. However, neither the free energy of adsorption (ΔGads) nor the heterogeneous electron-transfer rate (kET) showed any significant differences among 1-3, albeit that the surface morphologies of the modified HOPG substrates showed domain structures that were characteristic for each Ru complex. In the case of 3, the average height changed from ∼2 to ∼4 nm upon increasing the concentration of the solution of 3 that was used for the surface modification. In contrast, the height for 1 and 2 remained constant (1.5-2 nm) upon increasing the concentration of the complexes in the corresponding solutions. While the molecular orientation of the Ru-Ru axis of 3 relative to the HOPG surface normal changed from parallel to perpendicular, the Ru-Ru axis in 1 and 2 remained parallel, which leads to an increased stability of 1 and 2.

Surface-Limited Platinum Electrodeposition on Highly Ordered Pyrolytic Graphite

Recently we reported an overpotential electrodeposition method to deposit contiguous Pt nanoplatelets/thin films directly onto the surface of self-standing electrospun carbon nanofiber mats, leading to Carbon Nanofibrous Electrodes (NFEs) [1]. We demonstrated the high electrocatalytic activity and improved stability over high-potential prolonged cycling compared to conventional Pt nanoparticles on carbon. In order to study more in detail the Pt growth and the morphology of the obtained Pt surfaces as a function of the experimental parameters, we investigated such surface-limited electrodeposition employing Highly Ordered Pyrolytic Graphite (HOPG) as a model surface.We studied Pt deposition on HOPG by contact-mode AFM imaging. Pt interconnected particles and Pt networks can be grown directly onto the substrate at high overpotential as a function of the deposition time, with no significant variation in thickness and size of the connected particles. A progressive coverage of the substrate surface is clearly present, eventually leading to the formation of Pt thin islands below 2 nm in thickness. We also show by TEM analysis that Pt(111) facets are preferentially deposited and grown on the substrate.We studied the deposition mechanism at high overpotential. We will show that the Pt deposition is not diffusion-limited and that it overlaps with other processes. We will discuss the effects of these other processes (H2 evolution on Pt and HOPG) on the Pt deposition. Additional indications can be derived from computer simulations (e.g. DigiElch®) that approximate the experimental conditions. The rate constants used for the simulations were obtained experimentally and their variation with HOPG surface preparation will also be presented.In this work we will present our advances towards understanding the nature of this surface-limited electrodeposition. The morphological and structural characterization of these Pt features on HOPG will be presented and discussed, along with some early insights on their growth mechanism.[1] G. Ercolano, F. Farina, S. Cavaliere, D.J. Jones, J. Rozière, J. Mater. Chem. A 5 (2017) 3974-3980.

Atomic layer deposition of 1D and 2D nickel nanostructures on graphite

One-dimensional (1D) nanowires (NWs) and two-dimensional (2D) thin films of Ni were deposited on highly ordered pyrolytic graphite (HOPG) by atomic layer deposition (ALD), using NH3 as a counter reactant. Thermal ALD using NH3 gas forms 1D NWs along step edges, while NH3 plasma enables the deposition of a continuous 2D film over the whole surface. The lateral and vertical growth rates of the Ni NWs are numerically modeled as a function of the number of ALD cycles. Pretreatment with NH3 gas promotes selectivity in deposition by the reduction of oxygenated functionalities on the HOPG surface. On the other hand, NH3 plasma pretreatment generates surface nitrogen species, and results in a morphological change in the basal plane of graphite, leading to active nucleation across the surface during ALD. The effects of surface nitrogen species on the nucleation of ALD Ni were theoretically studied by density functional theory calculations. Our results suggest that the properties of Ni NWs, such as their density and width, and the formation of Ni thin films on carbon surfaces can be controlled by appropriate use of NH3.

Scanning tunneling microscopy/spectroscopy measurements and density functional theory calculations on self-assembled monolayer of octanoic acid on graphite

Here, we report Scanning Tunneling Microscopy/Spectroscopy (STM/STS) data on self-assembled monolayer of octanoic acid on highly ordered pyrolytic graphite (HOPG) surface at solid-liquid interface. In addition to the experimental work, we investigated the system with Density Functional Theory (DFT) calculations. In order to maximize the interactions with the substrate, octanoic acid molecules lay flat on the surface. The molecules in neighboring lamella assemble with opposite faces to establish hydrogen bonding between carboxyl groups. STS measurements and DFT calculations reveal that local density of states of octanoic acid covered HOPG surface is similar to the local density of states of pristine HOPG. We attribute this to the fact that the molecules are only physisorbed on the surface.

