Graphene Islands Research Articles

Seebeck Coefficient Modulation of Graphene Grown on Faceted Cu Surfaces

The thermoelectric properties of polycrystalline copper (Cu) surfaces partially covered with graphene grown by Joule‐heating chemical vapor deposition using scanning thermoelectric microscopy are investigated. Atomic‐resolution atomic force microscopy topographic images of graphene grown on Cu(100) surfaces showed a 1D stripe pattern of Moiré superlattices, while thermoelectric voltage images clearly distinguish wrinkle defects caused by thermal mismatch between graphene and Cu substrate. Regions of different signs were found in the thermoelectric voltage image of the graphene island, which are attributed to the faceted surface of the Cu substrate. In addition, faceted surfaces consisting of low‐ and high‐index Cu surfaces are formed on the Cu grain to minimize the surface energy. Due to these structural changes, charge transfer and chemical interactions at the interface between the graphene and Cu facets affect the electronic structure of the graphene, which is understood as the observed Seebeck coefficients with different signs in the thermoelectric microscopy measurements, which are sensitive to the local density of states.

Growth Kinetics of Graphene on Cu(111) Foils from Methane, Ethyne, Ethylene, and Ethane

AbstractChemical vapor deposition of carbon precursors on Cu‐based substrates at temperatures exceeding 1000 °C is currently a typical route for the scalable synthesis of large‐area high‐quality single‐layer graphene (SLG) films. Using molecules with higher activities than CH4 may afford lower growth temperatures that might yield fold‐ and wrinkle‐free graphene. The kinetics of growth of graphene using hydrocarbons other than CH4 are of interest to the scientific and industrial communities. We measured the growth rates of graphene islands on Cu(111) foils by using C2H2, C2H4, C2H6 and CH4, respectively (each mixed with H2). From such kinetics data we obtain the activation enthalpy (ΔH≠) of graphene growth as shown in parentheses (C2H2 (0.93±0.09 eV); C2H4 (2.05±0.19 eV); C2H6 (2.50±0.11 eV); CH4 (4.59±0.26 eV)); C2Hy (y=2, 4, 6) show similar growth behavior but CH4 is different. Computational fluid dynamics and density functional theory simulations suggest that C2Hy differs from CH4 due to different values of adsorption energy and the lifetime of relevant carbon precursors on the Cu(111) surface. Combining experimental and simulation results, we find that the rate determining step (RDS) is the dissociation of the first C−H bond of CH4 molecules in the gas phase, while the RDS using C2Hy is the first dehydrogenation of adsorbed C2Hy that happens with assistance of H atoms adsorbed on the Cu(111) surface. By using C2H2 as the carbon precursor, high‐quality single‐crystal adlayer‐free SLG films are achieved on Cu(111) foils at 900 °C.

Growth Kinetics of Graphene on Cu(111) Foils from Methane, Ethyne, Ethylene, and Ethane.

Chemical vapor deposition of carbon precursors on Cu-based substrates at temperatures exceeding 1000 °C is currently a typical route for the scalable synthesis of large-area high-quality single-layer graphene (SLG) films. Using molecules with higher activities than CH4 may afford lower growth temperatures that might yield fold- and wrinkle-free graphene. The kinetics of growth of graphene using hydrocarbons other than CH4 are of interest to the scientific and industrial communities. We measured the growth rates of graphene islands on Cu(111) foils by using C2H2, C2H4, C2H6 and CH4, respectively (each mixed with H2). From such kinetics data we obtain the activation enthalpy (ΔH≠) of graphene growth as shown in parentheses (C2H2 (0.93±0.09 eV); C2H4 (2.05±0.19 eV); C2H6 (2.50±0.11 eV); CH4 (4.59±0.26 eV)); C2Hy (y=2, 4, 6) show similar growth behavior but CH4 is different. Computational fluid dynamics and density functional theory simulations suggest that C2Hy differs from CH4 due to different values of adsorption energy and the lifetime of relevant carbon precursors on the Cu(111) surface. Combining experimental and simulation results, we find that the rate determining step (RDS) is the dissociation of the first C-H bond of CH4 molecules in the gas phase, while the RDS using C2Hy is the first dehydrogenation of adsorbed C2Hy that happens with assistance of H atoms adsorbed on the Cu(111) surface. By using C2H2 as the carbon precursor, high-quality single-crystal adlayer-free SLG films are achieved on Cu(111) foils at 900 °C.

