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Sample records for atomic layer graphene

  1. A DFT study of halogen atoms adsorbed on graphene layers.

    PubMed

    Medeiros, Paulo V C; Mascarenhas, Artur J S; de Brito Mota, F; de Castilho, Caio M C

    2010-12-03

    In this work, ab initio density functional theory calculations were performed in order to study the structural and electronic properties of halogens (X = fluorine, chlorine, bromine or iodine) that were deposited on both sides of graphene single layers (X-graphene). The adsorption of these atoms on only one side of the layer with hydrogen atoms adsorbed on the other was also considered (H,X-graphene). The results indicate that the F-C bond in the F-graphene system causes an sp(2) to sp(3) transition of the carbon orbitals, and similar effects seem to occur in the H,X-graphene systems. For the other cases, two configurations are found: bonded (B) and non-bonded (NB). For the B configuration, the structural arrangement of the atoms was similar to F-graphene and H-graphene (graphane), although the electronic structures present some differences. In the NB configuration, the interaction between the adsorbed atoms and the graphene layer seems to be essentially of the van der Waals type. In these cases, the original shape of the graphene layer presents only small deviations from the pristine form and the adsorbed atoms reach equilibrium far from the sheet. The F-graphene structure has a direct bandgap of approximately 3.16 eV at the Γ point, which is a value that is close to the value of 3.50 eV that was found for graphane. The Cl-graphene (B configuration), H,F-graphene and H,Cl-graphene systems have smaller bandgap values. All of the other systems present metallic behaviours. Energy calculations indicate the possible stability of these X-graphene layers, although some considerations about the possibility of spontaneous formation have to be taken into account.

  2. Mode Locking of Lasers with Atomic Layer Graphene

    DTIC Science & Technology

    2012-07-01

    method to produce the few atomic layers graphene . In a typical experiment , a SiO2/Si substrate with 300 nm Ni film was loaded into a CVD chamber...by ANSI Std Z39-18 2 Abstract: Large size atomic layer graphene was fabricated using the chemical vapor deposition ( CVD ) technique. The...order to achieve the optimized mode locking performance of a laser, the parameters of a saturable absorber, these are the saturable modulation strength

  3. Damage evaluation in graphene underlying atomic layer deposition dielectrics

    PubMed Central

    Tang, Xiaohui; Reckinger, Nicolas; Poncelet, Olivier; Louette, Pierre; Ureña, Ferran; Idrissi, Hosni; Turner, Stuart; Cabosart, Damien; Colomer, Jean-François; Raskin, Jean-Pierre; Hackens, Benoit; Francis, Laurent A.

    2015-01-01

    Based on micro-Raman spectroscopy (μRS) and X-ray photoelectron spectroscopy (XPS), we study the structural damage incurred in monolayer (1L) and few-layer (FL) graphene subjected to atomic-layer deposition of HfO2 and Al2O3 upon different oxygen plasma power levels. We evaluate the damage level and the influence of the HfO2 thickness on graphene. The results indicate that in the case of Al2O3/graphene, whether 1L or FL graphene is strongly damaged under our process conditions. For the case of HfO2/graphene, μRS analysis clearly shows that FL graphene is less disordered than 1L graphene. In addition, the damage levels in FL graphene decrease with the number of layers. Moreover, the FL graphene damage is inversely proportional to the thickness of HfO2 film. Particularly, the bottom layer of twisted bilayer (t-2L) has the salient features of 1L graphene. Therefore, FL graphene allows for controlling/limiting the degree of defect during the PE-ALD HfO2 of dielectrics and could be a good starting material for building field effect transistors, sensors, touch screens and solar cells. Besides, the formation of Hf-C bonds may favor growing high-quality and uniform-coverage dielectric. HfO2 could be a suitable high-K gate dielectric with a scaling capability down to sub-5-nm for graphene-based transistors. PMID:26311131

  4. Damage evaluation in graphene underlying atomic layer deposition dielectrics

    NASA Astrophysics Data System (ADS)

    Tang, Xiaohui; Reckinger, Nicolas; Poncelet, Olivier; Louette, Pierre; Ureña, Ferran; Idrissi, Hosni; Turner, Stuart; Cabosart, Damien; Colomer, Jean-François; Raskin, Jean-Pierre; Hackens, Benoit; Francis, Laurent A.

    2015-08-01

    Based on micro-Raman spectroscopy (μRS) and X-ray photoelectron spectroscopy (XPS), we study the structural damage incurred in monolayer (1L) and few-layer (FL) graphene subjected to atomic-layer deposition of HfO2 and Al2O3 upon different oxygen plasma power levels. We evaluate the damage level and the influence of the HfO2 thickness on graphene. The results indicate that in the case of Al2O3/graphene, whether 1L or FL graphene is strongly damaged under our process conditions. For the case of HfO2/graphene, μRS analysis clearly shows that FL graphene is less disordered than 1L graphene. In addition, the damage levels in FL graphene decrease with the number of layers. Moreover, the FL graphene damage is inversely proportional to the thickness of HfO2 film. Particularly, the bottom layer of twisted bilayer (t-2L) has the salient features of 1L graphene. Therefore, FL graphene allows for controlling/limiting the degree of defect during the PE-ALD HfO2 of dielectrics and could be a good starting material for building field effect transistors, sensors, touch screens and solar cells. Besides, the formation of Hf-C bonds may favor growing high-quality and uniform-coverage dielectric. HfO2 could be a suitable high-K gate dielectric with a scaling capability down to sub-5-nm for graphene-based transistors.

  5. Damage evaluation in graphene underlying atomic layer deposition dielectrics.

    PubMed

    Tang, Xiaohui; Reckinger, Nicolas; Poncelet, Olivier; Louette, Pierre; Ureña, Ferran; Idrissi, Hosni; Turner, Stuart; Cabosart, Damien; Colomer, Jean-François; Raskin, Jean-Pierre; Hackens, Benoit; Francis, Laurent A

    2015-08-27

    Based on micro-Raman spectroscopy (μRS) and X-ray photoelectron spectroscopy (XPS), we study the structural damage incurred in monolayer (1L) and few-layer (FL) graphene subjected to atomic-layer deposition of HfO2 and Al2O3 upon different oxygen plasma power levels. We evaluate the damage level and the influence of the HfO2 thickness on graphene. The results indicate that in the case of Al2O3/graphene, whether 1L or FL graphene is strongly damaged under our process conditions. For the case of HfO2/graphene, μRS analysis clearly shows that FL graphene is less disordered than 1L graphene. In addition, the damage levels in FL graphene decrease with the number of layers. Moreover, the FL graphene damage is inversely proportional to the thickness of HfO2 film. Particularly, the bottom layer of twisted bilayer (t-2L) has the salient features of 1L graphene. Therefore, FL graphene allows for controlling/limiting the degree of defect during the PE-ALD HfO2 of dielectrics and could be a good starting material for building field effect transistors, sensors, touch screens and solar cells. Besides, the formation of Hf-C bonds may favor growing high-quality and uniform-coverage dielectric. HfO2 could be a suitable high-K gate dielectric with a scaling capability down to sub-5-nm for graphene-based transistors.

  6. Interfacial Atomic Structure of Twisted Few-Layer Graphene.

    PubMed

    Ishikawa, Ryo; Lugg, Nathan R; Inoue, Kazutoshi; Sawada, Hidetaka; Taniguchi, Takashi; Shibata, Naoya; Ikuhara, Yuichi

    2016-02-18

    A twist in bi- or few-layer graphene breaks the local symmetry, introducing a number of intriguing physical properties such as opening new bandgaps. Therefore, determining the twisted atomic structure is critical to understanding and controlling the functional properties of graphene. Combining low-angle annular dark-field electron microscopy with image simulations, we directly determine the atomic structure of twisted few-layer graphene in terms of a moiré superstructure which is parameterized by a single twist angle and lattice constant. This method is shown to be a powerful tool for accurately determining the atomic structure of two-dimensional materials such as graphene, even in the presence of experimental errors. Using coincidence-site-lattice and displacement-shift-complete theories, we show that the in-plane translation state between layers is not a significant structure parameter, explaining why the present method is adequate not only for bilayer graphene but also a few-layered twisted graphene.

  7. Buffer layer engineering on graphene via various oxidation methods for atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Takahashi, Nobuaki; Nagashio, Kosuke

    2016-12-01

    The integration of a high-k oxide on graphene using atomic layer deposition requires an electrically reliable buffer layer. In this study, Y was selected as the buffer layer due to its highest oxidation ability among the rare-earth elements, and various oxidation methods (atmospheric, and high-pressure O2 and ozone annealing) were applied to the Y metal buffer layer. By optimizing the oxidation conditions of the top-gate insulator, we successfully improved the capacitance of the top gate Y2O3 insulator and demonstrated a large I on/I off ratio for bilayer graphene under an external electric field.

  8. Atomic layer deposition of metal oxides on pristine and functionalized graphene.

    PubMed

    Wang, Xinran; Tabakman, Scott M; Dai, Hongjie

    2008-07-02

    We investigate atomic layer deposition (ALD) of metal oxide on pristine and functionalized graphene. On pristine graphene, ALD coating can only actively grow on edges and defect sites, where dangling bonds or surface groups react with ALD precursors. This affords a simple method to decorate and probe single defect sites in graphene planes. We used perylene tetracarboxylic acid (PTCA) to functionalize the graphene surface and selectively introduced densely packed surface groups on graphene. Uniform ultrathin ALD coating on PTCA graphene was achieved over a large area. The functionalization method could be used to integrate ultrathin high-kappa dielectrics in future graphene electronics.

  9. Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

    PubMed Central

    Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

    2013-01-01

    Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

  10. Interactions between C and Cu atoms in single-layer graphene: direct observation and modelling.

    PubMed

    Kano, Emi; Hashimoto, Ayako; Kaneko, Tomoaki; Tajima, Nobuo; Ohno, Takahisa; Takeguchi, Masaki

    2016-01-07

    Metal doping into the graphene lattice has been studied recently to develop novel nanoelectronic devices and to gain an understanding of the catalytic activities of metals in nanocarbon structures. Here we report the direct observation of interactions between Cu atoms and single-layer graphene by transmission electron microscopy. We document stable configurations of Cu atoms in the graphene sheet and unique transformations of graphene promoted by Cu atoms. First-principles calculations based on density functional theory reveal a reduction of energy barrier that caused rotation of C-C bonds near Cu atoms. We discuss two driving forces, electron irradiation and in situ heating, and conclude that the observed transformations were mainly promoted by electron irradiation. Our results suggest that individual Cu atoms can promote reconstruction of single-layer graphene.

  11. Large energy mode locking of an erbium-doped fiber laser with atomic layer graphene.

    PubMed

    Zhang, H; Tang, D Y; Zhao, L M; Bao, Q L; Loh, K P

    2009-09-28

    We report on large energy pulse generation in an erbium-doped fiber laser passively mode-locked with atomic layer graphene. Stable mode locked pulses with single pulse energy up to 7.3 nJ and pulse width of 415 fs have been directly generated from the laser. Our results show that atomic layer graphene could be a promising saturable absorber for large energy mode locking.

  12. Inhomogeneous longitudinal distribution of Ni atoms on graphene induced by layer-number-dependent internal diffusion

    NASA Astrophysics Data System (ADS)

    Hasegawa, M.; Tashima, K.; Kotsugi, M.; Ohkochi, T.; Suemitsu, M.; Fukidome, H.

    2016-09-01

    The intrinsic transport properties, such as carrier mobility and saturation velocity, of graphene are the highest among materials owing to its linear band dispersion and weak backscattering. However, the reported field-effect mobility of transistors using graphene as a channel is much lower than the intrinsic channel mobility. One of the reasons for this low mobility is the high contact resistance between graphene and metals used for the source and drain electrodes, which results from the interfacial roughness. Even Ni, which is a promising contact metal for many materials because of its high adhesion and lower contact resistance, does not meet the requirement as a contact metal for graphene. Noticing that the interfacial roughness between the a metal and graphene is strongly related to the onset of the contact resistance, we performed transmission electron microscopy and photoemission electron microscopy measurements to evaluate the microscopic lateral and longitudinal distributions of Ni atoms at the Ni/graphene interface formed on epitaxial graphene (EG) on 4H-SiC(0001). Our data revealed that the deposited Ni atoms diffused into the EG layers, but they did not reach the EG/SiC interface, and the diffusion was stronger on bilayered graphene than on monolayered graphene. We thus ascribe the layer-number-dependent internal diffusion of Ni atoms in EG as a cause of the microscopic interfacial roughness between graphene and the metal. Ensuring homogeneous distribution of the number of EG layers should be key to lowering the contact resistance.

  13. Atomic-Layer-Deposition Growth of an Ultrathin HfO2 Film on Graphene.

    PubMed

    Xiao, Mengmeng; Qiu, Chenguang; Zhang, Zhiyong; Peng, Lian-Mao

    2017-10-04

    Direct growth of an ultrathin gate dielectric layer with high uniformity and high quality on graphene remains a challenge for developing graphene-based transistors due to the chemically inert surface properties of graphene. Here, we develop a method to realize atomic-layer-deposition (ALD) growth of an ultrathin high-κ dielectric layer on graphene through premodifying the graphene surface using electron beam irradiation. An amorphous carbon layer induced by electron beam scanning is formed on graphene and then acts as seeds for ALD growth of high-κ dielectrics. A uniform HfO2 layer with an equivalent oxide thickness of 1.3 nm was grown as a gate dielectric for top-gate graphene field-effect transistors (FETs). The achieved gate capacitance is up to 2.63 μF/cm(2), which is the highest gate capacitance on a graphene solid-state device to date. In addition, the fabricated top-gate graphene FETs present a high carrier mobility of up to 2500 cm(2)/(V·s) and a negligible gate leakage current of down to 0.1 mA/cm(2), showing that the ALD-grown HfO2 dielectric layer is highly uniform and of very high quality.

  14. Graphene devices with bottom-up contacts by area-selective atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Thissen, Nick F. W.; Vervuurt, René H. J.; Mackus, Adriaan J. M.; Mulders, Johannes J. L.; Weber, Jan-Willem; Kessels, Wilhelmus M. M.; Bol, Ageeth A.

    2017-06-01

    Graphene field-effect transistor devices were fabricated using a bottom-up and resist-free method, avoiding common compatibility issues such as contamination by resist residues. Large-area CVD graphene sheets were structured into device channels by patterning with a focused ion beam. Platinum contacts were then deposited by direct-write atomic layer deposition (ALD), which is a combination between electron beam induced deposition (EBID) and bottom-up area-selective ALD. This is a unique approach that enables nucleation of Pt ALD on graphene, and therefore these devices are the first reported graphene devices with contacts deposited by ALD. Electrical characterization of the devices confirms ambipolar transistor behaviour with typical field-effect mobilities in the range of 1000-1800 cm2 V-1 s-1. We observe clear signs of strong Pt-graphene coupling and contact induced hole doping, implying good contact properties in contrast to the conventionally weak bonding between Pt and graphene. We attribute these observations to the reduced amount of resist residue under the contacts, the improved wettability of the Pt due to the use of ALD, and the formation of a graphitic interlayer that bonds the Pt more strongly to the graphene. We conclude that direct-write ALD is a very suitable technique for metallization of graphene devices and to study the intrinsic properties of metal-graphene contacts in more detail. In addition, it offers unique opportunities to control the metal-graphene coupling strength.

  15. Atomic layer deposition of Al2O3 on NF3-pre-treated graphene

    NASA Astrophysics Data System (ADS)

    Junige, Marcel; Oddoy, Tim; Yakimova, Rositsa; Darakchieva, Vanya; Wenger, Christian; Lupina, Grzegorz; Kitzmann, Julia; Albert, Matthias; Bartha, Johann W.

    2015-06-01

    Graphene has been considered for a variety of applications including novel nanoelectronic device concepts. However, the deposition of ultra-thin high-k dielectrics on top of graphene has still been challenging due to graphene's lack of dangling bonds. The formation of large islands and leaky films has been observed resulting from a much delayed growth initiation. In order to address this issue, we tested a pre-treatment with NF3 instead of XeF2 on CVD graphene as well as epitaxial graphene monolayers prior to the Atomic Layer Deposition (ALD) of Al2O3. All experiments were conducted in vacuo; i. e. the pristine graphene samples were exposed to NF3 in the same reactor immediately before applying 30 (TMA-H2O) ALD cycles and the samples were transferred between the ALD reactor and a surface analysis unit under high vacuum conditions. The ALD growth initiation was observed by in-situ real-time Spectroscopic Ellipsometry (irtSE) with a sampling rate above 1 Hz. The total amount of Al2O3 material deposited by the applied 30 ALD cycles was cross-checked by in-vacuo X-ray Photoelectron Spectroscopy (XPS). The Al2O3 morphology was determined by Atomic Force Microscopy (AFM). The presence of graphene and its defect status was examined by in-vacuo XPS and Raman Spectroscopy before and after the coating procedure, respectively.

  16. Atomic-scale friction modulated by potential corrugation in multi-layered graphene materials

    SciTech Connect

    Zhuang, Chunqiang; Liu, Lei

    2015-03-21

    Friction is an important issue that has to be carefully treated for the fabrication of graphene-based nano-scale devices. So far, the friction mechanism of graphene materials on the atomic scale has not yet been clearly presented. Here, first-principles calculations were employed to unveil the friction behaviors and their atomic-scale mechanism. We found that potential corrugations on sliding surfaces dominate the friction force and the friction anisotropy of graphene materials. Higher friction forces correspond to larger corrugations of potential energy, which are tuned by the number of graphene layers. The friction anisotropy is determined by the regular distributions of potential energy. The sliding along a fold-line path (hollow-atop-hollow) has a relatively small potential energy barrier. Thus, the linear sliding observed in macroscopic friction experiments may probably be attributed to the fold-line sliding mode on the atomic scale. These findings can also be extended to other layer-structure materials, such as molybdenum disulfide (MoS{sub 2}) and graphene-like BN sheets.

  17. Encapsulation of graphene transistors and vertical device integration by interface engineering with atomic layer deposited oxide

    NASA Astrophysics Data System (ADS)

    Alexander-Webber, Jack A.; Sagade, Abhay A.; Aria, Adrianus I.; Van Veldhoven, Zenas A.; Braeuninger-Weimer, Philipp; Wang, Ruizhi; Cabrero-Vilatela, Andrea; Martin, Marie-Blandine; Sui, Jinggao; Connolly, Malcolm R.; Hofmann, Stephan

    2017-03-01

    We demonstrate a simple, scalable approach to achieve encapsulated graphene transistors with negligible gate hysteresis, low doping levels and enhanced mobility compared to as-fabricated devices. We engineer the interface between graphene and atomic layer deposited (ALD) Al2O3 by tailoring the growth parameters to achieve effective device encapsulation whilst enabling the passivation of charge traps in the underlying gate dielectric. We relate the passivation of charge trap states in the vicinity of the graphene to conformal growth of ALD oxide governed by in situ gaseous H2O pretreatments. We demonstrate the long term stability of such encapsulation techniques and the resulting insensitivity towards additional lithography steps to enable vertical device integration of graphene for multi-stacked electronics fabrication.

  18. Atomic layer deposition of HfO{sub 2} on graphene through controlled ion beam treatment

    SciTech Connect

    Kim, Ki Seok; Oh, Il-Kwon; Jung, Hanearl; Kim, Hyungjun; Yeom, Geun Young E-mail: gyyeom@skku.edu; Kim, Kyong Nam E-mail: gyyeom@skku.edu

    2016-05-23

    The polymer residue generated during the graphene transfer process to the substrate tends to cause problems (e.g., a decrease in electron mobility, unwanted doping, and non-uniform deposition of the dielectric material). In this study, by using a controllable low-energy Ar{sup +} ion beam, we cleaned the polymer residue without damaging the graphene network. HfO{sub 2} grown by atomic layer deposition on graphene cleaned using an Ar{sup +} ion beam showed a dense uniform structure, whereas that grown on the transferred graphene (before Ar{sup +} ion cleaning) showed a non-uniform structure. A graphene–HfO{sub 2}–metal capacitor fabricated by growing 20-nm thick HfO{sub 2} on graphene exhibited a very low leakage current (<10{sup −11} A/cm{sup 2}) for Ar{sup +} ion-cleaned graphene, whereas a similar capacitor grown using the transferred graphene showed high leakage current.

  19. Selective metal deposition at graphene line defects by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Kim, Kwanpyo; Lee, Han-Bo-Ram; Johnson, Richard W.; Tanskanen, Jukka T.; Liu, Nan; Kim, Myung-Gil; Pang, Changhyun; Ahn, Chiyui; Bent, Stacey F.; Bao, Zhenan

    2014-09-01

    One-dimensional defects in graphene have a strong influence on its physical properties, such as electrical charge transport and mechanical strength. With enhanced chemical reactivity, such defects may also allow us to selectively functionalize the material and systematically tune the properties of graphene. Here we demonstrate the selective deposition of metal at chemical vapour deposited graphene’s line defects, notably grain boundaries, by atomic layer deposition. Atomic layer deposition allows us to deposit Pt predominantly on graphene’s grain boundaries, folds and cracks due to the enhanced chemical reactivity of these line defects, which is directly confirmed by transmission electron microscopy imaging. The selective functionalization of graphene defect sites, together with the nanowire morphology of deposited Pt, yields a superior platform for sensing applications. Using Pt-graphene hybrid structures, we demonstrate high-performance hydrogen gas sensors at room temperature and show its advantages over other evaporative Pt deposition methods, in which Pt decorates the graphene surface non-selectively.

  20. New metallic quasi-two-dimensional structures of graphene and molybdenum disulfide layers with embedded rhenium atoms

    NASA Astrophysics Data System (ADS)

    Demin, V. A.; Chernozatonskii, L. A.

    2015-01-01

    New metallic structures in the system of graphene and molybdenum disulfide layers with embedded rhenium atoms, in which the graphene layer is rotated by 30° to the molybdenum disulfide layer and the Re atom either substitutes the molybdenum atom in the MoS2 layer or is located between the layers mainly interacting with three sulfur atoms and six carbon atoms, are examined. In the latter case, a high electron density of states has been found in the Fermi level, which indicates a high metallicity of the graphene30°-(Re)-MoS2 bilayer in comparison with other bilayer structures considered earlier. All proposed structures are energetically stable. Possible applications of the studied bilayers have been considered as well.

  1. Parameter Space of Atomic Layer Deposition of Ultrathin Oxides on Graphene

    PubMed Central

    2016-01-01

    Atomic layer deposition (ALD) of ultrathin aluminum oxide (AlOx) films was systematically studied on supported chemical vapor deposition (CVD) graphene. We show that by extending the precursor residence time, using either a multiple-pulse sequence or a soaking period, ultrathin continuous AlOx films can be achieved directly on graphene using standard H2O and trimethylaluminum (TMA) precursors even at a high deposition temperature of 200 °C, without the use of surfactants or other additional graphene surface modifications. To obtain conformal nucleation, a precursor residence time of >2s is needed, which is not prohibitively long but sufficient to account for the slow adsorption kinetics of the graphene surface. In contrast, a shorter residence time results in heterogeneous nucleation that is preferential to defect/selective sites on the graphene. These findings demonstrate that careful control of the ALD parameter space is imperative in governing the nucleation behavior of AlOx on CVD graphene. We consider our results to have model system character for rational two-dimensional (2D)/non-2D material process integration, relevant also to the interfacing and device integration of the many other emerging 2D materials. PMID:27723305

  2. Direct graphene growth on (111) Cu2O templates with atomic Cu surface layer

    SciTech Connect

    Liu, Jianwei; Liu, Qingfeng; Baca, Javier; Xu, Guowei; Rochford, Caitlin; Lu, Rongtao; Edwards, Christina M.; Berrie, Cindy L.; Maroni, Victor A.; Wu, Judy

    2015-12-01

    This work explores nucleation and epitaxy of graphene on crystalline Cu2O templates formed via self assembly and surface reduction of Cu2O nanocrystallites on the cubic textured (100) orientation Cu (CTO-Cu) and polycrystalline Cu (poly-Cu) substrates, respectively. It has been found that the presence of sub-surface oxygen causes the reconstruction of Cu surface due to the formation of oriented Cu2O nanocrystallites at a low H2 gas flow. Self-assembly of the Cu2O nanocrystallites into a textured surface template provides direct nucleation sites for graphene growth after the oxygen-sublattice on the template surface is reduced. The atomic Cu surface layer provides advantages of high graphene growth rate due to the catalytic role of Cu and in-plane alignment of graphene nuclei. It is particularly important that the Cu2O crystallites have predominantly (111) orientation aligned to each other in the plane of the (100) CTO-Cu substrates, which allows epitaxy of graphene with much lower defect density as compared to that in the poly-Cu case. Since Cu2O (111) templates may be developed on lattice matched (100) surfaces of other dielectric materials, this self-assembly approach provides a promising pathway for large-scale, transfer free graphene epitaxy on nonmetallic surfaces.

  3. Uniform Atomic Layer Deposition of Al2O3 on Graphene by Reversible Hydrogen Plasma Functionalization

    PubMed Central

    2017-01-01

    A novel method to form ultrathin, uniform Al2O3 layers on graphene using reversible hydrogen plasma functionalization followed by atomic layer deposition (ALD) is presented. ALD on pristine graphene is known to be a challenge due to the absence of dangling bonds, leading to nonuniform film coverage. We show that hydrogen plasma functionalization of graphene leads to uniform ALD of closed Al2O3 films down to 8 nm in thickness. Hall measurements and Raman spectroscopy reveal that the hydrogen plasma functionalization is reversible upon Al2O3 ALD and subsequent annealing at 400 °C and in this way does not deteriorate the graphene’s charge carrier mobility. This is in contrast with oxygen plasma functionalization, which can lead to a uniform 5 nm thick closed film, but which is not reversible and leads to a reduction of the charge carrier mobility. Density functional theory (DFT) calculations attribute the uniform growth on both H2 and O2 plasma functionalized graphene to the enhanced adsorption of trimethylaluminum (TMA) on these surfaces. A DFT analysis of the possible reaction pathways for TMA precursor adsorption on hydrogenated graphene predicts a binding mechanism that cleans off the hydrogen functionalities from the surface, which explains the observed reversibility of the hydrogen plasma functionalization upon Al2O3 ALD. PMID:28405059

  4. Atomically Thin Heterostructures Based on Single-Layer Tungsten Diselenide and Graphene [Plus Supplemental Information

    DOE PAGES

    Lin, Yu-Chuan; Chang, Chih-Yuan S.; Ghosh, Ram Krishna; ...

    2014-11-10

    Heterogeneous engineering of two-dimensional layered materials, including metallic graphene and semiconducting transition metal dichalcogenides, presents an exciting opportunity to produce highly tunable electronic and optoelectronic systems. We report the direct growth of highly crystalline, monolayer tungsten diselenide (WSe2) on epitaxial graphene (EG). Raman spectroscopy and photoluminescence confirms high-quality WSe2 monolayers; while transmission electron microscopy shows an atomically sharp interface and low energy electron diffraction confirms near perfect orientation between WSe2 and EG. Vertical transport measurements across the WSe2/EG heterostructure provides evidence that a tunnel barrier exists due to the van der Waals gap, and is supported by density functional theorymore » that predicts a 1.6 eV barrier for transport from WSe2 to graphene.« less

  5. Atomically Thin Heterostructures Based on Single-Layer Tungsten Diselenide and Graphene [Plus Supplemental Information

    SciTech Connect

    Lin, Yu-Chuan; Chang, Chih-Yuan S.; Ghosh, Ram Krishna; Li, Jie; Zhu, Hui; Addou, Rafik; Diaconescu, Bogdan; Ohta, Taisuke; Peng, Xin; Lu, Ning; Kim, Moon J.; Robinson, Jeremy T.; Wallace, Robert M.; Mayer, Theresa S.; Datta, Suman; Li, Lain-Jong; Robinson, Joshua A.

    2014-11-10

    Heterogeneous engineering of two-dimensional layered materials, including metallic graphene and semiconducting transition metal dichalcogenides, presents an exciting opportunity to produce highly tunable electronic and optoelectronic systems. We report the direct growth of highly crystalline, monolayer tungsten diselenide (WSe2) on epitaxial graphene (EG). Raman spectroscopy and photoluminescence confirms high-quality WSe2 monolayers; while transmission electron microscopy shows an atomically sharp interface and low energy electron diffraction confirms near perfect orientation between WSe2 and EG. Vertical transport measurements across the WSe2/EG heterostructure provides evidence that a tunnel barrier exists due to the van der Waals gap, and is supported by density functional theory that predicts a 1.6 eV barrier for transport from WSe2 to graphene.

  6. High sensitive formaldehyde graphene gas sensor modified by atomic layer deposition zinc oxide films

    SciTech Connect

    Mu, Haichuan; Zhang, Zhiqiang; Wang, Keke; Xie, Haifen; Zhao, Xiaojing; Liu, Feng

    2014-07-21

    Zinc oxide (ZnO) thin films with various thicknesses were fabricated by Atomic Layer Deposition on Chemical Vapor Deposition grown graphene films and their response to formaldehyde has been investigated. It was found that 0.5 nm ZnO films modified graphene sensors showed high response to formaldehyde with the resistance change up to 52% at the concentration of 9 parts-per-million (ppm) at room temperature. Meanwhile, the detection limit could reach 180 parts-per-billion (ppb) and fast response of 36 s was also obtained. The high sensitivity could be attributed to the combining effect from the highly reactive, top mounted ZnO thin films, and high conductive graphene base network. The dependence of ZnO films surface morphology and its sensitivity on the ZnO films thickness was also investigated.

  7. Sensitivity analysis of single-layer graphene resonators using atomic finite element method

    SciTech Connect

    Lee, Haw-Long; Hsu, Jung-Chang; Lin, Shu-Yu; Chang, Win-Jin

    2013-09-28

    Atomic finite element simulation is applied to study the natural frequency and sensitivity of a single-layer graphene-based resonator with CCCC, SSSS, CFCF, SFSF, and CFCF boundary conditions using the commercial code ANSYS. The fundamental frequencies of the graphene sheet are compared with the results of the previous finite element study. In addition, the sensitivity of the resonator is compared with the early work based on nonlocal elasticity theory. The results of the comparison are very good in all considered cases. The sensitivities of the resonator with different boundary conditions are obtained, and the order based on the boundary condition is CCCC > SSSS > CFCF > SFSF > CFFF. The highest sensitivity is obtained when the attached mass is located at the center of the resonator. This is useful for the design of a highly sensitive graphene-based mass sensor.

  8. Synthesis of atomic layers of hybridized h-BNC by depositing h-BN on graphene via ion beam sputtering

    NASA Astrophysics Data System (ADS)

    Meng, J. H.; Zhang, X. W.; Liu, H.; Yin, Z. G.; Wang, D. G.; Wang, Y.; You, J. B.; Wu, J. L.

    2016-10-01

    We report the deposition of hexagonal boron nitride (h-BN) on graphene by ion beam sputtering deposition. Both graphene domains and films synthesized by chemical vapor deposition were used as substrates. In the case of graphene domains, it was found that the h-BN domains were preferentially grown on the baked Cu surface instead of graphene due to the highly catalytic activity of Cu. On the other hand, the higher ejection energy of sputtered particles leads to the mixing of boron/nitrogen atoms and carbon atoms. Consequently, the h-BNC films consisting of the hybrid atomic layers of h-BN and graphene domains were formed when the graphene films were used as substrates. This work provides a promising and accessible route for the synthesis of hybridized h-BNC material.

  9. Atomically thin heterostructures based on single-layer tungsten diselenide and graphene.

    PubMed

    Lin, Yu-Chuan; Chang, Chih-Yuan S; Ghosh, Ram Krishna; Li, Jie; Zhu, Hui; Addou, Rafik; Diaconescu, Bogdan; Ohta, Taisuke; Peng, Xin; Lu, Ning; Kim, Moon J; Robinson, Jeremy T; Wallace, Robert M; Mayer, Theresa S; Datta, Suman; Li, Lain-Jong; Robinson, Joshua A

    2014-12-10

    Heterogeneous engineering of two-dimensional layered materials, including metallic graphene and semiconducting transition metal dichalcogenides, presents an exciting opportunity to produce highly tunable electronic and optoelectronic systems. In order to engineer pristine layers and their interfaces, epitaxial growth of such heterostructures is required. We report the direct growth of crystalline, monolayer tungsten diselenide (WSe2) on epitaxial graphene (EG) grown from silicon carbide. Raman spectroscopy, photoluminescence, and scanning tunneling microscopy confirm high-quality WSe2 monolayers, whereas transmission electron microscopy shows an atomically sharp interface, and low energy electron diffraction confirms near perfect orientation between WSe2 and EG. Vertical transport measurements across the WSe2/EG heterostructure provides evidence that an additional barrier to carrier transport beyond the expected WSe2/EG band offset exists due to the interlayer gap, which is supported by theoretical local density of states (LDOS) calculations using self-consistent density functional theory (DFT) and nonequilibrium Green's function (NEGF).

  10. Atomic layer deposition of dielectrics on graphene using reversibly physisorbed ozone.

    PubMed

    Jandhyala, Srikar; Mordi, Greg; Lee, Bongki; Lee, Geunsik; Floresca, Carlo; Cha, Pil-Ryung; Ahn, Jinho; Wallace, Robert M; Chabal, Yves J; Kim, Moon J; Colombo, Luigi; Cho, Kyeongjae; Kim, Jiyoung

    2012-03-27

    Integration of graphene field-effect transistors (GFETs) requires the ability to grow or deposit high-quality, ultrathin dielectric insulators on graphene to modulate the channel potential. Here, we study a novel and facile approach based on atomic layer deposition through ozone functionalization to deposit high-κ dielectrics (such as Al(2)O(3)) without breaking vacuum. The underlying mechanisms of functionalization have been studied theoretically using ab initio calculations and experimentally using in situ monitoring of transport properties. It is found that ozone molecules are physisorbed on the surface of graphene, which act as nucleation sites for dielectric deposition. The physisorbed ozone molecules eventually react with the metal precursor, trimethylaluminum to form Al(2)O(3). Additionally, we successfully demonstrate the performance of dual-gated GFETs with Al(2)O(3) of sub-5 nm physical thickness as a gate dielectric. Back-gated GFETs with mobilities of ~19,000 cm(2)/(V·s) are also achieved after Al(2)O(3) deposition. These results indicate that ozone functionalization is a promising pathway to achieve scaled gate dielectrics on graphene without leaving a residual nucleation layer. © 2012 American Chemical Society

  11. Highly Stable and Effective Doping of Graphene by Selective Atomic Layer Deposition of Ruthenium.

    PubMed

    Kim, Minsu; Kim, Ki-Ju; Lee, Seung-Joon; Kim, Hyun-Mi; Cho, Seong-Yong; Kim, Min-Sik; Kim, Soo-Hyun; Kim, Ki-Bum

    2017-01-11

    The sheet resistance of graphene synthesized by chemical vapor deposition is found to be significantly reduced by the selective atomic layer deposition (ALD) of Ru onto defect sites such as wrinkles and grain boundaries. With 200 ALD cycles, the sheet resistance is reduced from ∼500 to <50 Ω/sq, and the p-type carrier density is drastically increased from 10(13) to 10(15) cm(-2). At the same time, the carrier mobility is reduced from ∼670 to less than 100 cm(2) V(-1) s(-1). This doping of graphene proved to be very stable, with the electrical properties remaining unchanged over eight weeks of measurement. Selective deposition of Ru on defect sites also makes it possible to obtain a graphene film that is both highly transparent and electrically conductive (e.g., a sheet resistance of 125 Ω/sq with 92% optical transmittance at 550 nm). Highly doped graphene layers achieved by Ru ALD are therefore expected to provide a viable basis for transparent conducting electrodes.

  12. An alumina stabilized ZnO-graphene anode for lithium ion batteries via atomic layer deposition.

    PubMed

    Yu, Mingpeng; Wang, Aiji; Wang, Yinshu; Li, Chun; Shi, Gaoquan

    2014-10-07

    Atomic layer deposition (ALD) was applied to deposit ZnO on graphene aerogel, and this composite was used as an anode material for lithium ion batteries. This electrode material was further modified by an ultrathin Al2O3 layer via ALD to stabilize its electrochemical stability. These two metal oxides were uniformly immobilized on graphene frameworks, and the Al2O3 coating strongly improved the electrochemical performances of ZnO-graphene aerogel composite anodes. Particularly, the composite with 10 ALD cycles of Al2O3 coating (denoted as ZnO-G-10) exhibited a high initial discharge capacity of 1513 mA h g(-1) and maintained a reversible capacity of 490 mA h g(-1) after 100 cycles at a current density of 100 mA g(-1). Furthermore, the capacity retention rate increased from 70% to 90% in comparison with its uncoated counterpart after 100 cycles. The ZnO-G-10 anode also showed good rate-capability, delivering a discharge capacity of 415 mA h g(-1) at 1000 mA g(-1). The improved electrochemical performance is attributed to the formation of an artificial solid electrolyte interphase layer, stabilizing ZnO and the electrolyte by preventing the aggregation of Zn/ZnO nanograins and the side reaction that would cause the degradation of anodes.

  13. Controllable synthesis of graphene-based titanium dioxide nanocomposites by atomic layer deposition.

    PubMed

    Meng, Xiangbo; Geng, Dongsheng; Liu, Jian; Li, Ruying; Sun, Xueliang

    2011-04-22

    Atomic layer deposition (ALD) was used to synthesize graphene-based metal oxide nanocomposites. This strategy was fulfilled on the preparation of TiO(2)-graphene nanosheet (TiO(2)-GNS) nanocomposites using titanium isopropoxide and water as precursors. The synthesized nanocomposites demonstrated that ALD exhibited many benefits in a controllable means. It was found that the as-deposited TiO(2) was tunable not only in its morphologies but also in its structural phases. As for the former, TiO(2) was transferable from nanoparticles to nanofilms with increased cycles. With regard to the latter, TiO(2) was changeable from amorphous to crystalline phase, and even a mixture of the two with increased growth temperatures (up to 250 °C). The underlying growth mechanisms were discussed and the resultant TiO(2)-GNS nanocomposites have great potentials for many applications, such as photocatalysis, lithium-ion batteries, fuel cells, and sensors.

  14. Controllable synthesis of graphene-based titanium dioxide nanocomposites by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Meng, Xiangbo; Geng, Dongsheng; Liu, Jian; Li, Ruying; Sun, Xueliang

    2011-04-01

    Atomic layer deposition (ALD) was used to synthesize graphene-based metal oxide nanocomposites. This strategy was fulfilled on the preparation of TiO2-graphene nanosheet (TiO2-GNS) nanocomposites using titanium isopropoxide and water as precursors. The synthesized nanocomposites demonstrated that ALD exhibited many benefits in a controllable means. It was found that the as-deposited TiO2 was tunable not only in its morphologies but also in its structural phases. As for the former, TiO2 was transferable from nanoparticles to nanofilms with increased cycles. With regard to the latter, TiO2 was changeable from amorphous to crystalline phase, and even a mixture of the two with increased growth temperatures (up to 250 °C). The underlying growth mechanisms were discussed and the resultant TiO2-GNS nanocomposites have great potentials for many applications, such as photocatalysis, lithium-ion batteries, fuel cells, and sensors.

  15. Tuning the mechanical properties of vertical graphene sheets through atomic layer deposition.

    PubMed

    Davami, Keivan; Jiang, Yijie; Cortes, John; Lin, Chen; Shaygan, Mehrdad; Turner, Kevin T; Bargatin, Igor

    2016-04-15

    We report the fabrication and characterization of graphene nanostructures with mechanical properties that are tuned by conformal deposition of alumina. Vertical graphene (VG) sheets, also called carbon nanowalls (CNWs), were grown on copper foil substrates using a radio-frequency plasma-enhanced chemical vapor deposition (RF-PECVD) technique and conformally coated with different thicknesses of alumina (Al2O3) using atomic layer deposition (ALD). Nanoindentation was used to characterize the mechanical properties of pristine and alumina-coated VG sheets. Results show a significant increase in the effective Young's modulus of the VG sheets with increasing thickness of deposited alumina. Deposition of only a 5 nm thick alumina layer on the VG sheets nearly triples the effective Young's modulus of the VG structures. Both energy absorption and strain recovery were lower in VG sheets coated with alumina than in pure VG sheets (for the same peak force). This may be attributed to the increase in bending stiffness of the VG sheets and the creation of connections between the sheets after ALD deposition. These results demonstrate that the mechanical properties of VG sheets can be tuned over a wide range through conformal atomic layer deposition, facilitating the use of VG sheets in applications where specific mechanical properties are needed.

  16. Tuning the mechanical properties of vertical graphene sheets through atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Davami, Keivan; Jiang, Yijie; Cortes, John; Lin, Chen; Shaygan, Mehrdad; Turner, Kevin T.; Bargatin, Igor

    2016-04-01

    We report the fabrication and characterization of graphene nanostructures with mechanical properties that are tuned by conformal deposition of alumina. Vertical graphene (VG) sheets, also called carbon nanowalls (CNWs), were grown on copper foil substrates using a radio-frequency plasma-enhanced chemical vapor deposition (RF-PECVD) technique and conformally coated with different thicknesses of alumina (Al2O3) using atomic layer deposition (ALD). Nanoindentation was used to characterize the mechanical properties of pristine and alumina-coated VG sheets. Results show a significant increase in the effective Young’s modulus of the VG sheets with increasing thickness of deposited alumina. Deposition of only a 5 nm thick alumina layer on the VG sheets nearly triples the effective Young’s modulus of the VG structures. Both energy absorption and strain recovery were lower in VG sheets coated with alumina than in pure VG sheets (for the same peak force). This may be attributed to the increase in bending stiffness of the VG sheets and the creation of connections between the sheets after ALD deposition. These results demonstrate that the mechanical properties of VG sheets can be tuned over a wide range through conformal atomic layer deposition, facilitating the use of VG sheets in applications where specific mechanical properties are needed.

  17. Epitaxial graphene surface preparation for atomic layer deposition of Al2O3

    NASA Astrophysics Data System (ADS)

    Garces, N. Y.; Wheeler, V. D.; Hite, J. K.; Jernigan, G. G.; Tedesco, J. L.; Nepal, Neeraj; Eddy, C. R.; Gaskill, D. K.

    2011-06-01

    Atomic layer deposition was employed to deposit relatively thick (˜30 nm) aluminum oxide (Al2O3) using trimethylaluminum and triply-distilled H2O precursors onto epitaxial graphene grown on the Si-face of silicon carbide. Ex situ surface conditioning by a simple wet chemistry treatment was used to render the otherwise chemically inert graphene surface more amenable to dielectric deposition. The obtained films show excellent morphology and uniformity over large (˜64 mm2) areas (i.e., the entire sample area), as determined by atomic force microscopy and scanning electron microscopy. X-ray photoelectron spectroscopy revealed a nearly stoichiometric film with reduced impurity content. Moreover, from capacitance-voltage measurements a dielectric constant of ˜7.6 was extracted and a positive Dirac voltage shift of ˜1.0 V was observed. The graphene mobility, as determined by van der Pauw Hall measurements, was not affected by the sequence of surface pretreatment and dielectric deposition.

  18. Density Functional Theory Study of Atomic Layer Deposition of Zinc Oxide on Graphene

    NASA Astrophysics Data System (ADS)

    Ali, Amgad Ahmed; Hashim, Abdul Manaf

    2015-07-01

    The dissociation of zinc ions (Zn2+) from vapor-phase zinc acetylacetonate, Zn(C5H7O2)2, or Zn(acac)2 and its adsorption onto graphene oxide via atomic layer deposition (ALD) were studied using a quantum mechanics approach. Density functional theory (DFT) was used to obtain an approximate solution to the Schrödinger equation. The graphene oxide cluster model was used to represent the surface of the graphene film after pre-oxidation. In this study, the geometries of reactants, transition states, and products were optimized using the B3LYB/6-31G** level of theory or higher. Furthermore, the relative energies of the various intermediates and products in the gas-phase radical mechanism were calculated at the B3LYP/6-311++G** and MP2/6-311 + G(2df,2p) levels of theory. Additionally, a molecular orbital (MO) analysis was performed for the products of the decomposition of the Zn(acac)2 complex to investigate the dissociation of Zn2+ and the subsequent adsorption of H atoms on the C5H7O2 cluster to form acetylacetonate enol. The reaction energies were calculated, and the reaction mechanism was accordingly proposed. A simulation of infrared (IR) properties was performed using the same approach to support the proposed mechanism via a complete explanation of bond forming and breaking during each reaction step.

  19. Density Functional Theory Study of Atomic Layer Deposition of Zinc Oxide on Graphene.

    PubMed

    Ali, Amgad Ahmed; Hashim, Abdul Manaf

    2015-12-01

    The dissociation of zinc ions (Zn(2+)) from vapor-phase zinc acetylacetonate, Zn(C5H7O2)2, or Zn(acac)2 and its adsorption onto graphene oxide via atomic layer deposition (ALD) were studied using a quantum mechanics approach. Density functional theory (DFT) was used to obtain an approximate solution to the Schrödinger equation. The graphene oxide cluster model was used to represent the surface of the graphene film after pre-oxidation. In this study, the geometries of reactants, transition states, and products were optimized using the B3LYB/6-31G** level of theory or higher. Furthermore, the relative energies of the various intermediates and products in the gas-phase radical mechanism were calculated at the B3LYP/6-311++G** and MP2/6-311 + G(2df,2p) levels of theory. Additionally, a molecular orbital (MO) analysis was performed for the products of the decomposition of the Zn(acac)2 complex to investigate the dissociation of Zn(2+) and the subsequent adsorption of H atoms on the C5H7O2 cluster to form acetylacetonate enol. The reaction energies were calculated, and the reaction mechanism was accordingly proposed. A simulation of infrared (IR) properties was performed using the same approach to support the proposed mechanism via a complete explanation of bond forming and breaking during each reaction step.

  20. Property transformation of graphene with Al{sub 2}O{sub 3} films deposited directly by atomic layer deposition

    SciTech Connect

    Zheng, Li; Cao, Duo; Wang, Zhongjian; Xia, Chao; Cheng, Xinhong Yu, Yuehui; Shen, Dashen

    2014-01-13

    Al{sub 2}O{sub 3} films are deposited directly onto graphene by H{sub 2}O-based atomic layer deposition (ALD), and the films are pinhole-free and continuously cover the graphene surface. The growth process of Al{sub 2}O{sub 3} films does not introduce any detective defects in graphene, suppresses the hysteresis effect and tunes the graphene doping to n-type. The self-cleaning of ALD growth process, together with the physically absorbed H{sub 2}O and oxygen-deficient ALD environment consumes OH{sup −} bonds, suppresses the p-doping of graphene, shifts Dirac point to negative gate bias and enhances the electron mobility.

  1. Controlling Edge Morphology in Graphene Layers Using Electron Irradiation: From Sharp Atomic Edges to Coalesced Layers Forming Loops

    SciTech Connect

    Cruz-Silva, E.; Botello-Mendez, A.R.; Barnett, Zachary M; Jia, Xiaoting; Dresselhaus, M; Terrones, H.; Terrones, M.; Sumpter, Bobby G; Meunier, Vincent

    2010-01-01

    Recent experimental reports indicate that Joule heating can atomically sharpen the edges of chemical vapor deposition grown graphitic nanoribbons. The absence or presence of loops between adjacent layers in the annealed materials is the topic of a growing debate that this Letter aims to put to rest. We offer a rationale explaining why loops do form if Joule heating is used alone, and why adjacent nanoribbon layers do not coalesce when Joule heating is applied after high-energy electrons first irradiate the sample. Our work, based on large-scale quantum molecular dynamics and electronic-transport calculations, shows that vacancies on adjacent graphene sheets, created by electron irradiation, inhibit the formation of edge loops.

  2. Seeding Atomic Layer Deposition of High-k Dielectrics on Epitaxial Graphene with Organic Self-assembled Monolayers

    SciTech Connect

    Alaboson, Justice M. P.; Wang, Qing Hua; Emery, Jonathan D.; Lipson, Albert L.; Bedzyk, Michael J.; Elam, Jeffrey W.; Pellin, Michael J.; Hersam, Mark C.

    2011-06-28

    The development of high-performance graphene-based nanoelectronics requires the integration of ultrathin and pinhole-free high-k dielectric films with graphene at the wafer scale. Here, we demonstrate that self-assembled monolayers of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) act as effective organic seeding layers for atomic layer deposition (ALD) of HfO₂ and Al₂O₃ on epitaxial graphene on SiC(0001). The PTCDA is deposited via sublimation in ultrahigh vacuum and shown to be highly ordered with low defect density by molecular-resolution scanning tunneling microscopy. Whereas identical ALD conditions lead to incomplete and rough dielectric deposition on bare graphene, the chemical functionality provided by the PTCDA seeding layer yields highly uniform and conformal films. The morphology and chemistry of the dielectric films are characterized by atomic force microscopy, ellipsometry, cross-sectional scanning electron microscopy, and X-ray photoelectron spectroscopy, while high-resolution X-ray reflectivity measurements indicate that the underlying graphene remains intact following ALD. Using the PTCDA seeding layer, metal-oxide-graphene capacitors fabricated with a 3 nm Al₂O₃ and 10 nm HfO₂ dielectric stack show high capacitance values of ~700 nF/cm² and low leakage currents of ~5 × 10{sup –9} A/cm² at 1 V applied bias. These results demonstrate the viability of sublimated organic self-assembled monolayers as seeding layers for high-k dielectric films in graphene-based nanoelectronics.

  3. Grains and grain boundaries in single-layer graphene atomic patchwork quilts.

    PubMed

    Huang, Pinshane Y; Ruiz-Vargas, Carlos S; van der Zande, Arend M; Whitney, William S; Levendorf, Mark P; Kevek, Joshua W; Garg, Shivank; Alden, Jonathan S; Hustedt, Caleb J; Zhu, Ye; Park, Jiwoong; McEuen, Paul L; Muller, David A

    2011-01-20

    The properties of polycrystalline materials are often dominated by the size of their grains and by the atomic structure of their grain boundaries. These effects should be especially pronounced in two-dimensional materials, where even a line defect can divide and disrupt a crystal. These issues take on practical significance in graphene, which is a hexagonal, two-dimensional crystal of carbon atoms. Single-atom-thick graphene sheets can now be produced by chemical vapour deposition on scales of up to metres, making their polycrystallinity almost unavoidable. Theoretically, graphene grain boundaries are predicted to have distinct electronic, magnetic, chemical and mechanical properties that strongly depend on their atomic arrangement. Yet because of the five-order-of-magnitude size difference between grains and the atoms at grain boundaries, few experiments have fully explored the graphene grain structure. Here we use a combination of old and new transmission electron microscopy techniques to bridge these length scales. Using atomic-resolution imaging, we determine the location and identity of every atom at a grain boundary and find that different grains stitch together predominantly through pentagon-heptagon pairs. Rather than individually imaging the several billion atoms in each grain, we use diffraction-filtered imaging to rapidly map the location, orientation and shape of several hundred grains and boundaries, where only a handful have been previously reported. The resulting images reveal an unexpectedly small and intricate patchwork of grains connected by tilt boundaries. By correlating grain imaging with scanning probe and transport measurements, we show that these grain boundaries severely weaken the mechanical strength of graphene membranes but do not as drastically alter their electrical properties. These techniques open a new window for studies on the structure, properties and control of grains and grain boundaries in graphene and other two

  4. Atomic Layer Deposition of Titanium Oxide on Single-Layer Graphene: An Atomic-Scale Study toward Understanding Nucleation and Growth

    PubMed Central

    2017-01-01

    Controlled synthesis of a hybrid nanomaterial based on titanium oxide and single-layer graphene (SLG) using atomic layer deposition (ALD) is reported here. The morphology and crystallinity of the oxide layer on SLG can be tuned mainly with the deposition temperature, achieving either a uniform amorphous layer at 60 °C or ∼2 nm individual nanocrystals on the SLG at 200 °C after only 20 ALD cycles. A continuous and uniform amorphous layer formed on the SLG after 180 cycles at 60 °C can be converted to a polycrystalline layer containing domains of anatase TiO2 after a postdeposition annealing at 400 °C under vacuum. Using aberration-corrected transmission electron microscopy (AC-TEM), characterization of the structure and chemistry was performed on an atomic scale and provided insight into understanding the nucleation and growth. AC-TEM imaging and electron energy loss spectroscopy revealed that rocksalt TiO nanocrystals were occasionally formed at the early stage of nucleation after only 20 ALD cycles. Understanding and controlling nucleation and growth of the hybrid nanomaterial are crucial to achieving novel properties and enhanced performance for a wide range of applications that exploit the synergetic functionalities of the ensemble. PMID:28356613

  5. Atomic Layer Deposition of Titanium Oxide on Single-Layer Graphene: An Atomic-Scale Study toward Understanding Nucleation and Growth.

    PubMed

    Zhang, Yucheng; Guerra-Nuñez, Carlos; Utke, Ivo; Michler, Johann; Agrawal, Piyush; Rossell, Marta D; Erni, Rolf

    2017-03-14

    Controlled synthesis of a hybrid nanomaterial based on titanium oxide and single-layer graphene (SLG) using atomic layer deposition (ALD) is reported here. The morphology and crystallinity of the oxide layer on SLG can be tuned mainly with the deposition temperature, achieving either a uniform amorphous layer at 60 °C or ∼2 nm individual nanocrystals on the SLG at 200 °C after only 20 ALD cycles. A continuous and uniform amorphous layer formed on the SLG after 180 cycles at 60 °C can be converted to a polycrystalline layer containing domains of anatase TiO2 after a postdeposition annealing at 400 °C under vacuum. Using aberration-corrected transmission electron microscopy (AC-TEM), characterization of the structure and chemistry was performed on an atomic scale and provided insight into understanding the nucleation and growth. AC-TEM imaging and electron energy loss spectroscopy revealed that rocksalt TiO nanocrystals were occasionally formed at the early stage of nucleation after only 20 ALD cycles. Understanding and controlling nucleation and growth of the hybrid nanomaterial are crucial to achieving novel properties and enhanced performance for a wide range of applications that exploit the synergetic functionalities of the ensemble.

