Highly Oriented Pyrolytic Graphite Research Articles

Atomic wetting of oil droplets into hexagons and stripes

HypothesisPrevious studies showed that liquid droplets can be spherical caps or polygonal shapes on patterned surfaces. We hypothesize that these phenomena can be narrowed down to nanoscale and affecting liquid molecular wetting. We anticipate observing preferential wetting on the underlying substrate with atomic crystalline lattice. ExperimentsThis study explores the wetting behavior of oil nanodroplets deposited on highly ordered pyrolytic graphite (HOPG) with atomic force microscope (AFM). Oil droplets were scanned with hydrophobic and hydrophilic AFM tips in water in peak force mode AFM, carefully controlling the scanning force. Simple modeling was carried out using Surface Evolver to simulate how oil droplets wet on HOPG with molecular lattice. FindingsThe results showed two distinct wetting behaviors: the hexagonal nanodroplets and stripe nanometric films. In both cases, the droplets appear to wet preferentially along preferred orientations which reflect the atomic periodicity of the underlying substrate. This preferential wetting occurs because the atomic roughness is significant at the length scale of the nanodroplets, while the eventual outcome of the wetting (i.e. whether the droplet settles to a finite contact angle, or wets completely into a nanometric film) is dependent on the spreading parameter of the droplet-substrate system, independent of scanning direction.

Lightweight Heat Pipe Radiator for Nuclear Reactor Power Systems on Lunar Surface

Heat rejection radiators of nuclear reactor power systems for space exploration and for planetary surface power are the largest component by volume and mass, depending on the radiator’s design and surface average temperature. This work developed designs for lightweight radiator modules for waste heat rejection on the lunar surface at a surface average temperature of 600 K. The modules each have a cesium (Cs)–titanium (Ti) heat pipe (HP) and highly oriented pyrolytic graphite (HOPG)/Ti heat spreading fins. The assembled panels of 10 Cs-HP modules hydraulically coupled in parallel are armored with carbon-carbon composite to protect against impacts by micrometeoroids and space debris for 10 years. The performance of the developed armored radiator panels is much superior to the current state of the art, with an areal density of 2.98 to 3.6 kg/m2, specific power of 3.36 to 3.98 kW/kg, rejected thermal power of 56.3 to 96.3 kW, and rejected power density of 7.56 kW/m2.

Reversible Redox‐Driven Crystallization in a Paracyclophane Monolayer at a Solid–Liquid Interface

AbstractThe development and integration of cyclophanes into future functional materials require a detailed understanding of the physicochemical principles that underlie their properties, phase behavior, and in particular the relationship between structure and function. Here, electrochemically switchable crystallization of a ferrocene‐bearing 3D Janus tecton (M‐Fc) at the interface between highly oriented pyrolytic graphite (HOPG) and an electrolyte solution is demonstrated. The M‐Fc adlayer is successfully visualized under both ambient and electrochemical conditions using scanning tunneling microscopy. Voltammetric measurements show a surface‐confined redox process for the M‐Fc modified surface that drives the phase transition between a visible 2D ordered linear phase (M‐Fc0, with ferrocene in the neutral state) and an invisible gas‐like adsorption layer with high mobility when ferrocene is oxidized, M‐Fc+, and a “square scheme” mechanism explains the data. Analogous experiments in a ferrocene‐free tecton adlayer show no phase transition and confirm that the dynamics in M‐Fc are redox‐driven. On‐surface 3D nanoarchitectures are also demonstrated by forming inclusion complexes between M‐Fc and β‐cyclodextrin and device behavior through electrochemical scanning tunneling spectroscopy (STS). These results showcase the functional potential of this class of cyclophanes, which can find use in actuators, optical crystals, and other smart materials.