Evolution of PTCDA-derived seeds prior to graphene nanoribbon growth on Ge(001)

The synthesis of graphene nanoribbons (GNRs) can be realized via CH4 chemical vapor deposition (CVD) on substrates such as Ge(001) that promote highly anisotropic growth. Small polycyclic aromatic hydrocarbons (PAHs) are first sublimed onto Ge at relatively low temperature to form graphene-like seeds that subsequently initiate GNR growth with CH4 exposure at 1173 K. The behaviors of PAHs between their sublimation onto Ge and GNR growth are unclear. Here, we study an archetypical PAH – perylene-3,4,9,10-tetracarboxyl acid dianhydride (PTCDA) – on Ge(001) using both scanning tunneling microscopy (STM) and density functional theory (DFT) to characterize PAH configuration, surface diffusivity, and clustering. PTCDA becomes mobile above 673 K, consistent with a DFT diffusion barrier of 1.74 eV. The mobile PTCDA molecules meet, cluster, and fuse at Ge step edges, dehydrogenating at higher temperatures. These clusters have a height of 0.4 nm, similar to small graphene islands, and grow laterally with increasing temperature – reaching 1.2–2.1 nm in width at 1173 K, consistent with extrapolated CVD experiments. These results provide a plausible picture for how PTCDA forms seeds for anisotropic GNR CVD and show that PAHs with reduced surface diffusivity and inter-molecular reactivity are needed to enable more monodisperse PAH-seeded GNR synthesis.

Luminescence of carbon quantum dots in amorphous carbon

Subject of study. The luminescence spectrum of amorphous protonated carbon (a-C:H) containing carbon quantum dots is studied. Aim of study. How the peak in the luminescence spectrum of a-C:H is affected by the presence of fragments with different configurations is determined. Method. The typical spectra are compared against those of the closest analogs: polycyclic aromatic hydrocarbons with a small number of aromatic rings. Main results. Bright blue fluorescence due to the presence of an ensemble of graphene islands embedded in a diamond-like matrix is experimentally observed in a-C:H [Opt. Express 19, 17935 (2011)10.1364/OE.19.017935] and similar materials. The experimental spectrum appears consistent with a theoretical spectrum generated by superposing the non-uniformly broadened spectra of three analogs, namely, acenaphthylene, pyrene, and azulene (with each spectrum being assigned different weights). This research can be generalized to a wider range of carbon materials that fluoresce at short wavelengths. Practical significance. The results from this study of the properties of carbon quantum dots in amorphous carbon can be used to develop materials for conversion of ultraviolet electromagnetic radiation into visible light.

Substrate Screening for the Epitaxial Growth of a Single-Crystal Graphene Wafer.

Epitaxial growth of a two-dimensional (2D) single crystal necessitates the symmetry group of the substrate being a subgroup of that of the 2D material. As a consequence of the theory of 2D material epitaxy, high-index surfaces, which own very low symmetry, have been successfully used to grow various 2D single crystals, while the rule of selecting the best substrates for 2D single crystal growth is still absent. Here, extensive density functional theory calculations were conducted to investigate the growth of graphene on abundant high-index Cu substrates. Although step edges are commonly regarded as the most active sites for graphene nucleation, our study reveals that, in some cases, graphene nucleation on terraces is superior than that near a step edge. To achieve parallel alignments of graphene islands, it is essential to either suppress terrace nucleation or ensure consistent orientations templated by both the terrace and step edge. In agreement with most experimental observations, we show that Cu substrates for the growth of single-crystalline graphene include vicinal Cu(111) surfaces, vicinal Cu(110) surfaces with Miller indices of (nn1) (n > 3), and vicinal Cu(100) surfaces with Miller indices of (n11) (n > 3).