  6. A non-destructive n-doping method for graphene with precise control of electronic properties via atomic layer deposition.

    PubMed

    Han, Kyu Seok; Kalode, Pranav Y; Koo Lee, Yong-Eun; Kim, Hongbum; Lee, Lynn; Sung, Myung Mo

    2016-03-07

    Graphene applications require high precision control of the Fermi level and carrier concentration via a nondestructive doping method. Here, we develop an effective n-doping technique using atomic layer deposition (ALD) of ZnO thin films on graphene through a reactive molecular layer. This ALD doping method is nondestructive, simple, and precise. The ZnO thin films on graphene are uniform, conformal, of good quality with a low density of pinholes, and finely tunable in thickness with 1 Å resolution. We demonstrate graphene transistor control in terms of the Dirac point, carrier density, and doping state as a function of the ZnO thickness. Moreover, ZnO functions as an effective thin-film barrier against air-borne water and oxygen on the graphene, resulting in extraordinary stability in air for graphene devices. ZnO ALD was also applied to other two-dimensional materials including MoS2 and WSe2, which substantially enhanced electron mobility.

  7. Atomic layer deposition of amorphous TiO2 on graphene as an anode for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Ban, Chunmei; Xie, Ming; Sun, Xiang; Travis, Jonathan J.; Wang, Gongkai; Sun, Hongtao; Dillon, Anne C.; Lian, Jie; George, Steven M.

    2013-10-01

    Atomic layer deposition (ALD) was used to deposit TiO2 anode material on high surface area graphene (reduced graphene oxide) sheets for Li-ion batteries. An Al2O3 ALD ultrathin layer was used as an adhesion layer for conformal deposition of the TiO2 ALD films at 120 ° C onto the conducting graphene sheets. The TiO2 ALD films on the Al2O3 ALD adhesion layer were nearly amorphous and conformal to the graphene sheets. These nanoscale TiO2 coatings minimized the effect of the low diffusion coefficient of lithium ions in bulk TiO2. The TiO2 ALD films exhibited stable capacities of ˜120 mAh g-1 and ˜100 mAh g-1 at high cycling rates of 1 A g-1 and 2 A g-1, respectively. The TiO2 ALD films also displayed excellent cycling stability with ˜95% of the initial capacity remaining after 500 cycles. These results illustrate that ALD can provide a useful method to deposit electrode materials on high surface area substrates for Li-ion batteries.

  8. Flexible integrated circuits and multifunctional electronics based on single atomic layers of MoS2 and graphene.

    PubMed

    Amani, Matin; Burke, Robert A; Proie, Robert M; Dubey, Madan

    2015-03-20

    Two-dimensional materials, such as graphene and its analogues, have been investigated by numerous researchers for high performance flexible and conformal electronic systems, because they offer the ultimate level of thickness scaling, atomically smooth surfaces and high crystalline quality. Here, we use layer-by-layer transfer of large area molybdenum disulphide (MoS2) and graphene grown by chemical vapor deposition (CVD) to demonstrate electronics on flexible polyimide (PI) substrates. On the same PI substrate, we are able to simultaneously fabricate MoS2 based logic, non-volatile memory cells with graphene floating gates, photo-detectors and MoS2 transistors with tunable source and drain contacts. We are also able to demonstrate that these flexible heterostructure devices have very high electronic performance, comparable to four point measurements taken on SiO2 substrates, with on/off ratios >10(7) and field effect mobilities as high as 16.4 cm(2) V(-1) s(-1). Additionally, the heterojunctions show high optoelectronic sensitivity and were operated as photodetectors with responsivities over 30 A W(-1). Through local gating of the individual graphene/MoS2 contacts, we are able to tune the contact resistance over the range of 322-1210 Ω mm for each contact, by modulating the graphene work function. This leads to devices with tunable and multifunctional performance that can be implemented in a conformable platform.

  9. Flexible integrated circuits and multifunctional electronics based on single atomic layers of MoS2 and graphene

    NASA Astrophysics Data System (ADS)

    Amani, Matin; Burke, Robert A.; Proie, Robert M.; Dubey, Madan

    2015-03-01

    Two-dimensional materials, such as graphene and its analogues, have been investigated by numerous researchers for high performance flexible and conformal electronic systems, because they offer the ultimate level of thickness scaling, atomically smooth surfaces and high crystalline quality. Here, we use layer-by-layer transfer of large area molybdenum disulphide (MoS2) and graphene grown by chemical vapor deposition (CVD) to demonstrate electronics on flexible polyimide (PI) substrates. On the same PI substrate, we are able to simultaneously fabricate MoS2 based logic, non-volatile memory cells with graphene floating gates, photo-detectors and MoS2 transistors with tunable source and drain contacts. We are also able to demonstrate that these flexible heterostructure devices have very high electronic performance, comparable to four point measurements taken on SiO2 substrates, with on/off ratios >107 and field effect mobilities as high as 16.4 cm2 V-1 s-1. Additionally, the heterojunctions show high optoelectronic sensitivity and were operated as photodetectors with responsivities over 30 A W-1. Through local gating of the individual graphene/MoS2 contacts, we are able to tune the contact resistance over the range of 322-1210 Ω mm for each contact, by modulating the graphene work function. This leads to devices with tunable and multifunctional performance that can be implemented in a conformable platform.

  10. Atomically Thin Layers of Graphene and Hexagonal Boron Nitride Made by Solvent Exfoliation of Their Phosphoric Acid Intercalation Compounds.

    PubMed

    Kovtyukhova, Nina I; Perea-López, Nestor; Terrones, Mauricio; Mallouk, Thomas E

    2017-07-25

    The development of scalable and reliable techniques for the production of the atomically thin layers of graphene and hexagonal boron nitride (h-BN) in bulk quantities could make these materials a powerful platform for devices and composites that impact a wide variety of technologies (Nature 2012, 490, 192-200). To date a number of practical exfoliation methods have been reported that are based on sonicating or stirring powdered graphite or h-BN in common solvents. However, the products of these experiments consist mainly of few-layer sheets and contain only a small fraction of monolayers. A possible reason for this is that splitting the crystals into monolayers starts from solvent intercalation, which must overcome the substantial interlayer cohesive energy (120-720 mJ/m(2)) of the van der Waals solids. Here we show that the yield of the atomically thin layers can be increased to near unity when stage-1 intercalation compounds of phosphoric acid are used as starting materials. The exfoliation to predominantly monolayers was achieved by stirring them in medium polarity organic solvents that can form hydrogen bonds. The exfoliation process does not disrupt the sp(2) π-system of graphene and is gentle enough to allow the preparation of graphene and h-BN monolayers that are tens of microns in their lateral dimensions.

  11. Topography, complex refractive index, and conductivity of graphene layers measured by correlation of optical interference contrast, atomic force, and back scattered electron microscopy

    SciTech Connect

    Vaupel, Matthias Dutschke, Anke; Wurstbauer, Ulrich; Pasupathy, Abhay; Hitzel, Frank

    2013-11-14

    The optical phase shift by reflection on graphene is measured by interference contrast microscopy. The height profile across graphene layers on 300 nm thick SiO{sub 2} on silicon is derived from the phase profile. The complex refractive index and conductivity of graphene layers on silicon with 2 nm thin SiO{sub 2} are evaluated from a phase profile, while the height profile of the layers is measured by atomic force microscopy. It is observed that the conductivity measured on thin SiO{sub 2} is significantly greater than on thick SiO{sub 2}. Back scattered electron contrast of graphene layers is correlated to the height of graphene layers.

  12. Atom-scale covalent electrochemical modification of single-layer graphene on SiC substrates by diaryliodonium salts

    SciTech Connect

    Gearba, Raluca I.; Mueller, Kory M.; Veneman, Peter A.; Holliday, Bradley J.; Chan, Calvin K.; Stevenson, Keith J.

    2015-05-09

    Owing to its high conductivity, graphene holds promise as an electrode for energy devices such as batteries and photovoltaics. However, to this end, the work function and doping levels in graphene need to be precisely tuned. One promising route for modifying graphene’s electronic properties is via controlled covalent electrochemical grafting of molecules. We show that by employing diaryliodonium salts instead of the commonly used diazonium salts, spontaneous functionalization is avoided. This then allows for precise tuning of the grafting density. Moreover, by employing bis(4-nitrophenyl)iodonium(III) tetrafluoroborate (DNP) salt calibration curves, the surface functionalization density (coverage) of glassy carbon was controlled using cyclic voltammetry in varying salt concentrations. These electro-grafting conditions and calibration curves translated directly over to modifying single layer epitaxial graphene substrates (grown on insulating 6H-SiC (0 0 0 1)). In addition to quantifying the functionalization densities using electrochemical methods, samples with low grafting densities were characterized by low-temperature scanning tunneling microscopy (LT-STM). We show that the use of buffer-layer free graphene substrates is required for clear observation of the nitrophenyl modifications. Furthermore, atomically-resolved STM images of single site modifications were obtained, showing no preferential grafting at defect sites or SiC step edges as supposed previously in the literature. Most of the grafts exhibit threefold symmetry, but occasional extended modifications (larger than 4 nm) were observed as well.

  13. Atom-scale covalent electrochemical modification of single-layer graphene on SiC substrates by diaryliodonium salts

    DOE PAGES

    Gearba, Raluca I.; Mueller, Kory M.; Veneman, Peter A.; ...

    2015-05-09

    Owing to its high conductivity, graphene holds promise as an electrode for energy devices such as batteries and photovoltaics. However, to this end, the work function and doping levels in graphene need to be precisely tuned. One promising route for modifying graphene’s electronic properties is via controlled covalent electrochemical grafting of molecules. We show that by employing diaryliodonium salts instead of the commonly used diazonium salts, spontaneous functionalization is avoided. This then allows for precise tuning of the grafting density. Moreover, by employing bis(4-nitrophenyl)iodonium(III) tetrafluoroborate (DNP) salt calibration curves, the surface functionalization density (coverage) of glassy carbon was controlled usingmore » cyclic voltammetry in varying salt concentrations. These electro-grafting conditions and calibration curves translated directly over to modifying single layer epitaxial graphene substrates (grown on insulating 6H-SiC (0 0 0 1)). In addition to quantifying the functionalization densities using electrochemical methods, samples with low grafting densities were characterized by low-temperature scanning tunneling microscopy (LT-STM). We show that the use of buffer-layer free graphene substrates is required for clear observation of the nitrophenyl modifications. Furthermore, atomically-resolved STM images of single site modifications were obtained, showing no preferential grafting at defect sites or SiC step edges as supposed previously in the literature. Most of the grafts exhibit threefold symmetry, but occasional extended modifications (larger than 4 nm) were observed as well.« less

  14. Atomic-scale friction behavior of layered graphene and graphene-like BN materials modulated by interaction potential

    NASA Astrophysics Data System (ADS)

    Zhuang, Chunqiang; Liu, Lei

    2017-08-01

    The understanding of fundamental issues related to friction at the atomic scale remains a great challenge due to the large difference between macroscopic and microscopic frictional behaviors. Here based on first-principles calculations, the applicability of macroscopic friction laws to the atomic scale is studied. The underlying mechanism that governs friction behavior is also explored. A completely new perspective of understanding the friction at the atomic scale is presented according to the observation of the applicability of friction law at the atomic scale and the variations of interaction potential induced by the number of layer and normal load.

  15. Sub-nanometer atomic layer deposition for spintronics in magnetic tunnel junctions based on graphene spin-filtering membranes.

    PubMed

    Martin, Marie-Blandine; Dlubak, Bruno; Weatherup, Robert S; Yang, Heejun; Deranlot, Cyrile; Bouzehouane, Karim; Petroff, Frédéric; Anane, Abdelmadjid; Hofmann, Stephan; Robertson, John; Fert, Albert; Seneor, Pierre

    2014-08-26

    We report on the successful integration of low-cost, conformal, and versatile atomic layer deposited (ALD) dielectric in Ni–Al2O3–Co magnetic tunnel junctions (MTJs) where the Ni is coated with a spin-filtering graphene membrane. The ALD tunnel barriers, as thin as 0.6 nm, are grown layer-by-layer in a simple, low-vacuum, ozone-based process, which yields high-quality electron-transport barriers as revealed by tunneling characterization. Even under these relaxed conditions, including air exposure of the interfaces, a significant tunnel magnetoresistance is measured highlighting the robustness of the process. The spin-filtering effect of graphene is enhanced, leading to an almost fully inversed spin polarization for the Ni electrode of −42%. This unlocks the potential of ALD for spintronics with conformal, layer-by-layer control of tunnel barriers in magnetic tunnel junctions toward low-cost fabrication and down-scaling of tunnel resistances.

  16. Chemistry and physics of a single atomic layer: strategies and challenges for functionalization of graphene and graphene-based materials.

    PubMed

    Yan, Liang; Zheng, Yue Bing; Zhao, Feng; Li, Shoujian; Gao, Xingfa; Xu, Bingqian; Weiss, Paul S; Zhao, Yuliang

    2012-01-07

    Graphene has attracted great interest for its superior physical, chemical, mechanical, and electrical properties that enable a wide range of applications from electronics to nanoelectromechanical systems. Functionalization is among the significant vectors that drive graphene towards technological applications. While the physical properties of graphene have been at the center of attention, we still lack the knowledge framework for targeted graphene functionalization. In this critical review, we describe some of the important chemical and physical processes for graphene functionalization. We also identify six major challenges in graphene research and give perspectives and practical strategies for both fundamental studies and applications of graphene (315 references).

  17. Atomic layer deposition of Y2O3 on h-BN for a gate stack in graphene FETs.

    PubMed

    Takahashi, N; Watanabe, K; Taniguchi, T; Nagashio, K

    2015-05-01

    The combination of h-BN and high-k dielectrics is required for a top gate insulator in miniaturized graphene field-effect transistors because of the low dielectric constant of h-BN. We investigated the deposition of Y(2)O(3) on h-BN using atomic layer deposition. The deposition of Y(2)O(3) on h-BN was confirmed without any buffer layer. An increase in the deposition temperature reduced the surface coverage. The deposition mechanism could be explained by the competition between the desorption and adsorption of the Y precursor on h-BN due to the polarization. Although a full surface coverage was difficult to achieve, the use of an oxidized metal seeding layer on h-BN resulted in a full surface coverage.

  18. Bottom-gate coplanar graphene transistors with enhanced graphene adhesion on atomic layer deposition Al{sub 2}O{sub 3}

    SciTech Connect

    Park, Dong-Wook; Mikael, Solomon; Chang, Tzu-Hsuan; Ma, Zhenqiang; Gong, Shaoqin

    2015-03-09

    A graphene transistor with a bottom-gate coplanar structure and an atomic layer deposition (ALD) aluminum oxide (Al{sub 2}O{sub 3}) gate dielectric is demonstrated. Wetting properties of ALD Al{sub 2}O{sub 3} under different deposition conditions are investigated by measuring the surface contact angle. It is observed that the relatively hydrophobic surface is suitable for adhesion between graphene and ALD Al{sub 2}O{sub 3}. To achieve hydrophobic surface of ALD Al{sub 2}O{sub 3}, a methyl group (CH{sub 3})-terminated deposition method has been developed and compared with a hydroxyl group (OH)-terminated deposition. Based on this approach, bottom-gate coplanar graphene field-effect transistors are fabricated and characterized. A post-thermal annealing process improves the performance of the transistors by enhancing the contacts between the source/drain metal and graphene. The fabricated transistor shows an I{sub on}/I{sub off} ratio, maximum transconductance, and field-effect mobility of 4.04, 20.1 μS at V{sub D} = 0.1 V, and 249.5 cm{sup 2}/V·s, respectively.

  19. Oxidation resistance of reactive atoms in graphene.

    PubMed

    Chisholm, Matthew F; Duscher, Gerd; Windl, Wolfgang

    2012-09-12

    We have found that reactive elements that are normally oxidized at room temperature are present as individual atoms or clusters on and in graphene. Oxygen is present in these samples but it is only detected in the thicker amorphous carbon layers present in the graphene specimens we have examined. However, we have seen no evidence that oxygen reacts with the impurity atoms and small clusters of these normally reactive elements when they are incorporated in the graphene layers. First principles calculations suggest that the oxidation resistance is due to kinetic effects such as preferential bonding of oxygen to nonincorporated atoms and H passivation. The observed oxidation resistance of reactive atoms in graphene may allow the use of these incorporated metals in catalytic applications. It also opens the possibility of designing and producing electronic, opto-electronic, and magnetic devices based on these normally reactive atoms.

  20. Oxidation Resistance of Reactive Atoms in Graphene

    SciTech Connect

    Chisholm, Matthew F; Duscher, Gerd; Windl, Wolfgang

    2012-01-01

    We have found that reactive elements that are normally oxidized at room temperature are present as individual atoms or clusters on and in graphene. Oxygen is present in these samples but it is only detected in the thicker amorphous carbon layers present in the graphene specimens we have examined. However, we have seen no evidence that oxygen reacts with the impurity atoms and small clusters of these normally reactive elements when they are incorporated in the graphene layers. First principles calculations suggest that the oxidation resistance is due to kinetic effects such as preferential bonding of oxygen to nonincorporated atoms and H passivation. The observed oxidation resistance of reactive atoms in graphene may allow the use of these incorporated metals in catalytic applications. It also opens the possibility of designing and producing electronic, opto-electronic, and magnetic devices based on these normally reactive atoms.

  1. Discrete Atomic Layers at the Molecular Level

    NASA Astrophysics Data System (ADS)

    Yorimitsu, Hideki; Bhanuchandra, M.

    2015-12-01

    In this review, we deal with the syntheses of large discrete atomic layers at the molecular level. Spectroscopic measurements as well as X-ray crystallographic analyses lead to unambiguous characterizations of these layers. The molecular atomic layers can be considered to be parts of graphenes and related atomic layers, thereby helping to understand such indefinitely huge atomic layers or serving as seeds for the controlled synthesis of nanocarbons.

  2. Thickness scaling of atomic-layer-deposited HfO2 films and their application to wafer-scale graphene tunnelling transistors

    PubMed Central

    Jeong, Seong-Jun; Gu, Yeahyun; Heo, Jinseong; Yang, Jaehyun; Lee, Chang-Seok; Lee, Min-Hyun; Lee, Yunseong; Kim, Hyoungsub; Park, Seongjun; Hwang, Sungwoo

    2016-01-01

    The downscaling of the capacitance equivalent oxide thickness (CET) of a gate dielectric film with a high dielectric constant, such as atomic layer deposited (ALD) HfO2, is a fundamental challenge in achieving high-performance graphene-based transistors with a low gate leakage current. Here, we assess the application of various surface modification methods on monolayer graphene sheets grown by chemical vapour deposition to obtain a uniform and pinhole-free ALD HfO2 film with a substantially small CET at a wafer scale. The effects of various surface modifications, such as N-methyl-2-pyrrolidone treatment and introduction of sputtered ZnO and e-beam-evaporated Hf seed layers on monolayer graphene, and the subsequent HfO2 film formation under identical ALD process parameters were systematically evaluated. The nucleation layer provided by the Hf seed layer (which transforms to the HfO2 layer during ALD) resulted in the uniform and conformal deposition of the HfO2 film without damaging the graphene, which is suitable for downscaling the CET. After verifying the feasibility of scaling down the HfO2 thickness to achieve a CET of ~1.5 nm from an array of top-gated metal-oxide-graphene field-effect transistors, we fabricated graphene heterojunction tunnelling transistors with a record-low subthreshold swing value of <60 mV/dec on an 8″ glass wafer. PMID:26861833

  3. Thickness scaling of atomic-layer-deposited HfO2 films and their application to wafer-scale graphene tunnelling transistors

    NASA Astrophysics Data System (ADS)

    Jeong, Seong-Jun; Gu, Yeahyun; Heo, Jinseong; Yang, Jaehyun; Lee, Chang-Seok; Lee, Min-Hyun; Lee, Yunseong; Kim, Hyoungsub; Park, Seongjun; Hwang, Sungwoo

    2016-02-01

    The downscaling of the capacitance equivalent oxide thickness (CET) of a gate dielectric film with a high dielectric constant, such as atomic layer deposited (ALD) HfO2, is a fundamental challenge in achieving high-performance graphene-based transistors with a low gate leakage current. Here, we assess the application of various surface modification methods on monolayer graphene sheets grown by chemical vapour deposition to obtain a uniform and pinhole-free ALD HfO2 film with a substantially small CET at a wafer scale. The effects of various surface modifications, such as N-methyl-2-pyrrolidone treatment and introduction of sputtered ZnO and e-beam-evaporated Hf seed layers on monolayer graphene, and the subsequent HfO2 film formation under identical ALD process parameters were systematically evaluated. The nucleation layer provided by the Hf seed layer (which transforms to the HfO2 layer during ALD) resulted in the uniform and conformal deposition of the HfO2 film without damaging the graphene, which is suitable for downscaling the CET. After verifying the feasibility of scaling down the HfO2 thickness to achieve a CET of ~1.5 nm from an array of top-gated metal-oxide-graphene field-effect transistors, we fabricated graphene heterojunction tunnelling transistors with a record-low subthreshold swing value of <60 mV/dec on an 8″ glass wafer.

  4. Atomic-Scale Peeling of Graphene

    NASA Astrophysics Data System (ADS)

    Ishikawa, Makoto; Ichikawa, Masaya; Okamoto, Hideki; Itamura, Noriaki; Sasaki, Naruo; Miura, Kouji

    2012-06-01

    We report the atomic-scale peeling of a single-layer graphene on a graphite substrate, in which stick-slip sliding of the single-layer graphene occurs at the atomic scale while maintaining AB-stacking registry with the graphite substrate. The peeling force curve clearly exhibits a transition from surface-contact to line-contact between the graphene and graphite surfaces. The amplitude of the peeling force depends on the lattice orientation of the surface, which is affected by the sliding force at the interface between the graphene and graphite surfaces. This study of peeling at the atomic scale will clarify the relationship among peeling, friction, adhesion, and superlubricity.

  5. Quantitative annular dark-field imaging of single-layer graphene-II: atomic-resolution image contrast.

    PubMed

    Yamashita, Shunsuke; Koshiya, Shogo; Nagai, Takuro; Kikkawa, Jun; Ishizuka, Kazuo; Kimoto, Koji

    2015-12-01

    We have investigated how accurately atomic-resolution annular dark-field (ADF) images match between experiments and simulations to conduct more reliable crystal structure analyses. Quantitative ADF imaging, in which the ADF intensity at each pixel represents the fraction of the incident probe current, allows us to perform direct comparisons with simulations without the use of fitting parameters. Although the conventional comparison suffers from experimental uncertainties such as an amorphous surface layer and specimen thickness, in this study we eliminated such uncertainties by using a single-layer graphene as a specimen. Furthermore, to reduce image distortion and shot noises in experimental images, multiple acquisitions with drift correction were performed, and the atomic ADF contrast was quantitatively acquired. To reproduce the experimental ADF contrast, we used three distribution functions as the effective source distribution in simulations. The optimum distribution function and its full-width at half-maximum were evaluated by measuring the residuals between the experimental and simulated images. It was found that the experimental images could be explained well by a linear combination of a Gaussian function and a Lorentzian function with a longer tail than the Gaussian function.

  6. Dispersion coefficients for the interactions of the alkali-metal and alkaline-earth-metal ions and inert-gas atoms with a graphene layer

    NASA Astrophysics Data System (ADS)

    Kaur, Kiranpreet; Arora, Bindiya; Sahoo, B. K.

    2015-09-01

    Largely motivated by a number of applications, the van der Waals dispersion coefficients C3 of the alkali-metal ions Li+,Na+,K+, and Rb+, the alkaline-earth-metal ions Ca+,Sr+,Ba+, and Ra+, and the inert-gas atoms He, Ne, Ar, and Kr with a graphene layer are determined precisely within the framework of the Dirac model. For these calculations, we evaluate the dynamic polarizabilities of the above atomic systems very accurately by evaluating the transition matrix elements employing relativistic many-body methods and using the experimental values of the excitation energies. The dispersion coefficients are given as functions of the separation distance of an atomic system from the graphene layer and the ambiance temperature during the interactions. For easy extraction of these coefficients, we give a logistic fit to the functional forms of the dispersion coefficients in terms of the separation distances at room temperature.

  7. Dual-protection of a graphene-sulfur composite by a compact graphene skin and an atomic layer deposited oxide coating for a lithium-sulfur battery.

    PubMed

    Yu, Mingpeng; Wang, Aiji; Tian, Fuyang; Song, Hongquan; Wang, Yinshu; Li, Chun; Hong, Jong-Dal; Shi, Gaoquan

    2015-03-12

    A reduced graphene oxide (rGO)-sulfur composite aerogel with a compact self-assembled rGO skin was further modified by an atomic layer deposition (ALD) of ZnO or MgO layer, and used as a free-standing electrode material of a lithium-sulfur (Li-S) battery. The rGO skin and ALD-oxide coating worked as natural and artificial barriers to constrain the polysulfides within the cathode region. As a result, the Li-S battery based on this electrode material exhibited superior cycling stability, good rate capability and high coulombic efficiency. Furthermore, ALD-ZnO coating was tested for performance improvement and found to be more effective than ALD-MgO coating. The ZnO modified G-S electrode with 55 wt% sulfur loading delivered a maximum discharge capacity of 998 mA h g(-1) at a current density of 0.2 C. A high capacity of 846 mA h g(-1) was achieved after charging/discharging for 100 cycles with a coulombic efficiency of over 92%. In the case of using LiNO3 as a shuttle inhibitor, this electrode showed an initial discharge capacity of 796 mA h g(-1) and a capacity retention of 81% after 250 cycles at a current density of 1 C with an average coulombic efficiency higher than 99.7%.

  8. Atomic structure of graphene on SiO2.

    PubMed

    Ishigami, Masa; Chen, J H; Cullen, W G; Fuhrer, M S; Williams, E D

    2007-06-01

    We employ scanning probe microscopy to reveal atomic structures and nanoscale morphology of graphene-based electronic devices (i.e., a graphene sheet supported by an insulating silicon dioxide substrate) for the first time. Atomic resolution scanning tunneling microscopy images reveal the presence of a strong spatially dependent perturbation, which breaks the hexagonal lattice symmetry of the graphitic lattice. Structural corrugations of the graphene sheet partially conform to the underlying silicon oxide substrate. These effects are obscured or modified on graphene devices processed with normal lithographic methods, as they are covered with a layer of photoresist residue. We enable our experiments by a novel cleaning process to produce atomically clean graphene sheets.

  9. Iron oxide/aluminum/graphene energetic nanocomposites synthesized by atomic layer deposition: Enhanced energy release and reduced electrostatic ignition hazard

    NASA Astrophysics Data System (ADS)

    Yan, Ning; Qin, Lijun; Hao, Haixia; Hui, Longfei; Zhao, Fengqi; Feng, Hao

    2017-06-01

    Nanocomposites consisting of iron oxide (Fe2O3) and nano-sized aluminum (Al), possessing outstanding exothermic redox reaction characteristics, are highly promising nanothermite materials. However, the reactant diffusion inhibited in the solid state system makes the fast and complete energy release very challenging. In this work, Al nanoparticles anchored on graphene oxide (GO/Al) was initially prepared by a solution assembly approach. Fe2O3 was deposited on GO/Al substrates by atomic layer deposition (ALD). Simultaneously thermal reduction of GO occurs, resulting in rGO/Al@Fe2O3 energetic composites. Differential scanning calorimetry (DSC) analysis reveals that rGO/Al@Fe2O3 composite containing 4.8 wt% of rGO exhibits a 50% increase of the energy release compared to the Al@Fe2O3 nanothermite synthesized by ALD, and an increase of about 130% compared to a random mixture of rGO/Al/Fe2O3 nanoparticles. The enhanced energy release of rGO/Al@Fe2O3 is attributed to the improved spatial distribution as well as the increased interfacial intimacy between the oxidizer and the fuel. Moreover, the rGO/Al@Fe2O3 composite with an rGO content of 9.6 wt% exhibits significantly reduced electrostatic discharge sensitivity. These findings may inspire potential pathways for engineering energetic nanocomposites with enhanced energy release and improved safety characteristics.

  10. Molecular memory with atomically smooth graphene contacts

    PubMed Central

    2013-01-01

    We report the use of bilayer graphene as an atomically smooth contact for nanoscale devices. A two-terminal bucky-ball (C60) based molecular memory is fabricated with bilayer graphene as a contact on the polycrystalline nickel electrode. Graphene provides an atomically smooth covering over an otherwise rough metal surface. The use of graphene additionally prohibits the electromigration of nickel into the C60 layer. The devices exhibit a low-resistance state in the first sweep cycle and irreversibly switch to a high-resistance state at 0.8 to 1.2 V bias. In the subsequent cycles, the devices retain the high-resistance state, thus making it write-once read-many memory. PMID:24225345

  11. Epitaxial Graphene Surface Preparation for Atomic Layer Deposition of Al2O3

    DTIC Science & Technology

    2011-06-01

    j dielectrics such as Al2O3 , HfO2, Ta2O5, and TiO2 , are important for the realization of graphene-based top-gated electronic devices including field... ALD pulse sequencing of NO2-trimethylaluminum (TMA); 16 oxidation of electron beam evaporated metallic Al, Hf, Ti, Ta;17,18 and spin- coating of a... ALD of Al2O3 films in promoting uni- form, high quality oxide deposition. Initial treatments resulted in partial coverage, while the optimized treatment

  12. Dual-protection of a graphene-sulfur composite by a compact graphene skin and an atomic layer deposited oxide coating for a lithium-sulfur battery

    NASA Astrophysics Data System (ADS)

    Yu, Mingpeng; Wang, Aiji; Tian, Fuyang; Song, Hongquan; Wang, Yinshu; Li, Chun; Hong, Jong-Dal; Shi, Gaoquan

    2015-03-01

    A reduced graphene oxide (rGO)-sulfur composite aerogel with a compact self-assembled rGO skin was further modified by an atomic layer deposition (ALD) of ZnO or MgO layer, and used as a free-standing electrode material of a lithium-sulfur (Li-S) battery. The rGO skin and ALD-oxide coating worked as natural and artificial barriers to constrain the polysulfides within the cathode region. As a result, the Li-S battery based on this electrode material exhibited superior cycling stability, good rate capability and high coulombic efficiency. Furthermore, ALD-ZnO coating was tested for performance improvement and found to be more effective than ALD-MgO coating. The ZnO modified G-S electrode with 55 wt% sulfur loading delivered a maximum discharge capacity of 998 mA h g-1 at a current density of 0.2 C. A high capacity of 846 mA h g-1 was achieved after charging/discharging for 100 cycles with a coulombic efficiency of over 92%. In the case of using LiNO3 as a shuttle inhibitor, this electrode showed an initial discharge capacity of 796 mA h g-1 and a capacity retention of 81% after 250 cycles at a current density of 1 C with an average coulombic efficiency higher than 99.7%.A reduced graphene oxide (rGO)-sulfur composite aerogel with a compact self-assembled rGO skin was further modified by an atomic layer deposition (ALD) of ZnO or MgO layer, and used as a free-standing electrode material of a lithium-sulfur (Li-S) battery. The rGO skin and ALD-oxide coating worked as natural and artificial barriers to constrain the polysulfides within the cathode region. As a result, the Li-S battery based on this electrode material exhibited superior cycling stability, good rate capability and high coulombic efficiency. Furthermore, ALD-ZnO coating was tested for performance improvement and found to be more effective than ALD-MgO coating. The ZnO modified G-S electrode with 55 wt% sulfur loading delivered a maximum discharge capacity of 998 mA h g-1 at a current density of 0.2 C. A

  13. Atomic Layer Deposition of Hafnium(IV) Oxide on Graphene Oxide: Probing Interfacial Chemistry and Nucleation by using X-ray Absorption and Photoelectron Spectroscopies.

    PubMed

    Alivio, Theodore E G; De Jesus, Luis R; Dennis, Robert V; Jia, Ye; Jaye, Cherno; Fischer, Daniel A; Singisetti, Uttam; Banerjee, Sarbajit

    2015-07-27

    Interfacing graphene with metal oxides is of considerable technological importance for modulating carrier density through electrostatic gating as well as for the design of earth-abundant electrocatalysts. Herein, we probe the early stages of the atomic layer deposition (ALD) of HfO2 on graphene oxide using a combination of C and O K-edge near-edge X-ray absorption fine structure spectroscopies and X-ray photoelectron spectroscopy. Dosing with water is observed to promote defunctionalization of graphene oxide as a result of the reaction between water and hydroxyl/epoxide species, which yields carbonyl groups that further react with migratory epoxide species to release CO2 . The carboxylates formed by the reaction of carbonyl and epoxide species facilitate binding of Hf precursors to graphene oxide surfaces. The ALD process is accompanied by recovery of the π-conjugated framework of graphene. The delineation of binding modes provides a means to rationally assemble 2D heterostructures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Tailoring graphene layer-to-layer growth

    NASA Astrophysics Data System (ADS)

    Li, Yongtao; Wu, Bin; Guo, Wei; Wang, Lifeng; Li, Jingbo; Liu, Yunqi

    2017-06-01

    A layered material grown between a substrate and the upper layer involves complex interactions and a confined reaction space, representing an unusual growth mode. Here, we show multi-layer graphene domains grown on liquid or solid Cu by the chemical vapor deposition method via this ‘double-substrate’ mode. We demonstrate the interlayer-induced coupling effect on the twist angle in bi- and multi-layer graphene. We discover dramatic growth disunity for different graphene layers, which is explained by the ideas of a chemical ‘gate’ and a material transport process within a confined space. These key results lead to a consistent framework for understanding the dynamic evolution of multi-layered graphene flakes and tailoring the layer-to-layer growth for practical applications.

  15. Anomalous Insulator-Metal Transition in Boron Nitride-Graphene Hybrid Atomic Layers

    DTIC Science & Technology

    2012-08-13

    locally centered atomic or- bital (LCAO) basis set, and the Perdew-Burke-Ernzerhof (PBE) exchange- correlation functional.36 The occupation of the Kohn-Sham...Stausholm-Møller, M. Strange, G. A. Tritsaris, M. Vanin, M. Walter, B. Hammer , H. Häkkinen, G. K. H. Madsen, R. M. Nieminen, J. K. Nørskov, M. Puska, T. T... Schmidt , and M. Martin, Nat. Mater. 7, 391 (2008). 43V. M. Pudalov, JETP Lett. 66, 175 (1997). 44S. Das Sarma and E. H. Hwang, Phys. Rev. Lett. 83, 164

  16. Interactions of Pb and Te atoms with graphene.

    PubMed

    Gong, Chuncheng; Robertson, Alex W; He, Kuang; Ford, Camden; Watt, Andrew A R; Warner, Jamie H

    2014-05-28

    PbTe nanocrystals were deposited onto the surface of graphene and used as a reservoir of Pb and Te atoms. Electron beam irradiation at 80 kV caused Pb and Te atoms to mobilize and disperse across the surface of graphene. We studied the dynamics of these atoms in real time using aberration-corrected transmission electron microscopy. The Pb and Te atoms were found to attach to the surface layer of amorphous carbon that resides upon the graphene, as well as its edge. Pb and Te atoms were not found residing on pristine graphene, but were found to bond to the free edge states along graphene hole edges. Small PbTe nanoclusters tended to only form on the surface of the amorphous carbon regions and not on pristine graphene.

  17. Physisorbed-precursor-assisted atomic layer deposition of reliable ultrathin dielectric films on inert graphene surfaces for low-power electronics

    NASA Astrophysics Data System (ADS)

    Jeong, Seong-Jun; Kim, Hyo Won; Heo, Jinseong; Lee, Min-Hyun; Song, Hyun Jae; Ku, JiYeon; Lee, Yunseong; Cho, Yeonchoo; Jeon, Woojin; Suh, Hwansoo; Hwang, Sungwoo; Park, Seongjun

    2016-09-01

    Among the most fundamental challenges encountered in the successful incorporation of graphene in silicon-based electronics is the conformal growth of ultrathin dielectric films, especially those with thicknesses lower than 5 nm, on chemically inert graphene surfaces. Here, we present physisorbed-precursor-assisted atomic layer deposition (pALD) as an extremely robust method for fabricating such films. Using atomic-scale characterisation, it is confirmed that conformal and intact ultrathin Al2O3 films can be synthesised on graphene by pALD. The mechanism underlying the pALD process is identified through first-principles calculations based on density functional theory. Further, this novel deposition technique is used to fabricate two types of wafer-scale devices. It is found that the incorporation of a 5 nm-thick pALD Al2O3 gate dielectric film improves the performance of metal-oxide-graphene field-effect transistors to a greater extent than does the incorporation of a conventional ALD Al2O3 film. We also employ a 5 nm-thick pALD HfO2 film as a highly scalable dielectric layer with a capacitance equivalent oxide thickness of 1 nm in graphene-based tunnelling field-effect transistors fabricated on a glass wafer and achieve a subthreshold swing of 30 mV/dec. This significant improvement in switching allows for the low-voltage operation of an inverter within 0.5 V of both the drain and the gate voltages, thus paving the way for low-power electronics.

  18. Atomic covalent functionalization of graphene.

    PubMed

    Johns, James E; Hersam, Mark C

    2013-01-15

    Although graphene's physical structure is a single atom thick, two-dimensional, hexagonal crystal of sp(2) bonded carbon, this simple description belies the myriad interesting and complex physical properties attributed to this fascinating material. Because of its unusual electronic structure and superlative properties, graphene serves as a leading candidate for many next generation technologies including high frequency electronics, broadband photodetectors, biological and gas sensors, and transparent conductive coatings. Despite this promise, researchers could apply graphene more routinely in real-world technologies if they could chemically adjust graphene's electronic properties. For example, the covalent modification of graphene to create a band gap comparable to silicon (∼1 eV) would enable its use in digital electronics, and larger band gaps would provide new opportunities for graphene-based photonics. Toward this end, researchers have focused considerable effort on the chemical functionalization of graphene. Due to its high thermodynamic stability and chemical inertness, new methods and techniques are required to create covalent bonds without promoting undesirable side reactions or irreversible damage to the underlying carbon lattice. In this Account, we review and discuss recent theoretical and experimental work studying covalent modifications to graphene using gas phase atomic radicals. Atomic radicals have sufficient energy to overcome the kinetic and thermodynamic barriers associated with covalent reactions on the basal plane of graphene but lack the energy required to break the C-C sigma bonds that would destroy the carbon lattice. Furthermore, because they are atomic species, radicals substantially reduce the likelihood of unwanted side reactions that confound other covalent chemistries. Overall, these methods based on atomic radicals show promise for the homogeneous functionalization of graphene and the production of new classes of two

  19. Interface Electrical Properties of Al2O3 Thin Films on Graphene Obtained by Atomic Layer Deposition with an in Situ Seedlike Layer.

    PubMed

    Fisichella, Gabriele; Schilirò, Emanuela; Di Franco, Salvatore; Fiorenza, Patrick; Lo Nigro, Raffaella; Roccaforte, Fabrizio; Ravesi, Sebastiano; Giannazzo, Filippo

    2017-03-01

    High-quality thin insulating films on graphene (Gr) are essential for field-effect transistors (FETs) and other electronics applications of this material. Atomic layer deposition (ALD) is the method of choice to deposit high-κ dielectrics with excellent thickness uniformity and conformal coverage. However, to start the growth on the sp(2) Gr surface, a chemical prefunctionalization or the physical deposition of a seed layer are required, which can effect, to some extent, the electrical properties of Gr. In this paper, we report a detailed morphological, structural, and electrical investigation of Al2O3 thin films grown by a two-steps ALD process on a large area Gr membrane residing on an Al2O3-Si substrate. This process consists of the H2O-activated deposition of a Al2O3 seed layer a few nanometers in thickness, performed in situ at 100 °C, followed by ALD thermal growth of Al2O3 at 250 °C. The optimization of the low-temperature seed layer allowed us to obtain a uniform, conformal, and pinhole-free Al2O3 film on Gr by the second ALD step. Nanoscale-resolution mapping of the current through the dielectric by conductive atomic force microscopy (CAFM) demonstrated an excellent laterally uniformity of the film. Raman spectroscopy measurements indicated that the ALD process does not introduce defects in Gr, whereas it produces a partial compensation of Gr unintentional p-type doping, as confirmed by the increase of Gr sheet resistance (from ∼300 Ω/sq in pristine Gr to ∼1100 Ω/sq after Al2O3 deposition). Analysis of the transfer characteristics of Gr field-effect transistors (GFETs) allowed us to evaluate the relative dielectric permittivity (ε = 7.45) and the breakdown electric field (EBD = 7.4 MV/cm) of the Al2O3 film as well as the transconductance and the holes field-effect mobility (∼1200 cm(2) V(-1) s(-1)). A special focus has been given to the electrical characterization of the Al2O3-Gr interface by the analysis of high frequency capacitance

  20. Electrochemical Atomic Layer Processing

    DTIC Science & Technology

    1994-06-25

    where an atomic layer of an element is deposited , or removed, in a surface limited reaction. The potentials used are referred to as underpotentials in...the electrochemical literature. The atomic layer deposition process is referred to as underpotential deposition (UPD). 14. SUBJECT TERMS 15, NUMBER OF...reaction. The potentials used are referred to as underpotentials in the electrochemical literature. The atomic layer deposition process is referred to as

  1. Atomic Covalent Functionalization of Graphene

    PubMed Central

    Johns, James E.; Hersam, Mark C.

    2012-01-01

    Conspectus Although graphene’s physical structure is a single atom thick, two-dimensional, hexagonal crystal of sp2 bonded carbon, this simple description belies the myriad interesting and complex physical properties attributed to this fascinating material. Because of its unusual electronic structure and superlative properties, graphene serves as a leading candidate for many next generation technologies including high frequency electronics, broadband photodetectors, biological and gas sensors, and transparent conductive coatings. Despite this promise, researchers could apply graphene more routinely in real-world technologies if they could chemically adjust graphene’s electronic properties. For example, the covalent modification of graphene to create a band gap comparable to silicon (~1 eV) would enable its use in digital electronics, and larger band gaps would provide new opportunities for graphene-based photonics. Towards this end, researchers have focused considerable effort on the chemical functionalization of graphene. Due to its high thermodynamic stability and chemical inertness, new methods and techniques are required to create covalent bonds without promoting undesirable side reactions or irreversible damage to the underlying carbon lattice. In this Account, we review and discuss recent theoretical and experimental work studying covalent modifications to graphene using gas phase atomic radicals. Atomic radicals have sufficient energy to overcome the kinetic and thermodynamic barriers associated with covalent reactions on the basal plane of graphene but lack the energy required to break the C-C sigma bonds that would destroy the carbon lattice. Furthermore, because they are atomic species, radicals substantially reduce the likelihood of unwanted side reactions that confound other covalent chemistries. Overall, these methods based on atomic radicals show promise for the homogeneous functionalization of graphene and the production of new classes of two

  2. Atomic intercalation to measure adhesion of graphene on graphite

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Sorescu, Dan C.; Jeon, Seokmin; Belianinov, Alexei; Kalinin, Sergei V.; Baddorf, Arthur P.; Maksymovych, Petro

    2016-10-01

    The interest in mechanical properties of two-dimensional materials has emerged in light of new device concepts taking advantage of flexing, adhesion and friction. Here we demonstrate an effective method to measure adhesion of graphene atop highly ordered pyrolytic graphite, utilizing atomic-scale `blisters' created in the top layer by neon atom intercalates. Detailed analysis of scanning tunnelling microscopy images is used to reconstruct atomic positions and the strain map within the deformed graphene layer, and demonstrate the tip-induced subsurface translation of neon atoms. We invoke an analytical model, originally devised for graphene macroscopic deformations, to determine the graphite adhesion energy of 0.221+/-0.011 J m-2. This value is in excellent agreement with reported macroscopic values and our atomistic simulations. This implies mechanical properties of graphene scale down to a few-nanometre length. The simplicity of our method provides a unique opportunity to investigate the local variability of nanomechanical properties in layered materials.

  3. Proximity effects in cold atom artificial graphene

    NASA Astrophysics Data System (ADS)

    Graß, Tobias; Chhajlany, Ravindra W.; Tarruell, Leticia; Pellegrini, Vittorio; Lewenstein, Maciej

    2017-03-01

    Cold atoms in an optical lattice with brick-wall geometry have been used to mimic graphene, a two-dimensional material with characteristic Dirac excitations. Here we propose to bring such artificial graphene into the proximity of a second atomic layer with a square lattice geometry. For non-interacting fermions, we find that such bilayer system undergoes a phase transition from a graphene-like semi-metal phase, characterized by a band structure with Dirac points, to a gapped band insulator phase. In the presence of attractive interactions between fermions with pseudospin-1/2 degree of freedom, a competition between semi-metal and superfluid behavior is found at the mean-field level. Using the quantum Monte Carlo method, we also investigate the case of strong repulsive interactions. In the Mott phase, each layer exhibits a different amount of long-range magnetic order. Upon coupling both layers, a valence-bond crystal is formed at a critical coupling strength. Finally, we discuss how these bilayer systems could be realized in existing cold atom experiments.

  4. Atomic Layer Epitaxy of h-BN(0001) Multilayers on Co(0001) and Molecular Beam Epitaxy Growth of Graphene on h-BN(0001)/Co(0001).

    PubMed

    Driver, M Sky; Beatty, John D; Olanipekun, Opeyemi; Reid, Kimberly; Rath, Ashutosh; Voyles, Paul M; Kelber, Jeffry A

    2016-03-22

    The direct growth of hexagonal boron nitride (h-BN) by industrially scalable methods is of broad interest for spintronic and nanoelectronic device applications. Such applications often require atomically precise control of film thickness and azimuthal registry between layers and substrate. We report the formation, by atomic layer epitaxy (ALE), of multilayer h-BN(0001) films (up to 7 monolayers) on Co(0001). The ALE process employs BCl3/NH3 cycles at 600 K substrate temperature. X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED) data show that this process yields an increase in h-BN average film thickness linearly proportional to the number of BCl3/NH3 cycles, with BN layers in azimuthal registry with each other and with the Co(0001) substrate. LEED diffraction spot profile data indicate an average BN domain size of at least 1900 Å. Optical microscopy data indicate the presence of some domains as large as ∼20 μm. Transmission electron microscopy (TEM) and ambient exposure studies demonstrate macroscopic and microscopic continuity of the h-BN film, with the h-BN film highly conformal to the Co substrate. Photoemission data show that the h-BN(0001) film is p-type, with band bending near the Co/h-BN interface. Growth of graphene by molecular beam epitaxy (MBE) is observed on the surface of multilayer h-BN(0001) at temperatures of 800 K. LEED data indicate azimuthal graphene alignment with the h-BN and Co(0001) lattices, with domain size similar to BN. The evidence of multilayer BN and graphene azimuthal alignment with the lattice of the Co(0001) substrate demonstrates that this procedure is suitable for scalable production of heterojunctions for spintronic applications.

  5. Atomic resolution imaging of graphene by transmission electron microscopy

    NASA Astrophysics Data System (ADS)

    Robertson, Alex W.; Warner, Jamie H.

    2013-05-01

    The atomic structure of a material influences its electronic, chemical, magnetic and mechanical properties. Characterising carbon nanomaterials, such as fullerenes, nanotubes and graphene, at the atomic level is challenging due to their chemical reactivity and low atomic mass. Transmission electron microscopy and scanning probe microscopy are two of the leading methods for imaging graphene at the atomic level. Here, we report on recent advances in atomic resolution imaging of graphene using aberration-corrected high resolution transmission electron microscopy and how it has revealed many of the structural deviations from the pristine monolayer form. Structures in graphene such as vacancy defects, edges, grain boundaries, linear chains, impurity dopants, layer number, layer stacking and bond rotations are explored.

  6. Intercalation of graphene on iridium with samarium atoms

    NASA Astrophysics Data System (ADS)

    Afanas'eva, E. Yu.; Rut'kov, E. V.; Gall, N. R.

    2016-07-01

    Intercalation of graphene on Ir (111) with Sm atoms is studied by methods of thermal desorption spectroscopy and thermionic emission. It is shown that adsorption of samarium at T = 300 K on graphene to concentrations of N ≤ 6 × 1014 atoms cm-2 followed by heating of the substrate leads to practically complete escape of adsorbate underneath the graphene layer. At N > 6 × 1014 atoms cm-2 and increasing temperature, a fraction of adsorbate remains on graphene in the form of two-dimensional "gas" and samarium islands and are desorbed in the range of temperatures of 1000-1200 K. Samarium remaining under the graphene is desorbed from the surface in the temperature range 1200-2150 K. Model conceptions for the samarium-graphene-iridium system in a wide temperature range are developed.

  7. Atomically precise bottom-up fabrication of graphene nanoribbons.

    PubMed

    Cai, Jinming; Ruffieux, Pascal; Jaafar, Rached; Bieri, Marco; Braun, Thomas; Blankenburg, Stephan; Muoth, Matthias; Seitsonen, Ari P; Saleh, Moussa; Feng, Xinliang; Müllen, Klaus; Fasel, Roman

    2010-07-22

    Graphene nanoribbons-narrow and straight-edged stripes of graphene, or single-layer graphite-are predicted to exhibit electronic properties that make them attractive for the fabrication of nanoscale electronic devices. In particular, although the two-dimensional parent material graphene exhibits semimetallic behaviour, quantum confinement and edge effects should render all graphene nanoribbons with widths smaller than 10 nm semiconducting. But exploring the potential of graphene nanoribbons is hampered by their limited availability: although they have been made using chemical, sonochemical and lithographic methods as well as through the unzipping of carbon nanotubes, the reliable production of graphene nanoribbons smaller than 10 nm with chemical precision remains a significant challenge. Here we report a simple method for the production of atomically precise graphene nanoribbons of different topologies and widths, which uses surface-assisted coupling of molecular precursors into linear polyphenylenes and their subsequent cyclodehydrogenation. The topology, width and edge periphery of the graphene nanoribbon products are defined by the structure of the precursor monomers, which can be designed to give access to a wide range of different graphene nanoribbons. We expect that our bottom-up approach to the atomically precise fabrication of graphene nanoribbons will finally enable detailed experimental investigations of the properties of this exciting class of materials. It should even provide a route to graphene nanoribbon structures with engineered chemical and electronic properties, including the theoretically predicted intraribbon quantum dots, superlattice structures and magnetic devices based on specific graphene nanoribbon edge states.

  8. Electrochemistry at Edge of Single Graphene Layer in a Nanopore

    PubMed Central

    Banerjee, Shouvik; Shim, Jiwook; Rivera, Jose; Jin, Xiaozhong; Estrada, David; Solovyeva, Vita; You, Xiuque; Pak, James; Pop, Eric; Aluru, Narayana; Bashir, Rashid

    2013-01-01

    We study the electrochemistry of single layer graphene edges using a nanopore-based structure consisting of stacked graphene and Al2O3 dielectric layers. Nanopores, with diameters ranging from 5 to 20 nm, are formed by an electron beam sculpting process on the stacked layers. This leads to unique edge structure which, along with the atomically thin nature of the embedded graphene electrode, demonstrates electrochemical current densities as high as 1.2 × 104 A/cm2. The graphene edge embedded structure offers a unique capability to study the electrochemical exchange at an individual graphene edge, isolated from the basal plane electrochemical activity. We also report ionic current modulation in the nanopore by biasing the embedded graphene terminal with respect to the electrodes in the fluid. The high electrochemical specific current density for a graphene nanopore-based device can have many applications in sensitive chemical and biological sensing, and energy storage devices. PMID:23249127

  9. Burning Graphene Layer-by-Layer

    NASA Astrophysics Data System (ADS)

    Ermakov, Victor A.; Alaferdov, Andrei V.; Vaz, Alfredo R.; Perim, Eric; Autreto, Pedro A. S.; Paupitz, Ricardo; Galvao, Douglas S.; Moshkalev, Stanislav A.

    2015-06-01

    Graphene, in single layer or multi-layer forms, holds great promise for future electronics and high-temperature applications. Resistance to oxidation, an important property for high-temperature applications, has not yet been extensively investigated. Controlled thinning of multi-layer graphene (MLG), e.g., by plasma or laser processing is another challenge, since the existing methods produce non-uniform thinning or introduce undesirable defects in the basal plane. We report here that heating to extremely high temperatures (exceeding 2000 K) and controllable layer-by-layer burning (thinning) can be achieved by low-power laser processing of suspended high-quality MLG in air in “cold-wall” reactor configuration. In contrast, localized laser heating of supported samples results in non-uniform graphene burning at much higher rates. Fully atomistic molecular dynamics simulations were also performed to reveal details of oxidation mechanisms leading to uniform layer-by-layer graphene gasification. The extraordinary resistance of MLG to oxidation paves the way to novel high-temperature applications as continuum light source or scaffolding material.

  10. Burning Graphene Layer-by-Layer

    PubMed Central

    Ermakov, Victor A.; Alaferdov, Andrei V.; Vaz, Alfredo R.; Perim, Eric; Autreto, Pedro A. S.; Paupitz, Ricardo; Galvao, Douglas S.; Moshkalev, Stanislav A.

