Highly Ordered Pyrolitic Graphite Research Articles

Growth and Characterization of Al2O3 Atomic Layer Deposition Films on sp(2)-Graphitic Carbon Substrates Using NO2/Trimethylaluminum Pretreatment.

The growth of Al2O3 films by atomic layer deposition (ALD) on model sp(2)-graphitic carbon substrates was evaluated following a nitrogen dioxide (NO2) and trimethylaluminum (TMA) pretreatment to deposit an Al2O3 adhesion layer. Al2O3 ALD using TMA and water (H2O) as the reactants was used to grow Al2O3 films on exfoliated highly ordered pyrolitic graphite (HOPG) at 150 °C with and without the pretreatment procedure consisting of five NO2/TMA cycles. The Al2O3 films on HOPG substrates were evaluated using spectroscopic ellipsometry and electrochemical analysis to determine film thickness and quality. These experiments revealed that five NO2/TMA cycles at 150 °C deposited an Al2O3 adhesion layer with a thickness of 5.7 ± 3.6 Å on the HOPG substrate. A larger number of NO2/TMA cycles at 150 °C deposited thicker Al2O3 films until reaching a limiting thickness of ∼80 Å. Electrochemical impedance spectroscopy (EIS) measurements revealed that five cycles of NO2/TMA pretreatment enabled the growth of high quality insulating Al2O3 films with high charge-transfer resistance after only 20 TMA/H2O Al2O3 ALD cycles. In contrast, with no NO2/TMA pretreatment, EIS measurements indicated that 100 TMA/H2O Al2O3 ALD cycles were necessary to produce an insulating Al2O3 film with high charge-transfer resistance. Al2O3 films grown after the NO2/TMA pretreatment at 150 °C were also demonstrated to have better resistance to dissolution in an aqueous environment.

Nanoscale friction properties of graphene and graphene oxide

Achieving superlow friction and wear at the micro/nano-scales through the uses of solid and liquid lubricants may allow superior performance and long-lasting operations in a range of micromechanical system including micro-electro mechanical systems (MEMS). Previous studies have indicated that conventional solid lubricants such as highly ordered pyrolitic graphite (HOPG) can only afford low friction in humid environments at micro/macro scales; however, HOPG is not suitable for practical micro-scale applications. In this study, we explored the nano-scale frictional properties of multi-layered graphene films as a potential solid lubricant for such applications. Atomic force microscopy (AFM) measurements have revealed that for high-purity multilayered graphene (7–9 layers), the friction force is significantly lower than what can be achieved by the use of HOPG, regardless of the counterpart AFM tip material. We have demonstrated that the quality and purity of multilayered graphene plays an important role in reducing lateral forces, while oxidation of graphene results in dramatically increased friction values. Also, for the first time, we demonstrated the possibility of achieving ultralow friction for CVD grown single layer graphene on silicon dioxide. This confirms that the deposition process insures a stronger adhesion to substrate and hence enables superior tribological performance than the previously reported mechanical exfoliation processes.

Characterization of a Robust CoII Fluorescent Complex Deposited Intact On HOPG

The new diimine fluorescent ligand ACRI-1 based on a central acridine yellow core is reported along with its coordination complex [Co2 (ACRI-1)2 ] (1), a fluorescent weak ferromagnet. Due to the strong fluorescence of the acridine yellow fluorophore, it is not completely quenched when the ligand is coordinated to Co(II) . The magnetic properties of bulk complex 1 and its stability in solution have been studied. Complex 1 has been deposited on highly ordered pyrolitic graphite (HOGP) from solution. The thin films prepared have been characterized by AFM, time-of-flight secondary ion mass spectrometry (TOF-SIMS), grazing incidence X-ray diffraction (GIXRD), X-ray absorption spectroscopy (XAS), X-ray magnetic circular dichroism (XMCD) and theoretical calculations. The data show that the complex is robust and remains intact on the surface of graphite.