RHEED Study of the Epitaxial Growth of Silicon and Germanium on Highly Oriented Pyrolytic Graphite

Two-dimensional silicon (silicene) and germanium (germanene) have attracted special attention from researchers in recent years. At the same time, highly oriented pyrolytic graphite (HOPG) and graphene are some of the promising substrates for growing silicene and germanene. However, to date, the processes occurring during the epitaxial growth of silicon and germanium on the surface of such substrates have been poorly studied. In this work, the epitaxial growth of silicon and germanium is studied directly during the process of the molecular beam epitaxy deposition of material onto the HOPG surface by reflection high-energy electron diffraction (RHEED). In addition, the obtained samples are studied by Raman spectroscopy and scanning electron microscopy. A wide range of deposition temperatures from 100 to 800 °C is considered and temperature intervals are determined for various growth modes of silicon and germanium on HOPG. Conditions for amorphous and polycrystalline growth are distinguished. Diffraction spots corresponding to the lattice constants of silicene and germanene are identified that may indicate the presence of areas of graphene-like 2D phases during epitaxial deposition of silicon and germanium onto the surface of highly oriented pyrolytic graphite.

Toward a Comprehensive Understanding of the Anomalously Small Contact Angle of Surface Nanobubbles.

Experimental studies have demonstrated that the gas phase contact angle (CA) of a surface nanobubble (SNB) is much smaller than that of a macroscopic gas bubble. This reduced CA plays a crucial role in prolonging the lifetime of SNBs by lowering the bubble pressure and preventing gas molecules from dissolving in the surrounding liquids. Despite extensive efforts to explain the anomalously small CA, a consensus about the underlying reasons is yet to be reached. In this study, we conducted experimental investigations to explore the influence of gas molecules adsorbed at the solid-liquid interface on the CA of SNBs created through the solvent exchange (SE) method and temperature difference (TD). Interestingly, no significant change is observed in the CA of SNBs on highly oriented pyrolytic graphite (HOPG) surfaces. Even for nanobubbles on micro/nano pancakes, the CA only exhibited a slight reduction compared to SNBs on bare HOPG surfaces. These findings suggest that gas adsorption at the immersed solid surface may not be the primary factor contributing to the small CA of the SNBs. Furthermore, the CA of SNBs formed on polystyrene (PS) and octadecyltrichlorosilane (OTS) substrates was also investigated, and a considerable increase in CA was observed. In addition, the effects of other factors including impurity, electric double layer (EDL) line tension, and pinning force upon the CA of SNBs were discussed, and a comprehensive model about multiple factors affecting the CA of SNBs was proposed, which is helpful for understanding the abnormally small CA and the stability of SNBs.

Nanostructure and Dynamics of Aprotic Ionic Liquids at Graphite Electrodes as a Function of Potential.

Atomic force microscope (AFM) videos reveal the near-surface nanostructure and dynamics of the ionic liquids (ILs) 1-butyl-3-methylimidazolium dicyanamide (BMIM DCA) and 1-hexyl-3-methylimidazolium dicyanamide (HMIM DCA) above highly oriented pyrolytic graphite (HOPG) electrodes as a function of surface potential. Molecular dynamics (MD) simulations reveal the molecular-level composition of the nanostructures. In combination, AFM and MD show that the near-surface aggregates form via solvophobic association of the cation alkyl chains at the electrode interface. The diffusion coefficients of interfacial nanostructures are ≈0.01nm2s-1 and vary with the cation alkyl chain length and the surface potential. For each IL, the nanostructure diffusion coefficients are similar at open-circuit potential (OCP) and OCP + 1V, but BMIM DCA moves about twice as fast as HMIM DCA. At negative potentials, the diffusion coefficient decreases for BMIM DCA and increases for HMIM DCA. When the surface potential is switched from negative to positive, a sudden change in the direction of the nanostructure motion is observed for both BMIM DCA and HMIM DCA. No transient dynamics are noted following other potential jumps. This study provides a new fundamental understanding regarding the dynamics of electrochemically stable ILs at electrodes vital for the rational development of IL-based electrochemical devices.