    2015-01-01

    Graphene, in single layer or multi-layer forms, holds great promise for future electronics and high-temperature applications. Resistance to oxidation, an important property for high-temperature applications, has not yet been extensively investigated. Controlled thinning of multi-layer graphene (MLG), e.g., by plasma or laser processing is another challenge, since the existing methods produce non-uniform thinning or introduce undesirable defects in the basal plane. We report here that heating to extremely high temperatures (exceeding 2000 K) and controllable layer-by-layer burning (thinning) can be achieved by low-power laser processing of suspended high-quality MLG in air in “cold-wall” reactor configuration. In contrast, localized laser heating of supported samples results in non-uniform graphene burning at much higher rates. Fully atomistic molecular dynamics simulations were also performed to reveal details of oxidation mechanisms leading to uniform layer-by-layer graphene gasification. The extraordinary resistance of MLG to oxidation paves the way to novel high-temperature applications as continuum light source or scaffolding material. PMID:26100466

  11. Fe-catalyzed etching of graphene layers

    NASA Astrophysics Data System (ADS)

    Cheng, Guangjun; Calizo, Irene; Hight Walker, Angela; PML, NIST Team

    We investigate the Fe-catalyzed etching of graphene layers in forming gas. Fe thin films are deposited by sputtering onto mechanically exfoliated graphene, few-layer graphene (FLG), and graphite flakes on a Si/SiO2 substrate. When the sample is rapidly annealed in forming gas, particles are produced due to the dewetting of the Fe thin film and those particles catalyze the etching of graphene layers. Monolayer graphene and FLG regions are severely damaged and that the particles catalytically etch channels in graphite. No etching is observed on graphite for the Fe thin film annealed in nitrogen. The critical role of hydrogen indicates that this graphite etching process is catalyzed by Fe particles through the carbon hydrogenation reaction. By comparing with the etched monolayer and FLG observed for the Fe film annealed in nitrogen, our Raman spectroscopy measurements identify that, in forming gas, the catalytic etching of monolayer and FLG is through carbon hydrogenation. During this process, Fe particles are catalytically active in the dissociation of hydrogen into hydrogen atoms and in the production of hydrogenated amorphous carbon through hydrogen spillover.

  12. Nano-soldering to single atomic layer

    DOEpatents

    Girit, Caglar O [Berkeley, CA; Zettl, Alexander K [Kensington, CA

    2011-10-11

    A simple technique to solder submicron sized, ohmic contacts to nanostructures has been disclosed. The technique has several advantages over standard electron beam lithography methods, which are complex, costly, and can contaminate samples. To demonstrate the soldering technique graphene, a single atomic layer of carbon, has been contacted, and low- and high-field electronic transport properties have been measured.

  13. Characterization of metal oxide layers grown on CVD graphene

    SciTech Connect

    Matsubayashi, Akitomo; Abel, Joseph; Prasad Sinha, Dhiraj; Lee, Ji Ung; LaBella, Vincent P.

    2013-03-15

    Growth of a fully oxidized aluminum oxide layer with low surface roughness on graphene grown by chemical vapor deposition is demonstrated. This is accomplished by the deposition of a 0.2 nm thick titanium seed layer on the graphene prior to the deposition of the aluminum under ultra high vacuum conditions, which was subsequently oxidized. The stoichiometry and surface roughness of the oxide layers were measured for a range of titanium and aluminum depositions utilizing ex situ x-ray photoelectron spectrometry and atomic force microscopy. These fully oxidized films are expected to produce good dielectric layers for use in graphene based electronic devices.

  14. EDITORIAL: Atomic layer deposition Atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Godlewski, Marek

    2012-07-01

    The growth method of atomic layer deposition (ALD) was introduced in Finland by Suntola under the name of atomic layer epitaxy (ALE). The method was originally used for deposition of thin films of sulphides (ZnS, CaS, SrS) activated with manganese or rare-earth ions. Such films were grown for applications in thin-film electroluminescence (TFEL) displays. The ALE mode of growth was also tested in the case of molecular beam epitaxy. Films grown by ALD are commonly polycrystalline or even amorphous. Thus, the name ALE has been replaced by ALD. In the 80s ALD was developed mostly in Finland and neighboring Baltic countries. Deposition of a range of different materials was demonstrated at that time, including II-VI semiconductors (e.g. CdTe, CdS) and III-V (e.g. GaAs, GaN), with possible applications in e.g. photovoltaics. The number of publications on ALD was slowly increasing, approaching about 100 each year. A real boom in interest came with the development of deposition methods of thin films of high-k dielectrics. This research was motivated by a high leakage current in field-effect transistors with SiO2-based gate dielectrics. In 2007 Intel introduced a new generation of integrated circuits (ICs) with thin films of HfO2 used as gate isolating layers. In these and subsequent ICs, films of HfO2 are deposited by the ALD method. This is due to their unique properties. The introduction of ALD to the electronics industry led to a booming interest in the ALD growth method, with the number of publications increasing rapidly to well above 1000 each year. A number of new applications were proposed, as reflected in this special issue of Semiconductor Science and Technology. The included articles cover a wide range of possible applications—in microelectronics, transparent electronics, optoelectronics, photovoltaics and spintronics. Research papers and reviews on the basics of ALD growth are also included, reflecting a growing interest in precursor chemistry and growth

  15. Visualizing Atomic-Scale Negative Differential Resistance in Bilayer Graphene

    NASA Astrophysics Data System (ADS)

    Kim, Keun Su; Kim, Tae-Hwan; Walter, Andrew L.; Seyller, Thomas; Yeom, Han Woong; Rotenberg, Eli; Bostwick, Aaron

    2013-01-01

    We investigate the atomic-scale tunneling characteristics of bilayer graphene on silicon carbide using the scanning tunneling microscopy. The high-resolution tunneling spectroscopy reveals an unexpected negative differential resistance (NDR) at the Dirac energy, which spatially varies within the single unit cell of bilayer graphene. The origin of NDR is explained by two near-gap van Hove singularities emerging in the electronic spectrum of bilayer graphene under a transverse electric field, which are strongly localized on two sublattices in different layers. Furthermore, defects near the tunneling contact are found to strongly impact on NDR through the electron interference. Our result provides an atomic-level understanding of quantum tunneling in bilayer graphene, and constitutes a useful step towards graphene-based tunneling devices.

  16. Electrochemical Atomic Layer Epitaxy

    NASA Astrophysics Data System (ADS)

    Gregory, Brian Wayne

    1992-01-01

    Presented here are initial investigations into an electrochemical method whereby thin films of compound semiconductors are produced by epitaxial growth of the constituent elements. This method is the electrochemical analogue of atomic layer epitaxy (ALE) (a vacuum-based technique which relies on sequential formation of atomic layers of the constituent elements) and has been termed "Electrochemical atomic layer epitaxy" (ECALE). These preliminary studies are centered on the formation of CdTe, though in principle they could be extended to a number of other compound semiconductors. A background introduction on topics relevant to epitaxial growth in electrochemical systems will be presented. Predictions of underpotential behavior in the CdTe system will be made using potential -pH (Pourbaix) diagrams. Development of the method will proceed from our initial studies of Cd and Te underpotential deposition (UPD) on a number of metallic substrates, followed by results demonstrating the ECALE formation of two monolayers of CdTe on polycrystalline and single crystal gold substrates. The final chapter will present current attempts to design and construct an automated, computer-controlled thin-layer electrochemical flow cell, which is to be used for the deposition of thicker layers (up to 1 mu m) of compound semiconductors.

  17. Opposite effects of Cu and Pt atoms on graphene edges

    NASA Astrophysics Data System (ADS)

    Kano, Emi; Hashimoto, Ayako; Takeguchi, Masaki

    2017-02-01

    Metal atoms at graphene edges are important because they can modify the structure and properties of graphene; however, there are very few reports on their direct observation. We performed electron microscopy to investigate the stability and dynamics of Cu and Pt atoms at graphene edges. We found that Cu atoms mended graphene edges, while Pt atoms etched them, and these transformations were promoted by electron irradiation. Cu and Pt atoms formed different atomic configurations at graphene edges.

  18. Fabrication of graphene-silicon layered heterostructures by carbon penetration of silicon film.

    PubMed

    Meng, Lei; Wang, Yeliang; Li, Linfei; Gao, H-J

    2017-02-24

    A new, easy, in situ technique for fabricating a two-dimensional graphene-silicon layered heterostructure has been developed to meet the demand for integration between graphene and silicon-based microelectronic technology. First, carbon atoms are stored in bulk iridium, and then silicon atoms are deposited onto the Ir(111) surface and annealed. With longer annealing times, the carbon atoms penetrate from the bulk iridium to the top of the silicon and eventually coalesce there into graphene islands. Atomically resolved scanning tunneling microscopy images, high-pass fast Fourier transform treatment and Raman spectroscopy demonstrate that the top graphene layer is intact and continuous, and beneath it is the silicon layer.

  19. Fabrication of graphene-silicon layered heterostructures by carbon penetration of silicon film

    NASA Astrophysics Data System (ADS)

    Meng, Lei; Wang, Yeliang; Li, Linfei; Gao, H.-J.

    2017-02-01

    A new, easy, in situ technique for fabricating a two-dimensional graphene-silicon layered heterostructure has been developed to meet the demand for integration between graphene and silicon-based microelectronic technology. First, carbon atoms are stored in bulk iridium, and then silicon atoms are deposited onto the Ir(111) surface and annealed. With longer annealing times, the carbon atoms penetrate from the bulk iridium to the top of the silicon and eventually coalesce there into graphene islands. Atomically resolved scanning tunneling microscopy images, high-pass fast Fourier transform treatment and Raman spectroscopy demonstrate that the top graphene layer is intact and continuous, and beneath it is the silicon layer.

  20. Comment on "Temperature dependence of atomic vibrations in mono-layer graphene" [J. Appl. Phys. 118, 074302 (2015)

    NASA Astrophysics Data System (ADS)

    Susi, T.; Kotakoski, J.

    2016-02-01

    In an interesting recent study [Allen et al., J. Appl. Phys. 118, 074302 (2015)] (see also their Erratum [Allen et al., J. Appl. Phys. 118, 159902 (2015)]), Allen and co-workers measured the mean square amplitudes of graphene lattice vibrations between 100 and 1300 K and used a simplified theoretical approximation for the acoustic phonon modes to evaluate the maximum phonon wavelengths supported by the lattice. By fitting their data using the smallest wave-vector as the fitting parameter, they found this to be significantly smaller than the physical size of the graphene crystallites.

  1. Surfactant-free single-layer graphene in water

    NASA Astrophysics Data System (ADS)

    Bepete, George; Anglaret, Eric; Ortolani, Luca; Morandi, Vittorio; Huang, Kai; Pénicaud, Alain; Drummond, Carlos

    2016-11-01

    Dispersing graphite in water to obtain true (single-layer) graphene in bulk quantity in a liquid has been an unreachable goal for materials scientists in the past decade. Similarly, a diagnostic tool to identify solubilized graphene in situ has been long awaited. Here we show that homogeneous stable dispersions of single-layer graphene (SLG) in water can be obtained by mixing graphenide (negatively charged graphene) solutions in tetrahydrofuran with degassed water and evaporating the organic solvent. In situ Raman spectroscopy of these aqueous dispersions shows all the expected characteristics of SLG. Transmission electron and atomic force microscopies on deposits confirm the single-layer character. The resulting additive-free stable water dispersions contain 400 m2 l-1 of developed graphene surface. Films prepared from these dispersions exhibit a conductivity of up to 32 kS m-1.

  2. Surfactant-free single-layer graphene in water.

    PubMed

    Bepete, George; Anglaret, Eric; Ortolani, Luca; Morandi, Vittorio; Huang, Kai; Pénicaud, Alain; Drummond, Carlos

    2017-04-01

    Dispersing graphite in water to obtain true (single-layer) graphene in bulk quantity in a liquid has been an unreachable goal for materials scientists in the past decade. Similarly, a diagnostic tool to identify solubilized graphene in situ has been long awaited. Here we show that homogeneous stable dispersions of single-layer graphene (SLG) in water can be obtained by mixing graphenide (negatively charged graphene) solutions in tetrahydrofuran with degassed water and evaporating the organic solvent. In situ Raman spectroscopy of these aqueous dispersions shows all the expected characteristics of SLG. Transmission electron and atomic force microscopies on deposits confirm the single-layer character. The resulting additive-free stable water dispersions contain 400 m(2) l(-1) of developed graphene surface. Films prepared from these dispersions exhibit a conductivity of up to 32 kS m(-1).

  3. Remote catalyzation for direct formation of graphene layers on oxides.

    PubMed

    Teng, Po-Yuan; Lu, Chun-Chieh; Akiyama-Hasegawa, Kotone; Lin, Yung-Chang; Yeh, Chao-Hui; Suenaga, Kazu; Chiu, Po-Wen

    2012-03-14

    Direct deposition of high-quality graphene layers on insulating substrates such as SiO(2) paves the way toward the development of graphene-based high-speed electronics. Here, we describe a novel growth technique that enables the direct deposition of graphene layers on SiO(2) with crystalline quality potentially comparable to graphene grown on Cu foils using chemical vapor deposition (CVD). Rather than using Cu foils as substrates, our approach uses them to provide subliming Cu atoms in the CVD process. The prime feature of the proposed technique is remote catalyzation using floating Cu and H atoms for the decomposition of hydrocarbons. This allows for the direct graphitization of carbon radicals on oxide surfaces, forming isolated low-defect graphene layers without the need for postgrowth etching or evaporation of the metal catalyst. The defect density of the resulting graphene layers can be significantly reduced by tuning growth parameters such as the gas ratios, Cu surface areas, and substrate-to-Cu distance. Under optimized conditions, graphene layers with nondiscernible Raman D peaks can be obtained when predeposited graphite flakes are used as seeds for extended growth. © 2012 American Chemical Society

  4. Effect of roughness on the layer-dependent friction of few-layer graphene

    NASA Astrophysics Data System (ADS)

    Ye, Zhijiang; Balkanci, Arda; Martini, Ashlie; Baykara, Mehmet Z.

    2017-09-01

    Friction on few-layer graphene is known to exhibit unique layer dependence where friction measured via atomic force microscopy (AFM) on the nanometer scale is generally observed to decrease with increasing number of layers. However, this trend is not always observed for AFM probe tips with different sizes and for graphene on different substrates. Within this context, the precise role played by the interface, in particular, the size of the contact and substrate roughness, in the layer dependence of friction on graphene is not yet completely understood. Here, we probe the origins of the roughness dependence of layer-dependent friction on graphene by a combination of AFM measurements and molecular dynamics (MD) simulations. In the experiments, friction is observed to monotonically decrease with increasing number of graphene layers for tips with various apex radii, while the roughness of the sample surface is observed to decrease. In the simulations, two opposite layer-dependence trends for friction are observed on few-layer graphene on substrates with different roughness values. The underlying mechanisms are investigated using atomistic details obtained from the simulations, where the different friction trends are found to originate from an interplay between surface roughness, the trajectory of the tip, and the number of atoms in contact. Finally, the effect of topographical correlation length on the layer dependence of friction on graphene is discussed.

  5. Backside absorbing layer microscopy: Watching graphene chemistry.

    PubMed

    Campidelli, Stéphane; Abou Khachfe, Refahi; Jaouen, Kevin; Monteiller, Jean; Amra, Claude; Zerrad, Myriam; Cornut, Renaud; Derycke, Vincent; Ausserré, Dominique

    2017-05-01

    The rapid rise of two-dimensional nanomaterials implies the development of new versatile, high-resolution visualization and placement techniques. For example, a single graphene layer becomes observable on Si/SiO2 substrates by reflected light under optical microscopy because of interference effects when the thickness of silicon oxide is optimized. However, differentiating monolayers from bilayers remains challenging, and advanced techniques, such as Raman mapping, atomic force microscopy (AFM), or scanning electron microscopy (SEM) are more suitable to observe graphene monolayers. The first two techniques are slow, and the third is operated in vacuum; hence, in all cases, real-time experiments including notably chemical modifications are not accessible. The development of optical microscopy techniques that combine the speed, large area, and high contrast of SEM with the topological information of AFM is therefore highly desirable. We introduce a new widefield optical microscopy technique based on the use of previously unknown antireflection and absorbing (ARA) layers that yield ultrahigh contrast reflection imaging of monolayers. The BALM (backside absorbing layer microscopy) technique can achieve the subnanometer-scale vertical resolution, large area, and real-time imaging. Moreover, the inverted optical microscope geometry allows its easy implementation and combination with other techniques. We notably demonstrate the potentiality of BALM by in operando imaging chemical modifications of graphene oxide. The technique can be applied to the deposition, observation, and modification of any nanometer-thick materials.

  6. Electronic and Quantum Transport Properties of Atomically Identified Si Point Defects in Graphene.

    PubMed

    Lopez-Bezanilla, Alejandro; Zhou, Wu; Idrobo, Juan-Carlos

    2014-05-15

    We report high-resolution scanning transmission electron microscopy images displaying a range of inclusions of isolated silicon atoms at the edges and inner zones of graphene layers. Whereas the incorporation of Si atoms to a graphene armchair edge involves no reconstruction of the neighboring carbon atoms, the inclusion of a Si atom to a zigzag graphene edge entails the formation of five-membered carbon rings. In all the observed atomic edge terminations, a Si atom is found bridging two C atoms in a 2-fold coordinated configuration. The atomic-scale observations are underpinned by first-principles calculations of the electronic and quantum transport properties of the structural anomalies. Experimental estimations of Si-doped graphene band gaps realized by means of transport measurements may be affected by a low doping rate of 2-fold coordinated Si atoms at the graphene edges, and 4-fold coordinated at inner zones due to the apparition of mobility gaps.

  7. Electronic and Quantum Transport Properties of Atomically Identified Si Point Defects in Graphene

    SciTech Connect

    Lopez-Bezanilla, Alejandro; Zhou, Wu; Idrobo, Juan-Carlos

    2014-05-01

    In this paper, we report high-resolution scanning transmission electron microscopy images displaying a range of inclusions of isolated silicon atoms at the edges and inner zones of graphene layers. Whereas the incorporation of Si atoms to a graphene armchair edge involves no reconstruction of the neighboring carbon atoms, the inclusion of a Si atom to a zigzag graphene edge entails the formation of five-membered carbon rings. In all the observed atomic edge terminations, a Si atom is found bridging two C atoms in a 2-fold coordinated configuration. The atomic-scale observations are underpinned by first-principles calculations of the electronic and quantum transport properties of the structural anomalies. Finally, experimental estimations of Si-doped graphene band gaps realized by means of transport measurements may be affected by a low doping rate of 2-fold coordinated Si atoms at the graphene edges, and 4-fold coordinated at inner zones due to the apparition of mobility gaps.

  8. Role of graphene layers on the radiation resistance of copper-graphene nanocomposite: Inhibiting the expansion of thermal spike

    NASA Astrophysics Data System (ADS)

    Huang, Hai; Tang, Xiaobin; Chen, Feida; Liu, Jian; Chen, Da

    2017-09-01

    Metal-graphene nanocomposites are expected to have excellent radiation resistance. The intrinsic role of the graphene layers (GrLs) in their performance has not been fully understood. Five copper-graphene nanocomposite (CGNC) systems were used to investigate the detailed mechanisms underpinning this behaviour by atomistic simulation. Results showed that GrLs can reduce the formation, growth, and intensity of the thermal spike of CGNC; this effect became more evident with the increasing number of layers of graphene. The role of the GrLs can be explained by three mechanisms: first, the ultra-strength C-C bonds of graphene hindered the penetration of high-energy atoms, second, the number of recoiled atoms decreased with the increasing number of layers of graphene, and third, the energy dissipation along the graphene planes also indirectly weakened the damage caused to the entire system. These mechanisms may provide a pathway to prevent material degradation in extreme radiation environments.

  9. Organic doping of rotated double layer graphene

    SciTech Connect

    George, Lijin; Jaiswal, Manu

    2016-05-06

    Charge transfer techniques have been extensively used as knobs to tune electronic properties of two- dimensional systems, such as, for the modulation of conductivity \\ mobility of single layer graphene and for opening the bandgap in bilayer graphene. The charge injected into the graphene layer shifts the Fermi level away from the minimum density of states point (Dirac point). In this work, we study charge transfer in rotated double-layer graphene achieved by the use of organic dopant, Tetracyanoquinodimethane. Naturally occurring bilayer graphene has a well-defined A-B stacking whereas in rotated double-layer the two graphene layers are randomly stacked with different rotational angles. This rotation is expected to significantly alter the interlayer interaction. Double-layer samples are prepared using layer-by-layer assembly of chemical vapor deposited single-layer graphene and they are identified by characteristic resonance in the Raman spectrum. The charge transfer and distribution of charges between the two graphene layers is studied using Raman spectroscopy and the results are compared with that for single-layer and A-B stacked bilayer graphene doped under identical conditions.

  10. Amorphous Ultrathin SnO2 Films by Atomic Layer Deposition on Graphene Network as Highly Stable Anodes for Lithium-Ion Batteries.

    PubMed

    Xie, Ming; Sun, Xiang; George, Steven M; Zhou, Changgong; Lian, Jie; Zhou, Yun

    2015-12-23

    Amorphous SnO2 (a-SnO2) thin films were conformally coated onto the surface of reduced graphene oxide (G) using atomic layer deposition (ALD). The electrochemical characteristics of the a-SnO2/G nanocomposites were then determined using cyclic voltammetry and galvanostatic charge/discharge curves. Because the SnO2 ALD films were ultrathin and amorphous, the impact of the large volume expansion of SnO2 upon cycling was greatly reduced. With as few as five formation cycles best reported in the literature, a-SnO2/G nanocomposites reached stable capacities of 800 mAh g(-1) at 100 mA g(-1) and 450 mAh g(-1) at 1000 mA g(-1). The capacity from a-SnO2 is higher than the bulk theoretical values. The extra capacity is attributed to additional interfacial charge storage resulting from the high surface area of the a-SnO2/G nanocomposites. These results demonstrate that metal oxide ALD on high surface area conducting carbon substrates can be used to fabricate high power and high capacity electrode materials for lithium-ion batteries.

  11. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    SciTech Connect

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; Eres, Gyula; Timpe, Olaf; Fu, Qiang; Ding, Feng; Willinger, Marc-Georg; Schloegl, R.

    2016-10-19

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.

  12. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    NASA Astrophysics Data System (ADS)

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; Eres, Gyula; Timpe, Olaf; Fu, Qiang; Ding, Feng; Schloegl, R.; Willinger, Marc-Georg

    2016-10-01

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene-graphene and graphene-substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.

  13. Trapping of metal atoms in vacancies of carbon nanotubes and graphene.

    PubMed

    Rodríguez-Manzo, Julio A; Cretu, Ovidiu; Banhart, Florian

    2010-06-22

    Lattice defects in carbon nanotubes and graphene are created by focusing an electron beam in a scanning transmission electron microscope onto a 0.1 nm spot on the objects. Metal atoms migrating on the graphenic surfaces are observed to be trapped by these defects. Depending on the size of the defect, single metal atoms or clusters of several atoms can be localized in or on nanotubes or graphene layers. Subsequent escape of the metal atoms from the trapping centers gives information about the bonding between the metal atom and the defect. The process of trapping and detrapping is studied in a temperature range of 20-670 degrees C. The technique allows one to place metal atoms with almost atomic precision in graphenic structures and to create a predefined pattern of foreign atoms in graphene or carbon nanotubes.

  14. Graphene-coated atomic force microscope tips for reliable nanoscale electrical characterization.

    PubMed

    Lanza, M; Bayerl, A; Gao, T; Porti, M; Nafria, M; Jing, G Y; Zhang, Y F; Liu, Z F; Duan, H L

    2013-03-13

    Graphene single-layer films are grown by chemical vapor deposition and transferred onto commercially available conductive tips for atomic force microscopy. Graphene-coated tips are much more resistant to both high currents and frictions than commercially available, metal-varnished, conductive atomic force microscopy tips, leading to much larger lifetimes and more reliable imaging due to a lower tip-sample interaction.

  15. Resolving Atomic Connectivity in Graphene Nanostructure Junctions.

    PubMed

    Dienel, Thomas; Kawai, Shigeki; Söde, Hajo; Feng, Xinliang; Müllen, Klaus; Ruffieux, Pascal; Fasel, Roman; Gröning, Oliver

    2015-08-12

    We report on the structural characterization of junctions between atomically well-defined graphene nanoribbons (GNRs) by means of low-temperature, noncontact scanning probe microscopy. We show that the combination of simultaneously acquired frequency shift and tunneling current maps with tight binding (TB) simulations allows a comprehensive characterization of the atomic connectivity in the GNR junctions. The proposed approach can be generally applied to the investigation of graphene nanomaterials and their interconnections and is thus expected to become an important tool in the development of graphene-based circuitry.

  16. Atomic intercalation to measure adhesion of graphene on graphite

    PubMed Central

    Wang, Jun; Sorescu, Dan C.; Jeon, Seokmin; Belianinov, Alexei; Kalinin, Sergei V.; Baddorf, Arthur P.; Maksymovych, Petro

    2016-01-01

    The interest in mechanical properties of two-dimensional materials has emerged in light of new device concepts taking advantage of flexing, adhesion and friction. Here we demonstrate an effective method to measure adhesion of graphene atop highly ordered pyrolytic graphite, utilizing atomic-scale ‘blisters' created in the top layer by neon atom intercalates. Detailed analysis of scanning tunnelling microscopy images is used to reconstruct atomic positions and the strain map within the deformed graphene layer, and demonstrate the tip-induced subsurface translation of neon atoms. We invoke an analytical model, originally devised for graphene macroscopic deformations, to determine the graphite adhesion energy of 0.221±0.011 J m−2. This value is in excellent agreement with reported macroscopic values and our atomistic simulations. This implies mechanical properties of graphene scale down to a few-nanometre length. The simplicity of our method provides a unique opportunity to investigate the local variability of nanomechanical properties in layered materials. PMID:27796294

  17. The edge- and basal-plane-specific electrochemistry of a single-layer graphene sheet

    PubMed Central

    Yuan, Wenjing; Zhou, Yu; Li, Yingru; Li, Chun; Peng, Hailin; Zhang, Jin; Liu, Zhongfan; Dai, Liming; Shi, Gaoquan

    2013-01-01

    Graphene has a unique atom-thick two-dimensional structure and excellent properties, making it attractive for a variety of electrochemical applications, including electrosynthesis, electrochemical sensors or electrocatalysis, and energy conversion and storage. However, the electrochemistry of single-layer graphene has not yet been well understood, possibly due to the technical difficulties in handling individual graphene sheet. Here, we report the electrochemical behavior at single-layer graphene-based electrodes, comparing the basal plane of graphene to its edge. The graphene edge showed 4 orders of magnitude higher specific capacitance, much faster electron transfer rate and stronger electrocatalytic activity than those of graphene basal plane. A convergent diffusion effect was observed at the sub-nanometer thick graphene edge-electrode to accelerate the electrochemical reactions. Coupling with the high conductivity of a high-quality graphene basal plane, graphene edge is an ideal electrode for electrocatalysis and for the storage of capacitive charges. PMID:23896697

  18. Single-layer behavior and its breakdown in twisted graphene layers

    NASA Astrophysics Data System (ADS)

    Luican-Mayer, Adina

    2013-03-01

    Stacking order plays a major role in the electronic properties of graphene layers because hopping between carbon atoms in neighboring layers is a key ingredient in their band structure. Twisting the layers away from the equilibrium Bernal stacking, which produces the superstructures known as Moiré patterns in scanning tunneling microscopy, decreases the overlap between atoms in adjacent layers and therefore significantly alters their electronic properties. Using scanning tunneling microscopy and spectroscopy, we obtained direct evidence for the electronic structure of twisted graphene layers.[2] The samples were membranes of CVD grown graphene and graphite crystals which contain areas with various twist angles. In topographic images the regions where layers are twisted away from Bernal stacking exhibit Moiré patterns with periods which depend on the twist angle. We find that the density of states on the twisted layers develops two Van Hove singularities that symmetrically flank the Dirac point at an energy that depends on the twist angle. High magnetic field scanning tunneling microscopy and Landau level spectroscopy of twisted graphene layers reveal that for twist angles exceeding ~3 degrees the low energy carriers exhibit Landau level spectra characteristic of massless Dirac fermions. Above 20 degrees the layers effectively decouple and the electronic properties are indistinguishable from those in single-layer graphene, while for smaller angles we observe a slowdown of the carrier velocity which is strongly angle dependent.[3] These results are compared with theoretical predictions. DOE-FG02-99ER45742, NSF DMR 1207108, Alcatel-Lucent

  19. Graphene: Atomically thin protective coating

    NASA Astrophysics Data System (ADS)

    Prasai, Dhiraj; Bolotin, Kirill; Tuberquia, Juan; Harl, Robert; Jennings, Kane

    2011-03-01

    We explore the properties of graphene as a cathodic coating to protect copper substrates from oxidation and further corrosion. High-quality and large area graphene films are grown on copper substrates by chemical vapor deposition. Samples were thermally oxidized in an oxygen-rich environment. X-ray photoelectron spectroscopy (XPS) characterization of a Graphene/copper and bare copper samples reveals the absence of oxidized copper at the graphene/copper interface indicating that the graphene monolayer protects the underlying copper. We also determine the protective properties of graphene in aqueous media using electrochemical characterization techniques. First, we use Electrochemical Impedance Spectroscopy (EIS) to show that graphene coated substrates lower frequencies (1Hz) exhibit impedance values 2 orders of magnitude higher compared to bare Cu substrates. Cyclic voltammetry also shows that a monolayer of graphene significantly reduces the oxygen reduction, thus exhibiting little charge transfer at the solid-liquid interface. Finally, we use Tafel analysis to estimate that the corrosion rate exhibited by Graphene/Cu is ~ 7 times lower than that of bare Cu substrates.

  20. Cleaning graphene with a titanium sacrificial layer

    SciTech Connect

    Joiner, C. A. Roy, T.; Hesabi, Z. R.; Vogel, E. M.; Chakrabarti, B.

    2014-06-02

    Graphene is a promising material for future electronic applications and chemical vapor deposition of graphene on copper is a promising method for synthesizing graphene on the wafer scale. The processing of such graphene films into electronic devices introduces a variety of contaminants which can be difficult to remove. An approach to cleaning residues from the graphene channel is presented in which a thin layer of titanium is deposited via thermal e-beam evaporation and immediately removed. This procedure does not damage the graphene as evidenced by Raman spectroscopy, greatly enhances the electrical performance of the fabricated graphene field effect transistors, and completely removes the chemical residues from the surface of the graphene channel as evidenced by x-ray photoelectron spectroscopy.

  1. Atomic intercalation to measure adhesion of graphene on graphite

    SciTech Connect

    Wang, Jun; Sorescu, Dan C.; Jeon, Seokmin; Belianinov, Alex; Kalinin, Sergei V.; Baddorf, Arthur P.; Maksymovych, Petro

    2016-10-31

    The interest in mechanical properties of layered and 2D materials has reemerged in light of device concepts that take advantage of flexing, adhesion and friction in such systems. Here we provide an effective measurement of the nanoscale elastic adhesion of a graphene sheet atop highly ordered pyrolytic graphite (HOPG) based on the analysis of atomic intercalates in graphite. Atomic intercalation is carried out using conventional ion sputtering, creating blisters in the top-most layer of the HOPG surface. Scanning tunneling microscopy coupled with image analysis and density functional theory are used to reconstruct the atomic positions and the strain map within the deformed graphene sheet, as well as to demonstrate subsurface diffusion of the ions creating such blisters. To estimate the adhesion energy we invoke an analytical model originally devised for macroscopic deformations of graphene. This model yields a value of 0.221 ± 0.011 J/m-2 for the adhesion energy of graphite, which is in surprisingly good agreement with reported experimental and theoretical values. This implies that macroscopic mechanical properties of graphene scale down to at least a few nanometers length. The simplicity of our method, compared to the macroscale characterization, enables analysis of elastic mechanical properties in two-dimensional layered materials and provides a unique opportunity to investigate the local variability of mechanical properties on the nanoscale.

  2. Atomic intercalation to measure adhesion of graphene on graphite

    DOE PAGES

    Wang, Jun; Sorescu, Dan C.; Jeon, Seokmin; ...

    2016-10-31

    The interest in mechanical properties of layered and 2D materials has reemerged in light of device concepts that take advantage of flexing, adhesion and friction in such systems. Here we provide an effective measurement of the nanoscale elastic adhesion of a graphene sheet atop highly ordered pyrolytic graphite (HOPG) based on the analysis of atomic intercalates in graphite. Atomic intercalation is carried out using conventional ion sputtering, creating blisters in the top-most layer of the HOPG surface. Scanning tunneling microscopy coupled with image analysis and density functional theory are used to reconstruct the atomic positions and the strain map withinmore » the deformed graphene sheet, as well as to demonstrate subsurface diffusion of the ions creating such blisters. To estimate the adhesion energy we invoke an analytical model originally devised for macroscopic deformations of graphene. This model yields a value of 0.221 ± 0.011 J/m-2 for the adhesion energy of graphite, which is in surprisingly good agreement with reported experimental and theoretical values. This implies that macroscopic mechanical properties of graphene scale down to at least a few nanometers length. The simplicity of our method, compared to the macroscale characterization, enables analysis of elastic mechanical properties in two-dimensional layered materials and provides a unique opportunity to investigate the local variability of mechanical properties on the nanoscale.« less

  3. Enhancement of the Stability of Fluorine Atoms on Defective Graphene and at Graphene/Fluorographene Interface.

    PubMed

    Ao, Zhimin; Jiang, Quanguo; Li, Shuang; Liu, Hao; Peeters, Francois M; Li, Sean; Wang, Guoxiu

    2015-09-09

    Fluorinated graphene is one of the most important derivatives of graphene and has been found to have great potential in optoelectronic and photonic nanodevices. However, the stability of F atoms on fluorinated graphene under different conditions, which is essential to maintain the desired properties of fluorinated graphene, is still unclear. In this work, we investigate the diffusion of F atoms on pristine graphene, graphene with defects, and at graphene/fluorographene interfaces by using density functional theory calculations. We find that an isolated F atom diffuses easily on graphene, but those F atoms can be localized by inducing vacancies or absorbates in graphene and by creating graphene/fluorographene interfaces, which would strengthen the binding energy of F atoms on graphene and increase the diffusion energy barrier of F atoms remarkably.

  4. Recognizing nitrogen dopant atoms in graphene using atomic force microscopy

    NASA Astrophysics Data System (ADS)

    van der Heijden, Nadine J.; Smith, Daniël; Calogero, Gaetano; Koster, Rik S.; Vanmaekelbergh, Daniel; van Huis, Marijn A.; Swart, Ingmar

    2016-06-01

    Doping graphene by heteroatoms such as nitrogen presents an attractive route to control the position of the Fermi level in the material. We prepared N-doped graphene on Cu(111) and Ir(111) surfaces via chemical vapor deposition of two different molecules. Using scanning tunneling microscopy images as a benchmark, we show that the position of the dopant atoms can be determined using atomic force microscopy. Specifically, the frequency shift-distance curves Δ f (z ) acquired above a N atom are significantly different from the curves measured over a C atom. Similar behavior was found for N-doped graphene on Cu(111) and Ir(111). The results are corroborated by density functional theory calculations employing a van der Waals functional.

  5. Surface potentials and layer charge distributions in few-layer graphene films.

    PubMed

    Datta, Sujit S; Strachan, Douglas R; Mele, E J; Johnson, A T Charlie

    2009-01-01

    Graphene-derived nanomaterials are emerging as ideal candidates for postsilicon electronics. Elucidating the electronic interaction between an insulating substrate and few-layer graphene (FLG) films is crucial for device applications. Here, we report electrostatic force microscopy (EFM) measurements revealing that the FLG surface potential increases with film thickness, approaching a "bulk" value for samples with five or more graphene layers. This behavior is in sharp contrast with that expected for conventional conducting or semiconducting films, and derives from unique aspects of charge screening by graphene's relativistic low energy carriers. EFM measurements resolve previously unseen electronic perturbations extended along crystallographic directions of structurally disordered FLGs, likely resulting from long-range atomic defects. These results have important implications for graphene nanoelectronics and provide a powerful framework by which key properties can be further investigated.

  6. Fabrication of a single layer graphene by copper intercalation on a SiC(0001) surface

    SciTech Connect

    Yagyu, Kazuma; Tochihara, Hiroshi; Tomokage, Hajime; Suzuki, Takayuki; Tajiri, Takayuki; Kohno, Atsushi; Takahashi, Kazutoshi

    2014-02-03

    Cu atoms deposited on a zero layer graphene grown on a SiC(0001) substrate, intercalate between the zero layer graphene and the SiC substrate after the thermal annealing above 600 °C, forming a Cu-intercalated single layer graphene. On the Cu-intercalated single layer graphene, a graphene lattice with superstructure due to moiré pattern is observed by scanning tunneling microscopy, and specific linear dispersion at the K{sup ¯} point as well as a characteristic peak in a C{sub 1s} core level spectrum, which is originated from a free-standing graphene, is confirmed by photoemission spectroscopy. The Cu-intercalated single layer graphene is found to be n-doped.

  7. Doping monolayer graphene with single atom substitutions.

    PubMed

    Wang, Hongtao; Wang, Qingxiao; Cheng, Yingchun; Li, Kun; Yao, Yingbang; Zhang, Qiang; Dong, Cezhou; Wang, Peng; Schwingenschlögl, Udo; Yang, Wei; Zhang, X X

    2012-01-11

    Functionalized graphene has been extensively studied with the aim of tailoring properties for gas sensors, superconductors, supercapacitors, nanoelectronics, and spintronics. A bottleneck is the capability to control the carrier type and density by doping. We demonstrate that a two-step process is an efficient way to dope graphene: create vacancies by high-energy atom/ion bombardment and fill these vacancies with desired dopants. Different elements (Pt, Co, and In) have been successfully doped in the single-atom form. The high binding energy of the metal-vacancy complex ensures its stability and is consistent with in situ observation by an aberration-corrected and monochromated transmission electron microscope.

  8. Superpermeable Atomic-Thin Graphene Membranes with High Selectivity.

    PubMed

    Wei, Gaoliang; Quan, Xie; Chen, Shuo; Yu, Hongtao

    2017-02-28

    Theoretical permeability of membrane is inversely proportional to its thickness, which indicates ultrathin membranes will be extremely permeable. Inspired by the atomic thickness of graphene, herein we report a four-layered graphene membrane with a thickness of about 2 nm. The ultrathin membrane is facilely fabricated by directly punching a complete graphene sheet through selective removal of some carbon atoms with metal oxide nanoparticles at high temperature. Their perpendicular pore channels spanning the whole thickness could, to a great extent, reduce hydrodynamic resistance for water transport. Experimental tests have revealed a flux of up to 4600 L m(-2) h(-1) of the membranes with a pore size of 50 nm and pore density of 1.0 × 10(7) cm(-2) at a pressure of 0.2 bar. This flux is 40-400 times higher than those of conventional ceramic membranes and track-etched membranes. The enhancement in water permeance is attributed to their atomic thickness and straight pore channels. High selectivity is also evidenced by selective separation of nanospheres with their narrowly distributed pores. These atomic-thin graphene membranes, in view of their outstanding permeability and selectivity, possess great potential as future advanced membranes and may inspire the design and development of other innovative membranes.

  9. Defects Mediated Corrosion in Graphene Coating Layer.

    PubMed

    Lei, Jincheng; Hu, Yaowu; Liu, Zishun; Cheng, Gary J; Zhao, Kejie

    2017-04-05

    Mixed results were reported on the anticorrosion of graphene-coated metal surfaces-while graphene serves as an effective short-term barrier against corrosion and oxidation due to its low permeability to gases, the galvanic cell between graphene and the metal substrate facilitates extensive corrosion in the long run. Defects in the graphene layer provide pathways for the permeation of oxidizing species. We study the role of defects in graphene in the anticorrosion using first-principles theoretical modeling. Experiments in the highly reactive environment indicate that the oxidized products primarily distribute along the grain boundaries of graphene. We analyze the thermodynamics of the absorption of S and O on the grain boundaries of graphene on the basis of density functional theory. The insertion of S and O at the vacancy sites is energetically favorable. The interstitial impurities facilitate structural transformation of graphene and significantly decrease the mechanical strength of the graphene layer. Furthermore, the presence of the interstitial S and O reduces the chemical stability of graphene by enhancing the formation of vacancies and promoting dispersive growth of corrosive reactants along the grain boundaries.

  10. Near-field scanning microwave microscopy of few-layer graphene.

    SciTech Connect

    Kalugin, Nikolai G.; Gonzales, Edward; Kalichava, Irakli; Gin, Aaron V.; Wickey, Lee; Del Barga, Christopher; Talanov, Vladimir V.; Shaner, Eric Arthur

    2010-08-01

    Near-field microwave microscopy can be used as an alternative to atomic-force microscopy or Raman microscopy in determination of graphene thickness. We evaluated the values of AC impedance for few layer graphene. The impedance of mono and few-layer graphene at 4GHz was found predominantly active. Near-field microwave microscopy allows simultaneous imaging of location, geometry, thickness, and distribution of electrical properties of graphene without device fabrication. Our results may be useful for design of future graphene-based microwave devices.

  11. On the nature of the stacking interaction between two graphene layers

    NASA Astrophysics Data System (ADS)

    Wang, Weizhou; Zhang, Yu; Sun, Tao; Wang, Yi-Bo

    2015-01-01

    The interlayer interaction energy and its components of the bilayer graphene were obtained by extrapolation of the interlayer interaction energies and their components of the dimers formed by graphene with benzene, naphthalene, anthracene, phenanthrene, pyrene, tetracene, perylene, pentacene and hexacene. The resulting interaction energy of the bilayer graphene is -1.82 kcal/mol (or -79 meV) per carbon atom. The dispersion energy represents 70% of the total attractive energy between two graphene layers. In contrast, the electrostatic component is responsible for 25% of the total attractive interaction and the induction term contributes 5% to the stability of two graphene layers.

  12. Imaging and dynamics of light atoms and molecules on graphene.

    PubMed

    Meyer, Jannik C; Girit, C O; Crommie, M F; Zettl, A

    2008-07-17

    Observing the individual building blocks of matter is one of the primary goals of microscopy. The invention of the scanning tunnelling microscope revolutionized experimental surface science in that atomic-scale features on a solid-state surface could finally be readily imaged. However, scanning tunnelling microscopy has limited applicability due to restrictions in, for example, sample conductivity, cleanliness, and data acquisition rate. An older microscopy technique, that of transmission electron microscopy (TEM), has benefited tremendously in recent years from subtle instrumentation advances, and individual heavy (high-atomic-number) atoms can now be detected by TEM even when embedded within a semiconductor material. But detecting an individual low-atomic-number atom, for example carbon or even hydrogen, is still extremely challenging, if not impossible, via conventional TEM owing to the very low contrast of light elements. Here we demonstrate a means to observe, by conventional TEM, even the smallest atoms and molecules: on a clean single-layer graphene membrane, adsorbates such as atomic hydrogen and carbon can be seen as if they were suspended in free space. We directly image such individual adatoms, along with carbon chains and vacancies, and investigate their dynamics in real time. These techniques open a way to reveal dynamics of more complex chemical reactions or identify the atomic-scale structure of unknown adsorbates. In addition, the study of atomic-scale defects in graphene may provide insights for nanoelectronic applications of this interesting material.

  13. Imaging and dynamics of light atoms and molecules on graphene

    NASA Astrophysics Data System (ADS)

    Meyer, Jannik C.; Girit, C. O.; Crommie, M. F.; Zettl, A.

    2008-07-01

    Observing the individual building blocks of matter is one of the primary goals of microscopy. The invention of the scanning tunnelling microscope revolutionized experimental surface science in that atomic-scale features on a solid-state surface could finally be readily imaged. However, scanning tunnelling microscopy has limited applicability due to restrictions in, for example, sample conductivity, cleanliness, and data acquisition rate. An older microscopy technique, that of transmission electron microscopy (TEM), has benefited tremendously in recent years from subtle instrumentation advances, and individual heavy (high-atomic-number) atoms can now be detected by TEM even when embedded within a semiconductor material. But detecting an individual low-atomic-number atom, for example carbon or even hydrogen, is still extremely challenging, if not impossible, via conventional TEM owing to the very low contrast of light elements. Here we demonstrate a means to observe, by conventional TEM, even the smallest atoms and molecules: on a clean single-layer graphene membrane, adsorbates such as atomic hydrogen and carbon can be seen as if they were suspended in free space. We directly image such individual adatoms, along with carbon chains and vacancies, and investigate their dynamics in real time. These techniques open a way to reveal dynamics of more complex chemical reactions or identify the atomic-scale structure of unknown adsorbates. In addition, the study of atomic-scale defects in graphene may provide insights for nanoelectronic applications of this interesting material.

  14. Anomalous Coulomb drag in bilayer graphene double layers

    NASA Astrophysics Data System (ADS)

    Liu, Xiaomeng; Taniguchi, Takashi; Watanabe, Kenji; Kim, Philip

    Bilayer graphene double-layer structure consists of two layers of bilayer graphene separated by atomically thin hexagonal boron nitride (hBN). With a perfect Fermi surface nesting and strong electron-electron interaction (ECoulomb > Ekinetic), such systems offer exciting platforms to study interaction driven phenomena, such as Coulomb drag and exciton condensation. We fabricate ultra-clean encapsulated bilayer graphene double layers with dry pick-up method. Room temperature drag measurement on our devices shows the sign of drag agree with the typical Fermi liquid behavior. However, at lower temperatures, the sign of drag reversed, indicating a new drag mechanism emerges and dominates. We measure this with different geometry, temperature, bias and gating to investigate the origin of such effect and discuss the implication of the drag sign changes.

  15. Atomically thin epitaxial template for organic crystal growth using graphene with controlled surface wettability.

    PubMed

    Nguyen, Nguyen Ngan; Jo, Sae Byeok; Lee, Seong Kyu; Sin, Dong Hun; Kang, Boseok; Kim, Hyun Ho; Lee, Hansol; Cho, Kilwon

    2015-04-08

    A two-dimensional epitaxial growth template for organic semiconductors was developed using a new method for transferring clean graphene sheets onto a substrate with controlled surface wettability. The introduction of a sacrificial graphene layer between a patterned polymeric supporting layer and a monolayer graphene sheet enabled the crack-free and residue-free transfer of free-standing monolayer graphene onto arbitrary substrates. The clean graphene template clearly induced the quasi-epitaxial growth of crystalline organic semiconductors with lying-down molecular orientation while maintaining the "wetting transparency", which allowed the transmission of the interaction between organic molecules and the underlying substrate. Consequently, the growth mode and corresponding morphology of the organic semiconductors on graphene templates exhibited distinctive dependence on the substrate hydrophobicity with clear transition from lateral to vertical growth mode on hydrophilic substrates, which originated from the high surface energy of the exposed crystallographic planes of the organic semiconductors on graphene. The optical properties of the pentacene layer, especially the diffusion of the exciton, also showed a strong dependency on the corresponding morphological evolution. Furthermore, the effect of pentacene-substrate interaction was systematically investigated by gradually increasing the number of graphene layers. These results suggested that the combination of a clean graphene surface and a suitable underlying substrate could serve as an atomically thin growth template to engineer the interaction between organic molecules and aromatic graphene network, thereby paving the way for effectively and conveniently tuning the semiconductor layer morphologies in devices prepared using graphene.

  16. Metal oxide nanoparticle growth on graphene via chemical activation with atomic oxygen.

    PubMed

    Johns, James E; Alaboson, Justice M P; Patwardhan, Sameer; Ryder, Christopher R; Schatz, George C; Hersam, Mark C

    2013-12-04

    Chemically interfacing the inert basal plane of graphene with other materials has limited the development of graphene-based catalysts, composite materials, and devices. Here, we overcome this limitation by chemically activating epitaxial graphene on SiC(0001) using atomic oxygen. Atomic oxygen produces epoxide groups on graphene, which act as reactive nucleation sites for zinc oxide nanoparticle growth using the atomic layer deposition precursor diethyl zinc. In particular, exposure of epoxidized graphene to diethyl zinc abstracts oxygen, creating mobile species that diffuse on the surface to form metal oxide clusters. This mechanism is corroborated with a combination of scanning probe microscopy, Raman spectroscopy, and density functional theory and can likely be generalized to a wide variety of related surface reactions on graphene.

  17. Surface-confined single-layer covalent organic framework on single-layer graphene grown on copper foil.

    PubMed

    Xu, Lirong; Zhou, Xin; Tian, Wei Quan; Gao, Teng; Zhang, Yan Feng; Lei, Shengbin; Liu, Zhong Fan

    2014-09-01

    The integration of 2D covalent organic frameworks (COFs) with atomic thickness with graphene will lead to intriguing two-dimensional materials. A surface-confined covalently bonded Schiff base network was prepared on single-layer graphene grown on copper foil and the dynamic reaction process was investigated with scanning tunneling microscopy. DFT simulations provide an understanding of the electronic structures and the interactions between the surface COF and graphene. Strong coupling between the surface COF and graphene was confirmed by the dispersive bands of the surface COF after interaction with graphene, and also by the experimental observation of tunneling condition dependent contrast of the surface COF.

  18. Selective growth of Pb islands on graphene/SiC buffer layers

    SciTech Connect

    Liu, X. T.; Miao, Y. P.; Ma, D. Y.; Hu, T. W.; Ma, F. E-mail: kwxu@mail.xjtu.edu.cn; Chu, Paul K.; Xu, K. W. E-mail: kwxu@mail.xjtu.edu.cn

    2015-02-14

    Graphene is fabricated by thermal decomposition of silicon carbide (SiC) and Pb islands are deposited by Pb flux in molecular beam epitaxy chamber. It is found that graphene domains and SiC buffer layer coexist. Selective growth of Pb islands on SiC buffer layer rather than on graphene domains is observed. It can be ascribed to the higher adsorption energy of Pb atoms on the 6√(3) reconstruction of SiC. However, once Pb islands nucleate on graphene domains, they will grow very large owing to the lower diffusion barrier of Pb atoms on graphene. The results are consistent with first-principle calculations. Since Pb atoms on graphene are nearly free-standing, Pb islands grow in even-number mode.

  19. van der Waals screening by single-layer graphene and molybdenum disulfide.

    PubMed

    Tsoi, Stanislav; Dev, Pratibha; Friedman, Adam L; Stine, Rory; Robinson, Jeremy T; Reinecke, Thomas L; Sheehan, Paul E

    2014-12-23

    A sharp tip of atomic force microscope is employed to probe van der Waals forces of a silicon oxide substrate with adhered graphene. Experimental results obtained in the range of distances from 3 to 20 nm indicate that single-, double-, and triple-layer graphenes screen the van der Waals forces of the substrate. Fluorination of graphene, which makes it electrically insulating, lifts the screening in the single-layer graphene. The van der Waals force from graphene determined per layer decreases with the number of layers. In addition, increased hole doping of graphene increases the force. Finally, we also demonstrate screening of the van der Waals forces of the silicon oxide substrate by single- and double-layer molybdenum disulfide.

  20. Protecting nickel with graphene spin-filtering membranes: A single layer is enough

    SciTech Connect

    Martin, M.-B.; Dlubak, B.; Piquemal-Banci, M.; Collin, S.; Petroff, F.; Anane, A.; Fert, A.; Seneor, P.; Yang, H.; Blume, R.; Schloegl, R.

    2015-07-06

    We report on the demonstration of ferromagnetic spin injectors for spintronics which are protected against oxidation through passivation by a single layer of graphene. The graphene monolayer is directly grown by catalytic chemical vapor deposition on pre-patterned nickel electrodes. X-ray photoelectron spectroscopy reveals that even with its monoatomic thickness, monolayer graphene still efficiently protects spin sources against oxidation in ambient air. The resulting single layer passivated electrodes are integrated into spin valves and demonstrated to act as spin polarizers. Strikingly, the atom-thick graphene layer is shown to be sufficient to induce a characteristic spin filtering effect evidenced through the sign reversal of the measured magnetoresistance.

  1. Fabrication of graphene flakes composed of multi-layer graphene sheets using a thermal plasma jet system

    NASA Astrophysics Data System (ADS)

    Kim, Juhan; Heo, Soo Bong; Hoi Gu, Geun; Suh, Jung Sang

    2010-03-01

    We have developed a method to fabricate graphene flakes composed of high quality multi-layer graphene sheets using a thermal plasma jet system. A carbon atomic beam was generated by injecting ethanol into Ar plasma continuously; the beam then flowed through a carbon tube attached to the anode. Graphene was made by epitaxial growth where a carbon atomic beam, having the proper energy, collided with a graphite plate. The graphene fabricated was very pure and showed a relatively good crystalline structure. We have demonstrated that the number of layers of graphene sheets could be controlled by controlling the rate of ethanol injection. Our process is a continuous process with a relatively high yield (~8%).

  2. Effects of heat treatment on Raman spectra of two-layer 12C/13C graphene.

    PubMed

    Kalbac, Martin; Frank, Otakar; Kavan, Ladislav

    2012-10-22

    The Raman spectra of two-layered graphene on a silicon substrate were studied in the temperature range from 298 to 1073 K in an inert atmosphere. Isotopic engineering was used to fabricate two-layer graphene specimens containing (13)C atoms in the top layer and (12)C atoms in the bottom layer, which allowed the behavior of each particular layer to be distinguished as a function of temperature. It is demonstrated that the top layer exhibits much lower Raman temperature coefficients than the bottom one for both the G and the G' modes. We suggest that the changes in the Raman spectra of graphene observed during thermal cycling are predominantly caused by a superposition of two effects, namely, the mechanical stress in graphene exerted by the substrate and the intrinsic changes in the graphene lattice caused by the temperature itself. The top graphene layer is proposed to be more relaxed than the bottom graphene layer and thus reflects almost exclusively the temperature variations as a freestanding graphene layer would.

