Highly Oriented Pyrolytic Graphite Research Articles

Site-Specific Stochastic Rates and Energetics of Ag Nucleation on Highly Ordered Pyrolytic Graphite.

Nucleation is a fundamentally important step in electrochemical phase transition reactions, e.g., in electrodeposition, which is pertinent for emerging battery technology, nanoparticle synthesis, and many industrial processes. Surface defects have been suggested to enhance nucleation rates. However, directly quantifying the nucleation rates at specific surface sites is challenging due to the ensemble averaging effect in bulk measurements. Herein, we report the measurement of rates and energetics of electronucleation across the model surface of highly oriented pyrolytic graphite (HOPG). Specifically, scanning electrochemical cell microscopy (SECCM) is used to confine the nucleation spatially in the nanoscale cell, allowing one nucleation event to be measured at one time. The scanning capability further allows the mapping of Ag nucleation at the step edge vs basal plane. A stochastic model is developed to extract the nucleation rate and energetics from voltammetric experiments. We observed a ∼57 mV difference in the median nucleation overpotential between the step edge and basal plane, corresponding to a ∼12 kJ mol-1 difference in the nucleation energy barrier. The voltammetric method to measure the nucleation rate explored here can be extended to understand the heterogeneity of nucleation rates in other electrochemical nucleation systems, e.g., metal anode batteries.

Morphology and structural properties of thin rubrene crystallites grown on graphite

Abstract Crystallization of rubrene, progressing from an amorphous phase to a triclinic meta-stable and ultimately to the orthorhombic stable phase, offers broad applications not only in organic electronic devices but also for in-depth studies of optical and electronic properties, including exciton distribution and dynamics. We investigate the crystallization of rubrene on highly oriented pyrolytic graphite (HOPG), aiming at the growth of the preferred rubrene orthorhombic phase, which has been reported to have one of the highest charge mobilities in organic semiconductors. This is achieved through controlled heating and enhanced partial pressure. Through precise control of the initial deposition on the substrate, we investigate the growth habit of rubrene crystals by high-rate heat treatment beyond the second crystallization temperature. Furthermore, this work addresses thermal stability and photodegradation across various morphologies.

Surfactant Molecules and Nano Gold on HOPG: Experiment and Theory

Excessive surfactant molecules within the solution adhere to highly ordered pyrolytic graphite (HOPG) when a droplet containing gold nanorods evaporates, leading to the emergence of a unique coffee-ring pattern. The combination of surface hydrophobicity and evaporation of the aqueous phase results in a stick-slip motion, which enhances the convective hydrodynamics of suspended particles. This phenomenon initiates interactions that influence the deposition and flow dynamics inside the droplet. High-resolution scanning electron microscopy (HRSEM) does not provide significant insights into regions potentially linked to cetyltrimethylammonium bromide (CTAB) molecules, whereas the atomic force microscope (AFM) displays the presence of gold nanoparticles arranged by CTAB within specific CTAB patches. The layers forms with varying heights and gaps between them, indicating diverse adhesion of CTAB. The analytical focus lies on the quantitative assessment of CTAB molecules, stripe dimensions, and energy profiles influenced by concentration and the effective positioning of CTAB-coated gold nanorods in CTAB-covered regions. AFM examination reveals CTAB molecular stripes on HOPG, showing a binding energy of -20 kJ/mol with the surface, -10 kJ/mol for nitrogen bonding with HOPG, and a total binding energy (BE) of -60 kJ/mol, considering various contributing factors. Completely parallel aligned molecules (CPAM) exhibit higher binding energy than non-perfectly aligned molecules (NPAM) due to maximum Van der Waals (VdW) interactions, ideal electrostatic interactions, and minimal steric repulsion. The difference in binding energy between perfectly and non-perfectly aligned molecules is around 20kJ/mol, emphasizing the importance of molecular orientation. As temperature rises from 298K to 348K, the likelihood of NPAM desorption increases significantly, with the binding energy shifting from 2.5kJ/mol to 4.1kJ/mol. Temperature significantly influences the equilibrium of molecules on HOPG surfaces. The emphasis is on elucidating the alterations in energy levels during nanorod aggregation on CTAB areas compared to bare HOPG surfaces, underscoring the impact of nanorods on CTAB micelle deformation energy. Observations on the variation in CTAB desorption rates with temperature changes underscore the dynamic nature of molecular binding energy associated with surface properties, underscoring the importance of molecular configuration and energy transfers in nanoscale systems.