Influence of morphological characteristics of graphene on its field emission properties

Graphene is one of the most potential field emission cathode materials due to its excellent electrical, thermal, and mechanical properties, as well as rich edge structures. In this paper, we study the growth parameters of graphene prepared by chemical vapor deposition, and prepare three kinds of morphologies of graphene: single-layer graphene, graphene islands, and graphene with buffer layers, and then we explore the influence of the morphological characteristics of graphene on its field emission properties, and analyze the mechanism of influence of the morphological characteristics of graphene on its field emission properties through COMSOL. Comparing with single-layer graphene, the turn-on field of graphene islands and that of graphene with buffer layers decrease to 5.55 V/μm and 5.85 V/μm, respectively. The current densities also increase to 40.3 μA/cm<sup>2</sup> and 26.4 μA/cm<sup>2</sup>, respectively. On the other hand, the field emission currents of single-layer graphene and graphene with buffer layers are more stable. In a 5-hour test, the current densities only decrease by 2% and 4%, respectively. COMSOL simulation shows that the morphological characteristics of graphene have significant influences on the electric field distribution characteristics and heat dissipation capacity. Graphene islands and graphene with buffer layers have exposed edges, leading to local electric field concentration, and thus improving field emission properties. The graphene islands are distributed discretely on the substrate, forming no continuous graphene film and lacking transverse heat dissipation channels, so the accumulation of heat will cause damage to the graphene emitter, and affect the stability of its field emission current. This study will be of great benefit to the understanding of the influence of the morphological characteristics of graphene on its field emission properties, and improving the field emission properties of graphene materials.

Graphene-Based Physically Unclonable Functions with Dual Source of Randomness.

There is growing interest in systems with randomized responses for generating physically unclonable functions (PUFs) in anticounterfeiting and authentication applications. Atomic-level control over its thickness and unique Raman spectrum make graphene an attractive material for PUF applications. Herein, we report graphene PUFs that emerge from two independent stochastic processes. Randomized variations in the shape and number of graphene adlayers were achieved by exploiting and improving the mechanistic understanding of the chemical vapor deposition of graphene. The randomized positioning of the graphene domains was then facilitated by dewetting the polymer film, followed by oxygen plasma etching. This approach yielded surfaces with randomly positioned and shaped graphene islands with varied numbers of layers and, therefore, Raman spectra. Raman mapping of surfaces resulted in multicolor images with a high encoding capacity. Advanced feature-matching algorithms were employed for the authentication of multicolor images. The use of two independent stochastic processes on a two-dimensional nanomaterial platform enables the creation of unique and complex surfaces that excessively challenge clonability.

Theoretical Study on Origin of CVD Growth Direction Difference in Graphene/hBN Heterostructures

The origin of chemical vapor deposition (CVD) growth direction difference in graphene/hexagonal boron nitride (hBN) heterostructures is theoretically studied. The study is focused on the advance in energy gain by H termination of the bare hBN N edge on the Cu(111) surface comparing with that of the bare graphene edge. It is found that the difference in the van der Waals correction method affects largely the advance. However, when the most reliable van der Waals correction of the vdw-DF2-B86R method is used, the results consist with our speculation stating that the edge termination of the existing island rather automatically changes depending on whether the island is graphene or hBN. Thus, it is proposed that the graphene island edge is automatically bare and the hBN island edge is automatically terminated by H during the CVD growth.

Structural identification of graphene films and nanoislands on 6H-SiC(0001) by direct height measurement

By combining non-contact atomic force microscopy (nc-AFM) and Kelvin probe microscopy (KPFM) in ultra high vacuum environment (UHV), we directly measure the height and work function of graphene monolayer on the Si-face of 6H-SiC(0001) with a precision that allows us to differentiate three different types of graphene structures : zero layer graphene (ZLG), Quasi free-standing monolayer graphene (QFMLG) and bilayer graphene (BLG). The height and work function of ZLG are 2.62 ± 0.22 Å and 4.42 ± 0.05 eV respectively, when they are 4.09 ± 0.11 Å and 4.63 ± 0.05 eV for QFMLG. The work function is 4.83 ± 0.05 eV for the BLG. Unlike any other available technique, the local nc-AFM/KPFM dual probe makes it possible to directly identify the nature of nanometer-sized graphene islands that constitute the early nuclei of graphene monolayer grown on 6H-SiC(0001) by chemical vapor deposition.