  3. Graphene on Ni(111): Electronic Corrugation and Dynamics from Helium Atom Scattering

    PubMed Central

    2015-01-01

    Using helium atom scattering, we have studied the structure and dynamics of a graphene layer prepared in situ on a Ni(111) surface. Graphene/Ni(111) exhibits a helium reflectivity of ∼20% for a thermal helium atom beam and a particularly small surface electron density corrugation ((0.06 ± 0.02) Å peak to peak height). The Debye–Waller attenuation of the elastic diffraction peaks of graphene/Ni(111) and Ni(111) was measured at surface temperatures between 150 and 740 K. A surface Debye temperature of θD = (784 ± 14) K is determined for the graphene/Ni(111) system and θD = (388 ± 7) K for Ni(111), suggesting that the interlayer interaction between graphene and the Ni substrate is intermediary between those for strongly interacting systems like graphene/Ru(0001) and weakly interacting systems like graphene/Pt(111). In addition we present measurements of low frequency surface phonon modes on graphene/Ni(111) where the phonon modes of the Ni(111) substrate can be clearly observed. The similarity of these findings with the graphene/Ru(0001) system indicates that the bonding of graphene to a metal substrate alters the dynamic properties of the graphene surface strongly and is responsible for the high helium reflectivity of these systems. PMID:26617683

  4. Graphene on Ni(111): Electronic Corrugation and Dynamics from Helium Atom Scattering.

    PubMed

    Tamtögl, Anton; Bahn, Emanuel; Zhu, Jianding; Fouquet, Peter; Ellis, John; Allison, William

    2015-11-19

    Using helium atom scattering, we have studied the structure and dynamics of a graphene layer prepared in situ on a Ni(111) surface. Graphene/Ni(111) exhibits a helium reflectivity of ∼20% for a thermal helium atom beam and a particularly small surface electron density corrugation ((0.06 ± 0.02) Å peak to peak height). The Debye-Waller attenuation of the elastic diffraction peaks of graphene/Ni(111) and Ni(111) was measured at surface temperatures between 150 and 740 K. A surface Debye temperature of θD = (784 ± 14) K is determined for the graphene/Ni(111) system and θD = (388 ± 7) K for Ni(111), suggesting that the interlayer interaction between graphene and the Ni substrate is intermediary between those for strongly interacting systems like graphene/Ru(0001) and weakly interacting systems like graphene/Pt(111). In addition we present measurements of low frequency surface phonon modes on graphene/Ni(111) where the phonon modes of the Ni(111) substrate can be clearly observed. The similarity of these findings with the graphene/Ru(0001) system indicates that the bonding of graphene to a metal substrate alters the dynamic properties of the graphene surface strongly and is responsible for the high helium reflectivity of these systems.

  5. Green synthesis of well-dispersed single-layer graphene colloids via an electrolytic method

    NASA Astrophysics Data System (ADS)

    Huang, Yilong; Tian, Yanhong; Wang, Shang

    2017-03-01

    Graphene has lots of attractive properties. However, most of its optimal properties are only associated with individual sheets. Producing a colloidal form of graphene can effectively avoid graphene aggregation and thus maintain its original performance. In this paper, an electrolytic method was utilized to prepare graphene colloids. Initially, graphene oxide (GO) was produced from graphite by a pressurized oxidation method. The high concentration of H+ or OH‑ was found to facilitate the aggregation of GO. Then, GO was reduced by nascent hydrogen, which was generated by reducing hydrogen ions on an iron cathode in the electrolytic method. X-ray diffraction, Raman spectrum, thermogravimetric analysis and x-ray photoelectron spectroscopy analyses indicated that the nascent hydrogen can effectively reduce GO to graphene. Atomic force microscopy analysis and dispersibility evaluation of graphene colloids proved that the novel electrolytic method can prepare well-dispersed single-layer graphene colloids.

  6. Effect of water layer at the SiO2/graphene interface on pentacene morphology.

    PubMed

    Chhikara, Manisha; Pavlica, Egon; Matković, Aleksandar; Gajić, Radoš; Bratina, Gvido

    2014-10-07

    Atomic force microscopy has been used to examine early stages of pentacene growth on exfoliated single-layer graphene transferred to SiO2 substrates. We have observed 2D growth with mean height of 1.5 ± 0.2 nm on as-transferred graphene. Three-dimensional islands of pentacene with an average height of 11 ± 2 nm were observed on graphene that was annealed at 350 °C prior to pentacene growth. Compellingly similar 3D morphology has been observed on graphene transferred onto SiO2 that was treated with hexamethyldisilazane prior to the transfer of graphene. On multilayer graphene we have observed 2D growth, regardless of the treatment of SiO2. We interpret this behavior of pentacene molecules in terms of the influence of the dipolar field that emerges from the water monolayer at the graphene/SiO2 interface on the surface energy of graphene.

  7. Atomic Scale Study on Growth and Heteroepitaxy of ZnO Monolayer on Graphene

    PubMed Central

    2016-01-01

    Atomically thin semiconducting oxide on graphene carries a unique combination of wide band gap, high charge carrier mobility, and optical transparency, which can be widely applied for optoelectronics. However, study on the epitaxial formation and properties of oxide monolayer on graphene remains unexplored due to hydrophobic graphene surface and limits of conventional bulk deposition technique. Here, we report atomic scale study of heteroepitaxial growth and relationship of a single-atom-thick ZnO layer on graphene using atomic layer deposition. We demonstrate atom-by-atom growth of zinc and oxygen at the preferential zigzag edge of a ZnO monolayer on graphene through in situ observation. We experimentally determine that the thinnest ZnO monolayer has a wide band gap (up to 4.0 eV), due to quantum confinement and graphene-like structure, and high optical transparency. This study can lead to a new class of atomically thin two-dimensional heterostructures of semiconducting oxides formed by highly controlled epitaxial growth. PMID:28002942

  8. Hidden Kekule Order of Ghost Atoms on Monolayer Graphene

    NASA Astrophysics Data System (ADS)

    Gutierrez, Christopher; Brown, Lola; Lochocki, Edward; Rosenthal, Ethan; Kim, Cheol-Joo; Ogawa, Yui; Shen, Kyle; Park, Jiwoong; Pasupathy, Abhay

    2015-03-01

    Various charge and spin ordered phases have been predicted to exist in graphene when the lattice symmetry is broken on the atomic scale. One such phase is the Kekule distortion, whereby the C-C bond symmetry is broken and the graphene unit cell is tripled. It has been proposed that when certain adatoms are placed on monolayer graphene, strong interactions can exist between them mediated by the graphene lattice. The graphene-adatom interaction can induce Kekule order in the graphene itself, and move the adatoms to produce a hidden Kekule ordering. In this talk I will discuss evidence from scanning tunneling microscopy, electron diffraction and angle resolved photoemission spectroscopy that shows the existence of this unique ordering in epitaxial graphene on copper. Interestingly, we find in this case that the Kekule order is induced by a dilute number of ``ghost atoms'' - unidentified atomic features - in the otherwise perfect copper lattice underneath monolayer graphene.

  9. Raman fingerprints of atomically precise graphene nanoribbons

    DOE PAGES

    Verzhbitskiy, Ivan A.; Corato, Marzio De; Ruini, Alice; ...

    2016-02-23

    Bottom-up approaches allow the production of ultranarrow and atomically precise graphene nanoribbons (GNRs) with electronic and optical properties controlled by the specific atomic structure. Combining Raman spectroscopy and ab initio simulations, we show that GNR width, edge geometry, and functional groups all influence their Raman spectra. As a result, the low-energy spectral region below 1000 cm–1 is particularly sensitive to edge morphology and functionalization, while the D peak dispersion can be used to uniquely fingerprint the presence of GNRs and differentiates them from other sp2 carbon nanostructures.

  10. Raman Fingerprints of Atomically Precise Graphene Nanoribbons

    NASA Astrophysics Data System (ADS)

    Verzhbitskiy, Ivan A.; Corato, Marzio De; Ruini, Alice; Molinari, Elisa; Narita, Akimitsu; Hu, Yunbin; Schwab, Matthias G.; Bruna, Matteo; Yoon, Duhee; Milana, Silvia; Feng, Xinliang; Müllen, Klaus; Ferrari, Andrea C.; Casiraghi, Cinzia; Prezzi, Deborah

    2016-06-01

    Bottom-up approaches allow the production of ultra-narrow and atomically precise graphene nanoribbons (GNRs), with electronic and optical properties controlled by the specific atomic structure. Combining Raman spectroscopy and ab-initio simulations, we show that GNR width, edge geometry and functional groups all influence their Raman spectra. The low-energy spectral region below 1000 cm-1 is particularly sensitive to edge morphology and functionalization, while the D peak dispersion can be used to uniquely fingerprint the presence of GNRs, and differentiates them from other sp2 carbon nanostructures.

  11. Changes in the reflectivity of a lithium niobate crystal decorated with a graphene layer

    NASA Astrophysics Data System (ADS)

    Salas, O.; Garcés, E.; Castillo, F. L.; Magaña, L. F.

    2017-01-01

    Density functional theory and molecular dynamics were used to study the interaction of a graphene layer with the surface of lithium niobate. The simulations were performed at atmospheric pressure and 300K. We found that the graphene layer is physisorbed with an adsorption energy of -0.8205 eV/C-atom. Subsequently, the optical absorption of the graphene-(lithium niobate) system was calculated and compared with that of graphene solo and lithium niobate alone, respectively. The calculations were performed using the Quantum Espresso code with the GGA approximation and Vdw-DF2 (which includes long-range correlation effects as Van der Waals interactions).

  12. Two-dimensional atomic crystals beyond graphene

    NASA Astrophysics Data System (ADS)

    Kaul, Anupama B.

    2014-06-01

    Carbon-based nanostructures have been the center of intense research and development for more than two decades now. Of these materials, graphene, a two-dimensional (2D) layered material system, has had a significant impact on science and technology over the past decade after monolayers of this material were experimentally isolated in 2004. The recent emergence of other classes of 2D graphene-like layered materials has added yet more exciting dimensions for research in exploring the diverse properties and applications arising from these 2D material systems. For example, hexagonal-BN, a layered material closest in structure to graphene, is an insulator, while NbSe2, a transition metal di-chalcogenide, is metallic and monolayers of other transition metal di-chalcogenides such as MoS2 are direct band-gap semiconductors. The rich spectrum of properties that 2D layered material systems offer can potentially be engineered ondemand, and creates exciting prospects for using such materials in applications ranging from electronics, sensing, photonics, energy harvesting and flexible electronics over the coming years.

  13. Graphene/ferroelectrics/graphene hybrid structure: Asymmetric doping of graphene layers

    SciTech Connect

    Duong, Dinh Loc; Lee, Si Young; Kim, Seong Kyu; Lee, Young Hee

    2015-06-15

    We report graphene/ferroelectric/graphene hybrid structure to demonstrate an asymmetrical doping in two graphene layers, one side with electrons and another side with holes. Two ferroelectrics, a poly(vinylidenefluoride) (PVDF) and a hydrofluorinated graphene, were used to demonstrate the concept with density functional calculations, revealing the Fermi level shift of 0.35 and 0.75 eV, respectively. This concept was confirmed by Raman spectroscopy using graphene/poly(vinylidenefluoride-co-trifluoroethylene) (P(VDF-TrFE))/graphene hybrid, which can easily form β-phase close to our simulation model. G-band peak position was downshifted for electron doping and upshifted for hole doping. This hybrid structure opens an opportunity to study bilayer graphene system with a controllable thickness for a wide range of high carrier concentration.

  14. Solution Synthesis of Atomically Precise Graphene Nanoribbons

    NASA Astrophysics Data System (ADS)

    Shekhirev, Mikhail; Sinitskii, Alexander

    2017-05-01

    Bottom-up fabrication of narrow strips of graphene, also known as graphene nanoribbons or GNRs, is an attractive way to open a bandgap in semimetallic graphene. In this chapter, we review recent progress in solution-based synthesis of GNRs with atomically precise structures. We discuss a variety of atomically precise GNRs and highlight theoretical and practical aspects of their structural design and solution synthesis. These GNRs are typically synthesized through a polymerization of rationally designed molecular precursors followed by a planarization through a cyclodehydrogenation reaction. We discuss various synthetic techniques for polymerization and planarization steps, possible approaches for chemical modification of GNRs, and compare the properties of GNRs that could be achieved by different synthetic methods. We also discuss the importance of the rational design of molecular precursors to avoid isomerization during the synthesis and achieve GNRs that have only one possible structure. Significant attention in this chapter is paid to the methods of material characterization of solution-synthesized GNRs. The chapter is concluded with the discussion of the most significant challenges in the field and the future outlook.

  15. Atomically precise nitrogen-doped graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Sinitskii, Alexander

    There is a considerable interest in graphene nanoribbons (GNRs), few-nm-wide strips of graphene with high aspect ratios, because of their intriguing physical properties. For example, GNRs with zigzag edges are predicted to exhibit low-dimensional magnetism, while GNRs with armchair edges can possess large energy band gaps, making them promising materials for future electronics and photovoltaics. The ability to control structural parameters of GNRs, such as their width, edge structure and termination, with atomic precision is the key for practical realization of these intriguing nanoscale properties. Physical properties of GNRs can also be modified by their doping with heteroatoms, such nitrogen, resulting in nitrogen-doped GNRs or N-GNRs. In this talk I will discuss several types of N-GNRs with different doping levels that have been synthesized and systematically studied by spectroscopic, microscopic and transport methods. Incorporation of nitrogen atoms in graphene lattice is shown to be an effective route to affect GNRs' band gap, doping level as well as aggregation behavior. The support from NSF CHE-1455330 is gratefully acknowledged.

  16. Antibacterial activity of graphene layers

    NASA Astrophysics Data System (ADS)

    Dybowska-Sarapuk, Ł.; Kotela, A.; Krzemiński, J.; Janczak, D.; Wróblewska, M.; Marchel, H.; Łegorz, P.; Jakubowska, M.

    2016-09-01

    The bacterial biofilm is a direct cause of complications in management of various medical conditions. There is an ongoing search for a feasible method to prevent its growth, as an alternative to antibiotics, which are ineffective. The aim of the study was to prepare and evaluate a detailed algorithm for production of graphene coatings, using economically efficient methods of printed electronics (such as ink-jet printing or spray coating), and assess their antibacterial properties. Based on the preliminary results of our work we suggest that graphene coating may inhibit the formation of microbial biofilms. Further research is needed to verify antibacterial properties of graphene coatings and its future applications in prevention of biofilm-related infections, e.g. by coating surgical instruments, catheters or tracheostomy tubes. In addition, we propose a series of hypotheses to be evaluated in further work.

  17. Enhanced intervalley scattering in artificially stacked double-layer graphene

    NASA Astrophysics Data System (ADS)

    Iqbal, M. Z.; Kelekçi, Özgür; Iqbal, M. W.; Jin, Xiaozhan; Hwang, Chanyong; Eom, Jonghwa

    2014-08-01

    We fabricated artificially stacked double-layer graphene by sequentially transferring graphene grown by chemical vapor deposition. The double-layer graphene was characterized by Raman spectroscopy and transport measurements. A weak localization effect was observed for different charge carrier densities and temperatures. The obtained intervalley scattering rate was unusually high compared to normal Bernal-stacked bilayer or single-layer graphene. The sharp point defects, local deformation, or bending of graphene plane required for intervalley scattering from one Dirac cone to another seemed to be enhanced by the artificially stacked graphene layers.

  18. Graphene and graphene-like layered transition metal dichalcogenides in energy conversion and storage.

    PubMed

    Wang, Hua; Feng, Hongbin; Li, Jinghong

    2014-06-12

    Being confronted with the energy crisis and environmental problems, the exploration of clean and renewable energy materials as well as their devices are urgently demanded. Two-dimensional (2D) atomically-thick materials, graphene and grpahene-like layered transition metal dichalcogenides (TMDs), have showed vast potential as novel energy materials due to their unique physicochemical properties. In this Review, we outline the typical application of graphene and grpahene-like TMDs in energy conversion and storage fields, and hope to promote the development of 2D TMDs in this field through the analysis and comparisons with the relatively natural graphene. First, a brief introduction of electronic structures and basic properties of graphene and TMDs are presented. Then, we summarize the exciting progress of these materials made in both energy conversion and storage field including solar cells, electrocatalysis, supercapacitors and lithium ions batteries. Finally, the prospects and further developments in these exciting fields of graphene and graphene-like TMDs materials are also suggested.

  19. Enhancement of absorption in vertically-oriented graphene sheets growing on a thin copper layer

    NASA Astrophysics Data System (ADS)

    Rozouvan, Tamara; Poperenko, Leonid; Kravets, Vasyl; Shaykevich, Igor

    2017-02-01

    The optical properties and surface structure of graphene films grown on thin copper Cu (1 μm) layer using chemical vapour deposition method were investigated via spectroscopic ellipsometry and nanoscopic measurements. Angle variable ellipsometry measurements were performed to analyze the features of dispersion of the complex refractive index and optical conductivity. It was observed significant enhancement of the absorption band in the vertically-oriented graphene sheets layer with respect to the bulk graphite due to interaction between excited localized surface plasmon at surface of thin Cu layer and graphene's electrons. Scanning tunneling microscopy measurements with atomic spatial resolution revealed vertical crystal lattice structure of the deposited graphene layer. The obtained results provide direct evidence of the strong influence of the growing condition and morphology of nanostructure on electronic and optical behaviours of graphene film.

  20. Absorption and reflectivity of the lithium niobate surface masked with a graphene layer

    NASA Astrophysics Data System (ADS)

    Salas, O.; Garcés, E.; Castillo, F. L.; Magaña, L. F.

    2017-01-01

    We performed simulations of the interaction of a graphene layer with the surface of lithium niobate utilizing density functional theory and molecular dynamics at 300K and atmospheric pressure. We found that the graphene layer is physisorbed on the lithium niobate surface with an adsorption energy of -0.8205 eV/(carbon-atom). Subsequently, the energy band structure, the optical absorption and reflectivity of the new system were calculated. We found important changes in these physical properties with respect to the corresponding ones of a graphene layer and of a lithium niobate crystal.

  1. Gamma ray-assisted irradiation of few-layer graphene films: a Raman spectroscopy study

    NASA Astrophysics Data System (ADS)

    Kleut, D. N.; Marković, Z. M.; Holclajtner Antunović, I. D.; Dramićanin, M. D.; Kepić, D. P.; Todorović Marković, B. M.

    2014-09-01

    This paper represents results of a Raman spectroscopy study of gamma-irradiated few-layer graphene thin films at three different doses: 25, 50 and 110 kGy. Graphene thin films were deposited by the vacuum filtration method and then transferred onto glass substrate. Raman spectroscopy and atomic force microscopy analysis have shown that the average in-plane crystallite size La of graphene thin films varies slightly when an irradiation dose is applied. Raman spectroscopy revealed that gamma irradiation of graphene thin films resulted in slight p-doping of the graphene thin film surface. It was found that during gamma irradiation at a dose of 110 kGy, the graphene sheets merged. As a result, the number of incorporated defects in the graphene structure was reduced (the ID/IG ratio decreased with the increase in the applied dose).

  2. Spectroscopic investigation of thermal conductivity in few-layer graphene

    NASA Astrophysics Data System (ADS)

    Denison, Joseph C., Jr.

    Carbon is an extremely versatile element due to the ability of its electronic structure to allow strong bonds with many elements including other carbon atoms. This allows for the formation of many types of large and complex architectures, such as fullerenes and carbon nanotubes, at the nanoscale. One of the most fascinating allotropes of carbon is graphene, a two-dimensional honeycomb lattice with carbon in sp2 hybridization, which building block for layered graphite and other nanocarbons.[1] Because of its unique structure, graphene displays several interesting properties including high thermal[2-4] and electrical mobility and conductivity[1,5]. The initial studies on graphene were performed on mechanically exfoliated samples, which were limited to few microns in size. In the recent years, large areas of single- and few-layer graphene (˜few cm x cm) are being produced by chemical vapor deposition technique for practical applications. However, chemical vapor deposition grown graphene is highly polycrystalline with interfaces such as edges, grain boundaries, dislocations, and point defects. This inevitable presence of defects in graphene influences its electrical and thermal transport. While many studies have previously focused on the influence of defects on electrical mobility and conductivity, there is little information on the influence of defects on the thermal properties of graphene. This study specifically investigates the effect of both intrinsic and extrinsic defects on the in-plane thermal properties of graphene using micro-Raman spectroscopy. The in-plane thermal conductivity of few-layered graphene (FLG) was measured using Raman spectroscopy, following the work of Balandin et al. [4]The thermal conductivity was estimated from a shift of the characteristic G-band of graphene as a function of the excitation laser power. The graphene samples were synthesized on nickel substrates using chemical vapor deposition, and transferred to copper TEM grids and

  3. Few layer graphene based superlattices as efficient thermal insulators

    NASA Astrophysics Data System (ADS)

    Ni, Yuxiang; Chalopin, Yann; Volz, Sebastian

    2013-09-01

    While graphene and few layer graphene (FLG) are considered as having the highest thermal conductivity in their in-plane directions, our molecular dynamics (MD) simulations however show that those systems are also characterized by a superior thermal contact resistance, which could be largely tuned with the layer number when in contact with a silica substrate. Taking advantages of such a resistive interface, MD simulations show that SiO2/FLG superlattices have a thermal conductivity as low as 0.30 W/m K, exhibiting a promising prospect in nano-scale thermal insulation. These findings pave the way for an improved thermal management of nanoscale systems such as thermal barrier coatings and phase change memory materials with atomic-scale super-insulators.

  4. Layer resolved capacitive probing of graphene bilayers

    NASA Astrophysics Data System (ADS)

    Zibrov, Alexander; Parmentier, François; Li, Jia; Wang, Lei; Hunt, Benjamin; Dean, Cory; Hone, James; Taniguchi, Takashi; Watanabe, Kenji; Young, Andrea

    Compared to single layer graphene, graphene bilayers have an additional ``which-layer'' degree of freedom that can be controlled by an external electric field in a dual-gated device geometry. We describe capacitance measurements capable of directly probing this degree of freedom. By performing top gate, bottom gate, and penetration field capacitance measurements, we directly extract layer polarization of both Bernal and twisted bilayers. We will present measurements of hBN encapsulated bilayers at both zero and high magnetic field, focusing on the physics of the highly degenerate zero-energy Landau level in the high magnetic field limit where spin, valley, and layer degeneracy are all lifted by electronic interactions.

  5. Atomically thin semiconducting layers and nanomembranes: a review

    NASA Astrophysics Data System (ADS)

    Dragoman, Mircea; Dragoman, Daniela; Tiginyanu, Ion

    2017-03-01

    This article reviews the main physical properties of atomically thin semiconductors and the electronic devices based on them. We start with graphene, describing its physical properties and growth methods, followed by a discussion of its electronic device applications. Then, transition metal dichalcogenides (TMDs) are analyzed as a prototype of atomically thin semiconductors, their physical properties, growth methods, and electronic devices are discussed in detail. Finally, non-layered semiconducting membranes with thicknesses ranging from a few nanometers to about 50 nm, and considered as counterparts of atomically thin semiconductors, are analyzed, and their applications presented.

  6. Graphene, other 2D atomic crystals and their heterostructures

    NASA Astrophysics Data System (ADS)

    Novoselov, Kostya S.

    2014-03-01

    Probably the most important ``property'' of graphene is that it has opened a floodgate of experiments on many other 2D atomic crystals: BN, NbSe2, TaS2, MoS2, etc. One can use similar strategies to those applied to graphene and obtain new materials by mechanical or liquid phase exfoliation of layered materials or CVD growth. An alternative strategy to create new 2D crystals is to start with an existing one (like graphene) and use it as an atomic scaffolding to modify it by chemical means (graphane and fluorographene are good examples). The resulting pool of 2D crystals is huge, and they cover a massive range of properties: from the most insulating to the most conductive, from the strongest to the softest. If 2D materials provide a large range of different properties, sandwich structures made up of 2, 3, 4 ...different layers of such materials can offer even greater scope. Since these 2D-based heterostructures can be tailored with atomic precision and individual layers of very different character can be combined together, - the properties of these structures can be tuned to study novel physical phenomena (Coulomb drag, Hostadter butterfly, metal-insulator transition, etc) or to fit an enormous range of possible applications, with the functionality of heterostructure stacks is ``embedded'' in their design (tunnelling or hot-electron transistors, photovoltaic devices). Of particular interest are the tunnelling structures. Being able to control the thickness with atomic precision and having a variety of different material in disposal allows us to modify both the height and the width of the tunnelling barrier in the wide range. The use of graphene as electrodes and utilising insulating (BN) or semiconducting (MoS2, WS2) materials as the tunnelling barrier led to the creation of tunnelling transistors and tunnelling photovoltaic devices and the observation of the resonance tunnelling associated with momentum conservation. We will also consider tunnelling in magnetic

  7. Symmetry breaking in few layer graphene films

    NASA Astrophysics Data System (ADS)

    Bostwick, Aaron; Ohta, Taisuke; McChesney, Jessica L.; Emtsev, Konstantin V.; Seyller, Thomas; Horn, Karsten; Rotenberg, Eli

    2007-10-01

    Recently, it was demonstrated that the quasiparticle dynamics, the layer-dependent charge and potential, and the c-axis screening coefficient could be extracted from measurements of the spectral function of few layer graphene films grown epitaxially on SiC using angle-resolved photoemission spectroscopy (ARPES). In this paper we review these findings, and present detailed methodology for extracting such parameters from ARPES. We also present detailed arguments against the possibility of an energy gap at the Dirac crossing ED.

  8. Symmetry Breaking in Few Layer Graphene Films

    SciTech Connect

    Bostwick, A.; Ohta, T.; McChesney, J.L.; Emtsev, K.; Seyller,Th.; Horn, K.; Rotenberg, E.

    2007-05-25

    Recently, it was demonstrated that the quasiparticledynamics, the layer-dependent charge and potential, and the c-axisscreening coefficient could be extracted from measurements of thespectral function of few layer graphene films grown epitaxially on SiCusing angle-resolved photoemission spectroscopy (ARPES). In this articlewe review these findings, and present detailed methodology for extractingsuch parameters from ARPES. We also present detailed arguments againstthe possibility of an energy gap at the Dirac crossing ED.

  9. Large-area, freestanding, single-layer graphene-gold: a hybrid plasmonic nanostructure.

    PubMed

    Iyer, Ganjigunte R Swathi; Wang, Jian; Wells, Garth; Guruvenket, Srinivasan; Payne, Scott; Bradley, Michael; Borondics, Ferenc

    2014-06-24

    Graphene-based plasmonic devices have recently drawn great attention. However, practical limitations in fabrication and device architectures prevent studies from being carried out on the intrinsic properties of graphene and their change by plasmonic structures. The influence of a quasi-infinite object (i.e., the substrate) on graphene, being a single sheet of carbon atoms, and the plasmonic device is overwhelming. To address this and put the intrinsic properties of the graphene-plasmonic nanostructures in focus, we fabricate large-area, freestanding, single-layer graphene-gold (LFG-Au) sandwich structures and Au nanoparticle decorated graphene (formed via thermal treatment) hybrid plasmonic nanostructures. We observed two distinct plasmonic enhancement routes of graphene unique to each structure via surface-enhanced Raman spectroscopy. The localized electronic structure variation in the LFG due to graphene-Au interaction at the nanoscale is mapped using scanning transmission X-ray microscopy. The measurements show an optical density of ∼0.007, which is the smallest experimentally determined for single-layer graphene thus far. Our results on freestanding graphene-Au plasmonic structures provide great insight for the rational design and future fabrication of graphene plasmonic hybrid nanostructures.

  10. Graphene coated with controllable N-doped carbon layer by molecular layer deposition as electrode materials for supercapacitors

    NASA Astrophysics Data System (ADS)

    Chen, Yao; Gao, Zhe; Zhang, Bin; Zhao, Shichao; Qin, Yong

    2016-05-01

    In this work, graphene is coated with nitrogen-doped carbon layer, which is produced by a carbonization process of aromatic polyimide (PI) films deposited on the surfaces of graphene by molecular layer deposition (MLD). The utilization of MLD not only allows uniform coating of PI layers on the surfaces of pristine graphene without any surface treatment, but also enables homogenous dispersion of doped nitrogen atoms in the carbonized products. The as-prepared N-doped carbon layer coated graphene (NC-G) exhibited remarkable capacitance performance as electrode materials for supercapacitor, showing a high specific capacitance of 290.2 F g-1 at current density of 1 A g-1 in 6 M KOH aqueous electrolyte, meanwhile maintaining good rate performance and stable cycle capability. The NC-G synthesized by this way represents an alternative promising candidate as electrode material for supercapacitors.

  11. Effective elastic mechanical properties of single layer graphene sheets.

    PubMed

    Scarpa, F; Adhikari, S; Srikantha Phani, A

    2009-02-11

    The elastic moduli of single layer graphene sheet (SLGS) have been a subject of intensive research in recent years. Calculations of these effective properties range from molecular dynamic simulations to use of structural mechanical models. On the basis of mathematical models and calculation methods, several different results have been obtained and these are available in the literature. Existing mechanical models employ Euler-Bernoulli beams rigidly jointed to the lattice atoms. In this paper we propose truss-type analytical models and an approach based on cellular material mechanics theory to describe the in-plane linear elastic properties of the single layer graphene sheets. In the cellular material model, the C-C bonds are represented by equivalent mechanical beams having full stretching, hinging, bending and deep shear beam deformation mechanisms. Closed form expressions for Young's modulus, the shear modulus and Poisson's ratio for the graphene sheets are derived in terms of the equivalent mechanical C-C bond properties. The models presented provide not only quantitative information about the mechanical properties of SLGS, but also insight into the equivalent mechanical deformation mechanisms when the SLGS undergoes small strain uniaxial and pure shear loading. The analytical and numerical results from finite element simulations show good agreement with existing numerical values in the open literature. A peculiar marked auxetic behaviour for the C-C bonds is identified for single graphene sheets under pure shear loading.

  12. Reversible loss of Bernal stacking during the deformation of few-layer graphene in nanocomposites.

    PubMed

    Gong, Lei; Young, Robert J; Kinloch, Ian A; Haigh, Sarah J; Warner, Jamie H; Hinks, Jonathan A; Xu, Ziwei; Li, Li; Ding, Feng; Riaz, Ibtsam; Jalil, Rashid; Novoselov, Kostya S

    2013-08-27

    The deformation of nanocomposites containing graphene flakes with different numbers of layers has been investigated with the use of Raman spectroscopy. It has been found that there is a shift of the 2D band to lower wavenumber and that the rate of band shift per unit strain tends to decrease as the number of graphene layers increases. It has been demonstrated that band broadening takes place during tensile deformation for mono- and bilayer graphene but that band narrowing occurs when the number of graphene layers is more than two. It is also found that the characteristic asymmetric shape of the 2D Raman band for the graphene with three or more layers changes to a symmetrical shape above about 0.4% strain and that it reverts to an asymmetric shape on unloading. This change in Raman band shape and width has been interpreted as being due to a reversible loss of Bernal stacking in the few-layer graphene during deformation. It has been shown that the elastic strain energy released from the unloading of the inner graphene layers in the few-layer material (~0.2 meV/atom) is similar to the accepted value of the stacking fault energies of graphite and few layer graphene. It is further shown that this loss of Bernal stacking can be accommodated by the formation of arrays of partial dislocations and stacking faults on the basal plane. The effect of the reversible loss of Bernal stacking upon the electronic structure of few-layer graphene and the possibility of using it to modify the electronic structure of few-layer graphene are discussed.

  13. Reversible Loss of Bernal Stacking during the Deformation of Few-Layer Graphene in Nanocomposites

    PubMed Central

    2013-01-01

    The deformation of nanocomposites containing graphene flakes with different numbers of layers has been investigated with the use of Raman spectroscopy. It has been found that there is a shift of the 2D band to lower wavenumber and that the rate of band shift per unit strain tends to decrease as the number of graphene layers increases. It has been demonstrated that band broadening takes place during tensile deformation for mono- and bilayer graphene but that band narrowing occurs when the number of graphene layers is more than two. It is also found that the characteristic asymmetric shape of the 2D Raman band for the graphene with three or more layers changes to a symmetrical shape above about 0.4% strain and that it reverts to an asymmetric shape on unloading. This change in Raman band shape and width has been interpreted as being due to a reversible loss of Bernal stacking in the few-layer graphene during deformation. It has been shown that the elastic strain energy released from the unloading of the inner graphene layers in the few-layer material (∼0.2 meV/atom) is similar to the accepted value of the stacking fault energies of graphite and few layer graphene. It is further shown that this loss of Bernal stacking can be accommodated by the formation of arrays of partial dislocations and stacking faults on the basal plane. The effect of the reversible loss of Bernal stacking upon the electronic structure of few-layer graphene and the possibility of using it to modify the electronic structure of few-layer graphene are discussed. PMID:23899378

  14. Diffusion and desorption of oxygen atoms on graphene.

    PubMed

    Dai, Yafei; Ni, Shuang; Li, Zhenyu; Yang, Jinlong

    2013-10-09

    To understand the reversible oxidation of graphene in a recent experiment, a density-functional theory study is performed. The adsorption energy of isolated oxygen atom on graphene is 2.3 eV, indicating a strong interaction between them. However, the migration barrier of oxygen atoms on graphene is only 0.8 eV and oxygen diffusion is still possible. Provided with this possibility, we find that, although a single oxygen atom is very difficult to desorb, cooperative desorption of two oxygen atoms is feasible.

  15. Aqueous proton transfer across single-layer graphene

    DOE PAGES

    Achtyl, Jennifer L.; Unocic, Raymond R.; Xu, Lijun; ...

    2015-03-17

    Proton transfer across single-layer graphene proceeds with large computed energy barriers and is thought to be unfavourable at room temperature unless nanoscale holes or dopants are introduced, or a potential bias is applied. Here we subject single-layer graphene supported on fused ​silica to cycles of high and low pH, and show that protons transfer reversibly from the aqueous phase through the graphene to the other side where they undergo acid–base chemistry with the silica hydroxyl groups. After ruling out diffusion through macroscopic pinholes, the protons are found to transfer through rare, naturally occurring atomic defects. Computer simulations reveal low energymore » barriers of 0.61–0.75 eV for aqueous proton transfer across hydroxyl-terminated atomic defects that participate in a Grotthuss-type relay, while ​pyrylium-like ether terminations shut down proton exchange. In conclusion, unfavourable energy barriers to helium and ​hydrogen transfer indicate the process is selective for aqueous protons.« less

  16. Aqueous proton transfer across single-layer graphene

    SciTech Connect

    Achtyl, Jennifer L.; Unocic, Raymond R.; Xu, Lijun; Cai, Yu; Raju, Muralikrishna; Zhang, Weiwei; Sacci, Robert L.; Vlassiouk, Ivan V.; Fulvio, Pasquale F.; Ganesh, Panchapakesan; Wesolowski, David J.; Dai, Sheng; van Duin, Adri C. T.; Neurock, Matthew; Geiger, Franz M.

    2015-03-17

    Proton transfer across single-layer graphene proceeds with large computed energy barriers and is thought to be unfavourable at room temperature unless nanoscale holes or dopants are introduced, or a potential bias is applied. Here we subject single-layer graphene supported on fused ​silica to cycles of high and low pH, and show that protons transfer reversibly from the aqueous phase through the graphene to the other side where they undergo acid–base chemistry with the silica hydroxyl groups. After ruling out diffusion through macroscopic pinholes, the protons are found to transfer through rare, naturally occurring atomic defects. Computer simulations reveal low energy barriers of 0.61–0.75 eV for aqueous proton transfer across hydroxyl-terminated atomic defects that participate in a Grotthuss-type relay, while ​pyrylium-like ether terminations shut down proton exchange. In conclusion, unfavourable energy barriers to helium and ​hydrogen transfer indicate the process is selective for aqueous protons.

  17. Aqueous proton transfer across single-layer graphene

    PubMed Central

    Achtyl, Jennifer L.; Unocic, Raymond R.; Xu, Lijun; Cai, Yu; Raju, Muralikrishna; Zhang, Weiwei; Sacci, Robert L.; Vlassiouk, Ivan V.; Fulvio, Pasquale F.; Ganesh, Panchapakesan; Wesolowski, David J.; Dai, Sheng; van Duin, Adri C. T.; Neurock, Matthew; Geiger, Franz M.

    2015-01-01

    Proton transfer across single-layer graphene proceeds with large computed energy barriers and is therefore thought to be unfavourable at room temperature unless nanoscale holes or dopants are introduced, or a potential bias is applied. Here we subject single-layer graphene supported on fused silica to cycles of high and low pH, and show that protons transfer reversibly from the aqueous phase through the graphene to the other side where they undergo acid–base chemistry with the silica hydroxyl groups. After ruling out diffusion through macroscopic pinholes, the protons are found to transfer through rare, naturally occurring atomic defects. Computer simulations reveal low energy barriers of 0.61–0.75 eV for aqueous proton transfer across hydroxyl-terminated atomic defects that participate in a Grotthuss-type relay, while pyrylium-like ether terminations shut down proton exchange. Unfavourable energy barriers to helium and hydrogen transfer indicate the process is selective for aqueous protons. PMID:25781149

  18. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    DOE PAGES

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; ...

    2016-10-19

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy andmore » density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.« less

  19. Fabricating Large-Area Sheets of Single-Layer Graphene by CVD

    NASA Technical Reports Server (NTRS)

    Bronikowski, Michael; Manohara, Harish

    2008-01-01

    This innovation consists of a set of methodologies for preparing large area (greater than 1 cm(exp 2)) domains of single-atomic-layer graphite, also called graphene, in single (two-dimensional) crystal form. To fabricate a single graphene layer using chemical vapor deposition (CVD), the process begins with an atomically flat surface of an appropriate substrate and an appropriate precursor molecule containing carbon atoms attached to substituent atoms or groups. These molecules will be brought into contact with the substrate surface by being flowed over, or sprayed onto, the substrate, under CVD conditions of low pressure and elevated temperature. Upon contact with the surface, the precursor molecules will decompose. The substituent groups detach from the carbon atoms and form gas-phase species, leaving the unfunctionalized carbon atoms attached to the substrate surface. These carbon atoms will diffuse upon this surface and encounter and bond to other carbon atoms. If conditions are chosen carefully, the surface carbon atoms will arrange to form the lowest energy single-layer structure available, which is the graphene lattice that is sought. Another method for creating the graphene lattice includes metal-catalyzed CVD, in which the decomposition of the precursor molecules is initiated by the catalytic action of a catalytic metal upon the substrate surface. Another type of metal-catalyzed CVD has the entire substrate composed of catalytic metal, or other material, either as a bulk crystal or as a think layer of catalyst deposited upon another surface. In this case, the precursor molecules decompose directly upon contact with the substrate, releasing their atoms and forming the graphene sheet. Atomic layer deposition (ALD) can also be used. In this method, a substrate surface at low temperature is covered with exactly one monolayer of precursor molecules (which may be of more than one type). This is heated up so that the precursor molecules decompose and form one

  20. Adsorption configurations of two nitrogen atoms on graphene

    SciTech Connect

    Rani, Babita; Jindal, V. K.; Dharamvir, Keya

    2014-04-24

    We present calculations for different possible configurations of two nitrogen adatoms on graphene using the code VASP, based on Density Functional Theory (DFT). Two N atoms adsorbed on the graphene sheet can share a bond in two ways. They take positions either just above two adjacent carbon atoms or they form a bridge across opposite bonds of a hexagon in the graphene sheet. Both these configurations result into structural distortion of the sheet. Another stable configuration involving two N atoms consists of an N{sub 2} molecule which is physisorbed at a distance 3.69 Å on the graphene sheet. Two N atoms can also be adsorbed on alternate bridge sites of neighbouring hexagons of graphene. This configuration again leads to distortion of the sheet in perpendicular direction.

  1. Graphene growth at the interface between Ni catalyst layer and SiO2/Si substrate.

    PubMed

    Lee, Jeong-Hoon; Song, Kwan-Woo; Park, Min-Ho; Kim, Hyung-Kyu; Yang, Cheol-Woong

    2011-07-01

    Graphene was synthesized deliberately at the interface between Ni film and SiO2/Si substrate as well as on top surface of Ni film using chemical vapor deposition (CVD) which is suitable for large-scale and low-cost synthesis of graphene. The carbon atom injected at the top surface of Ni film can penetrate and reach to the Ni/SiO2 interface for the formation of graphene. Once we have the graphene in between Ni film and SiO2/Si substrate, the substrate spontaneously provides insulating SiO2 layer and we may easily get graphene/SiO2/Si structure simply by discarding Ni film. This growth of graphene at the interface can exclude graphene transfer step for electronic application. Raman spectroscopy and optical microscopy show that graphene was successfully synthesized at the back of Ni film and the coverage of graphene varies with temperature and time of synthesis. The coverage of graphene at the interface depends on the amount of carbon atoms diffused into the back of Ni film.

  2. Synthesis of layer-tunable graphene: A combined kinetic implantation and thermal ejection approach

    DOE PAGES

    Wang, Gang; Zhang, Miao; Liu, Su; ...

    2015-05-04

    Layer-tunable graphene has attracted broad interest for its potentials in nanoelectronics applications. However, synthesis of layer-tunable graphene by using traditional chemical vapor deposition (CVD) method still remains a great challenge due to the complex experimental parameters and the carbon precipitation process. Herein, by performing ion implantation into a Ni/Cu bilayer substrate, the number of graphene layers, especially single or double layer, can be controlled precisely by adjusting the carbon ion implant fluence. The growth mechanism of the layer-tunable graphene is revealed by monitoring the growth process is observed that the entire implanted carbon atoms can be expelled towards the substratemore » surface and thus graphene with designed layer number can be obtained. Such a growth mechanism is further confirmed by theoretical calculations. The proposed approach for the synthesis of layer-tunable graphene offers more flexibility in the experimental conditions. Being a core technology in microelectronics processing, ion implantation can be readily implemented in production lines and is expected to expedite the application of graphene to nanoelectronics.« less

  3. Synthesis of layer-tunable graphene: A combined kinetic implantation and thermal ejection approach

    SciTech Connect

    Wang, Gang; Zhang, Miao; Liu, Su; Xie, Xiaoming; Ding, Guqiao; Wang, Yongqiang; Chu, Paul K.; Gao, Heng; Ren, Wei; Yuan, Qinghong; Zhang, Peihong; Wang, Xi; Di, Zengfeng

    2015-05-04

    Layer-tunable graphene has attracted broad interest for its potentials in nanoelectronics applications. However, synthesis of layer-tunable graphene by using traditional chemical vapor deposition (CVD) method still remains a great challenge due to the complex experimental parameters and the carbon precipitation process. Herein, by performing ion implantation into a Ni/Cu bilayer substrate, the number of graphene layers, especially single or double layer, can be controlled precisely by adjusting the carbon ion implant fluence. The growth mechanism of the layer-tunable graphene is revealed by monitoring the growth process is observed that the entire implanted carbon atoms can be expelled towards the substrate surface and thus graphene with designed layer number can be obtained. Such a growth mechanism is further confirmed by theoretical calculations. The proposed approach for the synthesis of layer-tunable graphene offers more flexibility in the experimental conditions. Being a core technology in microelectronics processing, ion implantation can be readily implemented in production lines and is expected to expedite the application of graphene to nanoelectronics.

  4. Resistance and rupture analysis of single- and few-layer graphene nanosheets impacted by various projectiles

    NASA Astrophysics Data System (ADS)

    Sadeghzadeh, Sadegh; Liu, Ling

    2016-09-01

    In this paper, a quasi-classical model for the collision of various nanoparticles with single- and few-layer graphene nanosheets was introduced as a multi-scale approach that couples non-equilibrium molecular dynamics with the Finite Element Method. As a resistance criterion, it was observed that the coefficient of restitution and the induced stresses depend on the impact velocity of projectile. These parameters were evaluated computationally, and it was revealed that certain resulting behaviors differ from behaviors at the macro scale. By obtaining an out-of-plane yield stress limit of 1.0 TPa for graphene, the stress analysis of single- and multi-layer graphene sheets revealed that the limit projectile velocity needed for the yielding of graphene sheets increases with the increase in the number of layers. For aluminum nanoparticles, this increase is almost linear, and for other metals, it slightly deviates from the linear trend. It was also observed that the graphene sheets have a different rupture form when impacted by gaseous molecules than by metal particles. Considering the very high momentum of gas molecules and their shock-like behavior during high-speed collisions with a graphene sheet, pores with a size of one carbon atom can be created in graphene sheets. Since a single-layer graphene sheet can withstand a projectile which is 3.64 times larger than a projectile impacting a 20-layer graphene sheet, spaced graphene sheets seem to be more effective in absorbing the impact energy of projectiles than conventional few-layer graphene sheets.

  5. Controlling single and few-layer graphene crystals growth in a solid carbon source based chemical vapor deposition

    SciTech Connect

    Papon, Remi; Sharma, Subash; Shinde, Sachin M.; Vishwakarma, Riteshkumar; Tanemura, Masaki; Kalita, Golap

    2014-09-29

    Here, we reveal the growth process of single and few-layer graphene crystals in the solid carbon source based chemical vapor deposition (CVD) technique. Nucleation and growth of graphene crystals on a polycrystalline Cu foil are significantly affected by the injection of carbon atoms with pyrolysis rate of the carbon source. We observe micron length ribbons like growth front as well as saturated growth edges of graphene crystals depending on growth conditions. Controlling the pyrolysis rate of carbon source, monolayer and few-layer crystals and corresponding continuous films are obtained. In a controlled process, we observed growth of large monolayer graphene crystals, which interconnect and merge together to form a continuous film. On the other hand, adlayer growth is observed with an increased pyrolysis rate, resulting few-layer graphene crystal structure and merged continuous film. The understanding of monolayer and few-layer crystals growth in the developed CVD process can be significant to grow graphene with controlled layer numbers.

  6. Growth of bi- and tri-layered graphene on silicon carbide substrate via molecular dynamics simulation

    SciTech Connect

    Min, Tjun Kit; Yoon, Tiem Leong; Lim, Thong Leng

    2015-04-24

    Molecular dynamics (MD) simulation with simulated annealing method is used to study the growth process of bi- and tri-layered graphene on a 6H-SiC (0001) substrate via molecular dynamics simulation. Tersoff-Albe-Erhart (TEA) potential is used to describe the inter-atomic interactions among the atoms in the system. The formation temperature, averaged carbon-carbon bond length, pair correlation function, binding energy and the distance between the graphene formed and the SiC substrate are quantified. The growth mechanism, graphitization of graphene on the SiC substrate and characteristics of the surface morphology of the graphene sheet obtained in our MD simulation compare well to that observed in epitaxially grown graphene experiments and other simulation works.

  7. Synthesis of few layer graphene by direct exfoliation of graphite and a Raman spectroscopic study

    SciTech Connect

    Gayathri, S.; Jayabal, P.; Ramakrishnan, V.; Kottaisamy, M.

    2014-02-15

    The exfoliation of graphene from pristine graphite in a liquid phase was achieved successfully via sonication followed by centrifugation method. Ultraviolet–visible (UV–vis) spectra of the obtained graphene dispersions at different exfoliation time indicated that the concentration of graphene dispersion increased markedly with increasing exfoliation time. The sheet-like morphology of the exfoliated graphene was revealed by Scanning Electron Microscopy (SEM) image. Further, the morphological change in different exfoliation time was investigated by Atomic Force Microscopy (AFM). A complete structural and defect characterization was probed using micro-Raman spectroscopic technique. The shape and position of the 2D band of Raman spectra revealed the formation of bilayer to few layer graphene. Also, Raman mapping confirmed the presence of uniformly distributed bilayer graphene sheets on the substrate.

  8. Optical and Electrical Characteristics of Graphene Double Layer Formed by a Double Transfer of Graphene Single Layers.

    PubMed

    Kim, Young Jun; Bae, Gi Yoon; Chun, Sungwoo; Park, Wanjun

    2016-03-01

    We demonstrate formation of double layer graphene by means of a double transfer using two single graphene layers grown by a chemical vapor deposition method. It is observed that shiftiness and broadness in the double-resonance of Raman scattering are much weaker than those of bilayer graphene formed naturally. Transport characteristics examined from transmission line measurements and field effect transistors show the similar behavior with those of single layer graphene. It indicates that interlayer separation, in electrical view, is large enough to avoid correlation between layers for the double layer structure. It is also observed from a transistor with the double layer graphene that molecules adsorpted on two inner graphene surfaces in the double layered structure are isolated and conserved from ambient environment.

  9. Experimental study on thermal conductivity of free-standing fluorinated single-layer graphene

    NASA Astrophysics Data System (ADS)

    Narasaki, Masahiro; Wang, Haidong; Nishiyama, Takashi; Ikuta, Tatsuya; Takahashi, Koji

    2017-08-01

    We measured the thermal conductivity of free-standing fluorinated single-layer graphene (FSLG) using a precise T-type method. Pristine graphene was fluorinated and suspended above the substrate using xenon difluoride gas. Compared with the thermal conductivity of pristine single-layer graphene (SLG) (˜2000 W/mK) previously measured by the same T-type method for the same original SLG, the FSLG exhibited a much lower thermal conductivity (˜80 W/mK) and a weak dependence of the thermal conductivity on nanohole defects. The experimental results suggest that the fluorine atoms and sp3 bonding in the FSLG strongly contributed to phonon scattering. The phonon scattering by the fluorine atoms and sp3 bonding has a dominant effect on the thermal conductivity decrease over the phonon scattering by nanohole defects. This study lays a foundation for the thermal measurement of 2D fluorinated materials and benefits future applications of fluorinated graphene.

  10. Electronic resonant tunneling on graphene superlattice heterostructures with a tunable graphene layer

    SciTech Connect

    Zhang, Shan; Cui, Liyong; Liu, Fen; Lu, Guang; Du, Lei; Liu, Yiping; Du, Guiqiang

    2016-05-15

    We have theoretically investigated the electronic resonant tunneling effect in graphene superlattice heterostructures, where a tunable graphene layer is inserted between two different superlattices. It is found that a complete tunneling state appears inside the enlarged forbidden gap of the heterostructure by changing the thickness of the inserted graphene layer and the transmittance of the tunneling state depends on the thickness of the inserted layer. Furthermore, the frequency of the tunneling state changes with the thickness of the inserted graphene layer but it always located in the little overlapped forbidden gap of two graphene superlattices. Therefore, both a perfect tunneling state and an ultrawide forbidden gap are realized in such heterostrutures. Since maximum probability densities of the perfect tunneling state are highly localized near the interface between the inserted graphene layer and one graphene superlattice, it can be named as an interface-like state. Such structures are important to fabricate high-Q narrowband electron wave filters.

  11. Water desalination using nanoporous single-layer graphene.

    PubMed

    Surwade, Sumedh P; Smirnov, Sergei N; Vlassiouk, Ivan V; Unocic, Raymond R; Veith, Gabriel M; Dai, Sheng; Mahurin, Shannon M

    2015-05-01

    By creating nanoscale pores in a layer of graphene, it could be used as an effective separation membrane due to its chemical and mechanical stability, its flexibility and, most importantly, its one-atom thickness. Theoretical studies have indicated that the performance of such membranes should be superior to state-of-the-art polymer-based filtration membranes, and experimental studies have recently begun to explore their potential. Here, we show that single-layer porous graphene can be used as a desalination membrane. Nanometre-sized pores are created in a graphene monolayer using an oxygen plasma etching process, which allows the size of the pores to be tuned. The resulting membranes exhibit a salt rejection rate of nearly 100% and rapid water transport. In particular, water fluxes of up to 10(6) g m(-2) s(-1) at 40 °C were measured using pressure difference as a driving force, while water fluxes measured using osmotic pressure as a driving force did not exceed 70 g m(-2) s(-1) atm(-1).

  12. Synthesis of few-layered graphene by H{sub 2}O{sub 2} plasma etching of graphite

    SciTech Connect

    Zhao Guixia; Shao Dadong; Chen Changlun; Wang Xiangke

    2011-05-02

    Herein, we reported an approach to synthesize few-layered graphene by etching of the graphite using H{sub 2}O{sub 2} plasma technique. The synthesized few-layered graphene was characterized by scanning electron microscopy, atomic force microscopy, Raman spectroscopy, and x-ray photoelectron spectroscopy (XPS). The analysis showed that few-layered graphene was formed in high quality level. The XPS analysis suggested that H{sub 2}O{sub 2} plasma etching of graphite could oxidize graphene and generated -C-OH and >C=O groups on the graphene surfaces. The H{sub 2}O{sub 2} plasma technique is an easy and environmental friendly method to synthesize few-layered graphene from the graphite.

  13. Characterization of few-layered graphene grown by carbon implantation

    SciTech Connect

    Lee, Kin Kiong; McCallum, Jeffrey C.; Jamieson, David N.

    2014-02-21

    Graphene is considered to be a very promising material for applications in nanotechnology. The properties of graphene are strongly dependent on defects that occur during growth and processing. These defects can be either detrimental or beneficial to device performance depending on defect type, location and device application. Here we present experimental results on formation of few-layered graphene by carbon ion implantation into nickel films and characteristics of graphene devices formed by graphene transfer and lithographic patterning. Micro-Raman spectroscopy was used to determine the number of graphene layers formed and identify defects arising from the device processing. The graphene films were cleaned by annealing in vacuum. Transport properties of cleaned graphene films were investigated by fabrication of back-gated field-effect transistors, which exhibited high hole and electron mobility of 1935 and 1905 cm2/Vs, respectively.

  14. ssDNA binding reveals the atomic structure of graphene.

    PubMed

    Husale, By Sudhir; Sahoo, Sangeeta; Radenovic, Aleksandra; Traversi, Floriano; Annibale, Paolo; Kis, Andras

    2010-12-07

    We used AFM to investigate the interaction of polyelectrolytes such as ssDNA and dsDNA molecules with graphene as a substrate. Graphene is an appropriate substrate due to its planarity, relatively large surfaces that are detectable via an optical microscope, and straightforward identification of the number of layers. We observe that in the absence of the screening ions deposited ssDNA will bind only to the graphene and not to the SiO(2) substrate, confirming that the binding energy is mainly due to the π-π stacking interaction. Furthermore, deposited ssDNA will map the graphene underlying structure. We also quantify the π-π stacking interaction by correlating the amount of deposited DNA with the graphene layer thickness. Our findings agree with reported electrostatic force microscopy (EFM) measurements. Finally, we inspected the suitability of using a graphene as a substrate for DNA origami-based nanostructures.