Coupling effect of gas solubility in a solvent and substrate structure on performance in nanobubble morphological changes

The distribution morphologies of nanobubbles on Highly Oriented Pyrolytic Graphite (HOPG) surfaces prepared using the alcohol-water exchange test method were observed using atomic force microscopy. In situ observation revealed the distinct growth evolution behavior of nanobubble morphology. Molecular dynamics simulation was employed to replicate the experimental test and investigate the influence of the coupling effect of gas solubility and substrate structure on the morphological features of nanobubble distribution in alcohol-water exchange experiments. The results demonstrate that gas solubility plays a pivotal role in the nucleation of surface nanobubbles during alcohol-water exchange. Specifically, stable surface nanobubbles form only when the solubility exceeds 0.02535. Furthermore, under conditions where gas solubility satisfies the nucleation criteria, the surface potential energy of concave and defective structures exhibits concave characteristics, giving rise to the nucleation of cap-shaped nanobubbles. In contrast, the step structure, characterized by the smallest average surface potential energy, results in relatively flat properties in the lowest area, with nanobubble nucleation taking the form of layer-shaped features. yields relatively uniform characteristics at the lowest level, where nanobubble nucleation manifests in the form of layered features. As time progresses, cap-shaped nanobubbles coalesce, leading to the escape of gas molecules and subsequent dissipation, whereas the layer-shaped nanobubbles adsorb gas molecules from the solution, prompting their expansion.

Domain wall currents and ferroelectric domain structures of PbTiO3 thin films on highly oriented pyrolytic graphite (HOPG) substrates

Domain wall currents and ferroelectric domain structures of PbTiO3 thin films on highly oriented pyrolytic graphite (HOPG) substrates

On the Nature of HOPG-Supported Pt1Ti2O7 and its Decomposition of a Nerve Agent Simulant: A Cluster Model of a Single Atom Catalyst Active Site.

Chemical weapons, including hyper lethal nerve agents, are a persistently looming threat across the modern geopolitical landscape. There is a pressing need for the design and development of improved protective materials, which can be substantially aided by the cultivation of a fundamental molecular-level understanding of candidate systems and the corresponding decomposition chemistry. The emergence of the exciting new class of single atom catalyst (SAC) materials has enhanced the prospect of subnanoscale design tailoring in the hopes of optimizing activity and selectivity for a variety of chemical applications. Here, we apply our recently developed experimental technique for modeling the active sites of such SAC materials through the preparation of surface supported size-selected single metal-atom doped metal oxide clusters. The propensity for an SAC cluster model system for Pt1/TiO2 materials, Pt1Ti2O7 supported on highly oriented pyrolytic graphite (HOPG), to adsorb and decompose nerve agent simulant dimethyl methylphosphonate (DMMP) was investigated through a combination of temperature-programmed desorption/reaction (TPD/R) and X-ray photoelectron spectroscopy (XPS). XPS measurements of the as-prepared Pt1Ti2O7 clusters supported the successful isolation of single Pt atoms in clusters monodispersed across the HOPG surface. TPD/R experiments showed that the reactivity exhibited by the Pt1Ti2O7 clusters was distinct from that of Ti2O7 clusters lacking the single Pt atom. It was found that DMMP decomposed over Pt1Ti2O7 upon heating to as low as room temperature, and higher temperature treatments evolved exclusively H2O, CO, and H2, while decomposition over Ti2O7 evolved only methanol and formaldehyde at elevated temperatures. This indicated the promotion of C-H and PO-C bond cleavage within DMMP due to the presence of single Pt atoms in the clusters. Further, the Pt1Ti2O7 clusters were found to desorb P-containing decomposition species, preventing active site poisoning; however, a change of reactivity reflecting that of Ti2O7 was observed following a single TPD/R cycle. This suggested the encapsulation of active Pt sites by titanium oxide during high temperature treatment and is thus an issue deserving of serious attention in the study of Pt1/Ti2O7 SAC materials.