Controlling Molecular Alignment on Highly Ordered Pyrolitic Graphite of Porphyrin-Tb(III) Double-Decker Single Molecular Magnets

Single molecular magnets (SMMs) that show slow magnetic relaxation properties at low temperatures have great potential for use as nanoscale memory devices or quantum computers. In our study, we focused on porphyrin-Tb(III) double-decker complexes and their magnetic properties.1,2 Our goal was to control the molecular alignment of SMMs on highly ordered pyrolitic graphite (HOPG) by a self-assembling process. We synthesized protonated, anionic, and radical forms of octaethylporphyrin (OEP)-Tb(III) double-decker complexes and observed the molecular alignment of each molecule on HOPG using scanning tunneling microscopy (STM). The STM observations demonstrated that all OEP-Tb(III) double-decker complexes had similar pseudo-hexagonal packing structure stability on HOPG, regardless of differences in the electronic structure (Figure 1). In particular, the lattice parameters of protonated form 1 (a = 1.41 ± 0.03 nm, b = 1.46 ± 0.05 nm) showed almost the same values as anionic form 2 (a = 1.34 ± 0.01 nm, b = 1.42 ± 0.01 nm) and radical form 3 (a = 1.39 ± 0.04 nm, b= 1.45 ± 0.06 nm).We also prepared and observed the molecular alignment of a protonated 5,15-bisdodecylporphyrin (BDP)-Tb(III) double-decker complex. This complex showed a lamellar packing structure on HOPG (Figure 2). Herein, we succeeded in isolating stable 2D supramolecular structures of all the OEP-Tb(III) double-decker complexes on HOPG. Control of molecular alignment was also realized by changing the substituents.

Absolute cross section for loss of supercoiled topology induced by 10 eV electrons in highly uniform /DNA/1,3-diaminopropane films deposited on highly ordered pyrolitic graphite.

It was recently shown that the affinity of doubly charged, 1-3 diaminopropane (Dap(2+)) for DNA permits the growth on highly ordered pyrolitic graphite (HOPG) substrates, of plasmid DNA films, of known uniform thickness [O. Boulanouar, A. Khatyr, G. Herlem, F. Palmino, L. Sanche, and M. Fromm, J. Phys. Chem. C 115, 21291-21298 (2011)]. Post-irradiation analysis by electrophoresis of such targets confirms that electron impact at 10 eV produces a maximum in the yield of single strand breaks that can be associated with the formation of a DNA(-) transient anion. Using a well-adapted deterministic survival model for the variation of electron damage with fluence and film thickness, we have determined an absolute cross section for strand-break damage by 10 eV electrons and inelastic scattering attenuation length in DNA-Dap complex films.

Multifunctionality of Organometallic Quinonoid Metal Complexes: Surface Chemistry, Coordination Polymers, and Catalysts