Atomic force microscopy investigation of DNA denaturation on a highly oriented pyrolytic graphite surface

Understanding of DNA interaction with carbonaceous surfaces (including graphite, graphene and carbon nanotubes) is important for the development of DNA-based biosensors and other biotechnological devices. Though many issues related to DNA adsorption on graphitic surfaces have been studied, some important aspects of DNA interaction with graphite remain unclear. In this work, we use atomic force microscopy (AFM) equipped with super-sharp cantilevers to analyze the morphology and conformation of relatively long DNA molecule adsorbed on a highly oriented pyrolytic graphite (HOPG) surface. We have revealed the effect of DNA embedding into an organic monolayer of N,N′-(decane-1,10-diyl)-bis(tetraglycinamide) (GM), which may “freeze” DNA conformation on a HOPG surface during drying. The dependence of the mean squared point-to-point distance on the contour length suggests that DNA adsorbs on a bare HOPG by a “kinetic trapping” mechanism. For the first time, we have estimated the unfolded fraction of DNA upon contact with a HOPG surface (24 ± 5 %). The obtained results represent a novel experimental model for investigation of the conformation and morphology of DNA adsorbed on graphitic surfaces and provide with a new insight into DNA interaction with graphite.

Effects of defect creation and passivation on graphite friction under ultra-high vacuum conditions

Graphite holds significant promise as a solid lubricating material for machine operation in ambient conditions. However, the intricacies of its mechanism remain a subject of debate at the nanoscale. In this study, atomic force microscopy (AFM) experiments conducted in ultrahigh vacuum (UHV) conditions provide direct evidence that the adsorption of water molecules significantly compromises friction performance, both on the basal plane and across step edges. This challenges the longstanding belief that the poor lubricating properties of graphite in a vacuum result from the desorption of water molecules. Moreover, the experimental findings put forth a compelling bond passivation hypothesis for graphite lubrication in ambient conditions. The process involves the introduction of defects with dangling bonds on graphite through annealing highly oriented pyrolytic graphite (HOPG) at elevated temperatures (≥773 K) in UHV conditions. Subsequently, these dangling bonds are gradually passivated by a small amount of residue atoms or molecules. Consequently, the continuously monitored friction force exhibits an exponential decrease over time following annealing. This study advances a molecular level understanding of low lubrication mechanism for graphite.

High-resolution scanning tunneling microscope and its adaptation for local thermopower measurements in 2D materials

We present the design, fabrication and discuss the performance of a new combined high-resolution Scanning Tunneling and Thermopower Microscope (STM/SThEM). We also describe the development of the electronic control, the user interface, the vacuum system, and arrangements to reduce acoustical noise and vibrations. We demonstrate the microscope’s performance with atomic-resolution topographic images of highly oriented pyrolytic graphite (HOPG) and local thermopower measurements in the semimetal Bi2Te3. Our system offers a tool to investigate the relationship between electronic structure and thermoelectric properties at the nanoscale.

Utilizing Constant Energy Difference between sp-Peak and C 1s Core Level in Photoelectron Spectra for Unambiguous Identification and Quantification of Diamond Phase in Nanodiamonds.

The modification of nanodiamond (ND) surfaces has significant applications in sensing devices, drug delivery, bioimaging, and tissue engineering. Precise control of the diamond phase composition and bond configurations during ND processing and surface finalization is crucial. In this study, we conducted a comparative analysis of the graphitization process in various types of hydrogenated NDs, considering differences in ND size and quality. We prepared three types of hydrogenated NDs: high-pressure high-temperature NDs (HPHT ND-H; 0-30 nm), conventional detonation nanodiamonds (DND-H; ~5 nm), and size- and nitrogen-reduced hydrogenated nanodiamonds (snr-DND-H; 2-3 nm). The samples underwent annealing in an ultra-high vacuum and sputtering by Ar cluster ion beam (ArCIB). Samples were investigated by in situ X-ray photoelectron spectroscopy (XPS), in situ ultraviolet photoelectron spectroscopy (UPS), and Raman spectroscopy (RS). Our investigation revealed that the graphitization temperature of NDs ranges from 600 °C to 700 °C and depends on the size and crystallinity of the NDs. Smaller DND particles with a high density of defects exhibit a lower graphitization temperature. We revealed a constant energy difference of 271.3 eV between the sp-peak in the valence band spectra (at around 13.7 eV) and the sp3 component in the C 1s core level spectra (at 285.0 eV). The identification of this energy difference helps in calibrating charge shifts and serves the unambiguous identification of the sp3 bond contribution in the C 1s spectra obtained from ND samples. Results were validated through reference measurements on hydrogenated single crystal C(111)-H and highly-ordered pyrolytic graphite (HOPG).