  15. Layer-to-layer compression and enhanced optical properties of few-layer graphene nanosheet induced by ion irradiation

    NASA Astrophysics Data System (ADS)

    Shang, Zhen; Tan, Yang; Zhou, Shengqiang; Chen, Feng

    2016-08-01

    We report on the first experimental study of the layer-to-layer compression and enhanced optical properties of few-layer graphene nanosheet by applying ion irradiation. The deformation of graphene layers is investigated both theoretically and experimentally. It is observed that after the irradiation of energetic ion beams, the space between separate graphene layers is reduced due to layer-to-layer compression, resulting in tighter contact of the graphene sheet with the surface of the substrate. This processing enables enhanced interaction of the graphene with the evanescent-field wave near the surface, which induces reinforced polarization-dependent light absorption of the graphene. Utilizing the ion-bombarded graphene nanosheets as saturable absorbers, we have realized efficient Q-switched waveguide lasing with enhanced performance through the interaction of the graphene and evanescent field.

  16. Characterization of graphene oxide nanofilms obtained by the SAW atomization

    NASA Astrophysics Data System (ADS)

    Balachova, O. V.; Balashov, S. M.; Kubota, L. T.; Timm, R. A.; Nascimento, P. H.; Pavani Filho, A.; Moshkalev, S.

    2015-03-01

    Due to its ability to absorb water molecules, graphene oxide (GO) is considered a promising material for sensitive coatings in fast surface acoustic wave (SAW) humidity sensors. In this work, we characterize GO films obtained by the SAW atomization technique. It is shown that the atomized submicroliter droplets of aqueous suspension of GO can be deposited onto the surface of Si, LiNbO3 or quartz substrates forming discrete or continuous films of nanometer thickness. The deposited films were examined using AFM and electron microscopy. We discuss the dependence of thickness and structure of the obtained GO films on the parameters of deposition: the number of atomized droplets, a volume of the initial droplet, a distance between the atomizer and the sample, etc. To evaluate the adsorption characteristics of the obtained GO films, we used them as sensitive coatings of the SAW humidity sensors. We found that the adsorption characteristics of the GO films are determined by fast adsorption on the surface of GO sheets and slow adsorption, attributed to limited penetration of water molecules between the sheets, and depend on the number of deposited layers.

  17. Dynamics of single Fe atoms in graphene vacancies.

    PubMed

    Robertson, Alex W; Montanari, Barbara; He, Kuang; Kim, Judy; Allen, Christopher S; Wu, Yimin A; Olivier, Jaco; Neethling, Jan; Harrison, Nicholas; Kirkland, Angus I; Warner, Jamie H

    2013-04-10

    Focused electron beam irradiation has been used to create mono and divacancies in graphene within a defined area, which then act as trap sites for mobile Fe atoms initially resident on the graphene surface. Aberration-corrected transmission electron microscopy at 80 kV has been used to study the real time dynamics of Fe atoms filling the vacancy sites in graphene with atomic resolution. We find that the incorporation of a dopant atom results in pronounced displacements of the surrounding carbon atoms of up to 0.5 Å, which is in good agreement with density functional theory calculations. Once incorporated into the graphene lattice, Fe atoms can transition to adjacent lattice positions and reversibly switch their bonding between four and three nearest neighbors. The C atoms adjacent to the Fe atoms are found to be more susceptible to Stone-Wales type bond rotations with these bond rotations associated with changes in the dopant bonding configuration. These results demonstrate the use of controlled electron beam irradiation to incorporate dopants into the graphene lattice with nanoscale spatial control.

  18. Ultrafast Nanofiltration through Large-Area Single-Layered Graphene Membranes.

    PubMed

    Qin, Yanzhe; Hu, Yongyou; Koehler, Stephan; Cai, Liheng; Wen, Junjie; Tan, Xiaojun; Xu, Weiwei L; Sheng, Qian; Hou, Xu; Xue, Jianming; Yu, Miao; Weitz, David

    2017-03-22

    Perforated single-layered graphene has demonstrated selectivity and flux that is orders of magnitude greater than state-of-the-art polymer membranes. However, only individual graphene sheets with sizes up to tens of micrometers have been successfully fabricated for pressurized permeation studies. Scaling-up and reinforcement of these atomic membranes with minimum cracks and pinholes remains a major hurdle for practical applications. We develop a large-area in situ, phase-inversion casting technique to create 63 cm(2) high-quality single-layered perforated graphene membranes for ultrafast nanofiltration that can operate at pressures up to 50 bar. This result demonstrates the feasibility of our technique for creating robust large-area, high quality, single-layered graphene and its potential use as a pressurized nanofiltration membrane.

  19. Direct observation of a long-lived single-atom catalyst chiseling atomic structures in graphene.

    PubMed

    Wang, Wei Li; Santos, Elton J G; Jiang, Bin; Cubuk, Ekin Dogus; Ophus, Colin; Centeno, Alba; Pesquera, Amaia; Zurutuza, Amaia; Ciston, Jim; Westervelt, Robert; Kaxiras, Efthimios

    2014-02-12

    Fabricating stable functional devices at the atomic scale is an ultimate goal of nanotechnology. In biological processes, such high-precision operations are accomplished by enzymes. A counterpart molecular catalyst that binds to a solid-state substrate would be highly desirable. Here, we report the direct observation of single Si adatoms catalyzing the dissociation of carbon atoms from graphene in an aberration-corrected high-resolution transmission electron microscope (HRTEM). The single Si atom provides a catalytic wedge for energetic electrons to chisel off the graphene lattice, atom by atom, while the Si atom itself is not consumed. The products of the chiseling process are atomic-scale features including graphene pores and clean edges. Our experimental observations and first-principles calculations demonstrated the dynamics, stability, and selectivity of such a single-atom chisel, which opens up the possibility of fabricating certain stable molecular devices by precise modification of materials at the atomic scale.

  20. Electromechanical coupling in atomically thin MoS2 and graphene

    NASA Astrophysics Data System (ADS)

    Manzeli, Sajedeh; Benameur, Muhammed Malik; Allain, Adrien; Ghadimi, Amirhossein; Tosun, Mahmut; Kis, Andras; Gargiulo, Fernando; Autès, Gabriel; Yazyev, Oleg V.

    Nanoelectromechanical systems (NEMS) based on novel materials such as graphene and MoS2 allow studying their electromechanical characteristics. Here, we incorporate single and bilayer MoS2 and graphene into NEMS and investigated their electromechanical behavior. We observe a Strain-induced bandgap modulation in atomically thin MoS2 membranes with a thickness dependent modulation rate. Finite element modeling is used to extract the piezoresistive gauge factor for MoS2. In the case of graphene, deflection of monolayer graphene nanoribbons results in a linear increase in their electrical resistance where an upper limit is estimated for the gauge factor. Surprisingly, we observe oscillations in the electromechanical response of bilayer graphene. Our numerical simulations indicate that these oscillations arise from quantum mechanical interference in the transition region induced by sliding of individual graphene layers with respect to each other. Our results reveal that atomically thin MoS2 membranes show strong piezoresistive effect, comparable to the state-of-the-art silicon sensors. Moreover, bilayer graphene conceals unexpectedly novel physics allowing the rare observation of room temperature electronic interference phenomena.

  1. Substrate-induced magnetism in epitaxial graphene buffer layers.

    PubMed

    Ramasubramaniam, A; Medhekar, N V; Shenoy, V B

    2009-07-08

    Magnetism in graphene is of fundamental as well as technological interest, with potential applications in molecular magnets and spintronic devices. While defects and/or adsorbates in freestanding graphene nanoribbons and graphene sheets have been shown to cause itinerant magnetism, controlling the density and distribution of defects and adsorbates is in general difficult. We show from first principles calculations that graphene buffer layers on SiC(0001) can also show intrinsic magnetism. The formation of graphene-substrate chemical bonds disrupts the graphene pi-bonds and causes localization of graphene states near the Fermi level. Exchange interactions between these states lead to itinerant magnetism in the graphene buffer layer. We demonstrate the occurrence of magnetism in graphene buffer layers on both bulk-terminated as well as more realistic adatom-terminated SiC(0001) surfaces. Our calculations show that adatom density has a profound effect on the spin distribution in the graphene buffer layer, thereby providing a means of engineering magnetism in epitaxial graphene.

  2. Controllable synthesis of graphene sheets with different numbers of layers and effect of the number of graphene layers on the specific capacity of anode material in lithium-ion batteries

    SciTech Connect

    Tong, Xin; Wang, Hui; Wang, Gang; Wan, Lijuan; Ren, Zhaoyu; Bai, Jintao; Bai, Jinbo

    2011-05-15

    High quality graphene sheets are synthesized through efficient oxidation process followed by rapid thermal expansion and reduction by H{sub 2}. The number of graphene layers is controlled by tuning the oxidation degree of GOs. The higher the oxidation degree of GOs is getting, the fewer the numbers of graphene layers can be obtained. The material is characterized by elemental analysis, thermo-gravimetric analysis, scanning electron microscopy, atomic force microscopy, transmission electron microscopy and Fourier transform infrared spectroscopies. The obtained graphene sheets with single, triple and quintuplicate layers as anode materials exhibit a high reversible capacity of 1175, 1007, and 842 mA h g{sup -1}, respectively, which show that the graphene sheets with fewer layers have higher reversible capacity. -- Graphical abstract: The typical TEM images of the graphene sheets derived from GO3(a), GO2(b) and GO1(c). Display Omitted Highlights: {yields} With the oxidation degree of GO increasing, the numbers of graphene layers decreased. {yields} With the numbers of graphene layers decreasing, the reversible capacity improved. {yields} Graphene sheets with single-layer exhibit the best electrochemical performances.

  3. Detection of interlayer interaction in few-layer graphene

    NASA Astrophysics Data System (ADS)

    Wu, Zefei; Han, Yu; Lin, Jiangxiazi; Zhu, Wei; He, Mingquan; Xu, Shuigang; Chen, Xiaolong; Lu, Huanhuan; Ye, Weiguang; Han, Tianyi; Wu, Yingying; Long, Gen; Shen, Junying; Huang, Rui; Wang, Lin; He, Yuheng; Cai, Yuan; Lortz, Rolf; Su, Dangsheng; Wang, Ning

    2015-08-01

    Bernal-stacked few-layer graphene has been investigated by analyzing its Landau-level spectra through quantum capacitance measurements. We find that surface relaxation, which is insignificant in trilayer graphene, starts to manifest in Bernal-stacked tetralayer graphene. In trilayer graphene, the interlayer interaction parameters are generally similar to those of graphite. However, in tetralayer graphene, the hopping parameters of the two bulk layers are quite different from those of the two outer layers. This represents direct evidence of the surface relaxation phenomenon. Traditionally, the van der Waals interaction between the carbon layers is thought to be insignificant. However, we suggest that the interlayer interaction is an important factor in explaining the observed results, and the symmetry-breaking effects in graphene sublattice are not negligible.

  4. Controllable chemical vapor deposition growth of few layer graphene for electronic devices.

    PubMed

    Wei, Dacheng; Wu, Bin; Guo, Yunlong; Yu, Gui; Liu, Yunqi

    2013-01-15

    Because of its atomic thickness, excellent properties, and widespread applications, graphene is regarded as one of the most promising candidate materials for nanoelectronics. The wider use of graphene will require processes that produce this material in a controllable manner. In this Account, we focus on our recent studies of the controllable chemical vapor deposition (CVD) growth of graphene, especially few-layer graphene (FLG), and the applications of this material in electronic devices. CVD provides various means of control over the morphologies of the produced graph ene. We studied several variables that can affect the CVD growth of graphene, including the catalyst, gas flow rate, growth time, and growth temperature and successfully achieved the controlled growth of hexagonal graphene crystals. Moreover, we developed several modified CVD methods for the controlled growth of FLGs. Patterned CVD produced FLGs with desired shapes in required areas. By introducing dopant precursor in the CVD process, we produced substitutionally doped FLGs, avoiding the typically complicated post-treatment processes for graphene doping. We developed a template CVD method to produce FLG ribbons with controllable morphologies on a large scale. An oxidation-activated surface facilitated the CVD growth of polycrystalline graphene without the use of a metal catalyst or a complicated postgrowth transfer process. In devices, CVD offers a controllable means to modulate the electronic properties of the graphene samples and to improve device performance. Using CVD-grown hexagonal graphene crystals as the channel materials in field-effect transistors (FETs), we improved carrier mobility. Substitutional doping of graphene in CVD opened a band gap for efficient FET operation and modulated the Fermi energy level for n-type or p-type features. The similarity between the chemical structure of graphene and organic semiconductors suggests potential applications of graphene in organic devices. We

  5. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    PubMed Central

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; Eres, Gyula; Timpe, Olaf; Fu, Qiang; Ding, Feng; Schloegl, R.; Willinger, Marc-Georg

    2016-01-01

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene–graphene and graphene–substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite. PMID:27759024

  6. Dielectric function for doped graphene layer with barium titanate

    NASA Astrophysics Data System (ADS)

    Martinez Ramos, Manuel; Garces Garcia, Eric; Magana, Fernado; Vazquez Fonseca, Gerardo Jorge

    2015-03-01

    The aim of our study is to calculate the dielectric function for a system formed with a graphene layer doped with barium titanate. Density functional theory, within the local density approximation, plane-waves and pseudopotentials scheme as implemented in Quantum Espresso suite of programs was used. We considered 128 carbon atoms with a barium titanate cluster of 11 molecules as unit cell with periodic conditions. The geometry optimization is achieved. Optimization of structural configuration is performed by relaxation of all atomic positions to minimize their total energies. Band structure, density of states and linear optical response (the imaginary part of dielectric tensor) were calculated. We thank Dirección General de Asuntos del Personal Académico de la Universidad Nacional Autónoma de México, partial financial support by Grant IN-106514 and we also thank Miztli Super-Computing center the technical assistance.

  7. Deformation of graphene on an oxidizing nickel surface: the role of graphene layer number

    NASA Astrophysics Data System (ADS)

    George, Lijin; Shaina, P. R.; Gupta, Aparna; Das Gupta, Nandita; Jaiswal, Manu

    2016-11-01

    Few-layer graphene grown on nickel substrates by chemical vapour deposition is typically characterised by thickness inhomogeneity. In this work, we investigate the thickness-dependent changes induced in graphene during the surface oxidation of the underlying metal. Temperature-dependent Raman spectroscopy and scanning electron microscopy are used to monitor the lattice strain and defect formation induced in graphene, as well as the oxidation of Ni surface. Significant lattice strain is induced in thin layers of graphene (1-2 layers) during the oxidation process, for T > 400 °C. This is followed by the formation of boundary-type defects, and graphene loses structural integrity. In contrast, lattice strain induced in thicker graphene (up to 7 layers) during the metal surface oxidation is quite subdued. These thicker layers de-pin and remain structurally intact even after the underneath metal surface has oxidized.

  8. Tunable hybrid surface waves supported by a graphene layer

    NASA Astrophysics Data System (ADS)

    Iorsh, I. V.; Shadrivov, I. V.; Belov, P. A.; Kivshar, Yu. S.

    2013-05-01

    We study electromagnetic waves localized near the surface of a semi-infinite dielectric medium covered by a graphene layer in the presence of a strong external magnetic field. We demonstrate that a novel type of hybrid TE-TM polarized surface plasmons can propagate along the graphene layer. We analyze the effect of the Hall conductivity on the polarization properties of these hybrid surface waves and suggest a possibility to tune the graphene plasmons by the external magnetic field.

  9. Single layer graphene protective gas barrier for copper photocathodes

    NASA Astrophysics Data System (ADS)

    Liu, Fangze; Moody, Nathan A.; Jensen, Kevin L.; Pavlenko, Vitaly; Narvaez Villarrubia, Claudia W.; Mohite, Aditya D.; Gupta, Gautam

    2017-01-01

    Photocathodes can benefit from a thin protection layer and attain long-term stability. Graphene is potentially a good candidate for such application. We report direct growth of single-layer graphene on single crystal Cu(110) photocathodes using chemical vapor deposition and the effective protection of copper photocathodes with graphene against degradation under atmospheric conditions. Due to the interaction and charge transfer between graphene and copper, the graphene-protected cathodes have 0.25 eV lower work function and 17% higher quantum efficiency at 250 nm compared with bare Cu cathodes. The graphene coating can protect copper photocathodes from degradation for more than 20 min in an exposure to 200 Torr of air. The validation of graphene-photocathode compatibility opens a new route to the lifetime-extension for photocathodes.

  10. Large area, Few Layer Graphene Films on Insulating Substrates

    NASA Astrophysics Data System (ADS)

    Kong, Jing

    2009-03-01

    Graphene has exceptional electronic, thermal and mechanical properties. For the realization of graphene-related applications, it is necessary to develop reliable and low cost fabrication methods of graphene-based structures, ideally on any substrates. In this talk I will present our method of fabricating large area (˜cm^2) films of single- to few-layer graphene and transferring the films to arbitrary substrates. The graphene films are synthesized by ambient pressure Chemical Vapor Deposition, consist of regions of 1 to ˜10 graphene layers and have an average thickness of 2-3 nm. Despite their ultra-thin nature, the films thus produced are continuous over the entire area. Regions of single- or bi-layer graphene with lateral sizes of up to 25 μm were observed. High Resolution Transmission Electron Microscopy (HRTEM) and electron diffraction revealed that they are crystalline over the entire area and their Raman features were compared to those of graphene derived from mechanical exfoliation of Highly Oriented Pyrolytic Graphite (HOPG). Transistor devices made from these graphene show similar characteristics to ones made from graphitized SiC. Scanning tunneling microscopy imaging reveals interesting Mori'e patterns and helpful insights for the growth of the graphene films on the Ni substrate. The method presented in this work can potentially be scaled to industrial production of graphene films, for applications such as ultra-thin conductive and transparent electrodes, or devices and interconnect for integrated circuits.

  11. Nanoporous Atomically Thin Graphene Membranes for Desalting and Dialysis Applications.

    PubMed

    Kidambi, Piran R; Jang, Doojoon; Idrobo, Juan-Carlos; Boutilier, Michael S H; Wang, Luda; Kong, Jing; Karnik, Rohit

    2017-09-01

    Dialysis is a ubiquitous separation process in biochemical processing and biological research. State-of-the-art dialysis membranes comprise a relatively thick polymer layer with tortuous pores, and suffer from low rates of diffusion leading to extremely long process times (often several days) and poor selectivity, especially in the 0-1000 Da molecular weight cut-off range. Here, the fabrication of large-area (cm(2) ) nanoporous atomically thin membranes (NATMs) is reported, by transferring graphene synthesized using scalable chemical vapor deposition (CVD) to polycarbonate track-etched supports. After sealing defects introduced during transfer/handling by interfacial polymerization, a facile oxygen-plasma etch is used to create size-selective pores (≤1 nm) in the CVD graphene. Size-selective separation and desalting of small model molecules (≈200-1355 Da) and proteins (≈14 000 Da) are demonstrated, with ≈1-2 orders of magnitude increase in permeance compared to state-of-the-art commercial membranes. Rapid diffusion and size-selectivity in NATMs offers transformative opportunities in purification of drugs, removal of residual reactants, biochemical analytics, medical diagnostics, therapeutics, and nano-bio separations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Spectroscopic characterization of charge carrier anisotropic motion in twisted few-layer graphene

    PubMed Central

    Kandyba, Viktor; Yablonskikh, Mikhail; Barinov, Alexei

    2015-01-01

    Graphene, a layer of carbon atoms in a honeycomb lattice, captures enormous interest as probably the most promising component of future electronics thanks to its mechanical robustness, flexibility, and unique charge carrier quasiparticles propagating like massless high energy Dirac fermions. If several graphene layers form a stack, the interaction between them is, on the one hand, weak, allowing realization of various registries between the layers and, on the other hand, strong enough for a wide range tuning of the electronic properties. Here we grow few layer graphene with various number of layers and twist configurations and address the electronic properties of individual atomic layers in single microscopic domains using angle-resolved photoelectron spectromicroscopy. The dependence of the interlayer coupling on the twist angle is analyzed and, in the domains with tri-layers and more, if different rotations are present, the electrons in weaker coupled adjacent layers are shown to have different properties manifested by coexisting van Hove singularities, moiré superlattices with corresponding superlattice Dirac points, and charge carrier group velocity renormalizations. Moreover, pronounced anisotropy in the charge carrier motion, opening a possibility to transform strongly coupled graphene bilayers into quasi one-dimensional conductors, is observed. PMID:26548567

  13. Nanomechanical cleavage of molybdenum disulphide atomic layers.

    PubMed

    Tang, Dai-Ming; Kvashnin, Dmitry G; Najmaei, Sina; Bando, Yoshio; Kimoto, Koji; Koskinen, Pekka; Ajayan, Pulickel M; Yakobson, Boris I; Sorokin, Pavel B; Lou, Jun; Golberg, Dmitri

    2014-04-03

    The discovery of two-dimensional materials became possible due to the mechanical cleavage technique. Despite its simplicity, the as-cleaved materials demonstrated surprising macro-continuity, high crystalline quality and extraordinary mechanical and electrical properties that triggered global research interest. Here such cleavage processes and associated mechanical behaviours are investigated by a direct in situ transmission electron microscopy probing technique, using atomically thin molybdenum disulphide layers as a model material. Our technique demonstrates layer number selective cleavage, from a monolayer to double layer and up to 23 atomic layers. In situ observations combined with molecular dynamics simulations reveal unique layer-dependent bending behaviours, from spontaneous rippling (<5 atomic layers) to homogeneous curving (~ 10 layers) and finally to kinking (20 or more layers), depending on the competition of strain energy and interfacial energy.

  14. Nanomechanical cleavage of molybdenum disulphide atomic layers

    NASA Astrophysics Data System (ADS)

    Tang, Dai-Ming; Kvashnin, Dmitry G.; Najmaei, Sina; Bando, Yoshio; Kimoto, Koji; Koskinen, Pekka; Ajayan, Pulickel M.; Yakobson, Boris I.; Sorokin, Pavel B.; Lou, Jun; Golberg, Dmitri

    2014-04-01

    The discovery of two-dimensional materials became possible due to the mechanical cleavage technique. Despite its simplicity, the as-cleaved materials demonstrated surprising macro-continuity, high crystalline quality and extraordinary mechanical and electrical properties that triggered global research interest. Here such cleavage processes and associated mechanical behaviours are investigated by a direct in situ transmission electron microscopy probing technique, using atomically thin molybdenum disulphide layers as a model material. Our technique demonstrates layer number selective cleavage, from a monolayer to double layer and up to 23 atomic layers. In situ observations combined with molecular dynamics simulations reveal unique layer-dependent bending behaviours, from spontaneous rippling (<5 atomic layers) to homogeneous curving (~ 10 layers) and finally to kinking (20 or more layers), depending on the competition of strain energy and interfacial energy.

  15. Water Desalination Using Nanoporous Single-Layer Graphene with Tunable Pore Size

    DOE PAGES

    Surwade, Sumedh P.; Smirnov, Sergei N.; Vlassiouk, Ivan V.; ...

    2015-03-23

    Graphene has great potential to serve as a separation membrane due to its unique properties such as chemical and mechanical stability, flexibility and most importantly its one-atom thickness. In this study, we demonstrate first experimental evidence of the use of single-layer porous graphene as a desalination membrane. Nanometer-sized pores are introduced into single layer graphene using a convenient oxygen plasma etching process that permits tuning of the pore size. The resulting porous graphene membrane exhibited high rejection of salt ions and rapid water transport, thus functioning as an efficient water desalination membrane. Salt rejection selectivity of nearly 100% and exceptionallymore » high water fluxes exceeding 105 g m-2 s-1 at 40 C were measured using saturated water vapor as a driving force.« less

  16. Water Desalination Using Nanoporous Single-Layer Graphene with Tunable Pore Size

    SciTech Connect

    Surwade, Sumedh P.; Smirnov, Sergei N.; Vlassiouk, Ivan V.; Unocic, Raymond R.; Veith, Gabriel M.; Dai, Sheng; Mahurin, Shannon Mark

    2015-03-23

    Graphene has great potential to serve as a separation membrane due to its unique properties such as chemical and mechanical stability, flexibility and most importantly its one-atom thickness. In this study, we demonstrate first experimental evidence of the use of single-layer porous graphene as a desalination membrane. Nanometer-sized pores are introduced into single layer graphene using a convenient oxygen plasma etching process that permits tuning of the pore size. The resulting porous graphene membrane exhibited high rejection of salt ions and rapid water transport, thus functioning as an efficient water desalination membrane. Salt rejection selectivity of nearly 100% and exceptionally high water fluxes exceeding 105 g m-2 s-1 at 40 C were measured using saturated water vapor as a driving force.

  17. Raman spectroscopy of few-layer graphene prepared by C2-C6 cluster ion implantation

    NASA Astrophysics Data System (ADS)

    Wang, Z. S.; Zhang, R.; Zhang, Z. D.; Huang, Z. H.; Liu, C. S.; Fu, D. J.; Liu, J. R.

    2013-07-01

    Few-layer graphene has been prepared on 300 nm-thick Ni films by C2-C6 cluster ion implantation at 20 keV/cluster. Raman spectroscopy reveals significant influence of the number of atoms in the cluster, the implantation dose, and thermal treatment on the structure of the graphene layers. In particular, the graphene samples exhibit a sharp G peak at 1584 cm-1 and 2D peaks at 2711-2717 cm-1. The IG/I2D ratios higher than 1.70 and IG/ID ratio as high as 1.95 confirm that graphene sheets with low density of defects have been synthesized with much improved quality by ion implantation with larger clusters of C4-C6.

  18. Fabrication of ATO/Graphene Multi-layered Transparent Conducting Thin Films

    NASA Astrophysics Data System (ADS)

    Li, Na; Chen, Fei; Shen, Qiang; Wang, Chuanbin; Zhang, Lianmeng

    2013-03-01

    A novel transparent conducting oxide based on the ATO/graphene multi-layered thin films has been developed to satisfy the application of transparent conductive electrode in solar cells. The ATO thin films are prepared by pulsed laser deposition method with high quality, namely the sheet resistance of 49.5 Ω/sq and average transmittance of 81.9 %. The prepared graphene sheet is well reduced and shows atomically thin, spotty distributed appearance on the top of the ATO thin films. The XRD and optical micrographs are used to confirm the successfully preparation of the ATO/graphene multi-layered thin films. The Hall measurements and UV-Vis spectrophotometer are conducted to evaluate the sheet resistance and optical transmittance of the innovative structure. It is found that graphene can improve the electrical properties of the ATO thin films with little influence on the optical transmittance.

  19. Dynamical screening of the van der Waals interaction between graphene layers.

    PubMed

    Dappe, Y J; Bolcatto, P G; Ortega, J; Flores, F

    2012-10-24

    The interaction between graphene layers is analyzed combining local orbital DFT and second order perturbation theory. For this purpose we use the linear combination of atomic orbitals-orbital occupancy (LCAO-OO) formalism, that allows us to separate the interaction energy as the sum of a weak chemical interaction between graphene layers plus the van der Waals interaction (Dappe et al 2006 Phys. Rev. B 74 205434). In this work, the weak chemical interaction is calculated by means of corrected-LDA calculations using an atomic-like sp(3)d(5) basis set. The van der Waals interaction is calculated by means of second order perturbation theory using an atom-atom interaction approximation and the atomic-like-orbital occupancies. We also analyze the effect of dynamical screening in the van der Waals interaction using a simple model. We find that this dynamical screening reduces by 40% the van der Waals interaction. Taking this effect into account, we obtain a graphene-graphene interaction energy of 70 ± 5 meV/atom in reasonable agreement with the experimental evidence.

  20. Ab initio calculations for structural, electronic and magnetic behaviors of nitrogenized monolayer graphene decorated with 5d transition metal atoms

    NASA Astrophysics Data System (ADS)

    Rafique, Muhammad; Shuai, Yong; Xu, Meng; Zhang, Guohua; Guo, Yanming

    2017-09-01

    Graphene-based magnetic materials have revealed great potential for developing high-performance electronic units at sub-nanometer such as spintronic data storage devices. However, a significant ferromagnetism behavior and ample band gap in the electronic structure of graphene is required before it can be used for actual engineering applications. Based on first-principles calculations, here we demonstrate the structural, electronic and magnetic behaviors of 5d transition metal (TM) atom-substituted nitrogenized monolayer graphene. We find that, during TMN(3)4 cluster-substitution, tight bonding occurs between impurity atoms and graphene with significant binding energies. Charge transfer occurs from graphene layer to the TMN(3)4 clusters. Interestingly, PtN3, TaN4 and ReN4 cluster-doped graphene structures exhibit dilute magnetic semiconductor behavior with 1.00 μB, 1.04 μB and 1.05 μB magnetic moments, respectively. While, OsN4 and PtN4 cluster-doped structures display nonmagnetic direct band gap semiconductor behavior. Remaining, TMN(3)4 cluster-doped graphene complexes exhibit half metal properties. Detailed analysis of density of states (DOS) plots indicate that d orbitals of TM atoms should be responsible for arising magnetic moments in graphene. Given results pave a new route for potential applications of dilute magnetic semiconductors and half-metals in spintronic devices by employing TMN(3)4 cluster-doped graphene complexes.

  1. Selective growth of graphene in layer-by-layer via chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Park, Jaehyun; An, Hyosub; Choi, Dong-Chul; Hussain, Sajjad; Song, Wooseok; An, Ki-Seok; Lee, Won-Jun; Lee, Naesung; Lee, Wan-Gyu; Jung, Jongwan

    2016-07-01

    Selective and precise control of the layer number of graphene remains a critical issue for the practical applications of graphene. First, it is highly challenging to grow a continuous and uniform few-layer graphene since once the monolayer graphene fully covers a copper (Cu) surface, the growth of the second layer stops, resulting in mostly nonhomogeneous films. Second, from the selective adlayer growth point of view, there is no clear pathway for achieving this. We have developed the selective growth of a graphene adlayer in layer-by-layer via chemical vapor deposition (CVD) which makes it possible to stack graphene on a specific position. The key idea is to deposit a thin Cu layer (~40 nm thick) on pre-grown monolayer graphene and to apply additional growth. The thin Cu atop the graphene/Cu substrate acts as a catalyst to decompose methane (CH4) gas during the additional growth. The adlayer is grown selectively on the pre-grown graphene, and the thin Cu is removed through evaporation during CVD, eventually forming large-area and uniform double layer graphene. With this technology, highly uniform graphene films with precise thicknesses of 1 to 5 layers and graphene check patterns with 1 to 3 layers were successfully demonstrated. This method provides precise LBL growth for a uniform graphene film and a technique for the design of new graphene devices.Selective and precise control of the layer number of graphene remains a critical issue for the practical applications of graphene. First, it is highly challenging to grow a continuous and uniform few-layer graphene since once the monolayer graphene fully covers a copper (Cu) surface, the growth of the second layer stops, resulting in mostly nonhomogeneous films. Second, from the selective adlayer growth point of view, there is no clear pathway for achieving this. We have developed the selective growth of a graphene adlayer in layer-by-layer via chemical vapor deposition (CVD) which makes it possible to stack graphene

  2. Multilayer films of cationic graphene-polyelectrolytes and anionic graphene-polyelectrolytes fabricated using layer-by-layer self-assembly

    NASA Astrophysics Data System (ADS)

    Rani, Adila; Oh, Kyoung Ah; Koo, Hyeyoung; Lee, Hyung jung; Park, Min

    2011-03-01

    Extremely thin sheets of carbon atoms called graphene have been predicted to possess excellent thermal properties, electrical conductivity, and mechanical stiffness. To harness such properties in composite materials for multifunctional applications, one would require the incorporation of graphene. In this study, new thin film composites were created using layer-by-layer (LBL) assembly of polymer-coated graphitic nanoplatelets. The positive and negative polyelectrolytes used to cover graphene sheets were poly allylamine hydrochloride (PAH) and poly sodium 4-styrenesulfonate (PSS). The synthesized poly allylamine hydrochloride-graphene (PAH-G) and poly sodium 4-styrenesulfonate-gaphene (PSS-G) were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and thermo gravimetric analysis (TGA). The multilayer films created by spontaneous sequential adsorption of PAH-G and PSS-G were characterized by ultra violet spectroscopy (UV-vis), scanning electron microscopy (SEM), and AFM. The electrical conductivity of the graphene/polyelectrolyte multilayer film composites measured by the four-point probe method was 0.2 S cm -1, which was sufficient for the construction of advanced electro-optical devices and sensors.

  3. Large changes of graphene conductance as a function of lattice orientation between stacked layers

    NASA Astrophysics Data System (ADS)

    Lee, Hyunsoo; Qi, Yabing; Kwon, Sangku; Salmeron, Miquel; Park, Jeong Young

    2015-01-01

    Using the conductive tip of an atomic force microscope as an electrode, we found that the electrical conductance of graphite terraces separated by steps can vary by large factors of up to 100, depending on the relative lattice orientation of the surface and subsurface layers. This effect can be attributed to interlayer interactions that, when stacked commensurately in a Bernal sequence (ABAB…), cause the band gap to open. Misaligned layers, on the other hand, behave like graphene. Angular misorientations of a few degrees were found to cause large increases in the conductance of the top layer, with the maximum occurring around 30°. These results suggest new applications for graphene multilayers by stacking layers at various angles to control the resistance of the connected graphene ribbons in devices.

  4. One-atom-thick 2D copper oxide clusters on graphene.

    PubMed

    Kano, Emi; Kvashnin, Dmitry G; Sakai, Seiji; Chernozatonskii, Leonid A; Sorokin, Pavel B; Hashimoto, Ayako; Takeguchi, Masaki

    2017-03-17

    The successful isolation and remarkable properties of graphene have recently triggered investigation of two-dimensional (2D) materials from layered compounds; however, one-atom-thick 2D materials without bulk layered counterparts are scarcely reported. Here we report the structure and properties of novel 2D copper oxide studied by experimental and theoretical methods. Electron microscopy observations reveal that copper oxide can form monoatomic layers with an unusual square lattice on graphene. Density functional theory calculations suggest that oxygen atoms at the centre of the square lattice stabilizes the 2D Cu structure, and that the 2D copper oxide sheets have unusual electronic and magnetic properties different from 3D bulk copper oxide.

  5. Atomic-Scale Interfacial Magnetism in Fe/Graphene Heterojunction

    PubMed Central

    Liu, W. Q.; Wang, W. Y.; Wang, J. J.; Wang, F. Q.; Lu, C.; Jin, F.; Zhang, A.; Zhang, Q. M.; Laan, G. van der; Xu, Y. B.; Li, Q. X.; Zhang, R.

    2015-01-01

    Successful spin injection into graphene makes it a competitive contender in the race to become a key material for quantum computation, or the spin-operation-based data processing and sensing. Engineering ferromagnetic metal (FM)/graphene heterojunctions is one of the most promising avenues to realise it, however, their interface magnetism remains an open question up to this day. In any proposed FM/graphene spintronic devices, the best opportunity for spin transport could only be achieved where no magnetic dead layer exists at the FM/graphene interface. Here we present a comprehensive study of the epitaxial Fe/graphene interface by means of X-ray magnetic circular dichroism (XMCD) and density functional theory (DFT) calculations. The experiment has been performed using a specially designed FM1/FM2/graphene structure that to a large extent restores the realistic case of the proposed graphene-based transistors. We have quantitatively observed a reduced but still sizable magnetic moments of the epitaxial Fe ML on graphene, which is well resembled by simulations and can be attributed to the strong hybridization between the Fe 3dz2 and the C 2pz orbitals and the sp-orbital-like behavior of the Fe 3d electrons due to the presence of graphene. PMID:26145155

  6. High temperature and current density induced degradation of multi-layer graphene

    SciTech Connect

    Wang, Baoming; Haque, M. A.; Mag-isa, Alexander E.; Kim, Jae-Hyun; Lee, Hak-Joo

    2015-10-19

    We present evidence of moderate current density, when accompanied with high temperature, promoting migration of foreign atoms on the surface of multi-layer graphene. Our in situ transmission electron microscope experiments show migration of silicon atoms at temperatures above 800 °C and current density around 4.2 × 10{sup 7} A/cm{sup 2}. Originating from the micro-machined silicon structures that clamp the freestanding specimen, the atoms are observed to react with the carbon atoms in the multi-layer graphene to produce silicon carbide at temperatures of 900–1000 °C. In the absence of electrical current, there is no migration of silicon and only pyrolysis of polymeric residue is observed.

  7. Controlling Interfacial Reactions and Intermetallic Compound Growth at the Interface of a Lead-free Solder Joint with Layer-by-Layer Transferred Graphene.

    PubMed

    Ko, Yong-Ho; Lee, Jong-Dae; Yoon, Taeshik; Lee, Chang-Woo; Kim, Taek-Soo

    2016-03-02

    The immoderate growth of intermetallic compounds (IMCs) formed at the interface of a solder metal and the substrate during soldering can degrade the mechanical properties and reliability of a solder joint in electronic packaging. Therefore, it is critical to control IMC growth at the solder joints between the solder and the substrate. In this study, we investigated the control of interfacial reactions and IMC growth by the layer-by-layer transfer of graphene during the reflow process at the interface between Sn-3.0Ag-0.5Cu (in wt %) lead-free solder and Cu. As the number of graphene layers transferred onto the surface of the Cu substrate increased, the thickness of the total IMC (Cu6Sn5 and Cu3Sn) layer decreased. After 10 repetitions of the reflow process for 50 s above 217 °C, the melting temperature of Sn-3.0Ag-0.5Cu, with a peak temperature of 250 °C, the increase in thickness of the total IMC layer at the interface with multiple layers of graphene was decreased by more than 20% compared to that at the interface of bare Cu without graphene. Furthermore, the average diameter of the Cu6Sn5 scallops at the interface with multiple layers of graphene was smaller than that at the interface without graphene. Despite 10 repetitions of the reflow process, the growth of Cu3Sn at the interface with multiple layers of graphene was suppressed by more than 20% compared with that at the interface without graphene. The multiple layers of graphene at the interface between the solder metal and the Cu substrate hindered the diffusion of Cu atoms from the Cu substrate and suppressed the reactions between Cu and Sn in the solder. Thus, the multiple layers of graphene transferred at the interface between dissimilar metals can control the interfacial reaction and IMC growth occurring at the joining interface.

  8. Nanoscale imaging of freestanding nitrogen doped single layer graphene.

    PubMed

    Iyer, Ganjigunte R S; Wang, Jian; Wells, Garth; Bradley, Michael P; Borondics, Ferenc

    2015-02-14

    Graphene can be p-type or n-type doped by introduction of specific species. Doping can modulate the electronic properties of graphene, but opening a sizable-well-tuned bandgap is essential for graphene-based tunable electronic devices. N-doped graphene is widely used for device applications and is mostly achieved by introducing ammonia into the synthesis gas during the chemical vapor deposition (CVD) process. Post synthesis treatment studies to fine-tune the electron hole doping in graphene are limited. In this work realization of N-doping in large area freestanding single layer graphene (LFG) is achieved by post treatment in nitrogen plasma. The changes in the chemical and electronic properties of graphene are followed with Raman microscopy and mapped via synchrotron based scanning transmission X-ray microscopy (STXM) at the nanoscale.

  9. Strong piezoelectricity in single-layer graphene deposited on SiO2 grating substrates.

    PubMed

    da Cunha Rodrigues, Gonçalo; Zelenovskiy, Pavel; Romanyuk, Konstantin; Luchkin, Sergey; Kopelevich, Yakov; Kholkin, Andrei

    2015-06-25

    Electromechanical response of materials is a key property for various applications ranging from actuators to sophisticated nanoelectromechanical systems. Here electromechanical properties of the single-layer graphene transferred onto SiO2 calibration grating substrates is studied via piezoresponse force microscopy and confocal Raman spectroscopy. The correlation of mechanical strains in graphene layer with the substrate morphology is established via Raman mapping. Apparent vertical piezoresponse from the single-layer graphene supported by underlying SiO2 structure is observed by piezoresponse force microscopy. The calculated vertical piezocoefficient is about 1.4 nm V(-1), that is, much higher than that of the conventional piezoelectric materials such as lead zirconate titanate and comparable to that of relaxor single crystals. The observed piezoresponse and achieved strain in graphene are associated with the chemical interaction of graphene's carbon atoms with the oxygen from underlying SiO2. The results provide a basis for future applications of graphene layers for sensing, actuating and energy harvesting.

  10. Characterization of Graphene and Transition Metal Dichalcogenide at the Atomic Scale

    NASA Astrophysics Data System (ADS)

    Liu, Zheng; Lin, Yung-Chang; Warner, Jamie H.; Teng, Po-Yuan; Yeh, Chao-Hui; Chiu, Po-Wen; Iijima, Sumio; Suenga, Kazu

    2015-12-01

    Edge structures and atomic defects are of fundamental importance since they can significantly affect the physical and chemical properties of low-dimensional materials, such as nanoribbons, and therefore merit thorough investigations at the atomic level. Recent developments of direct imaging and analytical techniques using an aberration-corrected scanning transmission electron microscope (STEM) have provided direct access to information on the local atomic structure and the chemical composition at the atomic scale. In this review, we report on the discrimination of single atoms including dopant atoms on a monolayered transition-metal dichalcogenide (TMD) nanoribbon and a single nitrogen adatom on graphene by time-resolved annular dark-field (ADF) imaging and spatially resolved electron energy loss spectroscopy (EELS). We also show that in situ scanning transmission electron microscopy can be used to monitor the structural transformation between semiconducting (2H) and metallic (1T) phases in monolayer MoS2, and can enable direct observation of in-plane graphene growth at a step edge of a bi-layer graphene and domain boundary formation during growth with atomic-resolution.

  11. Nanoscale imaging of freestanding nitrogen doped single layer graphene

    NASA Astrophysics Data System (ADS)

    Iyer, Ganjigunte R. S.; Wang, Jian; Wells, Garth; Bradley, Michael P.; Borondics, Ferenc

    2015-01-01

    Graphene can be p-type or n-type doped by introduction of specific species. Doping can modulate the electronic properties of graphene, but opening a sizable-well-tuned bandgap is essential for graphene-based tunable electronic devices. N-doped graphene is widely used for device applications and is mostly achieved by introducing ammonia into the synthesis gas during the chemical vapor deposition (CVD) process. Post synthesis treatment studies to fine-tune the electron hole doping in graphene are limited. In this work realization of N-doping in large area freestanding single layer graphene (LFG) is achieved by post treatment in nitrogen plasma. The changes in the chemical and electronic properties of graphene are followed with Raman microscopy and mapped via synchrotron based scanning transmission X-ray microscopy (STXM) at the nanoscale.Graphene can be p-type or n-type doped by introduction of specific species. Doping can modulate the electronic properties of graphene, but opening a sizable-well-tuned bandgap is essential for graphene-based tunable electronic devices. N-doped graphene is widely used for device applications and is mostly achieved by introducing ammonia into the synthesis gas during the chemical vapor deposition (CVD) process. Post synthesis treatment studies to fine-tune the electron hole doping in graphene are limited. In this work realization of N-doping in large area freestanding single layer graphene (LFG) is achieved by post treatment in nitrogen plasma. The changes in the chemical and electronic properties of graphene are followed with Raman microscopy and mapped via synchrotron based scanning transmission X-ray microscopy (STXM) at the nanoscale. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05385k

  12. Atomic oxidation of large area epitaxial graphene on 4H-SiC(0001)

    SciTech Connect

    Velez-Fort, E.; Ouerghi, A.; Silly, M. G.; Sirtti, F.; Eddrief, M.; Marangolo, M.; Shukla, A.

    2014-03-03

    Structural and electronic properties of epitaxial graphene on 4H-SiC were studied before and after an atomic oxidation process. X-ray photoemission spectroscopy indicates that oxygen penetrates into the substrate and decouples a part of the interface layer. Raman spectroscopy demonstrates the increase of defects due to the presence of oxygen. Interestingly, we observed on the near edge x-ray absorption fine structure spectra a splitting of the π* peak into two distinct resonances centered at 284.7 and 285.2 eV. This double structure smears out after the oxidation process and permits to probe the interface architecture between graphene and the substrate.

  13. Energetics of atomic scale structure changes in graphene.

    PubMed

    Skowron, Stephen T; Lebedeva, Irina V; Popov, Andrey M; Bichoutskaia, Elena

    2015-05-21

    The presence of defects in graphene has an essential influence on its physical and chemical properties. The formation, behaviour and healing of defects are determined by energetic characteristics of atomic scale structure changes. In this article, we review recent studies devoted to atomic scale reactions during thermally activated and irradiation-induced processes in graphene. The formation energies of vacancies, adatoms and topological defects are discussed. Defect formation, healing and migration are quantified in terms of activation energies (barriers) for thermally activated processes and by threshold energies for processes occurring under electron irradiation. The energetics of defects in the graphene interior and at the edge is analysed. The effects of applied strain and a close proximity of the edge on the energetics of atomic scale reactions are overviewed. Particular attention is given to problems where further studies are required.

  14. Production of few-layer graphene by microfluidization

    NASA Astrophysics Data System (ADS)

    Paton, Keith R.; Anderson, James; Pollard, Andrew J.; Sainsbury, Toby

    2017-02-01

    Production of few-layer graphene by liquid phase exfoliation using a microfluidizer has been demonstrated. Using natural flake graphite in water-surfactant solutions, few-layer graphene has been produced, with size selection demonstrating fractions with flake thicknesses down to an average of 2 layers. The yield from this route is superior to that obtained by alternative production methods, highlighting the utility of this technique.

  15. Atomic resolution electrostatic potential mapping of graphene sheets by off-axis electron holography

    SciTech Connect

    Cooper, David; Pan, Cheng-Ta; Haigh, Sarah

    2014-06-21

    Off-axis electron holography has been performed at atomic resolution with the microscope operated at 80 kV to provide electrostatic potential maps from single, double, and triple layer graphene. These electron holograms have been reconstructed in order to obtain information about atomically resolved and mean inner potentials. We propose that off-axis electron holography can now be used to measure the electrical properties in a range of two-dimensional semiconductor materials and three dimensional devices comprising stacked layers of films to provide important information about their electrical properties.

  16. Electronic interaction between nitrogen atoms in doped graphene.

    PubMed

    Tison, Yann; Lagoute, Jérôme; Repain, Vincent; Chacon, Cyril; Girard, Yann; Rousset, Sylvie; Joucken, Frédéric; Sharma, Dimpy; Henrard, Luc; Amara, Hakim; Ghedjatti, Ahmed; Ducastelle, François

    2015-01-27

    Many potential applications of graphene require either the possibility of tuning its electronic structure or the addition of reactive sites on its chemically inert basal plane. Among the various strategies proposed to reach these objectives, nitrogen doping, i.e., the incorporation of nitrogen atoms in the carbon lattice, leads in most cases to a globally n-doped material and to the presence of various types of point defects. In this context, the interactions between chemical dopants in graphene have important consequences on the electronic properties of the systems and cannot be neglected when interpreting spectroscopic data or setting up devices. In this report, the structural and electronic properties of complex doping sites in nitrogen-doped graphene have been investigated by means of scanning tunneling microscopy and spectroscopy, supported by density functional theory and tight-binding calculations. In particular, based on combined experimental and simulation works, we have systematically studied the electronic fingerprints of complex doping configurations made of pairs of substitutional nitrogen atoms. Localized bonding states are observed between the Dirac point and the Fermi level in contrast with the unoccupied state associated with single substitutional N atoms. For pyridinic nitrogen sites (i.e., the combination of N atoms with vacancies), a resonant state is observed close to the Dirac energy. This insight into the modifications of electronic structure induced by nitrogen doping in graphene provides us with a fair understanding of complex doping configurations in graphene, as it appears in real samples.

  17. Graphene-based multilayers constructed from layer-by-layer self-assembly techniques.

    PubMed

    Yu, Bing; Liu, Xiaomian; Cong, Hailin; Yuan, Hua; Wang, Dong; Li, Zejing

    2014-02-01

    This paper reviews the recent research and development of graphene-based multilayers fabricated from layer-by-layer (LBL) self-assembly technique. Graphene multilayer films, due to their excellent performances and specific applications, have attracted widespread attention during recent decades. In this paper, the preparation and property of self-assembled graphene multilayer films are introduced. The application of different graphene multilayer films in transparent conducting films (TCFs), field effect transistors (FETs), lithium ion batteries (LIBs), supercapacitors, and solar cells are summarized and discussed. The perspectives for the future developments of self-assembled graphene multilayer films are proposed.

  18. Atomic intercalation - a practical method to determine the nanoscale adhesion energy of graphene on HOPG

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Sorescu, Dan; Jeon, Seokmin; Belianinov, Alexei; Kalinin, Sergei; Baddorf, Arthur; Maksymovych, Petro

    A detailed analysis of atomic intercalates in graphite provides a direct estimate of the nanoscale elastic adhesion of a graphene sheet atop highly ordered pyrolytic graphite (HOPG). Atomic intercalation is carried out using conventional ion sputtering, creating ``blisters'' in the top-most layer of the HOPG surface. Scanning tunneling microscopy coupled with image analysis and density functional theory is used to reconstruct the atomic positions and the strain map within the deformed graphene sheet. To estimate the adhesion energy we invoke an analytical model originally devised for macroscopic deformations of graphene. This model yields a value of is 0.221 +/- 0.011 J/m2 for the adhesion energy of graphite, which is in surprisingly good agreement with reported experimental and theoretical values. This implies that mechanical properties of graphene scale at least to lengths of a few nanometers. The simplicity of our method enables analysis of elastic mechanical properties in many two-dimensional layered materials and provides a unique opportunity to investigate the local variability of mechanical properties on the nanoscale. Acknowledgements: Experiments were conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.

  19. Driving Forces of Conformational Changes in Single-Layer Graphene Oxide

    PubMed Central

    2012-01-01

    The extensive oxygen-group functionality of single-layer graphene oxide proffers useful anchor sites for chemical functionalization in the controlled formation of graphene architecture and composites. However, the physicochemical environment of graphene oxide and its single-atom thickness facilitate its ability to undergo conformational changes due to responses to its environment, whether pH, salinity, or temperature. Here, we report experimental and molecular simulations confirming the conformational changes of single-layer graphene oxide sheets from the wet or dry state. MD, PM6, and ab initio simulations of dry SLG and dry and wetted SLGO and electron microscopy imaging show marked differences in the properties of the materials that can explain variations in previously observed results for the pH dependent behavior of SLGO and electrical conductivity of chemically modified graphene-polymer composites. Understanding the physicochemical responses of graphene and graphene oxide architecture and performing selected chemistry will ultimately facilitate greater tunability of their performance. PMID:22494387

  20. Atomic-Scale Sliding Friction on Graphene in Water.

    PubMed

    Vilhena, J G; Pimentel, Carlos; Pedraz, Patricia; Luo, Feng; Serena, Pedro A; Pina, Carlos M; Gnecco, Enrico; Pérez, Rubén

    2016-04-26

    The sliding of a sharp nanotip on graphene completely immersed in water is investigated by molecular dynamics (MD) and atomic force microscopy. MD simulations predict that the atomic-scale stick-slip is almost identical to that found in ultrahigh vacuum. Furthermore, they show that water plays a purely stochastic role in sliding (solid-to-solid) friction. These observations are substantiated by friction measurements on graphene grown on Cu and Ni, where, oppositely of the operation in air, lattice resolution is readily achieved. Our results promote friction force microscopy in water as a robust alternative to ultra-high-vacuum measurements.

  1. SrO(001) on graphene: a universal buffer layer for integration of complex oxides

    NASA Astrophysics Data System (ADS)

    Ahmed, Adam; Wen, Hua; Pinchuk, Igor; Zhu, Tiancong; Kawakami, Roland

    2015-03-01

    We report the successful growth of high-quality crystalline SrO on highly-ordered pyrolytic graphite (HOPG) and single layer graphene by molecular beam epitaxy. The epitaxial SrO layers have (001) orientation as confirmed by x-ray diffraction (XRD), and atomic force microscopy measurements show rms surface roughness of optimal films to be 1.2 Å. Transport measurements of exfoliated graphene after SrO deposition show a strong dependence between the Dirac point and Sr oxidation. To show the utility of SrO as a buffer layer for complex oxide integration, we grew perovskite crystal SrTiO3 on SrO, and it was also confirmed to have (001) orientation from x-ray diffraction. This materials advancement opens the door to integration of many other complex oxides to explore novel correlated electron physics in graphene.

  2. Raman and ellipsometry spectroscopic analysis of graphene films grown directly on Si substrate via CVD technique for estimating the graphene atomic planes number

    NASA Astrophysics Data System (ADS)

    Al-Hazmi, F. S.; Beall, Gary W.; Al-Ghamdi, A. A.; Alshahrie, Ahmed; Shokr, F. S.; Mahmoud, Waleed E.

    2016-08-01

    Two reliable approaches for estimating the number of atomic planes of graphene films grown on Si substrate were demonstrated by Raman and ellipsometry spectroscopies. The first approach depends on the measurement of the ratio of the integrated Raman scattering intensity of the graphene G band to the optical phonon band of Si substrate (IG/ISi). The second approach belongs to ellipsometry measurement of the ratio of the amplitude of the reflected polarized light from the surface of the graphene films to the amplitude of reflected polarized light from the surface of the Si substrate (ΨG/ΨSi). These two approaches could efficiently recognize the number of atomic planes in the graphene films (1 ≤ n ≤ 10). The results were compared with atomic force microscopy (AFM) measurement and showed a linear regression with slope of 0.36 ± 0.01 nm/graphene layer. The Two approaches will open a new avenue to efficiently count the number of graphene layers during the preparation process.

  3. Graphene Layer Growth Chemistry: Five-Six-Ring Flip Reaction

    SciTech Connect

    Whitesides, Russell; Domin, Dominik; Lester Jr., William A.; Frenklach, Michael

    2007-03-24

    A theoretical study revealed a new reaction pathway, in which a fused five and six-membered ring complex on the zigzag edge of a graphene layer isomerizes to reverse its orientation, or 'flips,' after activation by a gaseous hydrogen atom. The process is initiated by hydrogen addition to or abstraction from the surface complex. The elementary steps of the migration pathway were analyzed using density-functional theory (DFT) calculations to examine the region of the potential energy surface associated with the pathway. The DFT calculations were performed on substrates modeled by the zigzag edges of tetracene and pentacene. Rate constants for the flip reaction were obtained by the solution of energy master equation utilizing the DFT energies, frequencies, and geometries. The results indicate that this reaction pathway is competitive with other pathways important to the edge evolution of aromatic species in high temperature environments.