Quinonoid metal complexes have potential applications in surface chemistry, coordination polymers, and catalysts. Although quinonoid manganese tricarbonyl complexes have been used as secondary building units (SBUs) in the formation of novel metal-organometallic coordination networks and polymers, the potentially wider applications of these versatile linkers have not yet been recognized. In this Account, we focus on these diverse new applications of quinonoid metal complexes, and report on the variety of quinonoid metal complexes that we have synthesized. Through the use of [(η(6)-hydroquinone)Mn(CO)3](+), we are able to modify the surface of Fe3O4 and FePt nanoparticles (NPs). This process occurs either by the replacement of oleylamine with neutral [(η(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(η(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(η(5)-semiquinone)Mn(CO)3] at the NP surface. We have demonstrated chemistry at the intersection of surface-modified NPs and coordination polymers through the growth of organometallic coordination polymers onto the surface modified Fe3O4 NPs. The resulting magnetic NP/organometallic coordination polymer hybrid material exhibited both the unique superparamagnetic behavior associated with Fe3O4 NPs and the paramagnetism attributable to the metal nodes, depending upon the magnetic range examined. By the use of functionalized [(η(5)-semiquinone)Mn(CO)3] complexes, we attained the formation of an organometallic monolayer on the surface of highly ordered pyrolitic graphite (HOPG). The resulting organometallic monolayer was not simply a random array of manganese atoms on the surface, but rather consisted of an alternating "up and down" spatial arrangement of Mn atoms extending from the HOPG surface due to hydrogen bonding of the quinonoid complexes. We also showed that the topology of metal atoms on the surface could be controlled through the use of quinonoid metal complexes. A quinonoid rhodium complex showed catalytic activity in Suzuki-Miyaura type reaction. As a result of the excellent stability of the homogeneous catalyst [(quinone)Rh(COD)](-) in water, we also successfully demonstrated catalyst recycling in 1,2- and 1,4-addition reactions. The compound [(quinone)Ir(COD)](-) showed significantly poorer catalytic activity in 1,4-addition reactions. Following upon the excellent coordination ability of the quinonoid rhodium complexes to metal centers, we synthesized organometallic coordination polymer nanocatalysts and silica gel-supported quinonoid rhodium catalysts, the latter using a surface sol-gel technique. The resulting heterogeneous catalysts showed activity in the stereospecific polymerization of phenylacetylene.

Decoration of Graphitic Surfaces with Sn Nanoparticles through Surface Functionalization Using Diazonium Chemistry

Composites of tin nanoparticles (Sn NP) and graphene are candidate materials for high capacity and mechanically stable negative electrodes in rechargeable Li ion batteries. A uniform dispersion of Sn NP with controlled size is necessary to obtain high electrochemical performance. We show that the nucleation of Sn particles on highly ordered pyrolitic graphite (HOPG) from solution can be controlled by functionalizing the HOPG surface by aryl groups prior to Sn deposition. On the contrary, we observe heterogeneous deposition of micrometer sized Sn islands on HOPG subjected to oxidation prior to deposition in the same conditions. We demonstrate that functional groups act as nucleation sites for Sn NP nucleation, and that homogeneous nucleation of small particles can be achieved by combining surface functionalization with diazonium chemistry and appropriate stabilizers in solution.

Surface contributions to the XPS spectra of nanostructured NiO deposited on HOPG

In this work we present an in situ X-ray photoelectron spectroscopy (XPS) study of the growth of NiO on highly ordered pyrolitic graphite (HOPG). The XPS spectra were measured as a function of the equivalent NiO coverage. Also, ex-situ atomic force microscopy (AFM) images were taken for some of these stages in order to follow the morphology of the NiO deposits. For low coverages the lineshapes of the Ni 2p spectra differ strongly from those of bulk NiO. This has been related to the large surface contribution. The O 1s XPS spectra also show a surface related structure which follows the same trend observed in the Ni 2p spectra.

STM study on the self-assembly of oligothiophene-based organic semiconductors

The self-assembly properties of a series of functionalized regioregular oligo(3-alkylthiophenes) were investigated by using scanning tunneling microscopy (STM) at the liquid–solid interface under ambient conditions. The characteristics of the 2-D crystals formed on the (0001) plane of highly ordered pyrolitic graphite (HOPG) strongly depend on the length of the π-conjugated oligomer backbone, on the functional groups attached to it, and on the alkyl substitution pattern on the individual thiophene units. Theoretical calculations were performed to analyze the geometry and electronic density of the molecular orbitals as well as to analyze the intermolecular interactions, in order to obtain models of the 2-D molecular ordering on the substrate.