Large and Pressure-Dependent c-Axis Piezoresistivity of Highly Oriented Pyrolytic Graphite near Zero Pressure.

The c-axis piezoresistivity is a fundamental and important parameter of graphite, but its value near zero pressure has not been well determined. Herein, a new method for studying the c-axis piezoresistivity of van der Waals materials near zero pressure is developed on the basis of in situ scanning electron microscopy and finite element simulation. The c-axis piezoresistivity of microscale highly oriented pyrolytic graphite (HOPG) is found to show a large value of 5.68 × 10-5 kPa-1 near zero pressure and decreases by 2 orders of magnitude to the established value of ∼10-7 kPa-1 when the pressure increases to 200 MPa. By modulating the serial tunneling barrier model on the basis of the stacking faults, we describe the c-axis electrical transport of HOPG under compression. The large c-axis piezoresistivity near zero pressure and its large decrease in magnitude with pressure are attributed to the rapid stiffening of the electromechanical properties under compression.

Rhombohedral stacking-faults in exfoliated highly oriented pyrolytic graphite

The recent observation of possible granular superconductivity in highly oriented pyrolytic graphite (HOPG) has attracted significant research interest. Here we report a novel investigation on the structural-properties of exfoliated-HOPG. We investigated two types of exfoliation methods, involving either a full (method-1) or partial (method-2) contact between adhesive tape and the main HOPG. Structural characterization was obtained by employing X-ray diffraction (XRD), Raman spectroscopy and electron microscopy (SEM). In particular, Raman point and mapping spectroscopy revealed significant structural-transitions from ABA (Bernal) to ABC (rhombohedral) stacking (stacking-faults), in those samples obtained with the method-2. Interestingly, strained regions exhibiting structural-deformations with a ridge-like morphology were reproducibly identified. The acquired Raman-spectra revealed a local enhancement of the D and D’ bands-intensity together with contributions arising from Electronic Raman Scattering (ERS) across the band-gap of rhombohedral-graphite, at middle (∼1870 cm−1) and high (∼ 2680 cm−1) frequency. HRTEM of the samples produced with the method-2 allowed also for the identification of local-coexistence of ripplocation-like defects with moiré superlattices, an indicator of non-uniform c-axis configuration.

FPGA and computer-vision-based atom tracking technology for scanning probe microscopy

Abstract Atom tracking technology enhanced with innovative algorithms has been implemented in this study, utilizing a comprehensive suite of controllers and software independently developed domestically. Leveraging an on-board field-programmable gate array (FPGA) with a core frequency of 100 MHz, our system facilitates reading and writing operations across 16 channels, performing discrete incremental proportional-integral-derivative (PID) calculations in as fast as 3.4 microseconds. Building upon this foundation, gradient and extremum algorithms are further integrated, incorporating circular and spiral scanning modes with a horizontal movement accuracy of 0.38 pm. This integration enhances real-time performance and significantly increases the accuracy of atom tracking. Atom tracking achieves an equivalent precision of at least 142 pm on a highly oriented pyrolytic graphite (HOPG) surface under room temperature atmospheric conditions. Through applying computer vision and image processing algorithms, atom tracking can be used when scanning a large area. The techniques primarily consist of two algorithms: the region of interest (ROI)-based feature matching algorithm, which achieves 97.92% accuracy, and the feature description-based matching algorithm, with an impressive 99.99% accuracy. Both implementation approaches have been tested for scanner drift measurements, and these technologies are scalable and applicable in various domains of scanning probe microscopy with broad application prospects in the field of nanoengineering.