Characterizing the surface compositions of supported bimetallic PtSn clusters: Effects of cluster-support interactions and surface adsorbates

PtSn bimetallic clusters on TiO2(110) and highly oriented pyrolytic graphite (HOPG) surfaces have been characterized by scanning tunneling microscopy, low energy ion scattering (LEIS), X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD); density functional theory (DFT) calculations have also been performed to better understand adsorption of CO and D2 on the PtSn surfaces. On TiO2 at coverages of 2 ML of Pt and 2 ML of Sn, exclusively bimetallic clusters are formed for both orders of deposition because clusters of the first metal completely cover the surface such that all atoms of the second metal are incorporated into the existing clusters. In contrast, on HOPG, the high mobility and weak cluster-support interactions on HOPG result in much larger 2 ML monometallic clusters (∼30 Å high) that do not completely cover the surface, and deposition of the second metal produces larger clusters as well as smaller ones. Despite the difference in cluster morphologies for the different orders of deposition and supports, the LEIS experiments demonstrate that in all cases, the PtSn clusters are rich in Sn at the surface, as expected based on the lower surface free energy for Sn compared to Pt. Furthermore, the +0.2 eV shift in the Sn(3d5/2) binding energy observed on all surfaces in the presence of Pt is consistent with PtSn alloy formation. Deposition of 2 ML of Sn on TiO2 produces two-dimensional clusters with oxidation of Sn and reduction of titania at the cluster-support interface, but addition of Pt to the Sn clusters causes Sn to diffuse away from this interface, leaving Sn in the metallic state. TPD experiments on 2 ML Pt/TiO2 with increasing coverages of Sn show that the number of adsorption sites for D2 sharply decreases to nearly zero at 0.5 ML, while CO adsorption decreases to zero only at much higher Sn coverages of 2 ML. DFT studies for Sn modified Pt surfaces and bulk structures demonstrate that for CO adsorption at low Sn coverages (≤0.25 ML), the strong Pt-CO interactions induce diffusion of Pt to the cluster surface and the formation of a bulk Pt3Sn alloy, whereas D2 adsorption does not lead to interactions with the Pt surface that are strong enough to induce alloy formation. A single Sn adatom prevents D2 adsorption on four neighboring Pt atoms via site-blocking and the donation of electron density to Pt.

Room-temperature superconductivity in carbons – a mini review

The search for room-temperature superconductivity in carbons is gathering momentum because it has a long history, impressive track record, clear advancement route, and theoretical backup. The report of a suspected Josephson current in Al-C-Al sandwiches at room temperature, published in Nature 50 years ago, led to the report of a voltage in nano-graphite films believed to mark the reverse Josephson effect. The report on oxygen-doped diamonds led to full-blown superconductivity in boron-doped diamonds. The reports on highly oriented pyrolytic graphite (HOPG) and water-treated graphite powder led to the claim of a current running by itself for 50 days in a ring of HOPG soaked with alkane at room temperature. It also led to a claim of a current running for 1,000 seconds in a ring of graphene soaked in hexane. The carbons are amicable to intercalation chemistry, electrostatic carrier doping, and surface-proving techniques to promote an increase in carrier density, metallization, and applicability of the Ashcroft proposal. Consequently, the high Debye temperatures (1,670, 2,230 and 2,500 K in graphene, diamond and HOPG) may be sufficient to underwrite superconductivity at T∼300 K in carbons, provided the phonon-exchange factor, λ, is around 3 to mark strong enough interactions between electrons and phonons.