Determining the high-pressure phase transition in highly-ordered pyrolitic graphite with time-dependent electrical resistance measurements

Long-duration, high-pressure resistance measurements on highly-ordered pyrolytic graphite in a diamond-anvil cell show a sluggish phase transition occurring at ∼19 GPa, as evidenced by the time-dependent behavior of the sample resistance. The instantaneous resistance response to pressure adjustment shows a ∼10 GPa hysteresis that has been observed previously, rendering the conjectured direct relationship between resistance and phase-transition tentative. In contrast, the evolution of the resistance with time after the instantaneous response shows a systematic, reproducible, and distinct behavior, which allows reducing the uncertainty in transition pressure to ∼2 GPa. This largely reduced hysteresis shows explicitly that the phase transition is directly related to changes in electronic structure and resistance and establishes consistency with other commonly used experimental techniques to explore phase transitions at high pressures. We augment our experiments with first-principle density-functional theory computations to evaluate the pressure dependence of the electronic density of states of proposed candidate structures for the post-graphite phase.

AFM Imaging of Adsorbed Nafion Polymer on Mica and Graphite at Molecular Level

Perfluorosulfonic acid ionomer (PFSA, specifically Nafion at EW = 975 g/mol) was visualized at the single molecule level using atomic force microscopy (AFM) in liquid. The diluted commercial Nafion dispersion shows an apparent M(w) = 1430 kg/mol and M(w)/M(n) = 3.81, which is assigned to chain aggregation. PFSA aggregates, imaged on mica and HOPG during adsorption from EtOH-H(2)O solvent at pH(e) 3.0 (below isoelectric point), showed a stable, segmented rod-like conformation. This structure is consistent with earlier NMR, SAXS/SANS, and TEM results that support a stiff helical Nafion conformation with long persistence length, a sharp solvent-polymer interface, and an extension of the sulfonated side chain into solution. Adsorption of Nafion structures on HOPG was observed at even higher pH(e) from EtOH due to screening of the repulsive electrostatic interaction in lower dielectric constant solvent, while the chain adopted an expanded coil conformation. These measurements provided direct evidence of the chain aggregation in EtOH-H(2)O solution and revealed their equilibrium conformations for adsorption on two model surfaces, highly ordered pyrolitic graphite (HOPG) and mica. The commercial Nafion dispersion was autoclaved at 0.10% w/w in nPrOH/H(2)O = 4:1 v/v solvent at 230 °C for 6 h to give a single-chain dispersion with M(w) = 310 kg/mol and M(w)/M(n) = 1.60. The autoclaved chains adopt an electrostatically stabilized compact globule conformation as observed by AFM imaging of the single PFSA molecules after rapid deposition on mica and HOPG at a low surface coverage.

Nano-structure formation due to impact of highly charged ions on HOPG

Highly ordered pyrolitic graphite (HOPG) was irradiated with slow highly charged Ar q+ and Xe q+ ions in a kinetic energy range of 150–360 keV and has been observed by scanning probe microscopy. Nano-sized hillock-like structures are found for all charge states and kinetic energies with both the scanning tunneling microscope and the atomic force microscope. However in the latter case, the dependence of the detected structures on scan conditions points towards a surface modification which manifests itself only in frictional forces and therefore in height measurement artifacts. Furthermore the generated defects are not stable but can be erased by continuous scanning in contact mode.

The effects of annealing and growth temperature on the morphologies of Bi nanostructures on HOPG

We report on the growth of ultra-thin bismuth (Bi) films on the basal plane of highly ordered pyrolitic graphite (HOPG) substrates; we investigate the morphologies of films grown at room temperature and then annealed at high temperature, and the morphologies of Bi structures grown at high temperature. Films grown at room temperature nucleate flat islands on the HOPG terraces, and 1D nanorods from HOPG step edges, the islands and rods both have heights in the range 1–3 nm. During annealing, the flat islands break up into groups of aligned, ∼ 2.5 nm tall rods. For films grown at high temperature, terrace nucleation is almost nonexistent, and 1D structures grow from step edges, with heights up to 30 nm. Finally, we observe rods with distinctively different morphologies corresponding to (110) and (111) orientations, and infer a surface energy driven Bi(110) to Bi(111) orientation transition. We speculate that the dominant mechanism for the reorientation is coalescence.