Growth and Properties of Graphene and Graphene Nanoribbons on Ge

The synthesis of graphene directly on Ge and on Ge deposited on Si provides a scalable route toward integrating graphene onto conventional semiconductors. This presentation will first survey the growth modes of graphene on Ge(001), Ge(011), Ge(111), Ge(112), Ge(001)-6°, and Ge(001)-9° via chemical vapor deposition (CVD), reporting on the effect of Ge surface orientation on graphene island formation and shape, strain in large-area graphene films, and the nanofaceting of the Ge below graphene.[1] We will then focus on the anisotropic growth of semiconducting graphene nanoribbons on Ge(001) and Ge(001)-9° and of nominally single crystal graphene on Ge(110).On Ge(001), we have discovered how to drive graphene crystal growth with a large shape anisotropy through control of kinetics.[2-6] This discovery enables the direct synthesis of narrow, armchair, semiconducting nanoribbons. The ribbons are self-orienting, self-defining, and have smooth edges. The ribbons exhibit excellent transport properties (e.g., high on-state conductance and on/off ratio at room temperature) and provide a promising pathway towards the direct integration of high-performance nanocarbon electronics onto conventional semiconductor wafer platforms.On Ge(001), nominally single crystal graphene has been reported in limited cases; however, conflicting studies have evidenced polycrystallinity. Here, the factors affecting the mosaicity of graphene on Ge(110) will be elucidated using low energy electron diffraction and microscopy data.[7][1] R. M. Jacobberger, D. E. Savage, X. Zheng, P. Sookchoo, R. R. Delgado, M. G. Lagally, M. S. Arnold, SUBMITTED (2022).[2] R. M. Jacobberger, M. S. Arnold, et al., Direct Oriented Growth of Armchair Graphene Nanoribbons on Germanium, NATURE COMMUNICATIONS, 6, 8006 (2015).[3] B. Kiraly, M. S. Arnold, M. C. Hersam, N. P. Guisinger et al., Sub-5 nm, Globally Aligned Graphene Nanoribbons on Ge (001), APPLIED PHYSICS LETTERS, 108, 213101 (2016).[4] A. J. Way, R. M. Jacobberger, M. S. Arnold, Seed-Initiated Anisotropic Growth of Unidirectional Armchair Graphene Nanoribbon Arrays on Germanium, NANO LETTERS, 18, 898 (2018).[5] V. Saraswat, Y. Yamamoto, H.J. Kim, R.M. Jacobberger, K.R. Jinkins, A.J. Way, N.P. Guisinger, M.S. Arnold Synthesis of armchair graphene nanoribbons on germanium-on-silicon, THE JOURNAL OF PHYSICAL CHEMISTRY C 123 (30), 18445-18454 (2019).[6] A. J. Way, R. M. Jacobberger, N. P. Guisinger, V. Saraswat, X. Zheng, A. Suresh, J. H. Dwyer, P. Gopalan, Michael S. Arnold, SUBMITTED (2022).[7] R. M. Jacobberger, Z. Miao, T. Yu, V. Saraswat, M. G. Lagally, M. S. Altman, M. S. Arnold, SUBMITTED (2022).

Morphology-Control Growth of Graphene Islands by Nonlinear Carbon Supply.

Controlling the morphology of graphene and other 2D materials in chemical vapor deposition (CVD) growth is crucial because the morphology reflects the crystal quality of as-synthesized nanomaterials in a certain way, and consequently it indirectly represents the physical properties of 2D materials such as bandgap, selective ion transportation, and impermeability. However, precise control of the morphology is limited by the complex formation mechanism and sensitive growth-environment factors of graphene. Therefore, the CVD synthesis of single-crystal hexagonal-shaped graphene islands with specific sizes is challenging. Herein, an unconventional nonlinear-carbon-supply growth strategy is proposed to realize controllable CVD growth of desired hexagonal graphene islands with specific sizes on Cu substrates. Large-area graphene films of isolated islands with desired densities, sizes, and distances between the islands aresuccessfully synthesized. Subsequently, the direct growth of a planar-tunnel-junction structure based on two parallel gapped graphene islands isachieved by specific adjustment of the growth and etching processes of graphene CVD synthesis. It is therefore demonstrated that the nonlinear-carbon-supply growth strategy is a reliable method for the synthesis of high-quality graphene and can facilitate the direct growth of graphene-based nanodevices in the future.