Graphite surface modification by quasi-periodically structured diazonium monolayer

In this study, a novel functionalization protocol of highly oriented pyrolytic graphite (HOPG) was proposed, in which a two dimensional (2D) porous network formed by alkoxy-substituted dehydrobenzo[12]annulene (DBA-OC12) was served as a sacrificial template for electrografting of 3,5-terbutyl diazonium (3,5-TBD). The 2D DBA-OC12 porous network was synthesized by drop-casting of the corresponding precursor followed by a drying process. The structural and electrochemical properties of pristine as well as functionalized HOPG surfaces were investigated by means of cyclic voltammetry (CV) and scanning tunneling microscopy (STM).

An ultracompact scanning tunneling microscope within a Φ 10 piezo tube in a 20T superconducting magnet.

Low-temperature scanning tunneling microscopy and spectroscopy (STM/S) help to better understand the fundamental physics of condensed matter. We present an ultracompact STM within a Φ 10 piezo tube in a 20T superconducting magnet. The carefully cut piezo tube contains the STM's coarse-positioning assembly. Loading an STM tip-sample mechanical loop into the piezo tube with special cut openings enables an ultracompact pencil-size dimension down to Φ 10mm, in which fine-machined nonmagnetic parts are assembled to enable slide-stick motion and xyz-scanning procedures. The small size leads to a higher resonant frequency, a typical feature of a rigid STM instrument, increasing its vibration immunity. Scanning by moving the sample while keeping the tip stationary improves the stability of the tip-sample junction compared to moving the tip. Taking advantage of its high-field compatibility and rigid design, our STM captures the atomically resolved topography of highly oriented pyrolytic graphite (HOPG) at 1.5K and in magnetic fields up to 17T. The topography of graphene lattice and graphite is simultaneously recorded on an atomic terrace of HOPG, unveiling a modified local charge density at a surface defect. The superconducting energy gaps of layered type-II superconductors NbSe2 and PdBi2 are well resolved through dI/dV tunneling spectra at sub-2K. Our unique STM is highly suitable for potential STM/S applications in world-class high-field facilities where the strong magnetic field can exceed 30T.

Positive Synergy between the Helical Poly(phenylacetylene) Backbones and the Helical L-Proline Oligopeptide Pendants for Enhanced Enantioseparation Properties.

A series of optically active helical poly(phenylacetylene)s (PPA-Pro1, PPA-Pro3, PPA-Pro6, PPA-Pro9, and PPA-Pro12) bearing different chain lengths of L-proline oligopeptide in the side chains were obtained by polymerizing the corresponding novel phenylacetylene monomers. The monomer adopted a trans-rich helix structure when the L-proline oligopeptide chain length was longer, according to the optical activities and 2D-NMR analysis. The helical structure could be maintained and significantly influenced the polymers' helical conformation by introducing the L-proline oligopeptide to the pendants. By the way, the morphology of PPA-Pro3 was observed by atomic force microscope (AFM) on highly oriented pyrolytic graphite (HOPG), and the information on the helix direction, pitch, and chain arrangement was obtained. Also, the chiral separation properties of these polymer-based chiral stationary phases (CSPs) were investigated using high-performance liquid chromatography (HPLC). The poly(phenylacetylene)s showed enhanced enantioseparation properties toward various racemates depending on the longer chain length of the L-proline oligopeptide in the pendants and the positive synergy between the helical backbone and helical side chains. Particularly, PPA-Pro9 showed comparable or even superior enantioseparation properties for racemates 2 and 9 to four commercial columns (Daicel Chiralpak or Chiralcel AD, AS, OD, and OT), indicating that these poly(phenylacetylene)-based CSPs have potential practical values. This work presented here provides inspiration for the further development of CSPs based on a new paradigm.

Phospholipid Epitaxial Assembly Behavior on a Hydrophobic Highly Ordered Pyrolytic Graphite Surface.