  4. Surface Chemistry in Electrochemical Atomic Layer Processing

    DTIC Science & Technology

    2007-11-02

    example, where a thin film of a material is formed an atomic layer at a time. That is, surface limited reactions are used to deposit individual atomic...The present studies were designed to investigate these surface limited reactions. To determine what the structures of the deposits were, and how that structure influenced subsequent deposition .

  5. Atomic structures of silicene layers grown on Ag(111): scanning tunneling microscopy and noncontact atomic force microscopy observations.

    PubMed

    Resta, Andrea; Leoni, Thomas; Barth, Clemens; Ranguis, Alain; Becker, Conrad; Bruhn, Thomas; Vogt, Patrick; Le Lay, Guy

    2013-01-01

    Silicene, the considered equivalent of graphene for silicon, has been recently synthesized on Ag(111) surfaces. Following the tremendous success of graphene, silicene might further widen the horizon of two-dimensional materials with new allotropes artificially created. Due to stronger spin-orbit coupling, lower group symmetry and different chemistry compared to graphene, silicene presents many new interesting features. Here, we focus on very important aspects of silicene layers on Ag(111): First, we present scanning tunneling microscopy (STM) and non-contact Atomic Force Microscopy (nc-AFM) observations of the major structures of single layer and bi-layer silicene in epitaxy with Ag(111). For the (3 × 3) reconstructed first silicene layer nc-AFM represents the same lateral arrangement of silicene atoms as STM and therefore provides a timely experimental confirmation of the current picture of the atomic silicene structure. Furthermore, both nc-AFM and STM give a unifying interpretation of the second layer (√3 × √3)R ± 30° structure. Finally, we give support to the conjectured possible existence of less stable, ~2% stressed, (√7 × √7)R ± 19.1° rotated silicene domains in the first layer.

  6. Atomic Structures of Silicene Layers Grown on Ag(111): Scanning Tunneling Microscopy and Noncontact Atomic Force Microscopy Observations

    PubMed Central

    Resta, Andrea; Leoni, Thomas; Barth, Clemens; Ranguis, Alain; Becker, Conrad; Bruhn, Thomas; Vogt, Patrick; Le Lay, Guy

    2013-01-01

    Silicene, the considered equivalent of graphene for silicon, has been recently synthesized on Ag(111) surfaces. Following the tremendous success of graphene, silicene might further widen the horizon of two-dimensional materials with new allotropes artificially created. Due to stronger spin-orbit coupling, lower group symmetry and different chemistry compared to graphene, silicene presents many new interesting features. Here, we focus on very important aspects of silicene layers on Ag(111): First, we present scanning tunneling microscopy (STM) and non-contact Atomic Force Microscopy (nc-AFM) observations of the major structures of single layer and bi-layer silicene in epitaxy with Ag(111). For the (3 × 3) reconstructed first silicene layer nc-AFM represents the same lateral arrangement of silicene atoms as STM and therefore provides a timely experimental confirmation of the current picture of the atomic silicene structure. Furthermore, both nc-AFM and STM give a unifying interpretation of the second layer (√3 × √3)R ± 30° structure. Finally, we give support to the conjectured possible existence of less stable, ~2% stressed, (√7 × √7)R ± 19.1° rotated silicene domains in the first layer. PMID:23928998

  7. Surface stress of graphene layers supported on soft substrate

    PubMed Central

    Du, Feng; Huang, Jianyong; Duan, Huiling; Xiong, Chunyang; Wang, Jianxiang

    2016-01-01

    We obtain the surface stress of a single layer and multilayers of graphene supported on silicone substrates by measuring the deformation of the graphene-covered substrates induced by the surface tension of liquid droplets together with the Neumann’s triangle concept. We find that the surface stress of the graphene-covered substrate is significant larger than that of the bare substrate, and it increases with increasing graphene layers, and finally reaches a constant value of about 120 mN/m on three and more layers of graphene. This work demonstrates that the apparent surface stress of graphene-substrate systems can be tuned by the substrate and the graphene layers. The surface stress and the tuning effect of the substrate on it may have applications in design and characterization of graphene-based ultra-sensitive sensors and other devices. Moreover, the method may also be used to measure the surface stress of other ultrathin films supported on soft substrates. PMID:27166087

  8. PREFACE: Ultrathin layers of graphene, h-BN and other honeycomb structures Ultrathin layers of graphene, h-BN and other honeycomb structures

    NASA Astrophysics Data System (ADS)

    Geber, Thomas; Oshima, Chuhei

    2012-08-01

    Since ancient times, pure carbon materials have been familiar in human society—not only diamonds in jewellery and graphite in pencils, but also charcoal and coal which have been used for centuries as fuel for living and industry. Carbon fibers are stronger, tougher and lighter than steel and increase material efficiency because of their lower weight. Today, carbon fibers and related composite materials are used to make the frames of bicycles, cars and even airplane parts. The two-dimensional allotrope, now called graphene, is just a single layer of carbon atoms, locked together in a strongly bonded honeycomb lattice. In plane, graphene is stiffer than diamond, but out-of-plane it is soft, like rubber. It is virtually invisible, may conduct electricity (heat) better than copper and weighs next to nothing. Carbon compounds with two carbon atoms as a base, such as graphene, graphite or diamond, have isoelectronic sister compounds made of boron-nitrogen pairs: hexagonal and cubic boron nitride, with almost the same lattice constant. Although the two 2D sisters, graphene and h-BN, have the same number of valence electrons, their electronic properties are very different: freestanding h-BN is an insulator, while charge carriers in graphene are highly mobile. The past ten years have seen a great expansion in studies of single-layer and few-layer graphene. This activity has been concerned with the π electron transport in graphene, in electric and magnetic fields. More than 30 years ago, however, single-layer graphene and h-BN on solid surfaces were widely investigated. It was noted that they drastically changed the chemical reactivity of surfaces, and they were known to 'poison' heterogeneous catalysts, to passivate surfaces, to prevent oxidation of surfaces and to act as surfactants. Also, it was realized that the controlled growth of h-BN and graphene on substrates yields the formation of mismatch driven superstructures with peculiar template functionality on the

  9. Resist-free method for contacting graphene and few-layer graphene

    NASA Astrophysics Data System (ADS)

    Soldano, Caterina; Mahmood, Ather; Grisolia, Jeremie; Savu, Veronica; Brugger, Juergen; Dujardin, Erik

    2009-03-01

    In recent years, discovery of graphene has offered the scientific community an important tool to investigate a variety of fundamental phenomena. Exceptional electronic transport render graphene a promising candidate for future high-performance electronic devices. Conventional techniques to fabricate graphene devices include lithographic approaches, which tend to alter the structure and surface of graphene, and therefore its properties. A graphene contacting method free of any surface damaging and/or modification is indeed in need. Here, we present a simple resist-free non-invasive approach for contacting graphene and/or few-layers graphene. SiN membrane were custum-made and used to mask samples, previously deposited on substrate. Then, evaporation of metal allows to fabricate electrical leads for testing. Further, we present preliminary measurements of the electronic properties (room- and low-temperatures) of one of our typical sample contacted by such technique.

  10. Advanced atom chips with two metal layers.

    SciTech Connect

    Stevens, James E.; Blain, Matthew Glenn; Benito, Francisco M.; Biedermann, Grant

    2010-12-01

    A design concept, device layout, and monolithic microfabrication processing sequence have been developed for a dual-metal layer atom chip for next-generation positional control of ultracold ensembles of trapped atoms. Atom chips are intriguing systems for precision metrology and quantum information that use ultracold atoms on microfabricated chips. Using magnetic fields generated by current carrying wires, atoms are confined via the Zeeman effect and controllably positioned near optical resonators. Current state-of-the-art atom chips are single-layer or hybrid-integrated multilayer devices with limited flexibility and repeatability. An attractive feature of multi-level metallization is the ability to construct more complicated conductor patterns and thereby realize the complex magnetic potentials necessary for the more precise spatial and temporal control of atoms that is required. Here, we have designed a true, monolithically integrated, planarized, multi-metal-layer atom chip for demonstrating crossed-wire conductor patterns that trap and controllably transport atoms across the chip surface to targets of interest.

  11. Tuning surface plasmons in graphene ribbons with liquid crystal layer

    NASA Astrophysics Data System (ADS)

    Reshetnyak, Viktor Yu.; Bunning, Timothy J.; Evans, Dean R.

    2016-09-01

    Surface plasmons in graphene possess stronger mode confinement and lower propagation loss. One way to excite the surface plasmons is placing a periodic array of graphene nano-ribbons on top of a dielectric substrate. However once the system is fabricated it is not possible to change its optical properties. Liquid crystals (LC) are a uniaxial medium with an optical axis easily controlled by external stimuli. We suggest tuning the surface plasmons in an array of graphene ribbons by placing a LC slab on top of the ribbons. A voltage applied to the LC layer shifts the graphene ribbons plasmonic notch and changes its depth.

  12. Wear Resistance Limited by Step Edge Failure: The Rise and Fall of Graphene as an Atomically Thin Lubricating Material.

    PubMed

    Qi, Yizhou; Liu, Jun; Zhang, Ji; Dong, Yalin; Li, Qunyang

    2017-01-11

    Owing to its intrinsically lubricious property, graphene has a high potential to be an atomically thin solid lubricant for sliding interfaces. Despite its ultrahigh breaking strength at the nanoscale, graphene often fails to maintain its integrity when subjected to macroscale tribological tests. To reveal the true wear characteristics of graphene, a nanoscale diamond tip was used to scratch monolayer graphene mechanically exfoliated to SiO2 substrates. Our experimental results show that while graphene exhibited extraordinary wear resistance in the interior region, it could be easily damaged at the step edge under a much lower normal load (∼2 orders of magnitude smaller). Similar behavior with substantially reduced wear resistance at the edge was also observed for monatomic graphene layer on graphite surface. Using molecular dynamics simulations, we attributed this markedly weak wear resistance at the step edge to two primary mechanisms, i.e., atom-by-atom adhesive wear and peel induced rupture. Our findings shed light on the paradox that graphene is nanoscopically strong yet macroscopically weak. As step edge is ubiquitous for two-dimensional materials at the macroscale, our study also provides a guiding direction for maximizing the mechanical and tribological performance of these atomically thin materials.

  13. Raman spectroscopic study of chemically-doped few layer graphenes

    NASA Astrophysics Data System (ADS)

    Tan, Pingheng; Zhao, Weijie; Zhang, Jun; Liu, Jian

    2011-03-01

    Graphene, the latest carbon allotrope discovered at 2004, has attracted intensively scientific interest owing to its distinctive properties. Chemical doping is expected to substantially increase the density of free charge carriers by charge transfer and to modify the Fermi level of doped materials. Here, we investigated charge transfer and optical phonon mixing in few layer graphenes in detail by utilizing sulfuric acid as an electron-acceptor dopant. Sulfuric acid molecules are found to be only physically adsorbed on the surface layers of graphenes and no intercalation happens. The top and bottom layers of bilayer graphenes can be intentionally doped differently by concentrated sulfuric acid. The difference of hole doping between the top and bottom layers results in phonon mixing of symmetric and antisymmetric modes in bilayer graphenes. The Raman frequency evolution with the doping level qualitatively agrees with recent ab initio theoretical calculations. Sulfuric acid molecules can be expected as a stable electron-acceptor dopant for graphenes to study the physical properties of few layer graphenes at different doping levels.

  14. An Introduction to Atomic Layer Deposition

    NASA Technical Reports Server (NTRS)

    Dwivedi, Vivek H.

    2017-01-01

    Atomic Layer Deposition has been instrumental in providing a deposition method for multiple space flight applications. It is well known that ALD is a cost effective nanoadditive-manufacturing technique that allows for the conformal coating of substrates with atomic control in a benign temperature and pressure environment. Through the introduction of paired precursor gases, thin films can be deposited on a myriad of substrates from flat surfaces to those with significant topography. By providing atomic layer control, where single layers of atoms can be deposited, the fabrication of metal transparent films, precise nano-laminates, and coatings of nano-channels, pores and particles is achievable. The feasibility of this technology for NASA line of business applications range from thermal systems, optics, sensors, to environmental protection. An overview of this technology will be presented.

  15. Reduction of graphene oxide to graphene, A study of changes in the atomic structure

    NASA Astrophysics Data System (ADS)

    Mittal, A.; Wagner, A.; Mattevi, C.; Chov, A.; Liao, K.; Macosko, C.; Chhowalla, M.; Mkhoyan, K. A.

    2012-02-01

    An economic method for large scale production of graphene is based on exfoliation of graphite into 1-atom thick sheets by oxidation, creating graphene oxide (GO) and subsequent reduction of GO into graphene. Reduced GO sheets approach the highly desired properties of graphene, such as electrical conductivity and mechanical strength, to various degrees, but not completely. To understand why, we must understand the nanostructure of the sheets. Different methods of reduction result in products that are similar to graphene, but these products retain some oxidized areas or contain regions with sp^3 bonded carbon. The concentration and distribution of these defects on the reduced GO sheet affect the properties of the 2D material. Here, we have characterized the atomic structure of GO and reduced GO via high resolution transmission electron microscopy, electron diffraction, and electron energy loss spectroscopy. Spectroscopic data taken during thermal reduction of GO shows changes in the fine structure of carbon K-edge as the carbon changes from an oxidized form to elemental amorphous carbon to graphite like form, clearly delineating the process of reduction of GO to graphene. Products of several other reduction methods are also characterized revealing information on electronic environment surrounding carbon atoms, distribution of crystalline areas, and oxygen removal from GO.

  16. Spin-induced band modifications of graphene through intercalation of magnetic iron atoms.

    PubMed

    Sung, S J; Yang, J W; Lee, P R; Kim, J G; Ryu, M T; Park, H M; Lee, G; Hwang, C C; Kim, Kwang S; Kim, J S; Chung, J W

    2014-04-07

    Intercalation of magnetic iron atoms through graphene formed on the SiC(0001) surface is found to induce significant changes in the electronic properties of graphene due mainly to the Fe-induced asymmetries in charge as well as spin distribution. From our synchrotron-based photoelectron spectroscopy data together with ab initio calculations, we observe that the Fe-induced charge asymmetry results in the formation of a quasi-free-standing bilayer graphene while the spin asymmetry drives multiple spin-split bands. We find that Fe adatoms are best intercalated upon annealing at 600 °C, exhibiting split linear π-bands, characteristic of a bilayer graphene, but much diffused. Subsequent changes in the C 1s, Si 2p, and Fe 3p core levels are consistently described in terms of Fe-intercalation. Our calculations together with a spin-dependent tight binding model ascribe the diffuse nature of the π-bands to the multiple spin-split bands originated from the spin-injected carbon atoms residing only in the lower graphene layer.

  17. Adsorption by design: Tuning atom-graphene van der Waals interactions via mechanical strain

    NASA Astrophysics Data System (ADS)

    Nichols, Nathan S.; Del Maestro, Adrian; Wexler, Carlos; Kotov, Valeri N.

    2016-05-01

    We aim to understand how the van der Waals force between neutral adatoms and a graphene layer is modified by uniaxial strain and electron correlation effects. A detailed analysis is presented for three atoms (He, H, and Na) and graphene strain ranging from weak to moderately strong. We show that the van der Waals potential can be significantly enhanced by strain, and present applications of our results to the problem of elastic scattering of atoms from graphene. In particular, we find that quantum reflection can be significantly suppressed by strain, meaning that dissipative inelastic effects near the surface become of increased importance. Furthermore, we introduce a method to independently estimate the Lennard-Jones parameters used in an effective model of He interacting with graphene, and determine how they depend on strain. At short distances, we find that strain tends to reduce the interaction strength by pushing the location of the adsorption potential minima to higher distances above the deformed graphene sheet. This opens up the exciting possibility of mechanically engineering an adsorption potential, with implications for the formation and observation of anisotropic low-dimensional superfluid phases.

  18. Ultraviolet laser deposition of graphene thin films without catalytic layers

    NASA Astrophysics Data System (ADS)

    Sarath Kumar, S. R.; Alshareef, H. N.

    2013-01-01

    In this letter, the formation of nanostructured graphene by ultraviolet laser ablation of a highly ordered pyrolytic graphite target under optimized conditions is demonstrated, without a catalytic layer, and a model for the growth process is proposed. Previously, graphene film deposition by low-energy laser (2.3 eV) was explained by photo-thermal models, which implied that graphene films cannot be deposited by laser energies higher than the C-C bond energy in highly ordered pyrolytic graphite (3.7 eV). Here, we show that nanostructured graphene films can in fact be deposited using ultraviolet laser (5 eV) directly over different substrates, without a catalytic layer. The formation of graphene is explained by bond-breaking assisted by photoelectronic excitation leading to formation of carbon clusters at the target and annealing out of defects at the substrate.

  19. Atomically Sharp Interface in an h-BN-epitaxial graphene van der Waals Heterostructure

    PubMed Central

    Sediri, Haikel; Pierucci, Debora; Hajlaoui, Mahdi; Henck, Hugo; Patriarche, Gilles; Dappe, Yannick J.; Yuan, Sheng; Toury, Bérangère; Belkhou, Rachid; Silly, Mathieu G.; Sirotti, Fausto; Boutchich, Mohamed; Ouerghi, Abdelkarim

    2015-01-01

    Stacking various two-dimensional atomic crystals is a feasible approach to creating unique multilayered van der Waals heterostructures with tailored properties. Herein for the first time, we present a controlled preparation of large-area h-BN/graphene heterostructures via a simple chemical deposition of h-BN layers on epitaxial graphene/SiC(0001). Van der Waals forces, which are responsible for the cohesion of the multilayer system, give rise to an abrupt interface without interdiffusion between graphene and h-BN, as shown by X-ray Photoemission Spectroscopy (XPS) and direct observation using scanning and High-Resolution Transmission Electron Microscopy (STEM/HRTEM). The electronic properties of graphene, such as the Dirac cone, remain intact and no significant charge transfer i.e. doping, is observed. These results are supported by Density Functional Theory (DFT) calculations. We demonstrate that the h-BN capped graphene allows the fabrication of vdW heterostructures without altering the electronic properties of graphene. PMID:26585245

  20. Few-layer graphene growth from polystyrene as solid carbon source utilizing simple APCVD method

    NASA Astrophysics Data System (ADS)

    Ahmadi, Shahrokh; Afzalzadeh, Reza

    2016-07-01

    This research article presents development of an economical, simple, immune and environment friendly process to grow few-layer graphene by controlling evaporation rate of polystyrene on copper foil as catalyst and substrate utilizing atmospheric pressure chemical vapor deposition (APCVD) method. Evaporation rate of polystyrene depends on molecular structure, amount of used material and temperature. We have found controlling rate of evaporation of polystyrene by controlling the source temperature is easier than controlling the material weight. Atomic force microscopy (AFM) as well as Raman Spectroscopy has been used for characterization of the layers. The frequency of G‧ to G band ratio intensity in some samples varied between 0.8 and 1.6 corresponding to few-layer graphene. Topography characterization by atomic force microscopy confirmed Raman results.

  1. The effects of oxygen on controlling the number of carbon layers in the chemical vapor deposition of graphene on a nickel substrate.

    PubMed

    Dou, Wei-Dong; Yang, Qingdan; Lee, Chun-Sing

    2013-05-10

    While oxygen is typically considered undesirable during the chemical vapor deposition (CVD) of graphene on metal substrates, we demonstrate that suitable amounts of oxygen in the CVD system can in fact improve the uniformity and thickness control of the graphene film. The role of oxygen on the CVD of graphene on a nickel substrate using a propylene precursor was investigated with various surface analytical techniques. It was found that the number of carbon layers in the deposited graphene sample decreases as the concentration of oxygen increases. In particular, single-layer graphene can be easily obtained with an oxygen/propylene ratio of 1/9. In the presence of oxygen, a thin layer of nickel oxide will form on the substrate. The oxide layer decreases the concentration of carbon atoms dissolved in the nickel substrate and results in graphene samples with a decreasing number of carbon layers.

  2. Extremely large magnetoresistance in few-layer graphene/boron–nitride heterostructures

    PubMed Central

    Gopinadhan, Kalon; Shin, Young Jun; Jalil, Rashid; Venkatesan, Thirumalai; Geim, Andre K.; Neto, Antonio H. Castro; Yang, Hyunsoo

    2015-01-01

    Understanding magnetoresistance, the change in electrical resistance under an external magnetic field, at the atomic level is of great interest both fundamentally and technologically. Graphene and other two-dimensional layered materials provide an unprecedented opportunity to explore magnetoresistance at its nascent stage of structural formation. Here we report an extremely large local magnetoresistance of∼2,000% at 400 K and a non-local magnetoresistance of >90,000% in an applied magnetic field of 9 T at 300 K in few-layer graphene/boron–nitride heterostructures. The local magnetoresistance is understood to arise from large differential transport parameters, such as the carrier mobility, across various layers of few-layer graphene upon a normal magnetic field, whereas the non-local magnetoresistance is due to the magnetic field induced Ettingshausen–Nernst effect. Non-local magnetoresistance suggests the possibility of a graphene-based gate tunable thermal switch. In addition, our results demonstrate that graphene heterostructures may be promising for magnetic field sensing applications. PMID:26388149

  3. Chemical storage of hydrogen in few-layer graphene

    PubMed Central

    Subrahmanyam, K. S.; Kumar, Prashant; Maitra, Urmimala; Govindaraj, A.; Hembram, K. P. S. S.; Waghmare, Umesh V.; Rao, C. N. R.

    2011-01-01

    Birch reduction of few-layer graphene samples gives rise to hydrogenated samples containing up to 5 wt % of hydrogen. Spectroscopic studies reveal the presence of sp3 C-H bonds in the hydrogenated graphenes. They, however, decompose readily on heating to 500 °C or on irradiation with UV or laser radiation releasing all the hydrogen, thereby demonstrating the possible use of few-layer graphene for chemical storage of hydrogen. First-principles calculations throw light on the mechanism of dehydrogenation that appears to involve a significant reconstruction and relaxation of the lattice. PMID:21282617

  4. Confining Cation Injection to Enhance CBRAM Performance by Nanopore Graphene Layer.

    PubMed

    Zhao, Xiaolong; Liu, Sen; Niu, Jiebin; Liao, Lei; Liu, Qi; Xiao, Xiangheng; Lv, Hangbing; Long, Shibing; Banerjee, Writam; Li, Wenqing; Si, Shuyao; Liu, Ming

    2017-09-01

    Conductive-bridge random access memory (CBRAM) is considered a strong contender of the next-generation nonvolatile memory technology. Resistive switching (RS) behavior in CBRAM is decided by the formation/dissolution of nanoscale conductive filament (CF) inside RS layer based on the cation injection from active electrode and their electrochemical reactions. Remarkably, RS is actually a localized behavior, however, cation injects from the whole area of active electrode into RS layer supplying excessive cation beyond the requirement of CF formation, leading to deterioration of device uniformity and reliability. Here, an effective method is proposed to localize cation injection into RS layer through the nanohole of inserted ion barrier between active electrode and RS layer. Taking an impermeable monolayer graphene as ion barrier, conductive atomic force microscopy results directly confirm that CF formation is confined through the nanohole of graphene due to the localized cation injection. Compared with the typical Cu/HfO2 /Pt CBRAM device, the novel Cu/nanohole-graphene/HfO2 /Pt device shows improvement of uniformity, endurance, and retention characteristics, because the cation injection is limited by the nanohole graphene. Scaling the nanohole of ion barrier down to several nanometers, the single-CF-based CBRAM device with high performance is expected to achieve by confining the cation injection at the atomic scale. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Adsorption of beryllium atoms and clusters both on graphene and in a bilayer of graphite investigated by DFT.

    PubMed

    Ferro, Yves; Fernandez, Nicolas; Allouche, Alain; Linsmeier, Christian

    2013-01-09

    We herein investigate the interaction of beryllium with a graphene sheet and in a bilayer of graphite by means of periodic DFT calculations. In all cases, we find the beryllium atoms to be more weakly bonded on graphene than in the bilayer. Be(2) forms both magnetic and non-magnetic structures on graphene depending on the geometrical configuration of adsorption. We find that the stability of the Be/bilayer system increases with the size of the beryllium clusters inserted into the bilayer of graphite. We also find a charge transfer from beryllium to the graphite layers. All these results are analysed in terms of electronic structure.

  6. Layer-by-Layer Insight into Electrostatic Charge Distribution of Few-Layer Graphene

    PubMed Central

    Rokni, Hossein; Lu, Wei

    2017-01-01

    In few-layer graphene (FLG) systems on a dielectric substrate such as SiO2, the addition of each extra layer of graphene can drastically alter their electronic and structural properties. Here, we map the charge distribution among the individual layers of finite-size FLG systems using a novel spatial discrete model that describes both electrostatic interlayer screening and fringe field effects. Our results reveal that the charge density in the region very close to the edges is screened out an order of magnitude more weakly than that across the central region of the layers. Our discrete model suggests that the interlayer charge screening length in 1–8 layer thick graphene systems depends mostly on the overall gate/molecular doping level rather than on temperature, in particular at an induced charge density >5 × 1012 cm−2, and can reliably be determined to be larger than half the interlayer spacing but shorter than the bilayer thickness. Our model can be used for designing FLG-based devices, and offers a simple rule regarding the charge distribution in FLG: approximately 70%, 20%, 6% and 3% (99% overall) of the total induced charge density reside within the four innermost layers, implying that the gate-induced electric field is not definitely felt by >4th layer. PMID:28220816

  7. Layer-by-Layer Insight into Electrostatic Charge Distribution of Few-Layer Graphene

    NASA Astrophysics Data System (ADS)

    Rokni, Hossein; Lu, Wei

    2017-02-01

    In few-layer graphene (FLG) systems on a dielectric substrate such as SiO2, the addition of each extra layer of graphene can drastically alter their electronic and structural properties. Here, we map the charge distribution among the individual layers of finite-size FLG systems using a novel spatial discrete model that describes both electrostatic interlayer screening and fringe field effects. Our results reveal that the charge density in the region very close to the edges is screened out an order of magnitude more weakly than that across the central region of the layers. Our discrete model suggests that the interlayer charge screening length in 1–8 layer thick graphene systems depends mostly on the overall gate/molecular doping level rather than on temperature, in particular at an induced charge density >5 × 1012 cm‑2, and can reliably be determined to be larger than half the interlayer spacing but shorter than the bilayer thickness. Our model can be used for designing FLG-based devices, and offers a simple rule regarding the charge distribution in FLG: approximately 70%, 20%, 6% and 3% (99% overall) of the total induced charge density reside within the four innermost layers, implying that the gate-induced electric field is not definitely felt by >4th layer.

  8. Formation of Compound Semiconductors by Electrochemical Atomic Layer Epitaxy (ECALE)

    DTIC Science & Technology

    1992-05-26

    by using Underpotential Deposition (UPD). UPD is a phenomena where an atomic layer of an element deposits at a potential prior to that needed to...atomic layers of the constituent elements. Atomic layers are formed in ECALE by using Underpotential Deposition (UPD). UPD is a phenomena where an atomic...atomic layers of the constituent elements which make up a compound. Deposition is limited to an atomic layer by the use of underpotential deposition (UPD

  9. Addressing Raman features of individual layers in isotopically labeled Bernal stacked bilayer graphene

    NASA Astrophysics Data System (ADS)

    Costa, Sara D.; Weis, Johan Ek; Frank, Otakar; Fridrichová, Michaela; Kalbac, Martin

    2016-06-01

    In this report important Raman modes for the evaluation of strain in graphene (the 2D and 2D‧) are analyzed. The isotope labeling is used to disentangle contribution of individual graphene layers of graphene bilayer to the studied Raman modes. It is shown that for Bernal-stacked bilayers, the 2D and the 2D‧ Raman modes have three distinct components that can be assigned to processes originating solely from the top graphene layer, bottom graphene layer, and from a combination of processes originating both from the top and bottom layers. The reported results thus enable addressing the properties of individual graphene layers in graphene bilayer by Raman spectroscopy.

  10. Visualizing Klein tunneling in graphene at the atomic limit

    NASA Astrophysics Data System (ADS)

    Gutierrez, Christopher; Brown, Lola; Lochocki, Edward B.; Kim, Cheol-Joo; Shen, Kyle M.; Park, Jiwoong; Pasupathy, Abhay N.

    Graphene has attracted much attention from both the solid-state and high-energy scientific communities because its elementary excitations mimic relativistic chiral fermions. This has allowed graphene to act as a table-top testbed for verifying certain longstanding theoretical predictions dating back to the very first formulation of relativistic quantum mechanics. One such prediction is Klein tunneling, the ability of chiral electrons to transmit perfectly through arbitrarily high potential barriers. Previous transport and point-spectroscopic studies confirmed Klein behavior of graphene electrons but lacked real-space resolution. Here we use scanning tunneling microscopy and spectroscopy (STM/STS) measurements to present the first real-space atomic images of Klein tunneling in graphene. In these CVD-grown samples, quasi-circular regions of the copper substrate underneath graphene act as potential barriers that can scatter and transmit electrons. At certain energies, the relativistic chiral fermions that Klein scatter from these barriers are shown to fulfill resonance conditions such that the transmitted electrons become trapped and form standing waves. These resonant modes are visualized with detailed spectroscopic images with atomic resolution that agree well with theoretical calculations. The trapping time is shown to depend critically on both the angular momenta quantum number of the resonant state and the radius of the trapping potential.

  11. Coulomb Drag and Magnetotransport in Graphene Double Layers

    NASA Astrophysics Data System (ADS)

    Tutuc, Emanuel

    2013-03-01

    Graphene double layers, a set of two closely spaced graphene monolayers seperated by an ultra-thin dielectric, represent an interesting electron system to explore correlated electron states. We discuss the fabrication of such samples using a layer-by-layer transfer approach, the electron transport in individual layers at zero and in a high magnetic field, and Coulomb drag measurements. Coulomb drag, probed by flowing a drive current in one layer, and measuring the voltage drop in the opposite layer provides a direct measurement of the electron-electron scattering between the two layers, and can be used to probe the electron system ground state. Coulomb drag in graphene, measured as a function of both layer densities and temperature reveals two distinct regimes: (i) diffusive drag at elevated temperatures, above 50 K, and (ii) mesoscopic fluctuations-dominated drag at low temperatures. A second topic discussed here is a technique that allows a direct measurement of the Fermi energy in an electron system with an accuracy independent of the sample size, using a graphene double layer heterostructure. The underlying principle of the technique is that an interlayer bias applied to bring the top layer to the charge neutrality point is equal to the Fermi energy of the bottom layer, which in effect renders the top graphene layer a resistively detected Kelvin probe. We illustrate this method by measuring the Fermi velocity, Landau level spacing, and Landau level broadening in monolayer graphene. Work done in collaboration with S. Kim, I. Jo, J. Nah, D. Dillen, K. Lee, B. Fallahazad, Z. Yao, and S. K. Banerjee. We thank ONR, NRI, and NSF for support.

  12. Nondestructive and in situ determination of graphene layers using optical fiber Fabry-Perot interference

    NASA Astrophysics Data System (ADS)

    Li, Cheng; Peng, Xiaobin; Liu, Qianwen; Gan, Xin; Lv, Ruitao; Fan, Shangchun

    2017-02-01

    Thickness measurement plays an important role for characterizing optomechanical behaviors of graphene. From the view of graphene-based Fabry-Perot (F-P) sensors, a simple, nondestructive and in situ method of determining the thickness of nanothick graphene membranes was demonstrated by using optical fiber F-P interference. Few-layer/multilayer graphene sheets were suspendedly adhered onto the endface of a ferrule with a 125 µm inner diameter by van der Waals interactions to construct micro F-P cavities. Along with the Fresnel’s law and complex index of refraction of the membrane working as a light reflector of an F-P interferometer, the optical reflectivity of graphene was modeled to investigate the effects of light wavelength and temperature. Then the average thickness of graphene membranes were extracted by F-P interference demodulation, and yielded a very strong cross-correlation coefficient of 99.95% with the experimental results observed by Raman spectrum and atomic force microscope. The method could be further extended for determining the number of layers of other 2D materials.

  13. Epitaxial growth of a single-crystal hybridized boron nitride and graphene layer on a wide-band gap semiconductor.

    PubMed

    Shin, Ha-Chul; Jang, Yamujin; Kim, Tae-Hoon; Lee, Jun-Hae; Oh, Dong-Hwa; Ahn, Sung Joon; Lee, Jae Hyun; Moon, Youngkwon; Park, Ji-Hoon; Yoo, Sung Jong; Park, Chong-Yun; Whang, Dongmok; Yang, Cheol-Woong; Ahn, Joung Real

    2015-06-03

    Vertical and lateral heterogeneous structures of two-dimensional (2D) materials have paved the way for pioneering studies on the physics and applications of 2D materials. A hybridized hexagonal boron nitride (h-BN) and graphene lateral structure, a heterogeneous 2D structure, has been fabricated on single-crystal metals or metal foils by chemical vapor deposition (CVD). However, once fabricated on metals, the h-BN/graphene lateral structures require an additional transfer process for device applications, as reported for CVD graphene grown on metal foils. Here, we demonstrate that a single-crystal h-BN/graphene lateral structure can be epitaxially grown on a wide-gap semiconductor, SiC(0001). First, a single-crystal h-BN layer with the same orientation as bulk SiC was grown on a Si-terminated SiC substrate at 850 °C using borazine molecules. Second, when heated above 1150 °C in vacuum, the h-BN layer was partially removed and, subsequently, replaced with graphene domains. Interestingly, these graphene domains possess the same orientation as the h-BN layer, resulting in a single-crystal h-BN/graphene lateral structure on a whole sample area. For temperatures above 1600 °C, the single-crystal h-BN layer was completely replaced by the single-crystal graphene layer. The crystalline structure, electronic band structure, and atomic structure of the h-BN/graphene lateral structure were studied by using low energy electron diffraction, angle-resolved photoemission spectroscopy, and scanning tunneling microscopy, respectively. The h-BN/graphene lateral structure fabricated on a wide-gap semiconductor substrate can be directly applied to devices without a further transfer process, as reported for epitaxial graphene on a SiC substrate.

  14. Synthesis of Extended Atomically Perfect Zigzag Graphene - Boron Nitride Interfaces

    PubMed Central

    Drost, Robert; Kezilebieke, Shawulienu; M. Ervasti, Mikko; Hämäläinen, Sampsa K.; Schulz, Fabian; Harju, Ari; Liljeroth, Peter

    2015-01-01

    The combination of several materials into heterostructures is a powerful method for controlling material properties. The integration of graphene (G) with hexagonal boron nitride (BN) in particular has been heralded as a way to engineer the graphene band structure and implement spin- and valleytronics in 2D materials. Despite recent efforts, fabrication methods for well-defined G-BN structures on a large scale are still lacking. We report on a new method for producing atomically well-defined G-BN structures on an unprecedented length scale by exploiting the interaction of G and BN edges with a Ni(111) surface as well as each other. PMID:26584674

  15. Intra- and inter-layer charge redistribution in biased bilayer graphene

    SciTech Connect

    Wang, Rui-Ning; Dong, Guo-Yi Wang, Shu-Fang; Fu, Guang-Sheng; Wang, Jiang-Long

    2016-03-15

    We investigate the spatial redistribution of the electron density in bilayer graphene in the presence of an interlayer bias within density functional theory. It is found that the interlayer charge redistribution is inhomogeneous between the upper and bottom layers and the transferred charge from the upper layer to the bottom layer linearly increases with the external voltage which further makes the gap at K point linearly increase. However, the band gap will saturate to 0.29 eV in the strong-field regime, but it displays a linear field dependence at the weak-field limit. Due to the AB-stacked way, two carbon atoms per unit cell in the same layer are different and there is also a charge transfer between them, making the widths of π valence bands reduced. In the bottom layer, the charge transfers from the direct atoms which directly face another carbon atom to the indirect atoms facing the center of the hexagon on the opposite layer, while the charge transfers from the indirect atoms to the direct atoms in the upper layer. Furthermore, there is a diploe between the upper and bottom layers which results in the reduction of the interlayer hopping interaction.

  16. In-situ Fabrication and Electronic Characterization of Junction-confined Single Layer Graphene Nanoribbons

    NASA Astrophysics Data System (ADS)

    Qi, Zhengqing John; Rodriguez-Manzo, Julio; Hong, Sung Ju; Drndic, Marija; Johnson, A. T. Charlie

    2013-03-01

    We report electronic measurements on high quality single layer junction-confined graphene nanoribbons fabricated in a transmission electron microscope (TEM). In this work, a process is demonstrated for the fabrication and confirmation of pristine single layer graphene nanoribbons using high vacuum current annealing and precision nano-sculpting, both conducted within the vacuum chamber of a TEM. Briefly, CVD-grown graphene is patterned into a freely-suspended nanoribbon connected to large area contacts. The sample is then mounted on a TEM holder with electrical feedthroughs to allow for simultaneous imaging and in-situ electrical transport measurements within the TEM. A focused electron beam is used to progressively narrow the ribbon, providing a platform to controllably sculpt and define the device geometry while characterizing its electrical properties. In-situ electrical measurements and TEM imaging with sub-nm resolution revealed the dependence of the nanoribbon resistance as a function of width in the range 17 - 280 nm. Monolayer graphene were found to sustain current densities in excess of 5 x 109 A/cm2, orders of magnitude higher than copper while the conductance varied approximately as w0.75, where w is the ribbon width in nanometers. These results demonstrates graphene's potential as a next generation, high performance interconnects material with the ability to reach single-digit technology nodes at the level of a single atomic layer. Funding for this work was provided by SRC contract # 2011-IN-2229.

  17. The Effect of Growth Parameters on the Intrinsic Properties of Large-Area Single Layer Graphene Grown by Chemical Vapor Deposition on Cu

    SciTech Connect

    Regmi, Murari; Chisholm, Matthew F; Eres, Gyula

    2012-01-01

    We present a comprehensive study of the parameter space for single layer graphene growth by chemical vapor deposition on Cu. The temperature is the most widely recognized parameter in single layer graphene growth. We show that the methane-to-hydrogen ratio and the growth pressure also are critical parameters that affect the structural perfection and the cleanliness of graphene. The optimal conditions for suppressing double and multilayer graphene growth occur near 1000 C, 1:20 methane-to-hydrogen ratio, and a total pressure in the range from 0.5 to 1 Torr. Raman mapping of a 40x30 m2 area shows single layer domains with 5-10 m linear dimensions. Atomic resolution imaging of suspended graphene by aberration corrected scanning transmission electron microscopy shows that the cleanest single layer graphene consists of areas of 10-15 nm linear dimensions and smaller patches of residual contamination that was undetected by other characterization methods.

  18. Wrinkled single-layer graphenes fabricated by silicon nanopillar arrays

    NASA Astrophysics Data System (ADS)

    Li, Zibo; Wu, Yutong; Nan, Jingjie; Tang, Xiaoduo; Zhang, Junhu; Yang, Bai

    2016-11-01

    The degree of crumpling affects the optoelectronic properties of graphene, which are very important for the performance of graphene-based devices and materials. In this article, we report an approach to tune the formation of wrinkles on single-layer graphene (SLG) by silicon nanopillar (SNP) arrays. By using gold nanoparticles as an etching mask, SNP arrays with different heights could be prepared by tuning the duration of etching. The formation of wrinkles on these SNP arrays was studied systematically. We found that thermal treatment could lead to a wrapping behavior of graphene around SNP arrays, which was accompanied by the emergence of many more wrinkles. Controllable wettability, conductivity and transmittance were demonstrated. This ability to tune wrinkles using SNP arrays can be employed to engineer the fabrication of graphene-related devices and other optoelectronic applications.

  19. Calculation of the superconducting transition temperature of a graphene layer doped with titanium and palladium

    NASA Astrophysics Data System (ADS)

    Vazquez, Gerardo; Magana, Fernando; Salas-Torres, Osiris

    We explore the structural interactions between graphene and transition metals such as palladium (Pd) and titanium (Ti) and the possibility of inducing superconductivity in a graphene sheet in two cases, one by doping its surface with palladium atoms sit on the center of the hexagons of the graphene layer and other by covering the graphene layer with two layers of titanium metal atoms. The results here were obtained from first-principles density functional theory in the local density approximation. The Quantum-Espresso package was used with norm conserving pseudopotentials. All of the structures considered were relaxed to their minimum energy configuration. Phonon frequencies were calculated using the linear-response technique on several phonon wave-vector mesh. The electron-phonon coupling parameter was calculated with several electron momentum k-mesh. The superconducting critical temperature was estimated using the Allen-Dynes formula with μ* = 0.1 - 0.15. We note that palladium and titanium are good candidate materials to show a metal-to-superconductor transition. We thank Dirección General de Asuntos del Personal Académico de la Universidad Nacional Autónoma de México, partial financial support by Grant IN-106514 and we also thank Miztli Super-Computing center the technical assistance.

  20. Atomic-scale studies of nanometer-sized graphene on semiconducting surfaces.

    NASA Astrophysics Data System (ADS)

    Koepke, Justin; Ritter, Kyle; He, Kevin; Lyding, Joseph

    2008-03-01

    We have performed atomic level studies of graphene on semiconducting surfaces using ultrahigh vacuum scanning tunneling microscopy (UHV-STM) [1]. By mechanically exfoliating graphite and using an in-situ dry contact transfer technique [2], we observe predominantly single and double layers of atomically clean graphene with lateral dimensions of 2-20 nm. Room temperature scanning tunneling spectroscopy measurements of the 2-10 nm monolayer pieces display a size-dependent energy gap ranging from 0.1-1 eV, while monolayers with lateral dimensions of 20 nm exhibit a finite density of states at the Fermi level. [1] K.A. Ritter and J.W. Lyding, Nanotechnology, in press (http://arxiv.org/pdf/0711.0050). [2] P.M. Albrecht and J.W. Lyding, APL 83, 5029 (2003).

  1. First-principles study of the alkali earth metal atoms adsorption on graphene

    NASA Astrophysics Data System (ADS)

    Sun, Minglei; Tang, Wencheng; Ren, Qingqiang; Wang, Sake; JinYu; Du, Yanhui; Zhang, Yajun

    2015-11-01

    Geometries, electronic structures, and magnetic properties for alkali earth metal atoms absorbed graphene have been studied by first-principle calculations. For Be and Mg atoms, the interactions between the adatom and graphene are weak van der Waals interactions. In comparison, Ca, Sr and Ba atoms adsorption on graphene exhibits strong ionic bonding with graphene. We found that these atoms bond to graphene at the hollow site with a significant binding energy and large electron transfer. It is intriguing that these adatoms may induce important changes in both the electronic and magnetic properties of graphene. Semimetal graphene becomes metallic and magnetic due to n-type doping. Detailed analysis shows that the s orbitals of these adatoms should be responsible for the arising of the magnetic moment. We believe that our results are suitable for experimental exploration and useful for graphene-based nanoelectronic and data storage.

  2. Giant edge state splitting at atomically precise graphene zigzag edges

    PubMed Central

    Wang, Shiyong; Talirz, Leopold; Pignedoli, Carlo A.; Feng, Xinliang; Müllen, Klaus; Fasel, Roman; Ruffieux, Pascal

    2016-01-01

    Zigzag edges of graphene nanostructures host localized electronic states that are predicted to be spin-polarized. However, these edge states are highly susceptible to edge roughness and interaction with a supporting substrate, complicating the study of their intrinsic electronic and magnetic structure. Here, we focus on atomically precise graphene nanoribbons whose two short zigzag edges host exactly one localized electron each. Using the tip of a scanning tunnelling microscope, the graphene nanoribbons are transferred from the metallic growth substrate onto insulating islands of NaCl in order to decouple their electronic structure from the metal. The absence of charge transfer and hybridization with the substrate is confirmed by scanning tunnelling spectroscopy, which reveals a pair of occupied/unoccupied edge states. Their large energy splitting of 1.9 eV is in accordance with ab initio many-body perturbation theory calculations and reflects the dominant role of electron–electron interactions in these localized states. PMID:27181701

  3. Layer-by-layer graphene/TCNQ stacked films as conducting anodes for organic solar cells.

    PubMed

    Hsu, Chang-Lung; Lin, Cheng-Te; Huang, Jen-Hsien; Chu, Chih-Wei; Wei, Kung-Hwa; Li, Lain-Jong

    2012-06-26

    Large-area graphene grown by chemical vapor deposition (CVD) is a promising candidate for transparent conducting electrode applications in flexible optoelectronic devices such as light-emitting diodes or organic solar cells. However, the power conversion efficiency (PCE) of the polymer photovoltaic devices using a pristine CVD graphene anode is still not appealing due to its much lower conductivity than that of conventional indium tin oxide. We report a layer-by-layer molecular doping process on graphene for forming sandwiched graphene/tetracyanoquinodimethane (TCNQ)/graphene stacked films for polymer solar cell anodes, where the TCNQ molecules (as p-dopants) were securely embedded between two graphene layers. Poly(3-hexylthiophene)/phenyl-C61-butyric acid methyl ester (P3HT/PCBM) bulk heterojunction polymer solar cells based on these multilayered graphene/TCNQ anodes are fabricated and characterized. The P3HT/PCBM device with an anode structure composed of two TCNQ layers sandwiched by three CVD graphene layers shows optimum PCE (∼2.58%), which makes the proposed anode film quite attractive for next-generation flexible devices demanding high conductivity and transparency.

  4. Number of graphene layers exhibiting an influence on oxidation of DNA bases: analytical parameters.

    PubMed

    Goh, Madeline Shuhua; Pumera, Martin

    2012-01-20

    This article investigates the analytical performance of double-, few- and multi-layer graphene upon oxidation of adenine and guanine. We observed that the sensitivity of differential pulse voltammetric response of guanine and adenine is significantly higher at few-layer graphene surface than single-layer graphene. We use glassy carbon electrode as substrate coated with graphenes. Our findings shall have profound influence on construction of graphene based genosensors.

  5. Nanoscale Mechanical Characterization of Graphene/Polymer Nanocomposites using Atomic Force Microscopy

    NASA Astrophysics Data System (ADS)

    Cai, Minzhen

    Graphene materials, exhibiting outstanding mechanical properties, are excellent candidates as reinforcement in high-performance polymer nanocomposites. In this dissertation, advanced atomic force microscopy (AFM) techniques are applied to study the nanomechanics of graphene/polymer nanocomposites, specifically the graphene/polymer interfacial strength and the stress transfer at the interface. Two novel methods to directly characterize the interfacial strength between individual graphene sheets and polymers using AFM are presented and applied to a series of polymers and graphene sheets. The interfacial strength of graphene/polymer varies greatly for different combinations. The strongest interaction is found between graphene oxide (GO) and polyvinyl alcohol (PVA), a strongly polar, water-based polymer. On the other hand, polystyrene, a non polar polymer, has the weakest interaction with GO. The interfacial bond strength is attributed to hydrogen bonding and physical adsorption. Further, the stress transfer in GO/PVA nanocomposites is studied quantitatively by monitoring the strain in individual GO sheet inside the polymer via AFM and Raman spectroscopy. For the first time, the strains of individual GO sheets in nanocomposites are imaged and quantified as a function of the applied external strains. The matrix strain is directly transferred to GO sheets for strains up to 8%. At higher strain levels, the onset of the nanocomposite failure and a stick-slip behavior is observed. This study reveals that GO is superior to pure graphene as reinforcement in nanocomposites. These results also imply the potential to make a new generation of nanocomposites with exceptional high strength and toughness. In the second part of this dissertation, AFM is used to study the structure of silk proteins and the morphology of spider silks. For the first time, shear-induced self-assembly of native silk fibroin is observed. The morphology of the Brown Recluse spider silk is investigated and a

  6. Single-layer graphene on silicon nitride micromembrane resonators

    SciTech Connect

    Schmid, Silvan; Guillermo Villanueva, Luis; Amato, Bartolo; Boisen, Anja; Bagci, Tolga; Zeuthen, Emil; Sørensen, Anders S.; Usami, Koji; Polzik, Eugene S.; Taylor, Jacob M.; Marcus, Charles M.; Cheol Shin, Yong; Kong, Jing

    2014-02-07

    Due to their low mass, high quality factor, and good optical properties, silicon nitride (SiN) micromembrane resonators are widely used in force and mass sensing applications, particularly in optomechanics. The metallization of such membranes would enable an electronic integration with the prospect for exciting new devices, such as optoelectromechanical transducers. Here, we add a single-layer graphene on SiN micromembranes and compare electromechanical coupling and mechanical properties to bare dielectric membranes and to membranes metallized with an aluminium layer. The electrostatic coupling of graphene covered membranes is found to be equal to a perfectly conductive membrane, without significantly adding mass, decreasing the superior mechanical quality factor or affecting the optical properties of pure SiN micromembranes. The concept of graphene-SiN resonators allows a broad range of new experiments both in applied physics and fundamental basic research, e.g., for the mechanical, electrical, or optical characterization of graphene.

  7. Thermal transport in suspended and supported few-layer graphene.

    PubMed

    Wang, Ziqian; Xie, Rongguo; Bui, Cong Tinh; Liu, Dan; Ni, Xiaoxi; Li, Baowen; Thong, John T L

    2011-01-12

    We report thermal conductivity (κ) measurements from 77 to 350 K on both suspended and supported few-layer graphene using a thermal-bridge configuration. The room temperature value of κ is comparable to that of bulk graphite for the largest flake, but reduces significantly for smaller flakes. The presence of a substrate lowers the value of κ, but the effect diminishes for the thermal transport in the top layers away from the substrate. For the suspended sample, the temperature dependence of κ follows a power law with an exponent of 1.4 ± 0.1, suggesting that the flexural phonon modes contribute significantly to the thermal transport of the suspended graphene. The measured values of κ are generally lower than those from theoretical studies. We attribute this deviation to the phonon-boundary scattering at the graphene-contact interfaces, which is shown to significantly reduce the apparent measured thermal conductance of graphene.

  8. Layered Atom Arrangements in Complex Materials

    SciTech Connect

    K.E. Sikafus; R.W.Grimes; S.M.Corish; A.R. Cleave; M.Tang; C.R.Stanek; B.P. Uberuaga; J.A.Valdez

    2005-04-15

    In this report, we develop an atom layer stacking model to describe systematically the crystal structures of complex materials. To illustrate the concepts, we consider a sequence of oxide compounds in which the metal cations progress in oxidation state from monovalent (M{sup 1+}) to tetravalent (M{sup 4+}). We use concepts relating to geometric subdivisions of a triangular atom net to describe the layered atom patterns in these compounds (concepts originally proposed by Shuichi Iida). We demonstrate that as a function of increasing oxidation state (from M{sup 1+} to M{sup 4+}), the layer stacking motifs used to generate each successive structure (specifically, motifs along a 3 symmetry axis), progress through the following sequence: MMO, MO, M{sub r}O, MO{sub r/s}O{sub u/v}, MOO (where M and O represent fully dense triangular atom nets and r/s and u/v are fractions used to describe partially filled triangular atom nets). We also develop complete crystallographic descriptions for the compounds in our oxidation sequence using trigonal space group R{bar 3}.

  9. Vacancy Interlayer Migration in Multi-layered Graphene

    NASA Astrophysics Data System (ADS)

    Liu, Lili; Gao, Junfeng; Zhang, Xiuyun; Yan, Tianying; Ding, Feng

    2014-03-01

    Graphene has innumerous applications due to its exceptional properties. Various defects that may be introduced into the graphene lattice during synthesis and/or post-treatments are known have significantly impact on these properties. So engineering graphene by introducing or annealing of defects is an important technology to achieve desired properties for various applications. Therefore a comprehensive understanding on the behavior of defects in graphene is critically important. Here, interlayer migration of the vacancies in multi-layered graphene (MLG) was investigated by density functional tight-binding molecular dynamic simulations and first principle calculations. Our study reveals that, although the direct vacancy migration between neighboring graphene layers (NGLs) is prohibited by a very high barrier up to ~ 7 eV, the interaction between vacancies or vacancy and holes in NGLs can greatly reduce the barrier to ~ 3 eV and expedites the migration process. Our study reveals a new mechanism of the defect self-healing in MLG and multi-walled carbon nanotubes and it can be used to engineer desired graphene materials.

  10. Nonlocal thermal transport across embedded few-layer graphene sheets

    SciTech Connect

    Liu, Ying; Huxtable, Scott T.; Yang, Bao; Sumpter, Bobby G.; Qiao, Rui

    2014-11-13

    Thermal transport across the interfaces between few-layer graphene sheets and soft materials exhibits intriguing anomalies when interpreted using the classical Kapitza model, e.g., the conductance of the same interface differs greatly for different modes of interfacial thermal transport. Using atomistic simulations, we show that such thermal transport follows a nonlocal flux-temperature drop constitutive law and is characterized jointly by a quasi-local conductance and a nonlocal conductance instead of the classical Kapitza conductance. Lastly, the nonlocal model enables rationalization of many anomalies of the thermal transport across embedded few-layer graphene sheets and should be used in studies of interfacial thermal transport involving few-layer graphene sheets or other ultra-thin layered materials.

  11. Nonlocal thermal transport across embedded few-layer graphene sheets

    DOE PAGES

    Liu, Ying; Huxtable, Scott T.; Yang, Bao; ...

    2014-11-13

    Thermal transport across the interfaces between few-layer graphene sheets and soft materials exhibits intriguing anomalies when interpreted using the classical Kapitza model, e.g., the conductance of the same interface differs greatly for different modes of interfacial thermal transport. Using atomistic simulations, we show that such thermal transport follows a nonlocal flux-temperature drop constitutive law and is characterized jointly by a quasi-local conductance and a nonlocal conductance instead of the classical Kapitza conductance. Lastly, the nonlocal model enables rationalization of many anomalies of the thermal transport across embedded few-layer graphene sheets and should be used in studies of interfacial thermal transportmore » involving few-layer graphene sheets or other ultra-thin layered materials.« less

  12. Nonlocal thermal transport across embedded few-layer graphene sheets.

    PubMed

    Liu, Ying; Huxtable, Scott T; Yang, Bao; Sumpter, Bobby G; Qiao, Rui

    2014-12-17

    Thermal transport across the interfaces between few-layer graphene sheets and soft materials exhibits intriguing anomalies when interpreted using the classical Kapitza model, e.g. the conductance of the same interface differs greatly for different modes of interfacial thermal transport. Using atomistic simulations, we show that such thermal transport follows a nonlocal flux-temperature drop constitutive law and is characterized jointly by a quasi-local conductance and a nonlocal conductance instead of the classical Kapitza conductance. The nonlocal model enables rationalization of many anomalies of the thermal transport across embedded few-layer graphene sheets and should be used in studies of interfacial thermal transport involving few-layer graphene sheets or other ultra-thin layered materials.