Comprehensive study of SrF2 growth on highly oriented pyrolytic graphite (HOPG): Temperature-dependent van der Waals epitaxy

This study explores the molecular beam epitaxy (MBE) growth of SrF2 on highly oriented pyrolytic graphite (HOPG) highlighting the temperature-dependent variations in growth morphology, crystalline structure and electronic properties. The comprehensive characterization of SrF2/HOPG interfaces was carried out using atomic force microscopy (AFM), reflection high-energy electron diffraction (RHEED), ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). The spectroscopy data suggest that the chemical interaction of the fluoride with the substrate is weak at each deposited thickness and temperature of the substrate during the deposition, indicating a growth under a van der Waals epitaxial regime. SrF2 nanostructures deposited on HOPG depict a distinctive bulk-like character, concerning their crystallinity and composition, even at the very initial growth stage. Remarkably, temperature plays a crucial role in driving the growth patterns, moving from coalescence of dendritic islands at room temperature to induce nearly 1D rows along the step-edges of HOPG terraces at higher temperatures (400 °C).

Out-of-Plane Electron Transport in Graphite Intercalation Compounds with Applications in Battery Anodes

Graphite intercalation compounds (GICs) are commonly used as anode materials for alkali metal-ion batteries, such as Li-ion and K-ion batteries. Although typically prepared as a low-stage intercalation compound (with a high concentration of the intercalating metal), over several electrochemical cycles, the distribution of intercalate within the graphite sample is expected to be non-uniform with domains of high-stage regions where the intercalant fraction is low [1]. The mechanism of interlayer electron transport in GICs strongly depends on the intercalation staging and temperature, and is expected to vary over the lifetime of a battery.High-stage GICs and highly oriented pyrolytic graphite (HOPG), which is the upper limit of infinite-stage GIC, have an out-of-plane electrical conductivity that exponentially increases with temperature, whereas low-stage GICs have a conductivity that decreases as a function of temperature [2, 3, 4]. Although out-of-plane electron transport in low-stage GICs can be described by a metallic conduction model, the mechanism of out-of-plane electron transport in HOPG and high-stage GICs is a hitherto unresolved problem [5]. Out-of-plane electrical conductivity for HOPG and high-stage GICs increases exponentially with temperature, which cannot be described by metallic conduction, nor by conventional impurity or defect hopping mechanisms [6].We propose a new mechanism of electron transport that takes place in HOPG and high-stage GICs at temperatures relevant to battery operation. Electrons are transferred between graphite and intercalant layers through tunneling that is enhanced by large amplitude out-of-plane phonon modes in graphite layers. Due to weak interlayer interactions in adjacent graphite layers, GICs can accommodate large amplitude phonon modes in the out-of-plane direction that locally enhance the interlayer electron tunneling probability. The tunneling enhancement is temperature dependent, and exponentially depends on the population of out-of-plane phonon modes excited at a given temperature. The expression for the conductivity 𝜎 for the phonon amplitude-driven tunneling mechanism as a function of temperature T is shown in Eq. 1; the exponential dependence of conductivity with temperature qualitatively agrees with experimental observations in HOPG and high-stage GICs. On a quantitative level, we also observe from Fig.1 that the theory agrees with experimental values for out-of-plane conductivity in HOPG.The phonon amplitude-driven tunneling mechanism of electron transport is relevant in describing the kinetic over-potential in batteries that employ layered materials as anodes in ambient temperature operating conditions, and optimally sizing the anode accounting for both electron transport and ion diffusion rates.