Bioinspired hybrid systems based on oligothiophenes and peptides (ALA-GLY)n: Computer-aided simulation of adsorption layers

This review presents the results of atomistic molecular dynamic simulation during the adsorption of hybrid molecules, which are co-oligomers of thiophene and peptide (biomimetic) segments. A surface of highly ordered pyrolitic graphite (HOPG) is used as an adsorbent. The processes of self-organization are investigated as a function of the temperature and adsorption intensity for two types of hybrids, such as diblock and triblock cooligomers (with a central thiophene block). The structure of the formed adsorption layers is studied in detail. In the self-organizing associates, the emergence of possible π stacking in the thiophene segment is considered. The motifs of the secondary structure in the peptide blocks and their evolution with increasing adsorption intensity are examined.

Engineering of Supramolecular H-Bonded Nanopolygons via Self-Assembly of Programmed Molecular Modules

Discrete and multicomponent nanoscale noncovalent assemblies on surfaces featuring polygonal porous domains are presented. The molecular engineering concept involves multivalent molecular modules that are preprogrammed to undergo heteromolecular recognition by exploiting complementary multiple H bonds. Two types of molecular modules have been engineered: (i) a linear unit of twofold symmetry exposing two 2,6-di(acylamino)pyridyl [donor-acceptor-donor (DAD)] recognition sites at its extremities with a 180 degree orientation relative to each other and (ii) an angular unit constituted by a 1,3,6,8-tetraethynylpyrene core peripherally functionalized with four uracil groups [acceptor-donor-acceptor (ADA)] positioned at 60 degrees and 120 degrees relative to each other. These molecular modules self-assemble through H-bonds between the complementary recognition sites, forming supramolecular architectures. Their symmetry depends upon the type of each individual subunit and the stoichiometry as well as on the combination and distribution of the main symmetry axes. These so-formed two-dimensional (2D) supramolecular oligomers have been studied in solution by optical spectroscopy and on highly ordered pyrolitic graphite (HOPG) substrates by scanning tunneling microscopy (STM) at the solid-liquid interface. Steady-state UV/vis absorption and emission titration measurements suggest the reversible formation of multiple oligomeric species with slightly modulated fluorescence spectra. This likely reflects the presence of various aggregates between the two polytopic receptors, which exhibit somewhat different electronic delocalization as a function of the aggregate size. The presence of multiple species is further confirmed by time-resolved luminescence measurements: lifetime values are fitted as double/multiple exponentials and are always shorter than 6.5 ns. The formation of several oligomeric species is further supported by in situ STM measurements at the solid-liquid interface that provided evidence, with submolecular resolution, for the formation of multicomponent and discrete 2D polygon-like assemblies. We highlight the role of accurate control of the concentration required to image on the surface the 2D oligomeric species formed in solution, which allows us to bypass the determinant role of the substrate-molecule interactions in forming the thermodynamically stable monocomponent architectures at the solid-liquid interface.

Supramolecular Assembly of Defined Polymer Nanoobjects

AbstractThe visualization of well defined supramacromolecules that are formed by poly(4‐vinylpyridine) (P4VP) partially neutralized with wedge‐shaped amphiphilic sulfonic acid molecules is reported. Molecules are depicted as deposited on highly ordered pyrolitic graphite (HOPG) by means of atomic force microscopy. Three P4VP polymers with different, uniform molecular weights were employed to prepare the complexes. Individual supramacromolecules have been observed consisting of polyvinylpyridine backbones wrapped by the noncovalently bound sulfonic acid groups. The length of the supramacromolecules is controlled by the length of the core P4VP chains. The complexes display a strictly defined orientation with respect to the 6‐fold symmetry of the HOPG substrate that is caused by the epitaxial adsorption of side alkyl chains that also enables the visualization of these single molecules.magnified image