Direct precipitation of multilayer graphene on c-plane sapphire using a crystallized Ni catalyst

Graphene was precipitated using crystallized Ni catalyst, which was crystallized using a MBE-grown Ni layer as a seed. In the thermal crystallization process, the additional deposition of amorphous Ni layer was effective to suppress the dewetting of the Ni catalyst. The resulted graphene was flat and free from folds, which are the large wrinkles folded on the substrate and the graphene islands were found smoothly stitched together. It is because the islands were precisely aligned by the crystal information inherited from the Ni layer. The insitu observation of the precipitation was also performed using high intensity X-ray beam from a synchrotron apparatus. Precipitation process was clearly revealed, and the crystallized Ni catalyst was found effectively reduced the formation of defective graphene, which was conventionally produced by the carbons diffused though grain boundaries at low temperature.

Flexibility of fluorinated graphene based memristor structures: current flow model in a multi-barrier system under tensile strain

The flexibility of two types of memristor structures with fluorinated graphene (FG) based active layers (FG with graphene islands on polyvinyl alcohol, FG/PVA, and films from nanoparticles of V2O5 capsulated with FG, FG/V2O5) under the tensile strain in bending conditions was investigated and compared in the present study. Both types of memristors show a similar mechanism of resistance switchings (current paths on traps without filaments). Multi-barrier model of current flow was used to estimate the barrier parameters connected to FG from experiments on resistive switching of memristor structures in the bending condition. The first type of structures (Ag/FG/PVA/Ag) demonstrates the record high values of flexibility: ON/OFF current relation is not changed up to 7% tensile strain created by bending. The second type of structures (Gr/FG/V2O5/Gr with graphene contacts) show a decrease in ON current already for tensile strain more than 2%. The similar mechanism of current flow allows us to use the similar theory for description of the current flow versus the tensile strain. In spite of different structures and morphology of memristors, the typical values of the barrier height extracted from the theoretical description were similar: ∼1.5 eV with an effective barrier thickness of ∼16.5 nm and ∼1.3–1.6 eV with thickness 13.5–15.0 nm for FG/PVA and FG/V2O5 structures, respectively. Increase in the barrier thickness over 19 nm in both cases leads to the strong decrease in ON current of memristors.

Boudouard reaction under graphene cover on Ni(1 1 1)

We investigated the interaction of CO with graphene/Ni(111) and the Boudouard reaction at 3.7 mbar by Near Ambient Pressure X-Ray Photoemission Spectroscopy (NAPXPS), i.e. at one order of magnitude higher pressure than previously explored in-operando conditions. In this regime, CO intercalates under the graphene layer causing its partial detachment from the Ni substrate. The so-obtained high local CO coverage opens the way to CO2 formation via the Boudouard reaction. Its onset is witnessed by observing physisorbed CO2 accumulating below the graphene cover. The so-generated additional carbon atoms transform carbide into graphene, causing the expansion of the graphene islands. In addition, CO adsorption occurs on the strongly interacting areas of the graphene layer, confirming previous results obtained by some of us at low temperatures and in ultra-high vacuum conditions.

Graphene Growth across the Twin Boundaries of Copper Substrate

AbstractTwin crystals, the formation energy of which is much smaller than that of ordinary grain boundaries, widely exist in the annealed copper and are hard to eliminate. The study of the effects of twin boundaries on graphene growth is of great significance to the understanding of graphene epitaxy. However, there are few studies on the effects of twin boundaries on the graphene growth process. Here, this article experimentally demonstrates that graphene islands are subjected to different compressive strains from the opposite copper crystal plane after growing across the twin boundary. Further results reveal that graphene can grow across different twin boundaries, such as atom steps, narrow valleys, and even micron‐scale ridges, without forming linear defect. Therefore, strain‐induced graphene doping can be manipulated with the type of twin boundaries and the location on the twin crystals. The transition region where the degree of doping changes monotonically across the twin boundary further confirms the different spatial doping phenomena of graphene islands. This work provides a new perspective for understanding the effect of twin boundaries on the graphene epitaxy, which is expected to have a potential impact on growing high‐quality graphene on twinned copper substrates.