(Invited) A Study of the SEI Layer Cross-Talk in Si/C Composite Li-Ion Anodes

Composite electrodes, especially silicon/carbon (Si/C) anodes, present significant opportunities for advancing the energy density of lithium-ion batteries (LIBs). However, challenges emerge, particularly in performance metrics when a high weight percentage of Si beyond 8-10 wt.% is employed 1. A nuanced understanding of the solid electrolyte interphase (SEI) in Si/C composites is imperative to overcome these limitations and enhance energy density. Conventional techniques such as ex-situ X-ray photoelectron spectroscopy and cryogenic electron microscopy face inherent drawbacks, including exposure to ultrahigh vacuum and the need for solvent washing, potentially altering the SEI layer 2. In contrast, nano-FTIR, utilizing Fourier transform infrared near-field spectroscopy, overcomes these challenges, enabling non-destructive probing of the SEI layer's chemistry and structure at room temperature within an inert atmosphere 3–5.In this study, we engineer custom-patterned electrodes featuring amorphous Si on atomically flat highly ordered pyrolytic graphite (HOPG) to emulate model composite electrodes. Leveraging nano-FTIR spectroscopy, near-field nanoscale white-light imaging, and atomic force microscopy measurements, our investigation reveals that the SEI on HOPG is enriched in organic lithium ethylene decarbonate (LiEDC), while the SEI on lithiated silicon unveils the presence of inorganic Li2CO3. Notably, we unveil a unique "mixed" SEI layer zone at the Si/HOPG interface, comprising a mixture of dominant SEI species from the surfaces of both the lithiated Si and the HOPG. The coexistence of these species suggests the formation of an SEI layer with presumably unique physicochemical properties, forming along Si-C interfaces in Si/C composite electrodes. These findings provide a comprehensive approach to studying model composite electrodes and offer valuable insights into optimizing the surface passivation of Si/C composite electrodes for high-performance LIBs. Acknowledgments This research was supported by the US Department of Energy (DOE)’s Vehicle Technologies Office under the Silicon Consortium Project directed by Brian Cunningham and managed by Anthony Burrell. References V. G. Khomenko and V. Z. Barsukov, Electrochim Acta, 52, 2829–2840 (2007).J. Wu, M. Ihsan-Ul-Haq, Y. Chen, and J. K. Kim, Nano Energy, 89, 106489 (2021).X. He, J. M. Larson, H. A. Bechtel, and R. Kostecki, Nat Commun, 13, 1398 (2022).I. Yoon, J. M. Larson, and R. Kostecki, ACS Nano, 17, 6943–6954 (2023).A. Dopilka, Y. Gu, J. M. Larson, V. Zorba, and R. Kostecki, ACS Appl Mater Interfaces, 15, 6755–6767 (2023).

Combining Nitrogen Doping and Vacancies for Tunable Resonant States in Graphite.

We investigate the combination of nitrogen doping and vacancies in highly ordered pyrolytic graphite (HOPG), to engineer defect sites with adjustable electronic properties. We combine scanning tunneling microscopy and spectroscopy and density functional theory calculations to reveal the synergistic effects of nitrogen and vacancies in HOPG. Our findings reveal a remarkable shift of the vacancy-induced resonance peak from an unoccupied state in pristine HOPG to an occupied state in nitrogen-doped HOPG. This shift directly correlates with the shift of the charge neutrality point resulting from the n-doping induced by substitutional nitrogen. These results open new avenues for defect engineering in graphite or graphene and achieving novel functionalities for chemical activity or electronic properties.

Nanostructure and Dynamics of the Locally Concentrated Ionic Liquid 2:1 (wt:wt) HMIM FAP:TFTFE and HMIM FAP on Graphite and Gold Electrodes as a Function of Potential.