  13. Imaging Stacking Order in Few-Layer Graphene

    SciTech Connect

    C Lui; Z Li; Z Chen; P Klimov; L Brus; T Heinz

    2011-12-31

    Few-layer graphene (FLG) has been predicted to exist in various crystallographic stacking sequences, which can strongly influence the material's electronic properties. We demonstrate an accurate and efficient method to characterize stacking order in FLG using the distinctive features of the Raman 2D-mode. Raman imaging allows us to visualize directly the spatial distribution of Bernal (ABA) and rhombohedral (ABC) stacking in tri- and tetralayer graphene. We find that 15% of exfoliated graphene tri- and tetralayers is composed of micrometer-sized domains of rhombohedral stacking, rather than of usual Bernal stacking. These domains are stable and remain unchanged for temperatures exceeding 800 C.

  14. Selective nano-patterning of graphene using a heated atomic force microscope tip

    SciTech Connect

    Choi, Young-Soo; Wu, Xuan; Lee, Dong-Weon

    2014-04-15

    In this study, we introduce a selective thermochemical nano-patterning method of graphene on insulating substrates. A tiny heater formed at the end of an atomic force microscope (AFM) cantilever is optimized by a finite element method. The cantilever device is fabricated using conventional micromachining processes. After preliminary tests of the cantilever device, nano-patterning experiments are conducted with various conducting and insulating samples. The results indicate that faster scanning speed and higher contact force are desirable to reduce the sizes of nano-patterns. With the experimental condition of 1 μm/s and 24 mW, the heated AFM tip generates a graphene oxide layer of 3.6 nm height and 363 nm width, on a 300 nm thick SiO{sub 2} layer, with a tip contact force of 100 nN.

  15. Spontaneous layer-pseudospin domain walls in bilayer graphene.

    PubMed

    Li, Xiao; Zhang, Fan; Niu, Qian; MacDonald, A H

    2014-09-12

    Bilayer graphene is susceptible to a family of unusual broken symmetry states with spin and valley dependent layer polarization. We report on a microscopic study of the domain walls in these systems, demonstrating that they have interesting microscopic structure related to the topological character of the ordered states. We use our results to show that the metal-insulator transition temperature in bilayer graphene is reduced from mean-field estimates by thermal excitation of domain walls.

  16. Electronic Structure and Morphology of Graphene Layers on SiC

    NASA Astrophysics Data System (ADS)

    Ohta, Taisuke

    2008-03-01

    Recent years have witnessed the discovery and the unique electronic properties of graphene, a sheet of carbon atoms arranged in a honeycomb lattice. The unique linear dispersion relation of charge carriers near the Fermi level (``Dirac Fermions'') lead to exciting transport properties, such as an unusual quantum Hall effect, and have aroused scientific and technological interests. On the way towards graphene-based electronics, a knowledge of the electronic band structure and the morphology of epitaxial graphene films on silicon carbide substrates is imperative. We have studied the evolution of the occupied band structure and the morphology of graphene layers on silicon carbide by systematically increasing the layer thickness. Using angle-resolved photoemission spectroscopy (ARPES), we examine this unique 2D system in its development from single layer to multilayers, by characteristic changes in the π band, the highest occupied state, and the dispersion relation in the out-of-plane electron wave vector in particular. The evolution of the film morphology is evaluated by the combination of low-energy electron microscopy and ARPES. By exploiting the sensitivity of graphene's electronic states to the charge carrier concentration, changes in the on-site Coulomb potential leading to a change of π and π* bands can be examined using ARPES. We demonstrate that, in a graphene bilayer, the gap between π and π* bands can be controlled by selectively adjusting relative carrier concentrations, which suggests a possible application of the graphene bilayer for switching functions in electronic devices. This work was done in collaboration with A. Bostwick, J. L. McChesney, and E. Rotenberg at Advanced Light Source, Lawrence Berkeley National Laboratory, K. Horn at Fritz-Haber-Institut, K. V. Emtsev and Th. Seyller at Lehrstuhl für Technische Physik, Universität Erlangen-Nürnberg, and F. El Gabaly and A. K. Schmid at National Center for Electron Microscopy, Lawrence Berkeley

  17. Tunable positive and negative group delays of light reflection from layer structures with a graphene layer

    NASA Astrophysics Data System (ADS)

    Wang, Lin; Wang, Li-Gang; Zubairy, M. Suhail

    2017-09-01

    In this paper, we investigate the propagation of a light pulse reflection from the layer system with a graphene layer. We show a tunable transition between positive and negative group delays of optical pulse reflection in such a layered system controlled by the properties of the graphene layer and reveal two mechanisms to control the propagation properties of the light pulse reflected from such systems. It is demonstrated that the reflected group delays are tunable from positive to negative values in both mechanisms of resonances and the excitations of surface plasmon resonances, which are also adjusted by tuning the Fermi energy and temperature of the graphene layer. Our results are helpful to control the pulse propagations and are useful for design of graphene-based optical devices.

  18. Reducing graphene device variability with yttrium sacrificial layers

    NASA Astrophysics Data System (ADS)

    Wang, Ning C.; Carrion, Enrique A.; Tung, Maryann C.; Pop, Eric

    2017-05-01

    Graphene technology has made great strides since the material was isolated more than a decade ago. However, despite improvements in growth quality and numerous "hero" devices, challenges of uniformity remain, restricting the large-scale development of graphene-based technologies. Here, we investigate and reduce the variability of graphene transistors by studying the effects of contact metals (with and without a Ti layer), resist, and yttrium (Y) sacrificial layers during the fabrication of hundreds of devices. We find that with optical photolithography, residual resist and process contamination are unavoidable, ultimately limiting the device performance and yield. However, using Y sacrificial layers to isolate the graphene from processing conditions improves the yield (from 73% to 97%), the average device performance (three-fold increase of mobility and 58% lower contact resistance), and the device-to-device variability (standard deviation of Dirac voltage reduced by 20%). In contrast to other sacrificial layer techniques, the removal of the Y sacrificial layer with dilute HCl does not harm surrounding materials, simplifying large-scale graphene fabrication.

  19. Infrared dynamics of cold atoms on hot graphene membranes

    NASA Astrophysics Data System (ADS)

    Sengupta, Sanghita; Kotov, Valeri N.; Clougherty, Dennis P.

    2016-06-01

    We study the infrared dynamics of low-energy atoms interacting with a sample of suspended graphene at finite temperature. The dynamics exhibits severe infrared divergences order by order in perturbation theory as a result of the singular nature of low-energy flexural phonon emission. Our model can be viewed as a two-channel generalization of the independent boson model with asymmetric atom-phonon coupling. This allows us to take advantage of the exact nonperturbative solution of the independent boson model in the stronger channel while treating the weaker one perturbatively. In the low-energy limit, the exact solution can be viewed as a resummation (exponentiation) of the most divergent diagrams in the perturbative expansion. As a result of this procedure, we obtain the atom's Green function which we use to calculate the atom damping rate, a quantity equal to the quantum sticking rate. A characteristic feature of our results is that the Green's function retains a weak, infrared cutoff dependence that reflects the reduced dimensionality of the problem. As a consequence, we predict a measurable dependence of the sticking rate on graphene sample size. We provide detailed predictions for the sticking rate of atomic hydrogen as a function of temperature and sample size. The resummation yields an enhanced sticking rate relative to the conventional Fermi golden rule result (equivalent to the one-loop atom self-energy), as higher-order processes increase damping at finite temperature.

  20. Direct observation of electrically induced Pauli paramagnetism in single-layer graphene using ESR spectroscopy

    PubMed Central

    Fujita, Naohiro; Matsumoto, Daisuke; Sakurai, Yuki; Kawahara, Kenji; Ago, Hiroki; Takenobu, Taishi; Marumoto, Kazuhiro

    2016-01-01

    Graphene has been actively investigated as an electronic material owing to many excellent physical properties, such as high charge mobility and quantum Hall effect, due to the characteristics of a linear band structure and an ideal two-dimensional electron system. However, the correlations between the transport characteristics and the spin states of charge carriers or atomic vacancies in graphene have not yet been fully elucidated. Here, we show the spin states of single-layer graphene to clarify the correlations using electron spin resonance (ESR) spectroscopy as a function of accumulated charge density using transistor structures. Two different electrically induced ESR signals were observed. One is originated from a Fermi-degenerate two-dimensional electron system, demonstrating the first observation of electrically induced Pauli paramagnetism from a microscopic viewpoint, showing a clear contrast to no ESR observation of Pauli paramagnetism in carbon nanotubes (CNTs) due to a one-dimensional electron system. The other is originated from the electrically induced ambipolar spin vanishments due to atomic vacancies in graphene, showing a universal phenomenon for carbon materials including CNTs. The degenerate electron system with the ambipolar spin vanishments would contribute to high charge mobility due to the decrease in spin scatterings in graphene. PMID:27731338

  1. Compression behavior of single-layer graphenes.

    PubMed

    Frank, Otakar; Tsoukleri, Georgia; Parthenios, John; Papagelis, Konstantinos; Riaz, Ibtsam; Jalil, Rashid; Novoselov, Kostya S; Galiotis, Costas

    2010-06-22

    Central to most applications involving monolayer graphenes is its mechanical response under various stress states. To date most of the work reported is of theoretical nature and refers to tension and compression loading of model graphenes. Most of the experimental work is indeed limited to the bending of single flakes in air and the stretching of flakes up to typically approximately 1% using plastic substrates. Recently we have shown that by employing a cantilever beam we can subject single graphenes to various degrees of axial compression. Here we extend this work much further by measuring in detail both stress uptake and compression buckling strain in single flakes of different geometries. In all cases the mechanical response is monitored by simultaneous Raman measurements through the shift of either the G or 2D phonons of graphene. Despite the infinitely small thickness of the monolayers, the results show that graphenes embedded in plastic beams exhibit remarkable compression buckling strains. For large length (l)-to-width (w) ratios (> or =0.2) the buckling strain is of the order of -0.5% to -0.6%. However, for l/w < 0.2 no failure is observed for strains even higher than -1%. Calculations based on classical Euler analysis show that the buckling strain enhancement provided by the polymer lateral support is more than 6 orders of magnitude compared to that of suspended graphene in air.

  2. Direct growth of high-quality Al2O3 dielectric on graphene layers by low-temperature H2O-based ALD

    NASA Astrophysics Data System (ADS)

    Zhang, Youwei; Qiu, Zhijun; Cheng, Xinhong; Xie, Hong; Wang, Haomin; Xie, Xiaomin; Yu, Yuehui; Liu, Ran

    2014-02-01

    A thin Al2O3 dielectric film was directly grown onto graphene layers without any surface treatment prior to H2O-based atomic layer deposition for the first time. The growth mechanism of Al2O3 dielectric film has been studied by changing the growth temperature and purge time. We found that the film morphology was influenced by the amount and distribution of physically adsorbed precursor molecules on the graphene, especially by physically adsorbed H2O molecules. Within an optimal temperature window, conformal and uniform Al2O3 thin films were obtained as confirmed by atomic force microscopy and transmission electron microscopy results. Raman spectroscopy revealed that no extra defects are generated in the graphene layers. Furthermore, the low leakage current and interface traps in dual-gated graphene field-effect transistors demonstrate the high-quality dielectric/graphene stack.

  3. Graphene as a flexible template for controlling magnetic interactions between metal atoms.

    PubMed

    Lee, Sungwoo; Kim, Dongwook; Robertson, Alex W; Yoon, Euijoon; Hong, Suklyun; Ihm, Jisoon; Yu, Jaejun; Warner, Jamie H; Lee, Gun-Do

    2017-03-01

    Metal-doped graphene produces magnetic moments that have potential application in spintronics. Here we use density function theory computational methods to show how the magnetic interaction between metal atoms doped in graphene can be controlled by the degree of flexure in a graphene membrane. Bending graphene by flexing causes the distance between two substitutional Fe atoms covalently bonded in graphene to gradually increase and these results in the magnetic moment disappearing at a critical strain value. At the critical strain, a carbon atom can enter between the two Fe atoms and blocks the interaction between relevant orbitals of Fe atoms to quench the magnetic moment. The control of interactions between doped atoms by exploiting the mechanical flexibility of graphene is a unique approach to manipulating the magnetic properties and opens up new opportunities for mechanical-magnetic 2D device systems.

  4. Graphene as a flexible template for controlling magnetic interactions between metal atoms

    NASA Astrophysics Data System (ADS)

    Lee, Sungwoo; Kim, Dongwook; Robertson, Alex W.; Yoon, Euijoon; Hong, Suklyun; Ihm, Jisoon; Yu, Jaejun; Warner, Jamie H.; Lee, Gun-Do

    2017-03-01

    Metal-doped graphene produces magnetic moments that have potential application in spintronics. Here we use density function theory computational methods to show how the magnetic interaction between metal atoms doped in graphene can be controlled by the degree of flexure in a graphene membrane. Bending graphene by flexing causes the distance between two substitutional Fe atoms covalently bonded in graphene to gradually increase and these results in the magnetic moment disappearing at a critical strain value. At the critical strain, a carbon atom can enter between the two Fe atoms and blocks the interaction between relevant orbitals of Fe atoms to quench the magnetic moment. The control of interactions between doped atoms by exploiting the mechanical flexibility of graphene is a unique approach to manipulating the magnetic properties and opens up new opportunities for mechanical-magnetic 2D device systems.

  5. Synthesis graphene layer at different waste cooking palm oil temperatures

    NASA Astrophysics Data System (ADS)

    Robaiah, M.; Rusop, M.; Abdullah, S.; khusaimi, Z.; Azhan, H.; Asli, N. A.

    2017-09-01

    Graphene is one of the most recent carbon nanomaterials that has attracted attention because of its superior properties. The formation of the graphene on the Ni surface appears due to segregation and precipitation of a high amount of carbon from the source material during the cooling process. The growth of graphene at different waste cooking palm oil (WCPO) temperatures using double thermal chemical vapour deposition method (DTCVD) was investigated. The samples were prepared at various vaporization temperatures of WCPO is range from 250 °C to 450 °C by increment 50 °C and the temperature of Ni substrate constant at 900 °C. The structural of the graphene were characterized by using field emission scanning electron microscopy (FESEM), Energy Dispersive X-Ray (EDX) Spectroscopy, UV-Visible and Raman's spectroscopy. FESEM images at optimum temperature (350 °C) display hexagonal shapes since the graphene layers were formed after precipitation of the carbon. It the meantime, UV-Visible spectra shows the sharp peak at 250 nm whereupon the highest of reflectivity value. This peak is an indication the presence of the graphene layers on Ni substrate. The position and half width 2D peak of the Raman spectra were subjected to detail analyses in order to determine the quantity and quality of the graphene layer. At the temperature 350°C, the Raman's spectroscopy result shown the multilayer of the graphene based on I2D/IG ratio is approximately constant (equal to˜0.43).

  6. Layer Number Dependence of Li(+) Intercalation on Few-Layer Graphene and Electrochemical Imaging of Its Solid-Electrolyte Interphase Evolution.

    PubMed

    Hui, Jingshu; Burgess, Mark; Zhang, Jiarui; Rodríguez-López, Joaquín

    2016-04-26

    A fundamental question facing electrodes made out of few layers of graphene (FLG) is if they display chemical properties that are different to their bulk graphite counterpart. Here, we show evidence that suggests that lithium ion intercalation on FLG, as measured via stationary voltammetry, shows a strong dependence on the number of layers of graphene that compose the electrode. Despite its extreme thinness and turbostratic structure, Li ion intercalation into FLG still proceeds through a staging process, albeit with different signatures than bulk graphite or multilayer graphene. Single-layer graphene does not show any evidence of ion intercalation, while FLG with four graphene layers displays limited staging peaks, which broaden and increase in number as the layer number increases to six. Despite these mechanistic differences on ion intercalation, the formation of a solid-electrolyte interphase (SEI) was observed on all electrodes. Scanning electrochemical microscopy (SECM) in the feedback mode was used to demonstrate changes in the surface conductivity of FLG during SEI evolution. Observation of ion intercalation on large area FLG was conditioned to the fabrication of "ionic channels" on the electrode. SECM measurements using a recently developed Li-ion sensitive imaging technique evidenced the role of these channels in enabling Li-ion intercalation through localized flux measurements. This work highlights the impact of nanostructure and microstructure on macroscopic electrochemical behavior and provides guidance to the mechanistic control of ion intercalation using graphene, an atomically thin interface where surface and bulk reactivity converge.

  7. The structural and electronic properties of metal atoms adsorbed on graphene

    NASA Astrophysics Data System (ADS)

    Liu, Wenjiang; Zhang, Cheng; Deng, Mingsen; Cai, Shaohong

    2017-09-01

    Based on density functional theory (DFT), we studied the structural and electronic properties of seven different metal atoms adsorbed on graphene (M + graphene). The geometries, adsorption energies, density of states (DOS), band structures, electronic dipole moment, magnetic moment and work function (WF) of M + graphene were calculated. The adsorption energies ΔE indicated that Li, Na, K, Ca and Fe adsorbed on graphene were tending to form stable structures. However, diffusion would occur on Cu and Ag adsorbed on graphene. In addition, the electronic structure near the Fermi level of graphene was significantly affected by Fe (Cu and Ag), compared with Li (Na, K and Ca). The electronic dipole moment and magnetic moment of M + graphene were sensitive to the adsorbed metal atoms. Moreover, we found electropositive (electronegative) adsorption can decrease (increase) the WF of the surface. Specially, the WF of Ag + graphene and Fe + graphene would increase because surface dipole moment make a contribution to electron.

  8. Atomic layer deposition of nanoporous biomaterials.

    SciTech Connect

    Narayan, R. J.; Adiga, S. P.; Pellin, M. J.; Curtiss, L. A.; Stafslien, S.; Chisholm, B.; Monteiro-Riviere, N. A.; Brigmon, R. L.; Elam, J. W.; Univ. of North Carolina; North Carolina State Univ.; Eastman Kodak Co.; North Dakota State Univ.; SRL

    2010-03-01

    Due to its chemical stability, uniform pore size, and high pore density, nanoporous alumina is being investigated for use in biosensing, drug delivery, hemodialysis, and other medical applications. In recent work, we have examined the use of atomic layer deposition for coating the surfaces of nanoporous alumina membranes. Zinc oxide coatings were deposited on nanoporous alumina membranes using atomic layer deposition. The zinc oxide-coated nanoporous alumina membranes demonstrated antimicrobial activity against Escherichia coli and Staphylococcus aureus bacteria. These results suggest that atomic layer deposition is an attractive technique for modifying the surfaces of nanoporous alumina membranes and other nanostructured biomaterials. Nanoporous alumina, also known as anodic aluminum oxide (AAO), is a nanomaterial that exhibits several unusual properties, including high pore densities, straight pores, small pore sizes, and uniform pore sizes. In 1953, Keller et al. showed that anodizing aluminum in acid electrolytes results in a thick layer of nearly cylindrical pores, which are arranged in a close-packed hexagonal cell structure. More recently, Matsuda & Fukuda demonstrated preparation of highly ordered platinum and gold nanohole arrays using a replication process. In this study, a negative structure of nanoporous alumina was initially fabricated and a positive structure of a nanoporous metal was subsequently fabricated. Over the past fifteen years, nanoporous alumina membranes have been used as templates for growth of a variety of nanostructured materials, including nanotubes, nanowires, nanorods, and nanoporous membranes.

  9. Synthesis, properties, and dispersion of few-layer graphene fluoride.

    PubMed

    Grayfer, Ekaterina D; Makotchenko, Viktor G; Kibis, Lidiya S; Boronin, Andrei I; Pazhetnov, Egor M; Zaikovskii, Vladimir I; Fedorov, Vladimir E

    2013-09-01

    We have fluorinated few-layer graphene (FLG) by using a low-temperature fluorination route with gaseous ClF3. The treatment process resulted in a new graphene derivative with a finite approximate composition of C2F. TEM studies showed that the product consisted of thin transparent sheets with no more than 10 fluorographene layers stacked together. Spectroscopic methods revealed a predominantly covalent nature of the C-F bonds in the as-synthesized product and we found no evidence for the existence of so-called "semi-ionic" C-F bonds, as observed in bulk C(x)F. In contrast to the case of graphite and typical (thick) expanded graphites, fluorination of FLG did not lead to the intercalation of ClF3 molecules, owing to the lack of a 3D layered structure. The approximate "critical" number of graphene layers that were necessary to form a phase of intercalated compound was estimated to be more than 12, thus providing a "chemical proof" of the difference between the properties of few-layered graphenes and bulk graphites. Fluorographene C2F was successfully delaminated into thinner layers in organic solvents, which is an important property for its integration into electronic devices, nanohybrids, etc.

  10. Dynamic Negative Compressibility of Few-Layer Graphene, h-BN, and MoS2

    NASA Astrophysics Data System (ADS)

    Neves, Bernardo; Barboza, Ana Paula; Chacham, Helio; Oliveira, Camilla; Fernandes, Thales; Martins Ferreira, Erlon; Archanjo, Braulio; Batista, Ronaldo; Oliveira, Alan

    2013-03-01

    We report a novel mechanical response of few-layer graphene, h-BN, and MoS2 to the simultaneous compression and shear by an atomic force microscope (AFM) tip. The response is characterized by the vertical expansion of these two-dimensional (2D) layered materials upon compression. Such effect is proportional to the applied load, leading to vertical strain values (opposite to the applied force) of up to 150%. The effect is null in the absence of shear, increases with tip velocity, and is anisotropic. It also has similar magnitudes in these solid lubricant materials (few-layer graphene, h-BN, and MoS2), but it is absent in single-layer graphene and in few-layer mica and Bi2Se3. We propose a physical mechanism for the effect where the combined compressive and shear stresses from the tip induce dynamical wrinkling on the upper material layers, leading to the observed flake thickening. The new effect (and, therefore, the proposed wrinkling) is reversible in the three materials where it is observed.[2] Financial support from CNPq, Fapemig, Rede Nacional de Pesquisa em Nanotubos de Carbono and INCT-Nano-Carbono

  11. Fabrication of graphene/polyaniline composite multilayer films by electrostatic layer-by-layer assembly

    SciTech Connect

    Cong, Jiaojiao; Chen, Yuze; Luo, Jing Liu, Xiaoya

    2014-10-15

    A novel graphene/polyaniline composite multilayer film was fabricated by electrostatic interactions induced layer-by-layer self-assembly technique, using water dispersible and negatively charged chemically converted graphene (CCG) and positively charged polyaniline (PANI) as building blocks. CCG was achieved through partly reduced graphene oxide, which remained carboxyl group on its surface. The remaining carboxyl groups not only retain the dispersibility of CCG, but also allow the growth of the multilayer films via electrostatic interactions between graphene and PANI. The structure and morphology of the obtained CCG/PANI multilayer film are characterized by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, Ultraviolet–visible absorption spectrum (UV–vis), scanning electron microscopy (SEM), Raman spectroscopy and X-Ray Diffraction (XRD). The electrochemical properties of the resulting film are studied using cyclic voltammetry (CV), which showed that the resulting CCG/PANI multilayer film kept electroactivity in neutral solution and showed outstanding cyclic stability up to 100 cycles. Furthermore, the composite film exhibited good electrocatalytic ability toward ascorbic acid (AA) with a linear response from 1×10{sup −4} to 1.2×10{sup −3} M with the detect limit of 5×10{sup −6} M. This study provides a facile and effective strategy to fabricate graphene/PANI nanocomposite film with good electrochemical property, which may find potential applications in electronic devices such as electrochemical sensor. - Graphical abstract: A novel graphene/polyaniline (CCG/PANI) film was prepared by layer-by-layer assembly. - Highlights: • A novel graphene/polyaniline (CCG/PANI) film was prepared by layer-by-layer assembly. • The water dispersible and negatively charged graphene (CCG) was used as building block. • CCG was achieved through partly reduced graphene oxide with carboxyl group on its surface. • CCG/PANI film kept

  12. Terahertz modulators based on multiple non-Bernal graphene layers

    NASA Astrophysics Data System (ADS)

    Chatzakis, Ioannis; Li, Zhen; Benderskii, Alexander; Cronin, Stephen

    2015-03-01

    We investigate a THz modulator based on a stack of disoriented the non-Bernal stacks graphene layers (GLs) grown by chemical vapor deposition method (CVD) on SiO2 substrate. The non-Bernal stacking GLs results in the electron decoupling of the GLs, higher interband absorption and exhibit the same energy spectrum of the charge carriers to that in individual GLs. The detection efficiency in room temperature is high due low probability of the high energy of the optical phonons (~ 0.2 eV) absorption. Using terahertz time- domain spectroscopy, we show that the multi graphene layers exhibit fairly high responsivity due to high quantum efficiency.

  13. Heat Conduction across Monolayer and Few-Layer Graphenes

    DTIC Science & Technology

    2010-05-01

    film. We note that even though the metal films were deposited in vacuum , water vapor that adsorbs on the substrate during the air exposure after the... developed approach based on Raman spectroscopy16 to count the number of layers n of the graphene flakes. In this approach, n is determined from the ratio...Au/Ti, we coated a monolayer graphene (1- LG) sample with a semitransparent layer of Au (8 nm)/Ti (2 nm) and compared the Raman spectrum of the sample

  14. High quality reduced graphene oxide through repairing with multi-layered graphene ball nanostructures

    PubMed Central

    Kim, Kyoung Hwan; Yang, MinHo; Cho, Kyeong Min; Jun, Young-Si; Lee, Sang Bok; Jung, Hee-Tae

    2013-01-01

    We present a simple and up-scalable method to produce highly repaired graphene oxide with a large surface area, by introducing spherical multi-layered graphene balls with empty interiors. These graphene balls are prepared via chemical vapor deposition (CVD) of Ni particles on the surface of the graphene oxides (GO). Transmission electron microscopy and Raman spectroscopy results reveal that defects in the GO surfaces are well repaired during the CVD process, with the help of nickel nanoparticles attached to the functional groups of the GO surface, further resulting in a high electrical conductivity of 18,620 S/m. In addition, the graphene balls on the GO surface effectively prevent restacking of the GO layers, thus providing a large surface area of 527 m2/g. Two electrode supercapacitor cells using this highly conductive graphene material demonstrate ideal electrical double layer capacitive behavior, due to the effective use of the outstanding electric conductivity and the large surface area. PMID:24248235

  15. Efficient Nitrogen Doping of Single-Layer Graphene Accompanied by Negligible Defect Generation for Integration into Hybrid Semiconductor Heterostructures.

    PubMed

    Sarau, George; Heilmann, Martin; Bashouti, Muhammad; Latzel, Michael; Tessarek, Christian; Christiansen, Silke

    2017-03-22

    While doping enables application-specific tailoring of graphene properties, it can also produce high defect densities that degrade the beneficial features. In this work, we report efficient nitrogen doping of ∼11 atom % without virtually inducing new structural defects in the initial, large-area, low defect, and transferred single-layer graphene. To shed light on this remarkable high-doping-low-disorder relationship, a unique experimental strategy consisting of analyzing the changes in doping, strain, and defect density after each important step during the doping procedure was employed. Complementary micro-Raman mapping, X-ray photoelectron spectroscopy, and optical microscopy revealed that effective cleaning of the graphene surface assists efficient nitrogen incorporation accompanied by mild compressive strain resulting in negligible defect formation in the doped graphene lattice. These original results are achieved by separating the growth of graphene from its doping. Moreover, the high doping level occurred simultaneously with the epitaxial growth of n-GaN micro- and nanorods on top of graphene, leading to the flow of higher currents through the graphene/n-GaN rod interface. Our approach can be extended toward integrating graphene into other technologically relevant hybrid semiconductor heterostructures and obtaining an ohmic contact at their interfaces by adjusting the doping level in graphene.

  16. Tribological characteristics of few-layer graphene over Ni grain and interface boundaries

    NASA Astrophysics Data System (ADS)

    Tripathi, Manoj; Awaja, Firas; Paolicelli, Guido; Bartali, Ruben; Iacob, Erica; Valeri, Sergio; Ryu, Seunghwa; Signetti, Stefano; Speranza, Giorgio; Pugno, Nicola Maria

    2016-03-01

    The tribological properties of metal-supported few-layered graphene depend strongly on the grain topology of the metal substrate. Inhomogeneous distribution of graphene layers at such regions led to variable landscapes with distinguishable roughness. This discrepancy in morphology significantly affects the frictional and wetting characteristics of the FLG system. We discretely measured friction characteristics of FLG covering grains and interfacial grain boundaries of polycrystalline Ni metal substrate via an atomic force microscopy (AFM) probe. The friction coefficient of FLG covered at interfacial grain boundaries is found to be lower than that on grains in vacuum (at 10-5 Torr pressure) and similar results were obtained in air condition. Sliding history with AFM cantilever, static and dynamic pull-in and pull-off adhesion forces were addressed in the course of friction measurements to explain the role of the out-of-plane deformation of graphene layer(s). Finite element simulations showed good agreement with experiments and led to a rationalization of the observations. Thus, with interfacial grain boundaries the FLG tribology can be effectively tuned.The tribological properties of metal-supported few-layered graphene depend strongly on the grain topology of the metal substrate. Inhomogeneous distribution of graphene layers at such regions led to variable landscapes with distinguishable roughness. This discrepancy in morphology significantly affects the frictional and wetting characteristics of the FLG system. We discretely measured friction characteristics of FLG covering grains and interfacial grain boundaries of polycrystalline Ni metal substrate via an atomic force microscopy (AFM) probe. The friction coefficient of FLG covered at interfacial grain boundaries is found to be lower than that on grains in vacuum (at 10-5 Torr pressure) and similar results were obtained in air condition. Sliding history with AFM cantilever, static and dynamic pull-in and pull

  17. Adsorption of two sodium atoms on graphene -- A first principles study

    SciTech Connect

    Kaur, Gagandeep; Rani, Babita; Gupta, Shuchi; Dharamvir, Keya

    2015-08-28

    We perform a systematic density functional theory (DFT) study of the adsorption of two sodium atoms on graphene using the SIESTA package, in the generalized gradient approximation (GGA). The adsorption energy, geometry, magnetic moment and charge transfer of the Na{sub n}-graphene (n=1, 2) system are calculated. Three initial horizontal orientations of the pair of sodium atoms on graphene are studied. Our calculations reveal that sodium atoms bind weakly to the graphene surface which is in agreement with previous results. We also notice a charge transfer of 0.288e from a sodium adatom to the graphene sheet altering its magnetic moment (−0.318 µ{sub B}) that is reduced from the gas phase value of the isolated atom (1 µ{sub B}). The calculated adsorption energies suggest that clustering of Na atoms on graphene is energetically favorable.

  18. Graphene-layered steps and their fields visualized by 4D electron microscopy

    PubMed Central

    Park, Sang Tae; Yurtsever, Aycan; Baskin, John Spencer; Zewail, Ahmed H.

    2013-01-01

    Enhanced image contrast has been seen at graphene-layered steps a few nanometers in height by means of photon-induced near-field electron microscopy (PINEM) using synchronous femtosecond pulses of light and electrons. The observed steps are formed by the edges of graphene strips lying on the surface of a graphene substrate, where the strips are hundreds of nanometers in width and many micrometers in length. PINEM measurements reflect the interaction of imaging electrons and induced (near) electric fields at the steps, and this leads to a much higher contrast than that achieved in bright-field transmission electron microscopy imaging of the same strips. Theory and numerical simulations support the experimental PINEM findings and elucidate the nature of the electric field at the steps formed by the graphene layers. These results extend the range of applications of the experimental PINEM methodology, which has previously been demonstrated for spherical, cylindrical, and triangular nanostructures, to shapes of high aspect ratio (rectangular strips), as well as into the regime of atomic layer thicknesses. PMID:23690572

  19. Local, global, and nonlinear screening in twisted double-layer graphene

    DOE PAGES

    Lu, Chih -Pin; Rodriguez-Vega, Martin; Li, Guohong; ...

    2016-06-02

    One-atom-thick crystalline layers and their vertical heterostructures carry the promise of designer electronic materials that are unattainable by standard growth techniques. To realize their potential it is necessary to isolate them from environmental disturbances, in particular those introduced by the substrate. However, finding and characterizing suitable substrates, and minimizing the random potential fluctuations they introduce, has been a persistent challenge in this emerging field. In this paper, we show that Landau-level (LL) spectroscopy offers the unique capability to quantify both the reduction of the quasiparticles’ lifetime and the long-range inhomogeneity due to random potential fluctuations. Harnessing this technique together withmore » direct scanning tunneling microscopy and numerical simulations we demonstrate that the insertion of a graphene buffer layer with a large twist angle is a very effective method to shield a 2D system from substrate interference that has the additional desirable property of preserving the electronic structure of the system under study. Finally, we further show that owing to its remarkable nonlinear screening capability a single graphene buffer layer provides better shielding than either increasing the distance to the substrate or doubling the carrier density and reduces the amplitude of the potential fluctuations in graphene to values even lower than the ones in AB-stacked bilayer graphene.« less

  20. Local, global, and nonlinear screening in twisted double-layer graphene

    PubMed Central

    Lu, Chih-Pin; Rodriguez-Vega, Martin; Li, Guohong; Luican-Mayer, Adina; Watanabe, Kenji; Taniguchi, Takashi; Rossi, Enrico; Andrei, Eva Y.

    2016-01-01

    One-atom-thick crystalline layers and their vertical heterostructures carry the promise of designer electronic materials that are unattainable by standard growth techniques. To realize their potential it is necessary to isolate them from environmental disturbances, in particular those introduced by the substrate. However, finding and characterizing suitable substrates, and minimizing the random potential fluctuations they introduce, has been a persistent challenge in this emerging field. Here we show that Landau-level (LL) spectroscopy offers the unique capability to quantify both the reduction of the quasiparticles’ lifetime and the long-range inhomogeneity due to random potential fluctuations. Harnessing this technique together with direct scanning tunneling microscopy and numerical simulations we demonstrate that the insertion of a graphene buffer layer with a large twist angle is a very effective method to shield a 2D system from substrate interference that has the additional desirable property of preserving the electronic structure of the system under study. We further show that owing to its remarkable nonlinear screening capability a single graphene buffer layer provides better shielding than either increasing the distance to the substrate or doubling the carrier density and reduces the amplitude of the potential fluctuations in graphene to values even lower than the ones in AB-stacked bilayer graphene. PMID:27302949

  1. Graphene-layered steps and their fields visualized by 4D electron microscopy.

    PubMed

    Park, Sang Tae; Yurtsever, Aycan; Baskin, John Spencer; Zewail, Ahmed H

    2013-06-04

    Enhanced image contrast has been seen at graphene-layered steps a few nanometers in height by means of photon-induced near-field electron microscopy (PINEM) using synchronous femtosecond pulses of light and electrons. The observed steps are formed by the edges of graphene strips lying on the surface of a graphene substrate, where the strips are hundreds of nanometers in width and many micrometers in length. PINEM measurements reflect the interaction of imaging electrons and induced (near) electric fields at the steps, and this leads to a much higher contrast than that achieved in bright-field transmission electron microscopy imaging of the same strips. Theory and numerical simulations support the experimental PINEM findings and elucidate the nature of the electric field at the steps formed by the graphene layers. These results extend the range of applications of the experimental PINEM methodology, which has previously been demonstrated for spherical, cylindrical, and triangular nanostructures, to shapes of high aspect ratio (rectangular strips), as well as into the regime of atomic layer thicknesses.

  2. Making patterns on graphene.

    PubMed

    Zhou, Yong; Loh, Kian Ping

    2010-08-24

    Graphene-based nanostructures are considered as promising alternatives to silicon-based mesostructures in future electronic nanodevices. The lithographical patterning of graphene, which are essential steps in any form of microelectronic processing, present interesting challenges because of the atomic layer thickness of graphene. Mesoscopic devices based on graphene require high spatial resolution patterning that will induce as little damage as possible. This research news highlights and evaluates recent developments in the nanostructuring and patterning of graphene.

  3. Spatially Resolved Electronic Structures of Atomically Precise Armchair Graphene Nanoribbons

    PubMed Central

    Huang, Han; Wei, Dacheng; Sun, Jiatao; Wong, Swee Liang; Feng, Yuan Ping; Neto, A. H. Castro; Wee, Andrew Thye Shen

    2012-01-01

    Graphene has attracted much interest in both academia and industry. The challenge of making it semiconducting is crucial for applications in electronic devices. A promising approach is to reduce its physical size down to the nanometer scale. Here, we present the surface-assisted bottom-up fabrication of atomically precise armchair graphene nanoribbons (AGNRs) with predefined widths, namely 7-, 14- and 21-AGNRs, on Ag(111) as well as their spatially resolved width-dependent electronic structures. STM/STS measurements reveal their associated electron scattering patterns and the energy gaps over 1 eV. The mechanism to form such AGNRs is addressed based on the observed intermediate products. Our results provide new insights into the local properties of AGNRs, and have implications for the understanding of their electrical properties and potential applications. PMID:23248746

  4. Toward Two-Dimensional All-Carbon Heterostructures via Ion Beam Patterning of Single-Layer Graphene.

    PubMed

    Kotakoski, Jani; Brand, Christian; Lilach, Yigal; Cheshnovsky, Ori; Mangler, Clemens; Arndt, Markus; Meyer, Jannik C

    2015-09-09

    Graphene has many claims to fame: it is the thinnest possible membrane, it has unique electronic and excellent mechanical properties, and it provides the perfect model structure for studying materials science at the atomic level. However, for many practical studies and applications the ordered hexagon arrangement of carbon atoms in graphene is not directly suitable. Here, we show that the atoms can be locally either removed or rearranged into a random pattern of polygons using a focused ion beam (FIB). The atomic structure of the disordered regions is confirmed with atomic-resolution scanning transmission electron microscopy images. These structural modifications can be made on macroscopic scales with a spatial resolution determined only by the size of the ion beam. With just one processing step, three types of structures can be defined within a graphene layer: chemically inert graphene, chemically active amorphous 2D carbon, and empty areas. This, along with the changes in properties, gives promise that FIB patterning of graphene will open the way for creating all-carbon heterostructures to be used in fields ranging from nanoelectronics and chemical sensing to composite materials.

  5. Atomic cobalt on nitrogen-doped graphene for hydrogen generation

    PubMed Central

    Fei, Huilong; Dong, Juncai; Arellano-Jiménez, M. Josefina; Ye, Gonglan; Dong Kim, Nam; Samuel, Errol L.G.; Peng, Zhiwei; Zhu, Zhuan; Qin, Fan; Bao, Jiming; Yacaman, Miguel Jose; Ajayan, Pulickel M.; Chen, Dongliang; Tour, James M.

    2015-01-01

    Reduction of water to hydrogen through electrocatalysis holds great promise for clean energy, but its large-scale application relies on the development of inexpensive and efficient catalysts to replace precious platinum catalysts. Here we report an electrocatalyst for hydrogen generation based on very small amounts of cobalt dispersed as individual atoms on nitrogen-doped graphene. This catalyst is robust and highly active in aqueous media with very low overpotentials (30 mV). A variety of analytical techniques and electrochemical measurements suggest that the catalytically active sites are associated with the metal centres coordinated to nitrogen. This unusual atomic constitution of supported metals is suggestive of a new approach to preparing extremely efficient single-atom catalysts. PMID:26487368

  6. Mode dependent lattice thermal conductivity of single layer graphene

    SciTech Connect

    Wei, Zhiyong; Yang, Juekuan; Bi, Kedong; Chen, Yunfei

    2014-10-21

    Molecular dynamics simulation is performed to extract the phonon dispersion and phonon lifetime of single layer graphene. The mode dependent thermal conductivity is calculated from the phonon kinetic theory. The predicted thermal conductivity at room temperature exhibits important quantum effects due to the high Debye temperature of graphene. But the quantum effects are reduced significantly when the simulated temperature is as high as 1000 K. Our calculations show that out-of-plane modes contribute about 41.1% to the total thermal conductivity at room temperature. The relative contribution of out-of-plane modes has a little decrease with the increase of temperature. Contact with substrate can reduce both the total thermal conductivity of graphene and the relative contribution of out-of-plane modes, in agreement with previous experiments and theories. Increasing the coupling strength between graphene and substrate can further reduce the relative contribution of out-of-plane modes. The present investigations also show that the relative contribution of different mode phonons is not sensitive to the grain size of graphene. The obtained phonon relaxation time provides useful insight for understanding the phonon mean free path and the size effects in graphene.

  7. Lattice-layer entanglement in Bernal-stacked bilayer graphene

    NASA Astrophysics Data System (ADS)

    Bittencourt, Victor A. S. V.; Bernardini, Alex E.

    2017-05-01

    The complete lattice-layer entanglement structure of Bernal-stacked bilayer graphene is obtained for the quantum system described by a tight-binding Hamiltonian which includes mass and bias voltage terms. Through a suitable correspondence with the parity-spin S U (2 )⊗S U (2 ) structure of a Dirac Hamiltonian, when it brings up tensor and pseudovector external field interactions, the lattice-layer degrees of freedom can be mapped into such a parity-spin two-qubit basis which supports the interpretation of the bilayer graphene eigenstates as entangled ones in a lattice-layer basis. The Dirac Hamiltonian mapping structure simply provides the tools for the manipulation of the corresponding eigenstates and eigenenergies of the Bernal-stacked graphene quantum system. The quantum correlational content is then quantified by means of quantum concurrence, in order to have the influence of mass and bias voltage terms quantified, and in order to identify the role of the trigonal warping of energy in the intrinsic entanglement. Our results show that while the mass term actively suppresses the intrinsic quantum entanglement of bilayer eigenstates, the bias voltage term spreads the entanglement in the Brillouin zone around the Dirac points. In addition, the interlayer coupling modifies the symmetry of the lattice-layer quantum concurrence around a given Dirac point. It produces some distortion on the quantum entanglement profile which follows the same pattern of the isoenergy line distortion in the Bernal-stacked bilayer graphene.

  8. Peeling process of thin-film solar cells using graphene layers

    NASA Astrophysics Data System (ADS)

    Ishikawa, Ryousuke; Kurokawa, Yasuyoshi; Miyajima, Shinsuke; Konagai, Makoto

    2017-08-01

    A novel peeling process for thin-film solar cells using graphene layers was demonstrated. We fabricated amorphous silicon (a-Si) solar cells as substitutes for the undeveloped nanostructured silicon solar cells on graphene layers in order to investigate the solar cell performance after peeling for the first time. The graphene layers functioned as transparent electrodes after the peeling process, even though the series resistance increased after the peeling. Next, we fabricated a silicon nanowire (SiNW) array on graphene layers by a combination of chemical etching and thermal crystallization. Finally, we successfully peeled a SiNW array using graphene layers.

  9. Electron transport in molecular junctions with graphene as protecting layer

    SciTech Connect

    Hüser, Falco; Solomon, Gemma C.

    2015-12-07

    We present ab initio transport calculations for molecular junctions that include graphene as a protecting layer between a single molecule and gold electrodes. This vertical setup has recently gained significant interest in experiment for the design of particularly stable and reproducible devices. We observe that the signals from the molecule in the electronic transmission are overlayed by the signatures of the graphene sheet, thus raising the need for a reinterpretation of the transmission. On the other hand, we see that our results are stable with respect to various defects in the graphene. For weakly physiosorbed molecules, no signs of interaction with the graphene are evident, so the transport properties are determined by offresonant tunnelling between the gold leads across an extended structure that includes the molecule itself and the additional graphene layer. Compared with pure gold electrodes, calculated conductances are about one order of magnitude lower due to the increased tunnelling distance. Relative differences upon changing the end group and the length of the molecule on the other hand, are similar.

  10. Short-channel field-effect transistors with 9-atom and 13-atom wide graphene nanoribbons.

    PubMed

    Llinas, Juan Pablo; Fairbrother, Andrew; Borin Barin, Gabriela; Shi, Wu; Lee, Kyunghoon; Wu, Shuang; Yong Choi, Byung; Braganza, Rohit; Lear, Jordan; Kau, Nicholas; Choi, Wonwoo; Chen, Chen; Pedramrazi, Zahra; Dumslaff, Tim; Narita, Akimitsu; Feng, Xinliang; Müllen, Klaus; Fischer, Felix; Zettl, Alex; Ruffieux, Pascal; Yablonovitch, Eli; Crommie, Michael; Fasel, Roman; Bokor, Jeffrey

    2017-09-21

    Bottom-up synthesized graphene nanoribbons and graphene nanoribbon heterostructures have promising electronic properties for high-performance field-effect transistors and ultra-low power devices such as tunneling field-effect transistors. However, the short length and wide band gap of these graphene nanoribbons have prevented the fabrication of devices with the desired performance and switching behavior. Here, by fabricating short channel (L ch ~ 20 nm) devices with a thin, high-κ gate dielectric and a 9-atom wide (0.95 nm) armchair graphene nanoribbon as the channel material, we demonstrate field-effect transistors with high on-current (I on > 1 μA at V d = -1 V) and high I on /I off ~ 10(5) at room temperature. We find that the performance of these devices is limited by tunneling through the Schottky barrier at the contacts and we observe an increase in the transparency of the barrier by increasing the gate field near the contacts. Our results thus demonstrate successful fabrication of high-performance short-channel field-effect transistors with bottom-up synthesized armchair graphene nanoribbons.Graphene nanoribbons show promise for high-performance field-effect transistors, however they often suffer from short lengths and wide band gaps. Here, the authors use a bottom-up synthesis approach to fabricate 9- and 13-atom wide ribbons, enabling short-channel transistors with 10(5) on-off current ratio.

  11. Self assembled multi-layer nanocomposite of graphene and metal oxide materials

    DOEpatents

    Liu, Jun; Aksay, Ilhan A; Choi, Daiwon; Kou, Rong; Nie, Zimin; Wang, Donghai; Yang, Zhenguo

    2015-04-28

    Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.

  12. Self assembled multi-layer nanocomposite of graphene and metal oxide materials

    DOEpatents

    Liu, Jun; Aksay, Ilhan A; Choi, Daiwon; Kou, Rong; Nie, Zimin; Wang, Donghai; Yang, Zhenguo

    2013-10-22

    Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.

  13. Self assembled multi-layer nanocomposite of graphene and metal oxide materials

    DOEpatents

    Liu, Jun; Choi, Daiwon; Kou, Rong; Nie, Zimin; Wang, Donghai; Yang, Zhenguo

    2014-09-16

    Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.

  14. Tunable electronic properties of graphene through controlling bonding configurations of doped nitrogen atoms

    PubMed Central

    Zhang, Jia; Zhao, Chao; Liu, Na; Zhang, Huanxi; Liu, Jingjing; Fu, Yong Qing; Guo, Bin; Wang, Zhenlong; Lei, Shengbin; Hu, PingAn

    2016-01-01

    Single–layer and mono–component doped graphene is a crucial platform for a better understanding of the relationship between its intrinsic electronic properties and atomic bonding configurations. Large–scale doped graphene films dominated with graphitic nitrogen (GG) or pyrrolic nitrogen (PG) were synthesized on Cu foils via a free radical reaction at growth temperatures of 230–300 °C and 400–600 °C, respectively. The bonding configurations of N atoms in the graphene lattices were controlled through reaction temperature, and characterized using Raman spectroscopy, X–ray photoelectron spectroscopy and scanning tunneling microscope. The GG exhibited a strong n–type doping behavior, whereas the PG showed a weak n–type doping behavior. Electron mobilities of the GG and PG were in the range of 80.1–340 cm2 V−1·s−1 and 59.3–160.6 cm2 V−1·s−1, respectively. The enhanced doping effect caused by graphitic nitrogen in the GG produced an asymmetry electron–hole transport characteristic, indicating that the long–range scattering (ionized impurities) plays an important role in determining the carrier transport behavior. Analysis of temperature dependent conductance showed that the carrier transport mechanism in the GG was thermal excitation, whereas that in the PG, was a combination of thermal excitation and variable range hopping. PMID:27325386

  15. Short-range ordering of ion-implanted nitrogen atoms in SiC-graphene

    SciTech Connect

    Willke, P.; Druga, T.; Wenderoth, M.; Amani, J. A.; Weikert, S.; Hofsäss, H.; Thakur, S.; Maiti, K.

    2014-09-15

    We perform a structural analysis of nitrogen-doped graphene on SiC(0001) prepared by ultra low-energy ion bombardment. Using scanning tunneling microscopy, we show that nitrogen atoms are incorporated almost exclusively as graphitic substitution in the graphene honeycomb lattice. With an irradiation energy of 25 eV and a fluence of approximately 5 × 10{sup 14 }cm{sup −2}, we achieve a nitrogen content of around 1%. By quantitatively comparing the position of the N-atoms in the topography measurements with simulated random distributions, we find statistically significant short-range correlations. Consequently, we are able to show that the dopants arrange preferably at lattice sites given by the 6 × 6-reconstruction of the underlying substrate. This selective incorporation is most likely triggered by adsorbate layers present during the ion bombardment. This study identifies low-energy ion irradiation as a promising method for controlled doping in epitaxial graphene.

  16. Tunable electronic properties of graphene through controlling bonding configurations of doped nitrogen atoms

    NASA Astrophysics Data System (ADS)

    Zhang, Jia; Zhao, Chao; Liu, Na; Zhang, Huanxi; Liu, Jingjing; Fu, Yong Qing; Guo, Bin; Wang, Zhenlong; Lei, Shengbin; Hu, Pingan

    2016-06-01

    Single–layer and mono–component doped graphene is a crucial platform for a better understanding of the relationship between its intrinsic electronic properties and atomic bonding configurations. Large–scale doped graphene films dominated with graphitic nitrogen (GG) or pyrrolic nitrogen (PG) were synthesized on Cu foils via a free radical reaction at growth temperatures of 230–300 °C and 400–600 °C, respectively. The bonding configurations of N atoms in the graphene lattices were controlled through reaction temperature, and characterized using Raman spectroscopy, X–ray photoelectron spectroscopy and scanning tunneling microscope. The GG exhibited a strong n–type doping behavior, whereas the PG showed a weak n–type doping behavior. Electron mobilities of the GG and PG were in the range of 80.1–340 cm2 V‑1·s‑1 and 59.3–160.6 cm2 V‑1·s‑1, respectively. The enhanced doping effect caused by graphitic nitrogen in the GG produced an asymmetry electron–hole transport characteristic, indicating that the long–range scattering (ionized impurities) plays an important role in determining the carrier transport behavior. Analysis of temperature dependent conductance showed that the carrier transport mechanism in the GG was thermal excitation, whereas that in the PG, was a combination of thermal excitation and variable range hopping.

  17. Novel Infrared Dynamics of Cold Atoms on Hot Graphene

    NASA Astrophysics Data System (ADS)

    Sengupta, Sanghita; Kotov, Valeri; Clougherty, Dennis

    The low-energy dynamics of cold atoms interacting with macroscopic graphene membranes exhibits severe infrared divergences when treated perturbatively. These infrared problems are even more pronounced at finite temperature due to the (infinitely) many flexural phonons excited in graphene. We have devised a technique to take account (resummation) of such processes in the spirit of the well-known exact solution of the independent boson model. Remarkably, there is also similarity to the infrared problems and their treatment (via the Bloch-Nordsieck scheme) in finite temperature ``hot'' quantum electrodynamics and chromodynamics due to the long-range, unscreened nature of gauge interactions. The method takes into account correctly the strong damping provided by the many emitted phonons at finite temperature. In our case, the inverse membrane size plays the role of an effective low-energy scale, and, unlike the above mentioned field theories, there remains an unusual, highly nontrivial dependence on that scale due to the 2D nature of the problem. We present detailed results for the sticking (atomic damping rate) rate of cold atomic hydrogen as a function of the membrane temperature and size. We find that the rate is very strongly dependent on both quantities.

  18. Atomic Layer Deposition of Metal Sulfide Materials

    SciTech Connect

    Dasgupta, Neil P.; Meng, Xiangbo; Elam, Jeffrey W.; Martinson, Alex B. F.

    2015-02-17

    The field of nanoscience is delivering increasingly intricate yet elegant geometric structures incorporating an ever-expanding palette of materials. Atomic layer deposition (ALD) is a powerful driver of this field, providing exceptionally conformal coatings spanning the periodic table and atomic-scale precision independent of substrate geometry. This versatility is intrinsic to ALD and results from sequential and self-limiting surface reactions. This characteristic facilitates digital synthesis, in which the film grows linearly with the number of reaction cycles. While the majority of ALD processes identified to date produce metal oxides, novel applications in areas such as energy storage, catalysis, and nanophotonics are motivating interest in sulfide materials. Recent progress in ALD of sulfides has expanded the diversity of accessible materials as well as a more complete understanding of the unique chalcogenide surface chemistry.