Boundary layer friction of solvate ionic liquids as a function of potential.

Atomic force microscopy (AFM) has been used to investigate the potential dependent boundary layer friction at solvate ionic liquid (SIL)-highly ordered pyrolytic graphite (HOPG) and SIL-Au(111) interfaces. Friction trace and retrace loops of lithium tetraglyme bis(trifluoromethylsulfonyl)amide (Li(G4) TFSI) at HOPG present clearer stick-slip events at negative potentials than at positive potentials, indicating that a Li+ cation layer adsorbed to the HOPG lattice at negative potentials which enhances stick-slip events. The boundary layer friction data for Li(G4) TFSI shows that at HOPG, friction forces at all potentials are low. The TFSI- anion rich boundary layer at positive potentials is more lubricating than the Li+ cation rich boundary layer at negative potentials. These results suggest that boundary layers at all potentials are smooth and energy is predominantly dissipated via stick-slip events. In contrast, friction at Au(111) for Li(G4) TFSI is significantly higher at positive potentials than at negative potentials, which is comparable to that at HOPG at the same potential. The similarity of boundary layer friction at negatively charged HOPG and Au(111) surfaces indicates that the boundary layer compositions are similar and rich in Li+ cations for both surfaces at negative potentials. However, at Au(111), the TFSI- rich boundary layer is less lubricating than the Li+ rich boundary layer, which implies that anion reorientations rather than stick-slip events are the predominant energy dissipation pathways. This is confirmed by the boundary friction of Li(G4) NO3 at Au(111), which shows similar friction to Li(G4) TFSI at negative potentials due to the same cation rich boundary layer composition, but even higher friction at positive potentials, due to higher energy dissipation in the NO3- rich boundary layer.

Fabrication of Photomagnetic Carbon Surfaces via Redox Assembly

3-Aminophenylboronic acid (APBA) and the complex Ru(bpy)2(phendione)2+ (bpy = 2,2′-bipyridine, phendione = 1,10-phenanthroline-5,6-dione) were found to be useful building blocks for preparing photomagnetic carbon surfaces. Scanning tunneling microscopy (STM) showed that when APBA was diazotized in acidic sodium nitrite solutions and cathodically reduced with highly ordered pyrolytic graphite (HOPG) electrodes, nanoscale films formed on the electrodes. The resulting HOPG had strong affinities for phendione and Ru(bpy)2(phendione)2+ as the electrodes were biased in the presence of them, respectively, with voltages more negative than the cathodic peak potentials for phendione/phendiol and Ru(bpy)2(phendione)2+/Ru(bpy)2(phendiol)2+ (phendiol = 1,10-phenanthroline-5,6-diol). However, if APBA was excluded, the affinities did not exist. Boronate ester formation featured prominently in these intermolecular interactions. The average increments in the HOPG surface roughness contributed by APBA and Ru(bpy)2(phendione)2+ were roughly 1 : 2, suggesting that the reaction stoichiometry between APBA and Ru(bpy)2(phendione)2+ be 1 : 1. Ru(bpy)2(phendione)2+ could also be grafted to carbon nanotubes (CNTs) under conditions similar to those for the HOPG using ascorbate as sacrificial donor. The resulting CNTs and HOPG exhibited photomagnetism when exposed to the 473 nm light. The ruthenium complex was shown to be a room-temperature photomagnetism precursor, and APBA was shown to be an effective molecular bridge for the complex and carbon substrates.

Deposition of copper from Cu(i) and Cu(ii) precursors onto HOPG surface: Role of surface defects and choice of a precursor.