Silica Particle-Mediated Growth of Single Crystal Graphene Ribbons on Cu(111) Foil.

The authors report the growth of micrometer-long single-crystal graphene ribbons (GRs) (tapered when grown above 900°C, but uniform width when grown in the range 850°C to 900°C) using silica particle seeds on single crystal Cu(111) foil. Tapered graphene ribbons grow strictly along the Cu<101> direction on Cu(111) and polycrystalline copper (Cu) foils. Silica particles on both Cu foils form (semi-)molten Cu-Si-O droplets at growth temperatures, then catalyze nucleation and drive the longitudinal growth of graphene ribbons. Longitudinal growth is likely by a vapor-liquid-solid (VLS) mechanism but edge growth (above 900°C) is due to catalytic activation of ethylene (C2 H4 ) and attachment of C atoms or species ("vapor solid" or VS growth) at the edges. It is found, based on the taper angle of the graphene ribbon, that the taper angle is determined by the growth temperature and the growth rates are independent of the particle size. The activation enthalpy (1.73± 0.03eV) for longitudinal ribbon growth on Cu(111) from ethylene is lower than that for VS growth at the edges of the GRs (2.78 ±0.15eV) and for graphene island growth (2.85± 0.07eV) that occurs concurrently.

Achievements and Challenges of Graphene Chemical Vapor Deposition Growth

AbstractGraphene, since the first successful exfoliation of graphite, has continuously attracted attention due to its remarkable properties and applications. Recently, the research focus on graphene synthesis has been directed to the controllable synthesis of large‐area and high‐quality graphene. In the last decade, there has been great progress in the chemical vapor deposition (CVD) growth of graphene. Theoretical investigations have led to an enhanced understanding of puzzles on hydrocarbon species stability, key reaction pathways, the role of hydrogen gas, the morphology of graphene islands, and the alignment of graphene on substrates. Experimentally, high‐quality graphene is epitaxially grown on both insulating and metal substrates. Progress has also been reported on low‐temperature graphene growth and on controlling the thickness and stacking of graphene layers. In this review, the authors summarize the previous theoretical and experimental studies on graphene CVD growth and discuss the future challenges on the growth of graphene i) on insulating substrates, ii) at low temperature, iii) with controllable thickness, and iv) with selected stacking twist angles. The authors assert that the key to the continuous advancement of graphene growth is the synergy of experimental and theoretical investigations.

Dynamics of Li deposition on epitaxial graphene/Ru(0001) islands

Li metal has been deposited on the surface of a Ru(0001) single crystal containing patches of monolayer-thick epitaxial graphene islands. The use of low-energy electron microscopy and diffraction allowed us to in situ monitor the process by measuring the local work function as well as to study the system in real and reciprocal space, comparing the changes taking place on the graphene with those on the bare Ru(0001) surface. It is found that Li deposition decreases the work function of the graphene islands but to a much smaller degree than of the Ru(0001) surface, as corresponds to its intercalation below the graphene overlayer. Finally, the diffusion process of Li out of the graphene islands has been monitored by photoelectron microscopy using a visible-light laser.

Strong suppression of graphene growth by sulfur superstructure on a nickel substrate

The formation of multilayer graphene on a nickel substrate is usually unavoidable due to the precipitation of carbon upon cooling after the growth of the single layer of graphene. We found that the growth rate of graphene on a Ni(110) surface was markedly reduced when the surface was covered by sulfur atoms arranged in a c($2\ifmmode\times\else\texttimes\fi{}2$) periodicity. An atomistic survey by scanning tunneling microscopy revealed a compression of the sulfur superstructure as a result of the growth of graphene-covered regions. Photoelectron emission microscopy showed that the growth rate of graphene is linear with time, which indicates that carbon atoms are supplied only at the growth front of graphene islands. Density functional theory calculations rationalized these experimental results and suggested a mechanism for suppressing the growth of graphene. Sulfur atoms might extend the utility of nickel substrates for the production of single-layer graphene or nanographenes.