Growth of nanorods and mesoscale stars prior to an orientation transition in thin Bi films on graphite

We report on the growth of unusual star shaped Bi islands and ordered arrays of nanorods on highly ordered pyrolitic graphite (HOPG) substrates. The rods and stars grow with {0 1 2}Bi||{0 0 1}HOPG and are preferentially aligned with the high symmetry directions of the substrate. As more Bi is deposited, the film undergoes a transition to the {0 0 1} orientation. These features are a result of a complex interplay between kinetics, thermodynamics, and the crystallography of the substrate and island material.

Structural Evolution of Hexa-peri-hexabenzocoronene Adlayers in Heteroepitaxy on n-Pentacontane Template Monolayers

The growth and structure of self-assembled adlayers of hexakis(n-dodecyl)-peri-hexabenzocoronene (HBC-C12) adsorbed on highly ordered pyrolitic graphite (HOPG) decorated by an n-pentacontane (n-C50H102) monolayer have been investigated by scanning tunneling microscopy (STM). Whereas on HOPG the HBC-C12 molecules readily self-assemble into a unique stable 2D structure, on the [n-C50H102 monolayer/graphite] system we observe morphological phase transitions with formation of time dependent alpha, beta, and gamma phases (alpha-->beta-->gamma). The initial alpha-phase is similar to that obtained on bare graphite, while intermediate beta- and final gamma-structures present molecular dimers and rows, respectively. The observed two-dimensional polymorphism is due to weak interaction between HBC-C12 molecules and n-C50H102-modified graphite substrate. Our results constitute an important step toward the control of the growth and structure of highly ordered monolayers of functional conjugated molecules by modifying the graphite surface with an n-alkane monolayer of appropriate chain length.

A crystallographic orientation transition and early stage growth characteristics of thin Bi films on HOPG

We report on the growth of ultra-thin bismuth films on the basal plane of highly ordered pyrolitic graphite (HOPG) substrates. Scanning electron microscopy and atomic force microscopy have been used to characterize the morphology, and the crystallographic orientation was obtained using electron back scatter diffraction. Low coverage films are comprised of islands with a striped surface morphology, and show the orientation relationship { 0 1 1 ¯ 2 } Bi ∥ { 0 0 0 1 } HOPG with preferred in-plane orientations 〈 1 1 2 ¯ 0 〉 Bi ∥ 〈 1 0 1 ¯ 0 〉 HOPG . With increasing film thickness, we identify an unusual orientation transformation to the commonly found Bi{0 0 0 1} (trigonal) orientation.

Highly Ordered Self‐Assembled Architectures of Modified Terpyridines on Highly Ordered Pyrolitic Graphite Imaged by Scanning Tunneling Microscopy

AbstractScanning tunneling microscopy has been used to study the adsorbed phases of functionalized terpyridines at the solid–liquid interface of highly ordered pyrolitic graphite (HOPG). Terpyridines are well‐known for their complexing behavior to transition metal ions, making them widely used ligands in organometallic and supramolecular chemistry. We found that solutions of 2,2′:6′,2″‐terpyridine‐4′‐oxydodecane (tpy‐O‐C12) and 2,2′:6′,2″‐4′‐oxyoctadecane (tpy‐O‐C18) form highly ordered two‐ dimensional (2D) arrays on HOPG in phenyloctane. For both compounds, large, well‐defined lamellar domains have been observed with domain sizes larger than 500 nm. Sequential scans of an area with two grain boundaries indicate that desorption–resorption is taking place along the domain edges. High‐resolution images of the lamella have been obtained, and the 2D packing within the lamella was determined in detail. The terpyridines align in long uniform double rows with their alkyl chains packing in an alternating, zipper‐like fashion. The terpyridines pack with the polar head‐groups head to head, and the observed size and shape of the molecules fit exactly to their modeled geometries.