Video-rate atomic force microscopy (AFM) is used to record the near-surface nanostructure and dynamics of one pure ionic liquid (IL), 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate (HMIM FAP), and a locally-concentrated IL comprising HMIM FAP with the low viscosity diluent 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (TFTFE), on highly oriented pyrolytic graphite (HOPG) and Au(111) electrodes as a function of potential. Over the potential range measured (open-circuit potential ± 1V), different near-surface nanostructures are observed. For pure HMIM FAP, globular aggregates align in rows on HOPG, whereas elongated and worm-like nanostructures form on Au(111). For 2:1 (wt:wt) HMIM FAP:TFTFE, larger and less defined diluent swollen IL aggregates are present on both electrodes. Long-lived near-surface nanostructures for HMIM FAP and the 2:1 (wt:wt) HMIM FAP:TFTFE persist on both electrodes. 2:1 (wt:wt) HMIM FAP:TFTFE mixture diffuses more rapidly than pure HMIM FAP on both electrodes with obviously higher diffusion coefficients on HOPG than on Au(111) due to weaker electrostatic and solvophobic interactions between near-surface aggregates and Stern layer ions. These outcomes provide valuable insights for a wide range of IL applications in interface sciences, including electrolytes, catalysts, lubricants, and sensors.

Participation of Surface Oxygen in the Stabilization of the Rh/HOPG System with Respect to NO₂

In this work, using the method of X-ray photoelectron spectroscopy (XPS), a comparative study of the nature of the interaction of NO₂ at room temperature and a pressure of 10⁻⁵ mbar with two samples of highly oriented pyrolytic graphite (HOPG), on the surface of which rhodium was preliminarily deposited by vacuum deposition, was carried out. Before metal deposition, one of the HOPG samples was annealed in vacuum at 600°C, and the other was subjected to bombardment with argon ions, followed by exposure to air at room temperature for an hour in order to introduce strongly bound oxygen atoms into the surface composition. After deposition of rhodium on two samples of HOPG prepared, two model catalysts were obtained, designated as Rh/C and Rh/C(A)-O. It was found that the interaction of NO₂ with Rh/C led to the oxidation of graphite with the destruction of the surface layer. The Rh particles remained in the metallic state, but at the same time they were introduced into the near-surface layer of the carbon support. On the contrary, when the Rh/C(A)-O sample was treated with NO₂, the deposited rhodium was partially converted into RH₂O₃, while the graphite was oxidized to an insignificant degree and retained its original structure. The role of surface oxygen in the stabilization of graphite with respect to oxidation to NO₂ was discussed.

Electrochemical exfoliation of graphene from pencil lead

Addressing an ever-increasing demand for graphene in recent years, simple, accessible, and effective graphene synthesis methods are essential. One of such methods is to use a highly oriented pyrolytic graphite (HOPG) to perform an electrochemical exfoliation. While this is one of the simplest and most cost-effective methods, the limited availability and price of HOPG hinders its usage. Our study proposed a simple and economical electrochemical exfoliation of pencil lead, producing graphene with properties comparable to that produced from HOPG. The electrical properties are determined by depositing graphene onto a screen-printed electrode. Graphene from pencil leads can achieve an electrical resistance as low as 1.86 kΩ, marking over 80% improvement in electrical performance compared to bare electrodes. This finding provides an alternative for the synthesis of graphene, increasing its availability and the cost-effectiveness as well as contributing towards a potential commercialization of the method in the future.

Microscopic growth of pyridinium oxime based amphipathic on graphite: Effect of relative position of substituents

AbstractAmphipathic molecules with surfactant like properties have several applications ranging from healthcare to the chemical industry. Their ability to form thin films on surfaces with ordered and controllable patterns determines their applicability. Here, we report two pyridinium oxime‐based surfactants, which possess similar aggregation properties in solution, but exhibit substantially different assembly on highly oriented pyrolytic graphite (HOPG) surface. The two compounds are regioisomers with the oxime unit placed either in meta or para position of the pyridinium ring. While the para isomer assembled to anisotropic one‐dimensional (1D) islands and long rod‐like structures, the meta isomer formed two‐dimensional (2D) islands on the HOPG surface. This difference is rationalized through molecular level force‐field calculations that show anisotropy in the growth of the para isomer resulting from an effective overlap of the alkyl chains and oxime groups, which is distinctly not feasible in the assembly of the meta isomer. The assembly of these compounds is compared with another oxime‐containing compound of similar structure, but without the charged pyridinium unit. The charged unit seems to be crucial for the preferential formation of multilayer islands even at low coverage.