The surface reactivity of two copper-containing precursors, (Cu(hfac)2 and Cu(hfac)VTMS, where hfac is hexafluoroacetyloacetonate and VTMS is vinyltrimethylsilane), was investigated by dosing the precursors onto a surface of highly ordered pyrolytic graphite (HOPG) at room temperature. The behavior of these precursors on a pristine HOPG was compared to that on a surface activated by ion sputtering and subsequent oxidation to induce controlled surface defects. X-ray photoelectron spectroscopy and energy dispersive X-ray spectroscopy were used to confirm copper deposition and its surface distribution, and to compare with the results of scanning electron microscopy and atomic force microscopy investigations. As expected, surface defects promote copper deposition; however, the specific structures deposited depend on the deposition precursor. Density functional theory was used to mimic the reactions of each precursor molecule on this surface and to determine the origins of this different reactivity.

3-Dimensional Structure of a Prototypical Ionic Liquid–Solid Interface: Ionic Crystal-Like Behavior Induced by Molecule–Substrate Interactions

The molecular structure of the ionic liquid–electrode interface has been recently investigated by atomic force microscopy (AFM) methods focusing either on the vertical structure of the ion layers or on the lateral structure of the innermost layer. Here, we combine high-resolution AFM imaging with atomic force spectroscopy measurements to elucidate the structure of the interface between the ionic liquid propylammonium nitrate (PAN) and highly ordered pyrolytic graphite (HOPG). The lateral structure of the innermost layer of adsorbed molecules (i.e., the Stern layer) is resolved on the molecular scale by means of amplitude modulation atomic force microscopy (AM-AFM). A quasi (4 × 4)R0° overlayer is formed by the ionic liquid molecules on the HOPG surface. Additional dynamic mode force spectroscopy measurements reveal the existence of a layered structure of the ionic liquid normal to the surface plane and allow for a precise determination of the layer spacing. We are able to infer the three-dimensional struc...

Nanoscale Friction Characteristics of a Contact Junction with a Field-Induced Water Meniscus

The effect of the field-induced water meniscus on the friction level and oscillation was studied using an atomic force microscopy tip sliding on a highly ordered pyrolytic graphite (HOPG) surface. The results showed that the friction characteristics were significantly affected by the bias voltage, humidity, and sliding velocity. The friction level increased when the bias voltage increased beyond a threshold value (V th). The stick–slip-type friction oscillation was observed at low velocity and periodicity, and intensity of the friction oscillation was diminished at high velocity. The velocity dependence of the friction oscillation indicated that the mechanical properties of the field-induced water meniscus were comparable to the solid state due to field-induced ordering of water molecules in the meniscus. The static friction and amplitude of the friction oscillation during scanning were inversely proportional to the scan velocity, suggesting that the hydrophobic HOPG surface turned hydrophilic due to the electrical field at the meniscus and demonstrating the possibility of manipulating the friction using an electrical bias, which can be useful for functionalizing nanoscale devices.

Electrochemical properties of modified highly ordered pyrolytic graphite by using ambient plasma

Surface of highly ordered pyrolytic graphite (HOPG) is reformed by using ambient plasma. The HOPG film shows various pore structures after the plasma treatment, indicating improved electrochemical properties for supercapacitor applications because of the increase of the surface area. We also compare water effect on the film during the plasma treatment. Water might protect HOPG surface from the plasma and provide oxygen functional groups onto it, resulting in lower infected pores and higher impedance compared with them of HOPG film without water. Ambient plasma, therefore, could be considered as an economic and effective method for sample reformations.

Electrochemical formation and characterization of Au nanostructures on a highly ordered pyrolytic graphite surface

The electrochemical formation of Au nanoparticles on a highly ordered pyrolytic graphite (HOPG) substrate using conventional electrochemical techniques and ex-situ AFM is reported. From the potentiostatic current transients studies, the Au electrodeposition process on HOPG surfaces was described, within the potential range considered, by a model involving instantaneous nucleation and diffusion controlled 3D growth, which was corroborated by the microscopic analysis. Initially, three-dimensional (3D) hemispherical nanoparticles distributed on surface defects (step edges) of the substrate were observed, with increasing particle size at more negative potentials. The double potential pulse technique allowed the formation of rounded deposits at low deposition potentials, which tend to form lines of nuclei aligned in defined directions leading to 3D ordered structures. By choosing suitable nucleation and growth pulses, one-dimensional (1D) deposits were possible, preferentially located on step edges of the HOPG substrate. Quantum-mechanical calculations confirmed the tendency of Au atoms to join selectively on surface defects, such as the HOPG step edges, at the early stages of Au electrodeposition.