Supported lipid bilayers (SLBs) are excellent models of cell membranes. However, most SLBs exist in the form of phospholipid molecules standing on a substrate, making it difficult to have a side view of the phospholipid membranes. In this study, the phospholipid striped lamella with the arrangement of their alkane tails lying on highly ordered pyrolytic graphite (HOPG) was constructed by a spin coating method. Atomic force microscopy and molecular dynamics simulations are utilized to study the self-assembly of phospholipids on HOPG. Results show that various phospholipids with different packing parameters and electrical property are able to epitaxially adsorb on HOPG. 0.1 mg/mL Plasm PC (0.1 mg/mL) could form a striped monolayer with a width of 5.93 ± 0.21 nm and form relatively stable four striped layers with the concentration increasing to 1 mg/mL. The width of the DOPS multilayer is more than that of electroneutral lipids due to the static electrical repulsion force. This universal strategy sheds light on direct observation of the membrane structure from the side view and modification of 2D materials with amphiphilic biomolecules.

Beam Profile Measurement Using the Highly-Oriented Pyrolytic Graphite

The mitigation of heat loading is one of the important issues for beam instrumentation to measure the high-power proton beam. Recently, the highly-oriented pyrolytic graphite (HOPG) material was used for the target probe of the bunch-shape monitor at the front end in the Japan Proton Accelerator Research Complex (J-PARC). Since the thermal conductivity of the HOPG is high, it is suitable to measure both transverse and longitudinal beam profiles under the condition of high heat loading. As an application of the HOPG, for example, the thin HOPG may be used as a substitutive material of the target wire for the transverse profile monitor such as the wire scanner monitor. The possibility of the HOPG target for both transverse and longitudinal beam profile monitors is discussed from some results of the test experiment using the 3 MeV negative hydrogen ion beam at the test stand.

Multistate switching of scanning tunnelling microscopy machined polyoxovanadate-dysprosium-phthalocyanine nanopatterns on graphite.

We demonstrate the first formation of stable, multistate switchable monolayers of polyoxometalates (POMs), which can be electronically triggered to higher charged states with increased conductance in the current-voltage profile at room temperature. These responsive two-dimensional monolayers are based on a fully oxidised dodecavanadate cage (POV12) equipped with Dy(III)-doped phthalocyanine (Pc) macrocycles adopting the face-on orientation on highly oriented pyrolytic graphite (HOPG). The layers can be lithographically processed by the tip of a scanning tunnelling microscope (STM) to machine patterns with diameters ranging from 30 to 150 nm2.

Nano-protrusions in intercalated graphite: understanding the structural and electronic effects through DFT.

Complex phenomena characterize the intercalation of ions inside stratified crystals. Their comprehension is crucial in view of exploiting the intercalation mechanism to change the transport properties of the crystal or obtaining a fine control of crystal delamination. In particular, the relationship between the concentration and nature of intercalated ions and surface structural modifications of the host stratified crystal is still under debate. Here, we discuss a theoretical effort to provide a rationale for some structural changes observed on the highly oriented pyrolytic graphite (HOPG) surface after electrochemical treatment in perchloric and sulphuric acid solutions. The formation of the so-called nano-protrusions on the basal plane of intercalated graphite was previously observed with scanning tunneling microscopy (STM). In this work, we employed both STM and density functional theory (DFT) simulations to elucidate the physical and chemical mechanisms driving the emergence of these nano-protrusions. The DFT results show that, in a bilayer graphene system, the presence of a single ion can generate a nano-protrusion with 2.49 Å height and 21.27 Å width. In the deformed area, the C-C bond length is stretched by about 2.5% more than the normal graphene bond. These values are of the same dimensional scale as those reported in previous STM experimental results.25 However, the simulated STM images obtained by increasing the amount of intercalated ions per area suggest that the presence of more than one ion is needed for the deformation of the uppermost graphite layer during the early stages of intercalation. In contrast, in a multilayer graphene system, no significant surface deformation is detected when ions are intercalated between the third and fourth layers. Charge analysis indicates an altered distribution of the charges as a consequence of the intercalation. The charge transfer from graphene layers to the intercalated ions results in a surface layer more prone to oxidation.