High repetition-rate dual-channel X-ray spectrometer for high-intensity laser-plasma experiments.

We describe the development and demonstration of a high-repetition-rate-capable dual-channel (DC) x-ray spectrometer designed for high-intensity laser-plasma experiments (≥1×1021 W/cm2). The spectrometer, which operates at high repetition rates, is limited only by the refresh rate of targets and the camera's frame rate. It features two channels, each equipped with a flat highly oriented pyrolytic graphite (HOPG) crystal and a unique detector plane, allowing it to resolve two distinct x-ray bands: approximately 7-10 and 10-13keV. Each detector plate carrier holds two slots for active (scintillators) or passive (imaging plates) x-ray detectors. We present the design and testing of the HR-DC-HOPG using both the COMET laser (10J, 0.5ps shot/4min) at LLNL's Jupiter Laser Facility and the SCARLET laser (10J, 30fs shot/min) at Ohio State University. The results demonstrate the spectrometer's performance across various laser energies, target materials, pulse shapes, and detector types.

Attosecond chronoscopy of the photoemission near a bandgap of a single-element layered dielectric.

We report on the energy dependence of the photoemission time delay from the single-element layered dielectric HOPG (highly oriented pyrolytic graphite). This system offers the unique opportunity to directly observe the Eisenbud-Wigner-Smith (EWS) time delays related to the bulk electronic band structure without being strongly perturbed by ubiquitous effects of transport, screening, and multiple scattering. We find the experimental streaking time shifts to be sensitive to the modulation of the density of states in the high-energy region (E ≈ 100 eV) of the band structure. The present attosecond chronoscopy experiments reveal an energy-dependent increase of the photoemission time delay when the final state energy of the excited electrons lies in the vicinity of the bandgap providing information difficult to access by conventional spectroscopy. Accompanying simulations further corroborate our interpretation.

Accurate detection of subsurface microcavity by bimodal atomic force microscopy

Subsurface detection capability of bimodal atomic force microscopy (AFM) was investigated using the buried microcavity as a reference sample, prepared by partially covering a piece of highly oriented pyrolytic graphite (HOPG) flake with different thickness on a piece of a cleaned CD-R disk substrate. This capability can be manifested as the image contrast between the locations with and without the buried microcavities. The theoretical and experimental results demonstrated that the image contrast is significantly affected by the critical parameters, including the second eigenmode amplitude and frequency as well as local structural and mechanical properties of the sample itself. Specifically, improper parameter settings generally lead to incorrect identification of the buried microcavity due to the contrast reduction, contrast reversal and even disappearance. For accurate detection, the second eigenmode amplitude should be as small as possible on the premise of satisfying the signal-to-noise ratio and second eigenmode frequency should be close to the resonance frequency of the cantilever. In addition, the detectable depth is closely related to microcavity dimension (thickness and width) of the HOPG flake and local stiffness of the sample. These results would be helpful for further understanding of the detection mechanism of bimodal AFM and facilitating its application in nano-characterization of subsurface structures, such as the micro-/nano- channels to direct the flow of liquids in lab-on-a-chip devices.

Highly aligned pyrolytic graphite blades for neutron monochromatization

Highly aligned pyrolytic graphite blades for neutron monochromatization have been fabricated successfully from smaller commercial highly oriented pyrolytic graphite (HOPG) crystals. These blades of a large coverage area, 136 mm wide × 2 mm high, are achieved with minimum increase of the mosaic over that of the original HOPG crystal. A specialized crystal cleavage device and soldering device are developed for the fabrication process. Furthermore, an optimized intermittent mode of the radio frequency magnetron sputtering technique is employed to deposit indium on HOPG crystals. The devices and procedure reported here could be applied to the development of the focusing monochromators and analyzers in neutron scattering instruments using a sizable neutron beam.