  19. Energetics of a Li Atom adsorbed on B/N doped graphene with monovacancy

    SciTech Connect

    Rani, Babita; Jindal, V.K.; Dharamvir, Keya

    2016-08-15

    We use density functional theory (DFT) to study the adsorption properties and diffusion of Li atom across B/N-pyridinic graphene. Regardless of the dopant type, B atoms of B-pyridinic graphene lose electron density. On the other hand, N atoms (p-type dopants) have tendency to gain electron density in N-pyridinic graphene. Higher chemical reactivity and electronic conductivity of B/N-pyridinic graphene are responsible for stronger binding of Li with the substrates as compared to pristine graphene. The binding energy of Li with B/N-pyridinic graphene exceeds the cohesive energy of bulk Li, making it energetically unfavourable for Li to form clusters on these substrates. Li atom gets better adsorbed on N-pyridinic graphene due to an additional p-p hybridization of the orbitals while Li on B-pyridinic prefers the ionic bonding. Also, significant distortion of N-pyridinic graphene upon Li adsorption is a consequence of the change in bonding mechanism between Li atom and the substrate. Our results show that bonding character and hence binding energies between Li and graphene can be tuned with the help of B/N doping of monovacancy defects. Further, the sites for most stable adsorption are different for the two types of doped and defective graphene, leading to greater Li uptake capacity of B-pyridinic graphene near the defect. In addition, B-pyridinic graphene offering lower diffusion barrier, ensures better Li kinetics. Thus, B-pyridinic graphene presents itself as a better anode material for LIBs as compared to N-pyridinic graphene. - Graphical abstract: Adsorption and diffusion of Li atom across the B/N doped monovacancy graphene is studied using ab-initio DFT calculations. Our results show that bonding mechanism and binding of Li with graphene can be tuned with the help of N/B doping of defects. Also, B-pyridinic graphene presents itself as a better anode material for lithium ion batteries as compared to N-pyridinic graphene. Display Omitted - Highlights: • Density

  20. Adsorption of Mn atom on pristine and defected graphene: a density functional theory study.

    PubMed

    Anithaa, V S; Shankar, R; Vijayakumar, S

    2017-04-01

    The functionalization of graphene with transition metals is of great interest due to its wide range of applications, such as hydrogen storage, spintronics, information storage, etc. Due to its magnetic property adsorption of Mn atom on graphene has a high consequence on the electronic properties of graphene. The increase in size of the graphene sheet with hydrogen termination has a high impact on the transformation of electronic properties of the graphene sheet. Hence in this work, we investigate the size as well as change in structural and electronic properties of pristine/defective graphene sheets on adsorption of Mn atom using density functional theory methods. From the results obtained a higher adsorption energy value of 3.04 eV is found for Mn adatom on the defected graphene sheet than the pristine, 1.85 eV. It is subject to the coverage effect which decreases on increasing number of carbon atoms. Moreover, a decrease in energy gap is observed in pristine and defected graphene sheets with a high number of carbon atoms. The density of states illustrates the significant effect for hydrogen termination in the conduction band of the Mn adsorbed graphene sheet with low carbon atoms. Graphical Abstract Mn adatom on graphene at different sites.

  1. Facile synthesis of few-layer graphene with a controllable thickness using rapid thermal annealing.

    PubMed

    Chu, Jae Hwan; Kwak, Jinsung; Kwon, Tae-Yang; Park, Soon-Dong; Go, Heungseok; Kim, Sung Youb; Park, Kibog; Kang, Seoktae; Kwon, Soon-Yong

    2012-03-01

    Few-layer graphene films with a controllable thickness were grown on a nickel surface by rapid thermal annealing (RTA) under vacuum. The instability of nickel films in air facilitates the spontaneous formation of ultrathin (<2-3 nm) carbon- and oxygen-containing compounds on a nickel surface; thus, the high-temperature annealing of the nickel samples without the introduction of intentional carbon-containing precursors results in the formation of graphene films. From annealing temperature and ambient studies during RTA, it was found that the evaporation of oxygen atoms from the surface is the dominant factor affecting the formation of graphene films. The thickness of the graphene layers is strongly dependent on the RTA temperature and time, and the resulting films have a limited thickness (<2 nm), even for an extended RTA time. The transferred films have a low sheet resistance of ~0.9 ± 0.4 kΩ/sq, with ~94% ± 2% optical transparency, making them useful for applications as flexible transparent conductors.

  2. Synthesis of few-layer graphene via microwave plasma-enhanced chemical vapour deposition.

    PubMed

    Malesevic, Alexander; Vitchev, Roumen; Schouteden, Koen; Volodin, Alexander; Zhang, Liang; Tendeloo, Gustaaf Van; Vanhulsel, Annick; Haesendonck, Chris Van

    2008-07-30

    If graphene is ever going to live up to the promises of future nanoelectronic devices, an easy and cheap route for mass production is an essential requirement. A way to extend the capabilities of plasma-enhanced chemical vapour deposition to the synthesis of freestanding few-layer graphene is presented. Micrometre-wide flakes consisting of four to six atomic layers of stacked graphene sheets have been synthesized by controlled recombination of carbon radicals in a microwave plasma. A simple and highly reproducible technique is essential, since the resulting flakes can be synthesized without the need for a catalyst on the surface of any substrate that withstands elevated temperatures up to 700 °C. A thorough structural analysis of the flakes is performed with electron microscopy, x-ray diffraction, Raman spectroscopy and scanning tunnelling microscopy. The resulting graphene flakes are aligned vertically to the substrate surface and grow according to a three-step process, as revealed by the combined analysis of electron microscopy and x-ray photoelectron spectroscopy.

  3. Nonlocal optical properties in periodic lattice of graphene layers.

    PubMed

    Chern, Ruey-Lin; Han, Dezhuan

    2014-02-24

    Based on the effective medium model, nonlocal optical properties in periodic lattice of graphene layers with the period much less than the wavelength are investigated. Strong nonlocal effects are found in a broad frequency range for TM polarization, where the effective permittivity tensor exhibits the Lorentzian resonance. The resonance frequency varies with the wave vector and coincides well with the polaritonic mode. Nonlocal features are manifest on the emergence of additional wave and the occurrence of negative refraction. By examining the characters of the eigenmode, the nonlocal optical properties are attributed to the excitation of plasmons on the graphene surfaces.

  4. Ruthenium / aerogel nanocomposits via Atomic Layer Deposition

    SciTech Connect

    Biener, J; Baumann, T F; Wang, Y; Nelson, E J; Kucheyev, S O; Hamza, A V; Kemell, M; Ritala, M; Leskela, M

    2006-08-28

    We present a general approach to prepare metal/aerogel nanocomposites via template directed atomic layer deposition (ALD). In particular, we used a Ru ALD process consisting of alternating exposures to bis(cyclopentadienyl)ruthenium (RuCp{sub 2}) and air at 350 C to deposit metallic Ru nanoparticles on the internal surfaces of carbon and silica aerogels. The process does not affect the morphology of the aerogel template and offers excellent control over metal loading by simply adjusting the number of ALD cycles. We also discuss the limitations of our ALD approach, and suggest ways to overcome these.

  5. Energetics of a Li Atom adsorbed on B/N doped graphene with monovacancy

    NASA Astrophysics Data System (ADS)

    Rani, Babita; Jindal, V. K.; Dharamvir, Keya

    2016-08-01

    We use density functional theory (DFT) to study the adsorption properties and diffusion of Li atom across B/N-pyridinic graphene. Regardless of the dopant type, B atoms of B-pyridinic graphene lose electron density. On the other hand, N atoms (p-type dopants) have tendency to gain electron density in N-pyridinic graphene. Higher chemical reactivity and electronic conductivity of B/N-pyridinic graphene are responsible for stronger binding of Li with the substrates as compared to pristine graphene. The binding energy of Li with B/N-pyridinic graphene exceeds the cohesive energy of bulk Li, making it energetically unfavourable for Li to form clusters on these substrates. Li atom gets better adsorbed on N-pyridinic graphene due to an additional p-p hybridization of the orbitals while Li on B-pyridinic prefers the ionic bonding. Also, significant distortion of N-pyridinic graphene upon Li adsorption is a consequence of the change in bonding mechanism between Li atom and the substrate. Our results show that bonding character and hence binding energies between Li and graphene can be tuned with the help of B/N doping of monovacancy defects. Further, the sites for most stable adsorption are different for the two types of doped and defective graphene, leading to greater Li uptake capacity of B-pyridinic graphene near the defect. In addition, B-pyridinic graphene offering lower diffusion barrier, ensures better Li kinetics. Thus, B-pyridinic graphene presents itself as a better anode material for LIBs as compared to N-pyridinic graphene.

  6. Atomic Layer Deposition for SRF Cavities

    SciTech Connect

    Proslier, Th.; Ha, Y.; Zasadzinski, J.; Ciovati, G.; Kneissel, P.; Reece, C.; Rimmer, R.; Gurevich, A.; Cooley, L.; Wu, G.; Pellin, M.; /Argonne

    2009-05-01

    We have begun using Atomic Layer Deposition (ALD) to synthesize a variety of surface coatings on coupons and cavities as part of an effort to produce rf structures with significantly better performance and yield than those obtained from bulk niobium, The ALD process offers the possibility of conformally coating complex cavity shapes with precise layered structures with tightly constrained morphology and chemical properties. Our program looks both at the metallurgy and superconducting properties of these coatings, and also their performance in working structures. Initial results include: (1) results from ALD coated cavities and coupons, (2) new evidence from point contact tunneling (PCT) showing magnetic oxides can be a significant limitation to high gradient operation, (3) a study of high pressure rinsing damage on niobium samples.

  7. Atomic Layer Deposition for SRF Cavities

    SciTech Connect

    Norem, J; Pellin, M J; Antoine, C Z; Ciovati, G; Kneisel, P; Reece, C E; Rimmer, R A; Cooley, L; Gurevich, A V; Ha, Y; Proslier, Th; Zasadzinski, J

    2009-05-01

    We have begun using Atomic Layer Deposition (ALD) to synthesize a variety of surface coatings on coupons and cavities as part of an effort to produce rf structures with significantly better performance and yield than those obtained from bulk niobium, The ALD process offers the possibility of conformally coating complex cavity shapes with precise layered structures with tightly constrained morphology and chemical properties. Our program looks both at the metallurgy and superconducting properties of these coatings, and also their performance in working structures. Initial results include: 1) evidence from point contact tunneling showing magnetic oxides can be a significant limitation to high gradient operation, 2) experimental results showing the production sharp niobium/oxide interfaces from a high temperature bake of ALD coated Al2O3 on niobium surfaces, 3) results from ALD coated structures.

  8. High-temperature scanning tunneling microscopy study of the ordering transition of an amorphous carbon layer into graphene on ruthenium(0001).

    PubMed

    Günther, Sebastian; Dänhardt, Sebastian; Ehrensperger, Martin; Zeller, Patrick; Schmitt, Stefan; Wintterlin, Joost

    2013-01-22

    The ordering transition of an amorphous carbon layer into graphene was investigated by high-temperature scanning tunneling microscopy. A disordered C layer was prepared on a Ru(0001) surface by chemical vapor deposition of ethylene molecules at ~660 K. The carbon layer grows in the form of dendritic islands that have almost the same density as graphene. Upon annealing of the fully covered surface, residual hydrogen desorbs and a coherent but still disordered carbon layer forms, with almost the same carbon coverage as in graphene. The ordering of this layer into graphene at 920 to 950 K was monitored as a function of time. A unique mechanism was observed that involves small topographic holes in the carbon layer. The holes are mobile, and on the trajectories of the holes the disordered carbon layer is transformed into graphene. The transport of C atoms across the holes or along the hole edges provides a low-energy pathway for the ordering transition. This mechanism is prohibited in a dense graphene layer, which offers an explanation for the difficulty of removing defects from graphene synthesized by chemical methods.

  9. Electrochemical double-layer capacitors based on functionalized graphene

    NASA Astrophysics Data System (ADS)

    Pope, Michael Allan

    Graphene is a promising electrode material for electrochemical double-layer capacitors (EDLCs) used for energy storage due to its high electrical conductivity and theoretical specific surface area. However, the intrinsic capacitance of graphene is known to be low and governed by the electronic side of the interface. Furthermore, graphene tends to aggregate and stack together when processed into thick electrode films. This significantly lowers the ion-accessible specific surface area (SSA). Maximizing both the SSA and the intrinsic capacitance are the main problems addressed in this thesis in an effort to improve the specific capacitance and energy density of EDLCs. In contrast to pristine graphene, functionalized graphene produced by the thermal exfoliation of graphite oxide contains residual functional groups and lattice defects. To study how these properties affect the double-layer capacitance, a model electrode system capable of measuring the intrinsic electrochemical properties of functionalized graphene was developed. To prevent artifacts and uncertainties related to measurements on porous electrodes, the functionalized graphene sheets (FGSs) were assembled as densely tiled monolayers using a Langmuir-Blodgett technique. In this way, charging can be studied in a well-defined 2D geometry. The possibility of measuring and isolating the intrinsic electrochemical properties of FGS monolayers was first demonstrated by comparing capacitance and redox probe measurements carried out on coatings deposited on passivated gold and single crystal graphite substrates. This monolayer system was then used to follow the double-layer capacitance of the FGS/electrolyte interface as the structure and chemistry of graphene was varied by thermal treatments ranging from 300 °C to 2100 °C. Elemental analysis and Raman spectroscopy were used to determine the resulting chemical and structural transformation upon heat treatment. It was demonstrated that intrinsically defective

  10. Oxidation and disorder in few-layered graphene induced by the electron-beam irradiation

    SciTech Connect

    Xu Zhiwei; Wang Rui; Qian Xiaoming; Chen Lei; Li Jialu; Song Xiaoyan; Liu Liangsen; Chen Guangwei

    2011-05-02

    Structural changes caused by an electron beam with the high irradiation energy of 5 MeV were investigated in few-layered graphene. Both the original and the irradiated few-layered graphene were characterized by x-ray diffraction, Raman spectroscopy, and x-ray photoelectron spectroscopy. It was found that a typical diffraction peak of graphene oxide emerged and this may be attributed to a partial oxidation in few-layered graphene which was induced by the irradiation. In addition, the graphitic structure of few-layered graphene was found to be disordered according to the increased intensity ratio of D to G band.

  11. Effect of the intra-layer potential distributions and spatial currents on the performance of graphene SymFETs

    SciTech Connect

    Hasan, Mehdi; Sensale-Rodriguez, Berardi

    2015-09-15

    In this paper, a two-dimensional (2-D) model for a graphene symmetric field effect transistor (SymFET), which considers (a) the intra-graphene layer potential distributions and (b) the internal current flows through the device, is presented and discussed. The local voltages along the graphene electrodes as well as the current-voltage characteristics of the device are numerically calculated based on a single-particle tunneling model. Our numerical results show that: (i) when the tunneling current is small, due to either a large tunneling thickness (≥ 2 atomic layers of BN) or a small coherence length, the voltage distributions along the graphene electrodes have almost zero variations upon including these distributed effects, (ii) when the tunnel current is large, due to either a small tunneling thickness (∼ 1 atomic layer of BN) or due to a large coherence length, the local voltage distributions along the graphene electrodes become appreciable and the device behavior deviates from that predicted by a 1-D approximation. These effects, which are not captured in one-dimensional SymFET models, can provide a better understanding about the electron dynamics in the device and might indicate potential novel applications for this proposed device.

  12. Intrinsic Negative Poisson's Ratio for Single-Layer Graphene.

    PubMed

    Jiang, Jin-Wu; Chang, Tienchong; Guo, Xingming; Park, Harold S

    2016-08-10

    Negative Poisson's ratio (NPR) materials have drawn significant interest because the enhanced toughness, shear resistance, and vibration absorption that typically are seen in auxetic materials may enable a range of novel applications. In this work, we report that single-layer graphene exhibits an intrinsic NPR, which is robust and independent of its size and temperature. The NPR arises due to the interplay between two intrinsic deformation pathways (one with positive Poisson's ratio, the other with NPR), which correspond to the bond stretching and angle bending interactions in graphene. We propose an energy-based deformation pathway criteria, which predicts that the pathway with NPR has lower energy and thus becomes the dominant deformation mode when graphene is stretched by a strain above 6%, resulting in the NPR phenomenon.

  13. Femtosecond laser patterning, synthesis, defect formation, and structural modification of atomic layered materials

    DOE PAGES

    Yoo, Jae-Hyuck; Kim, Eunpa; Hwang, David J.

    2016-12-06

    This article summarizes recent research on laser-based processing of twodimensional (2D) atomic layered materials, including graphene and transition metal dichalcogenides (TMDCs). Ultrafast lasers offer unique processing routes that take advantage of distinct interaction mechanisms with 2D materials to enable extremely localized energy deposition. Experiments have shown that ablative direct patterning of graphene by ultrafast lasers can achieve resolutions of tens of nanometers, as well as single-step pattern transfer. Ultrafast lasers also induce non-thermal excitation mechanisms that are useful for the thinning of TMDCs to tune the 2D material bandgap. Laser-assisted site-specific doping was recently demonstrated where ultrafast laser radiation undermore » ambient air environment could be used for the direct writing of high-quality graphene patterns on insulating substrates. This article concludes with an outlook towards developing further advanced laser processing with scalability, in situ monitoring strategies and potential applications.« less

  14. Femtosecond laser patterning, synthesis, defect formation, and structural modification of atomic layered materials

    SciTech Connect

    Yoo, Jae-Hyuck; Kim, Eunpa; Hwang, David J.

    2016-12-06

    This article summarizes recent research on laser-based processing of twodimensional (2D) atomic layered materials, including graphene and transition metal dichalcogenides (TMDCs). Ultrafast lasers offer unique processing routes that take advantage of distinct interaction mechanisms with 2D materials to enable extremely localized energy deposition. Experiments have shown that ablative direct patterning of graphene by ultrafast lasers can achieve resolutions of tens of nanometers, as well as single-step pattern transfer. Ultrafast lasers also induce non-thermal excitation mechanisms that are useful for the thinning of TMDCs to tune the 2D material bandgap. Laser-assisted site-specific doping was recently demonstrated where ultrafast laser radiation under ambient air environment could be used for the direct writing of high-quality graphene patterns on insulating substrates. This article concludes with an outlook towards developing further advanced laser processing with scalability, in situ monitoring strategies and potential applications.

  15. Catalyst design with atomic layer deposition

    DOE PAGES

    O'Neill, Brandon J.; Jackson, David H. K.; Lee, Jechan; ...

    2015-02-06

    Atomic layer deposition (ALD) has emerged as an interesting tool for the atomically precise design and synthesis of catalytic materials. Herein, we discuss examples in which the atomic precision has been used to elucidate reaction mechanisms and catalyst structure-property relationships by creating materials with a controlled distribution of size, composition, and active site. We highlight ways ALD has been utilized to design catalysts with improved activity, selectivity, and stability under a variety of conditions (e.g., high temperature, gas and liquid phase, and corrosive environments). In addition, due to the flexibility and control of structure and composition, ALD can create myriadmore » catalytic structures (e.g., high surface area oxides, metal nanoparticles, bimetallic nanoparticles, bifunctional catalysts, controlled microenvironments, etc.) that consequently possess applicability for a wide range of chemical reactions (e.g., CO2 conversion, electrocatalysis, photocatalytic and thermal water splitting, methane conversion, ethane and propane dehydrogenation, and biomass conversion). Lastly, the outlook for ALD-derived catalytic materials is discussed, with emphasis on the pending challenges as well as areas of significant potential for building scientific insight and achieving practical impacts.« less

  16. Improved graphene growth in UHV: Pit-free surfaces by selective Si etching of SiC(0001)-Si with atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Sandin, Andreas; Rowe, J. E. (Jack); Dougherty, Daniel B.

    2013-05-01

    We present a novel technique of growing UHV graphene using atomic hydrogen etching of SiC(0001)-Si surfaces. Hydrogen atoms generated from a hot tungsten filament selectively etch silicon surface atoms thereby facilitating the Si-sublimation process at temperatures around 1000 °C according to Auger Electron Spectroscopy. This allows for separate, non-thermal control of the rate of formation of the interfacial buffer layer formation to yield reduced pit formation observed by scanning tunneling microscopy during subsequent UHV graphene growth.

  17. Electronic structure of epitaxial graphene layers on SiC: effects of the substrate

    SciTech Connect

    Varchon, F.; Feng, R.; Hass, J.; Li, X.; Nguyen, B. Ngoc; Naud, C.; Mallet, P.; Veuillen, J.-Y.; Berger, C.; Conrad, E.H.; Magaud, L.

    2008-10-17

    A strong substrate-graphite bond is found in the first all-carbon layer by density functional theory calculations and x-ray diffraction for few graphene layers grown epitaxially on SiC. This first layer is devoid of graphene electronic properties and acts as a buffer layer. The graphene nature of the film is recovered by the second carbon layer grown on both the (0001) and (0001{sup -}) 4H-SiC surfaces. We also present evidence of a charge transfer that depends on the interface geometry. Hence the graphene is doped and a gap opens at the Dirac point after three Bernal stacked carbon layers are formed.

  18. Investigation on optical properties of BSA protein on single-layer graphene using terahertz spectroscopy technology

    NASA Astrophysics Data System (ADS)

    Yang, Shengxin; Du, Pengju; Sun, Yiwen

    2016-11-01

    Terahertz (THz) spectroscopy is sensitive to probe several aspects of biological systems. In THz frequency, electrically controllable Drude-like intraband absorption makes graphene a promising platform for building graphene-based optoelectronic devices such as THz biosensor. In this work, BSA protein thin films were spin-coated and incubated on single-layer graphene. IR lasers with different power were used as the pump light to stimulate the sandwich-like sample respectively. The graphene monolayer complex conductivity was calculated using the transmission method. The novel optical properties of single-layer graphene and BSA protein on graphene in the THz range will be discussed in this paper.

  19. Initial evaluation and comparison of plasma damage to atomic layer carbon materials using conventional and low T{sub e} plasma sources

    SciTech Connect

    Jagtiani, Ashish V.; Miyazoe, Hiroyuki; Chang, Josephine; Farmer, Damon B.; Engel, Michael; Neumayer, Deborah; Han, Shu-Jen; Engelmann, Sebastian U. Joseph, Eric A.; Boris, David R.; Hernández, Sandra C.; Walton, Scott G.; Lock, Evgeniya H.

    2016-01-15

    The ability to achieve atomic layer precision is the utmost goal in the implementation of atomic layer etch technology. Carbon-based materials such as carbon nanotubes (CNTs) and graphene are single atomic layers of carbon with unique properties and, as such, represent the ultimate candidates to study the ability to process with atomic layer precision and assess impact of plasma damage to atomic layer materials. In this work, the authors use these materials to evaluate the atomic layer processing capabilities of electron beam generated plasmas. First, the authors evaluate damage to semiconducting CNTs when exposed to beam-generated plasmas and compare these results against the results using typical plasma used in semiconductor processing. The authors find that the beam generated plasma resulted in significantly lower current degradation in comparison to typical plasmas. Next, the authors evaluated the use of electron beam generated plasmas to process graphene-based devices by functionalizing graphene with fluorine, nitrogen, or oxygen to facilitate atomic layer deposition (ALD). The authors found that all adsorbed species resulted in successful ALD with varying impact on the transconductance of the graphene. Furthermore, the authors compare the ability of both beam generated plasma as well as a conventional low ion energy inductively coupled plasma (ICP) to remove silicon nitride (SiN) deposited on top of the graphene films. Our results indicate that, while both systems can remove SiN, an increase in the D/G ratio from 0.08 for unprocessed graphene to 0.22 to 0.26 for the beam generated plasma, while the ICP yielded values from 0.52 to 1.78. Generally, while some plasma-induced damage was seen for both plasma sources, a much wider process window as well as far less damage to CNTs and graphene was observed when using electron beam generated plasmas.

  20. Atomic-scale scanning tunneling microscopy and spectroscopy studies of nanometer-sized graphene on the Si(111)-7x7 surface.

    NASA Astrophysics Data System (ADS)

    Koepke, Justin; Lyding, Joseph

    2009-03-01

    We have used ultrahigh vacuum scanning tunneling microscopy to perform atomic-level studies of graphene on the Si(111)-7x7 surface. We used a dry contact transfer technique (DCT) developed by Albrecht and Lyding [1] to deposit mechanically exfoliated graphene in-situ [2] onto atomically clean Si(111)-7x7 surfaces. The DCT method deposits single, double, and thicker layers of atomically clean graphene. We observe varying degrees of transparency of the graphene monolayers and bilayers on the Si(111)-7x7 surface, where the substrate atomic structure is clearly seen through the graphene. We believe that the electronic structure of a graphene monolayer on the Si(111)-7x7 surface leads to the transparency of monolayers and bilayers, similar to the findings of Rutter, et al [3]. Room-temperature scanning tunneling spectroscopy (STS) measurements of the graphene monolayers and bilayers on the Si(111)-7x7 surface show predominantly metallic behavior. [1] P.M. Albrecht and J.W. Lyding, Appl. Phys. Lett. 83, 5029 (2003) [2] K.A. Ritter and J.W. Lyding, Nanotechnology 19, 015704 (2008) [3] G.M. Rutter, et al, Phys. Rev. B 76, 235416 (2007)

  1. Cross-sectional imaging of individual layers and buried interfaces of graphene-based heterostructures and superlattices

    NASA Astrophysics Data System (ADS)

    Haigh, S. J.; Gholinia, A.; Jalil, R.; Romani, S.; Britnell, L.; Elias, D. C.; Novoselov, K. S.; Ponomarenko, L. A.; Geim, A. K.; Gorbachev, R.

    2012-09-01

    By stacking various two-dimensional (2D) atomic crystals on top of each other, it is possible to create multilayer heterostructures and devices with designed electronic properties. However, various adsorbates become trapped between layers during their assembly, and this not only affects the resulting quality but also prevents the formation of a true artificial layered crystal upheld by van der Waals interaction, creating instead a laminate glued together by contamination. Transmission electron microscopy (TEM) has shown that graphene and boron nitride monolayers, the two best characterized 2D crystals, are densely covered with hydrocarbons (even after thermal annealing in high vacuum) and exhibit only small clean patches suitable for atomic resolution imaging. This observation seems detrimental for any realistic prospect of creating van der Waals materials and heterostructures with atomically sharp interfaces. Here we employ cross sectional TEM to take a side view of several graphene-boron nitride heterostructures. We find that the trapped hydrocarbons segregate into isolated pockets, leaving the interfaces atomically clean. Moreover, we observe a clear correlation between interface roughness and the electronic quality of encapsulated graphene. This work proves the concept of heterostructures assembled with atomic layer precision and provides their first TEM images.

  2. Plasmons in spatially separated double-layer graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Bagheri, Mehran; Bahrami, Mousa

    2014-05-01

    Motivated by innovative progresses in designing multi-layer graphene nanostructured materials in the laboratory, we theoretically investigate the Dirac plasmon modes of a spatially separated double-layer graphene nanoribbon system, made up of a vertically offset armchair and metallic graphene nanoribbon pair. We find striking features of the collective excitations in this novel Coulomb correlated system, where both nanoribbons are supposed to be either intrinsic (undoped/ungated) or extrinsic (doped/gated). In the former, it is shown the low-energy acoustical and the high-energy optical plasmon modes are tunable only by the inter-ribbon charge separation. In the later, the aforementioned plasmon branches are modified by the added doping factor. As a result, our model could be useful to examine the existence of a linear Landau-undamped low-energy acoustical plasmon mode tuned via the inter-ribbon charge separation as well as doping. This study might also be utilized for devising novel quantum optical waveguides based on the Coulomb coupled graphene nanoribbons.

  3. Plasmons in spatially separated double-layer graphene nanoribbons

    SciTech Connect

    Bagheri, Mehran; Bahrami, Mousa

    2014-05-07

    Motivated by innovative progresses in designing multi-layer graphene nanostructured materials in the laboratory, we theoretically investigate the Dirac plasmon modes of a spatially separated double-layer graphene nanoribbon system, made up of a vertically offset armchair and metallic graphene nanoribbon pair. We find striking features of the collective excitations in this novel Coulomb correlated system, where both nanoribbons are supposed to be either intrinsic (undoped/ungated) or extrinsic (doped/gated). In the former, it is shown the low-energy acoustical and the high-energy optical plasmon modes are tunable only by the inter-ribbon charge separation. In the later, the aforementioned plasmon branches are modified by the added doping factor. As a result, our model could be useful to examine the existence of a linear Landau-undamped low-energy acoustical plasmon mode tuned via the inter-ribbon charge separation as well as doping. This study might also be utilized for devising novel quantum optical waveguides based on the Coulomb coupled graphene nanoribbons.

  4. Corrugated graphene layers for sea water desalination using capacitive deionization.

    PubMed

    Dahanayaka, Madhavi; Liu, Bo; Hu, Zhongqiao; Chen, Zhong; Law, Adrian Wing-Keung; Zhou, Kun

    2017-03-14

    The effect of the electric field and surface morphology of corrugated graphene (GE) layers on their capacitive deionization process is studied using molecular dynamics simulations. Deionization performances are evaluated in terms of water flow rate and ion adsorption and explained by analysing the water density distribution, radial distribution function and distribution of the ions inside the GE layers. The simulation results reveal that corrugation of GE layers reduces the water flow rate but largely enhances ion adsorption in comparison to the flat GE layers. Such enhancement is mainly due to the adsorption of ions on the GE layers due to the anchoring effect in the regions with wide interlayer distances. Moreover, it reveals that the entrance configuration of the GE layers also has a significant effect on the performance of deionization. Overall, the results from this study will be helpful in designing effective electrode configurations for capacitive deionization.

  5. Stacking-dependent transport properties in few-layers graphene

    NASA Astrophysics Data System (ADS)

    Lima, Matheus Paes; Padilha, José Eduardo; Pontes, Renato Borges; Fazzio, Adalberto; Silva, Antônio José Roque da

    2017-01-01

    By performing ab initio electronic structure and transport calculations, we investigated the effects of the stacking order (Bernal (AB) and rhombohedral (ABC)) as well as the number of layers, in the electronic structure and charge transport of few-layers graphene (FLG). We observed that for the ABC stack the transport properties are derived from surface states close to the Fermi level connected to dispersive states with an exponential penetration towards the inner layers, whereas for the AB stacking the transport is distributed over all layers. We present a simple model for the resistances as a function of the number of layers which contemplates the different contribution of the surface and inner layers for the transport. However, even if the stackings AB and ABC present completely different electronic and transport properties, both present the same cohesive energies, showing the absence of a thermodynamical preference for a given kind of stacking.

  6. Touch stimulated pulse generation in biomimetic single-layer graphene

    NASA Astrophysics Data System (ADS)

    Sul, Onejae; Chun, Hyunsuk; Choi, Eunseok; Choi, Jungbong; Cho, Kyeongwon; Jang, Dongpyo; Chun, Sungwoo; Park, Wanjun; Lee, Seung-Beck

    2016-02-01

    Detecting variation in contact pressure is a separate sensing mode in the human somatosensory system that differs from the detection of pressure magnitude. If pressure magnitude and variation sensing can be achieved simultaneously, an advanced biomimetic tactile system that better emulates human senses may be developed. We report on a novel single-layer graphene based artificial mechanoreceptor that generates a resistance pulse as the contact stimulus passes a specific threshold pressure, mimicking the generation of action potentials in a biological fast-adapting mechanoreceptor. The electric field from a flexible membrane gate electrode placed above a graphene channel raises the Fermi level from the valence band as pressure deflects the membrane. The threshold pressure is reached when the Fermi level crosses the Dirac point in the graphene energy band, which generates a sharp peak in the measured resistance. We found that by changing the gate potential it was possible to modulate the threshold pressure and using a series of graphene channels, a train of pulses were generated during a transient pressurizing stimulus demonstrating biomimetic behaviour.Detecting variation in contact pressure is a separate sensing mode in the human somatosensory system that differs from the detection of pressure magnitude. If pressure magnitude and variation sensing can be achieved simultaneously, an advanced biomimetic tactile system that better emulates human senses may be developed. We report on a novel single-layer graphene based artificial mechanoreceptor that generates a resistance pulse as the contact stimulus passes a specific threshold pressure, mimicking the generation of action potentials in a biological fast-adapting mechanoreceptor. The electric field from a flexible membrane gate electrode placed above a graphene channel raises the Fermi level from the valence band as pressure deflects the membrane. The threshold pressure is reached when the Fermi level crosses the Dirac

  7. Self-organized arrays of graphene and few-layer graphene quantum dots in fluorographene matrix: Charge transient spectroscopy

    SciTech Connect

    Antonova, Irina V.; Nebogatikova, Nadezhda A.; Prinz, Victor Ya.

    2014-05-12

    Arrays of graphene or few-layer graphene quantum dots (QDs) embedded in a partially fluorinated graphene matrix were created by chemical functionalization of layers. Charge transient spectroscopy employed for investigation of obtained QD systems (size 20–70 nm) has allowed us to examine the QD energy spectra and the time of carrier emission (or charge relaxation) from QDs as a function of film thickness. It was found that the characteristic time of carrier emission from QDs decreased markedly (by about four orders of magnitude) on increasing the QD thickness from one graphene monolayer to 3 nm. Daylight-assisted measurements also demonstrate a strong decrease of the carrier emission time.

  8. Fabrication and applications of multi-layer graphene stack on transparent polymer

    NASA Astrophysics Data System (ADS)

    Krajewska, Aleksandra; Pasternak, Iwona; Sobon, Grzegorz; Sotor, Jaroslaw; Przewloka, Aleksandra; Ciuk, Tymoteusz; Sobieski, Jan; Grzonka, Justyna; Abramski, Krzysztof M.; Strupinski, Wlodek

    2017-01-01

    In this report, we demonstrate the preparation method of a multi-layer stack with a pre-defined number of graphene layers, which was obtained using chemical vapor deposition graphene deposited on a copper substrate and subsequently transferred onto a poly(methyl methacrylate) (PMMA) substrate. The prepared multi-layer stack can also be transferred onto an arbitrary substrate and in the end, the polymer can be removed, which in consequence significantly increases the range of possible graphene applications. The multi-layer character was confirmed by optical transmittance measurements and Raman spectroscopy, whereas the microstructure of the multi-layer graphene stack was investigated using Scanning Electron Microscopy. The electrical properties in the function of the number of graphene layers were assessed with standard Hall Effect measurements. Finally, we showed the practical application of the multi-layer graphene stack as a saturable absorber of a mode-locked Er-doped fiber laser.

  9. Single-atom spectroscopy of phosphorus dopants implanted into graphene

    NASA Astrophysics Data System (ADS)

    Susi, Toma; Hardcastle, Trevor P.; Hofsäss, Hans; Mittelberger, Andreas; Pennycook, Timothy J.; Mangler, Clemens; Drummond-Brydson, Rik; Scott, Andrew J.; Meyer, Jannik C.; Kotakoski, Jani

    2017-06-01

    One of the keys behind the success of modern semiconductor technology has been the ion implantation of silicon, which allows its electronic properties to be tailored. For similar purposes, heteroatoms have been introduced into carbon nanomaterials both during growth and using post-growth methods. However, due to the nature of the samples, it has been challenging to determine whether the heteroatoms have been incorporated into the lattice as intended. Direct observations have so far been limited to N and B dopants, and incidental Si impurities. Furthermore, ion implantation of these materials is challenging due to the requirement of very low ion energies and atomically clean surfaces. Here, we provide the first atomic-resolution imaging and electron energy loss spectroscopy (EELS) evidence of phosphorus atoms in the graphene lattice, implanted by low-energy ion irradiation. The measured P L 2,3-edge shows excellent agreement with an ab initio spectrum simulation, conclusively identifying the P in a buckled substitutional configuration. While advancing the use of EELS for single-atom spectroscopy, our results demonstrate the viability of phosphorus as a lattice dopant in sp 2-bonded carbon structures and provide its unmistakable fingerprint for further studies.

  10. Role of barrier layer on dielectric function of graphene double layer system at finite temperature

    NASA Astrophysics Data System (ADS)

    Patel, Digish K.; Ambavale, Sagar K.; Prajapati, Ketan; Sharma, A. C.

    2016-05-01

    We have theoretically investigated the static dielectric function of graphene double layer system (GDLS) at finite temperatures within the random phase approximation. GDLS has been suspended on a substrate and barrier layer of three different materials; h-BN, Al2O3 and HfO2 has been introduced between two graphene sheets of GDLS. We have reported dependence of the overall dielectric function of GDLS on interlayer distance and the effect of the dielectric environment at finite temperatures. Results show close relation between changing environment and behavior of dielectric constant of GDLS.

  11. Low-energy phase change memory with graphene confined layer

    NASA Astrophysics Data System (ADS)

    Zhu, Chengqiu; Ma, Jun; Ge, Xiaoming; Rao, Feng; Ding, Keyuan; Lv, Shilong; Wu, Liangcai; Song, Zhitang

    2016-06-01

    How to reduce the Reset operation energy is the key scientific and technological problem in the field of phase change memory (PCM). Here, we show in the Ge2Sb2Te5 based PCM cell, inserting an additional graphene monolayer in the Ge2Sb2Te5 layer can remarkably decrease both the Reset current and energy. Because of the small out-of-plane electrical and thermal conductivities of such monolayer graphene, the Set resistance and the heat dissipation towards top TiN electrode of the modified PCM cell are significantly increased and decreased, respectively. The mushroom-typed larger active phase transition volume thus can be confined inside the underlying thinner GST layer, resulting in the lower power consumption.

  12. Buckling instability of circular double-layered graphene sheets.

    PubMed

    Natsuki, Toshiaki; Shi, Jin-Xing; Ni, Qing-Qing

    2012-04-04

    In this paper, we study the buckling properties of circular double-layered graphene sheets (DLGSs), using plate theory. The two graphene layers are modeled as two individual sheets whose interactions are determined by the Lennard-Jones potential of the carbon-carbon bond. An analytical solution of coupled governing equations is proposed for predicting the buckling properties of circular DLGSs. Using the present theoretical approach, the influences of boundary conditions, plate sizes, and buckling-mode shapes on the buckling behaviors are investigated in detail. The buckling stability is significantly affected by the buckling-mode shapes. As a result of van der Waals interactions, the buckling stress of circular DLGSs is much larger for the anti-phase mode than for the in-phase mode.

  13. Graphene growth by transfer-free chemical vapour deposition on a cobalt layer

    NASA Astrophysics Data System (ADS)

    Macháč, Petr; Hejna, Ondřej; Slepička, Petr

    2017-01-01

    The contribution deals with the preparation of graphene films by a transfer-free chemical vapour deposition process utilizing a thin cobalt layer. This method allows growing graphene directly on a dielectric substrate. The process was carried out in a cold-wall reactor with methane as carbon precursor. We managed to prepare bilayer graphene. The best results were obtained for a structure with a cobalt layer with a thickness of 50 nm. The quality of prepared graphene films and of the number of graphene layers were estimated using Raman spectroscopy. with a minimal dots diameter of 180 nm and spacing of 1000 nm were successfully developed.

  14. Chemical etching of copper foils for single-layer graphene growth by chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Yoshihara, Naoki; Noda, Masaru

    2017-10-01

    Chemical etching on copper surface is essential as a pre-treatment for single-layer graphene growth by chemical vapor deposition (CVD). Here, we investigated the effect of chemical etching treatment on copper foils for single-layer graphene CVD growth. The chemical etching conditions, such as the type of chemical etchants and the treatment time, were found to strongly influence the graphene domain size. Moreover, a drastic change in the layer structure of graphene sheets, which was attributed to the surface morphology of the etched copper foil, was confirmed by graphene transmittance and Raman mapping measurements.

  15. Graphene-like single-layered covalent organic frameworks: synthesis strategies and application prospects.

    PubMed

    Liu, Xuan-He; Guan, Cui-Zhong; Wang, Dong; Wan, Li-Jun

    2014-10-29

    Two-dimensional (2D) nanomaterials, such as graphene and transition metal chalcogenides, show many interesting dimension-related materials properties. Inspired by the development of 2D inorganic nanomaterials, single-layered covalent organic frameworks (sCOFs), featuring atom-thick sheets and crystalline extended organic structures with covalently bonded building blocks, have attracted great attention in recent years. With their unique graphene-like topological structure and the merit of structural diversity, sCOFs promise to possess novel and designable properties. However, the synthesis of sCOFs with well-defined structures remains a great challenge. Herein, the recent development of the bottom-up synthesis methods of 2D sCOFs, such as thermodynamic equilibrium control methods, growth-kinetics control methods, and surface-assisted covalent polymerization methods, are reviewed. Finally, some of the critical properties and application prospects of these materials are outlined.

  16. Atom-by-atom observation of grain boundary migration in graphene.

    PubMed

    Kurasch, Simon; Kotakoski, Jani; Lehtinen, Ossi; Skákalová, Viera; Smet, Jurgen; Krill, Carl E; Krasheninnikov, Arkady V; Kaiser, Ute

    2012-06-13

    Grain boundary (GB) migration in polycrystalline solids is a materials science manifestation of survival of the fittest, with adjacent grains competing to add atoms to their outer surfaces at each other's expense. This process is thermodynamically favored when it lowers the total GB area in the sample, thereby reducing the excess free energy contributed by the boundaries. In this picture, a curved boundary is expected to migrate toward its center of curvature with a velocity proportional to the local radius of boundary curvature (R). Investigating the underlying mechanism of boundary migration in a 3D material, however, has been reserved for computer simulation or analytical theory, as capturing the dynamics of individual atoms in the core region of a GB is well beyond the spatial and temporal resolution limits of current characterization techniques. Here, we similarly overcome the conventional experimental limits by investigating a 2D material, polycrystalline graphene, in an aberration-corrected transmission electron microscope, exploiting the energy of the imaging electrons to stimulate individual bond rotations in the GB core region. The resulting morphological changes are followed in situ, atom-by-atom, revealing configurational fluctuations that take on a time-averaged preferential direction only in the presence of significant boundary curvature, as confirmed by Monte Carlo simulations. Remarkably, in the extreme case of a small graphene grain enclosed within a larger one, we follow its shrinkage to the point of complete disappearance.

  17. Layered quantum Hall insulators with ultracold atoms

    SciTech Connect

    Zamora, A.; Szirmai, G.; Lewenstein, M.

    2011-11-15

    We consider a generalization of the two-dimensional (2D) quantum Hall insulator to a noncompact, non-Abelian gauge group, the Heisenberg-Weyl group. We show that this kind of insulator is actually a layered three-dimensional (3D) insulator with nontrivial topology. We further show that nontrivial combinations of quantized transverse conductivities can be engineered with the help of a staggered potential. We investigate the robustness and topological nature of this conductivity and connect it to the surface modes of the system. We also propose a simple experimental realization with ultracold atoms in 3D confined to a 2D square lattice with the third dimension being mapped to a gauge coordinate.

  18. Nanoengineering Heterogeneous Catalysts by Atomic Layer Deposition.

    PubMed

    Singh, Joseph A; Yang, Nuoya; Bent, Stacey F

    2017-02-27

    A new generation of catalysts is needed to meet society's energy and resource requirements. Current catalyst synthesis does not fully achieve optimum control of composition, size, and structure. Atomic layer deposition (ALD) is an emerging technique that allows synthesizing of highly controlled catalysts in the forms of films, nanoparticles, and single sites. The addition of ALD coatings can also be used to introduce promoters and improve the stability of traditional catalysts. Evolving research shows promise for applying ALD to understand catalytically active sites and create next-generation catalysts using advanced 3D nanostructures. Expected final online publication date for the Annual Review of Chemical and Biomolecular Engineering Volume 8 is June 7, 2017. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

  19. Size-Selective Cu Nanocrystals Growth on Single and 2-3 Layers Graphene Films.

    PubMed

    Gao, Hui; Li, Xiaolong; Wang, Yunfei; Guo, Haijie; Wang, Yuhua

    2015-09-01

    Cu nanoparticles decorated CVD growth single layer and 2-3 layers graphene films have been synthesized by sputtering deposition and annealing process. The wrinkles were observed on single layer graphene due to high annealing temperature (700 degrees C) and rapid cooling process, which were proved by HRSEM and Raman spectra. Smaller mean diameter and narrower size distribution of Cu nanoparticles were observed on 2-3 layers graphene film than that on single layer graphene. The large particles grow at the expense of small particles, and the particle growth was governed by the Ostwald ripening process.

  20. Direct in situ observations of single Fe atom catalytic processes and anomalous diffusion at graphene edges.

    PubMed

    Zhao, Jiong; Deng, Qingming; Avdoshenko, Stanislav M; Fu, Lei; Eckert, Jürgen; Rümmeli, Mark H

    2014-11-04

    Single-atom catalysts are of great interest because of their high efficiency. In the case of chemically deposited sp(2) carbon, the implementation of a single transition metal atom for growth can provide crucial insight into the formation mechanisms of graphene and carbon nanotubes. This knowledge is particularly important if we are to overcome fabrication difficulties in these materials and fully take advantage of their distinct band structures and physical properties. In this work, we present atomically resolved transmission EM in situ investigations of single Fe atoms at graphene edges. Our in situ observations show individual iron atoms diffusing along an edge either removing or adding carbon atoms (viz., catalytic action). The experimental observations of the catalytic behavior of a single Fe atom are in excellent agreement with supporting theoretical studies. In addition, the kinetics of Fe atoms at graphene edges are shown to exhibit anomalous diffusion, which again, is in agreement with our theoretical investigations.

  1. Direct in situ observations of single Fe atom catalytic processes and anomalous diffusion at graphene edges

    PubMed Central

    Zhao, Jiong; Deng, Qingming; Avdoshenko, Stanislav M.; Fu, Lei; Eckert, Jürgen; Rümmeli, Mark H.

    2014-01-01

    Single-atom catalysts are of great interest because of their high efficiency. In the case of chemically deposited sp2 carbon, the implementation of a single transition metal atom for growth can provide crucial insight into the formation mechanisms of graphene and carbon nanotubes. This knowledge is particularly important if we are to overcome fabrication difficulties in these materials and fully take advantage of their distinct band structures and physical properties. In this work, we present atomically resolved transmission EM in situ investigations of single Fe atoms at graphene edges. Our in situ observations show individual iron atoms diffusing along an edge either removing or adding carbon atoms (viz., catalytic action). The experimental observations of the catalytic behavior of a single Fe atom are in excellent agreement with supporting theoretical studies. In addition, the kinetics of Fe atoms at graphene edges are shown to exhibit anomalous diffusion, which again, is in agreement with our theoretical investigations. PMID:25331874

  2. Chemical nature of boron and nitrogen dopant atoms in graphene strongly influences its electronic properties.

    PubMed

    Lazar, Petr; Zbořil, Radek; Pumera, Martin; Otyepka, Michal

    2014-07-21

    Boron and nitrogen doped graphenes are highly promising materials for electrochemical applications, such as energy storage, generation and sensing. The doped graphenes can be prepared by a broad variety of chemical approaches. The substitution of a carbon atom should induce n-type behavior in the case of nitrogen and p-type behavior in the case of boron-doped graphene; however, the real situation is more complex. The electrochemical experiments show that boron-doped graphene prepared by hydroboration reaction exhibits similar properties as the nitrogen doped graphene; according to theory, the electrochemical behavior of B and N doped graphenes should be opposite. Here we analyze the electronic structure of N/B-doped graphene (at ∼5% coverage) by theoretical calculations. We consider graphene doped by both substitution and addition reactions. The density of states (DOS) plots show that graphene doped by substitution of the carbon atom by N/B behaves as expected, i.e., as an n/p-doped material. N-doped graphene also has a lower value of the workfunction (3.10 eV) with respect to that of the pristine graphene (4.31 eV), whereas the workfunction of B-doped graphene is increased to the value of 5.57 eV. On the other hand, the workfunctions of graphene doped by addition of -NH2 (4.77 eV) and -BH2 (4.54 eV) groups are both slightly increased and therefore the chemical nature of the dopant is less distinguishable. This shows that mode of doping depends significantly on the synthesis method used, as it leads to different types of behaviour, and, in turn, different electronic and electrochemical properties of doped graphene, as observed in electrocatalytic experiments. This study has a tremendous impact on the design of doped graphene systems from the point of view of synthetic chemistry.

  3. Examination of humidity effects on measured thickness and interfacial phenomena of exfoliated graphene on silicon dioxide via amplitude modulation atomic force microscopy

    SciTech Connect

    Jinkins, K.; Farina, L.; Wu, Y.; Camacho, J.

    2015-12-14

    The properties of Few-Layer Graphene (FLG) change with the number of layers and Amplitude Modulation (AM) Atomic Force Microscopy (AFM) is commonly used to determine the thickness of FLG. However, AFM measurements have been shown to be sensitive to environmental conditions such as relative humidity (RH). In the present study, AM-AFM is used to measure the thickness and loss tangent of exfoliated graphene on silicon dioxide (SiO{sub 2}) as RH is increased from 10% to 80%. We show that the measured thickness of graphene is dependent on RH. The loss tangent values of the graphene and oxide regions are both affected by humidity, with generally higher loss tangent for graphene than SiO{sub 2}. As RH increases, we observe the loss tangent of both materials approaches the same value. We hypothesize that there is a layer of water trapped between the graphene and SiO{sub 2} substrate to explain this observation. Using this interpretation, the loss tangent images also indicate movement and change in this trapped water layer as RH increases, which impacts the measured thickness of graphene using AM-AFM.

  4. High resolution transmission electron microscope Imaging and first-principles simulations of atomic-scale features in graphene membrane

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Bhandari, Sagar; Yi, Wei; Bell, David; Westervelt, Robert; Kaxiras, Efthimios

    2012-02-01

    Ultra-thin membranes such as graphene[1] are of great importance for basic science and technology applications. Graphene sets the ultimate limit of thinness, demonstrating that a free-standing single atomic layer not only exists but can be extremely stable and strong [2--4]. However, both theory [5, 6] and experiments [3, 7] suggest that the existence of graphene relies on intrinsic ripples that suppress the long-wavelength thermal fluctuations which otherwise spontaneously destroy long range order in a two dimensional system. Here we show direct imaging of the atomic features in graphene including the ripples resolved using monochromatic aberration-corrected transmission electron microscopy (TEM). We compare the images observed in TEM with simulated images based on an accurate first-principles total potential. We show that these atomic scale features can be mapped through accurate first-principles simulations into high resolution TEM contrast. [1] Geim, A. K. & Novoselov, K. S. Nat. Mater. 6, 183-191, (2007). [2] Novoselov, K. S.et al. Science 306, 666-669, (2004). [3] Meyer, J. C. et al. Nature 446, 60-63, (2007). [4] Lee, C., Wei, X. D., Kysar, J. W. & Hone, J. Science 321, 385-388, (2008). [5] Nelson, D. R. & Peliti, L. J Phys-Paris 48, 1085-1092, (1987). [6] Fasolino, A., Los, J. H. & Katsnelson, M. I. Nat. Mater. 6, 858-861, (2007). [7] Meyer, J. C. et al. Solid State Commun. 143, 101-109, (2007).

  5. Optical properties of few layered graphene quantum dots

    NASA Astrophysics Data System (ADS)

    Pratap Choudhary, Raghvendra; Shukla, Shobha; Vaibhav, Kumar; Bhagwan Pawar, Pranav; Saxena, Sumit

    2015-09-01

    Quantum dots provide a unique opportunity to study the confinement effects of electronic wave function on the properties of materials. We have investigated the optical properties of graphene quantum dots synthesized using ultra-fast light-matter interactions followed by one step reduction process. Atomic-scale morphological information suggests the presence of both zigzag and armchair edges in these quantum dots. Optical characterizations were performed using absorption, photoluminescence, and infrared spectroscopy. A shift in the emission spectrum and disappearance of n → π* transition in the absorption spectrum on reduction of the ablated samples confirmed the formation of graphene quantum dots. First principles calculations are in good agreement with the experimentally reported infrared data.

  6. Nanolaminates with Novel Properties Fabricated Using Atomic Layer Deposition Techniques

    DTIC Science & Technology

    2006-07-01

    ALD can be deposited on the A120 3 ALD layer to form a conducting layer . Subsequently, an...additional A120 3 ALD layer can be deposited on the W ALD layer to form an additional insulating layer . This A120 3/W/ A120 3 layer on the carbon nanotube...NOTES 14. ABSTRACT This AFOSR grant worked on the development, understanding and applications of atomic layer deposition ( ALD ) for nanolaminates. ALD

  7. Ultrathin-layer chromatography nanostructures modified by atomic layer deposition.

    PubMed

    Jim, S R; Foroughi-Abari, A; Krause, K M; Li, P; Kupsta, M; Taschuk, M T; Cadien, K C; Brett, M J

    2013-07-19

    Stationary phase morphology and surface chemistry dictate the properties of ultrathin-layer chromatography (UTLC) media and interactions with analytes in sample mixtures. In this paper, we combined two powerful thin film deposition techniques to create composite chromatography nanomaterials. Glancing angle deposition (GLAD) produces high surface area columnar microstructures with aligned macropores well-suited for UTLC. Atomic layer deposition (ALD) enables precise fabrication of conformal, nanometer-scale coatings that can tune surfaces of these UTLC films. We coated ∼5μm thick GLAD SiO2 UTLC media with <10nm thick ALD metal oxides (Al2O3, ZrO2, and ZnO) to decouple surface chemistry from the underlying GLAD scaffold microstructure. The effects of ALD coatings on GLAD UTLC media were investigated using transmission electron microscopy (TEM), gas adsorption porosimetry, and lipophilic dye separations. The results collectively show that the most significant changes occur over the first few nanometers of ALD coating. They further demonstrate independent control of film microstructure and surface characteristics. ALD coatings can enhance complex GLAD microstructures to engineer new composite nanomaterials potentially useful in analytical chromatography.

  8. Atomically controlled substitutional boron-doping of graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Kawai, Shigeki; Saito, Shohei; Osumi, Shinichiro; Yamaguchi, Shigehiro; Foster, Adam S.; Spijker, Peter; Meyer, Ernst

    2015-08-01

    Boron is a unique element in terms of electron deficiency and Lewis acidity. Incorporation of boron atoms into an aromatic carbon framework offers a wide variety of functionality. However, the intrinsic instability of organoboron compounds against moisture and oxygen has delayed the development. Here, we present boron-doped graphene nanoribbons (B-GNRs) of widths of N=7, 14 and 21 by on-surface chemical reactions with an employed organoboron precursor. The location of the boron dopant is well defined in the centre of the B-GNR, corresponding to 4.8 atom%, as programmed. The chemical reactivity of B-GNRs is probed by the adsorption of nitric oxide (NO), which is most effectively trapped by the boron sites, demonstrating the Lewis acid character. Structural properties and the chemical nature of the NO-reacted B-GNR are determined by a combination of scanning tunnelling microscopy, high-resolution atomic force microscopy with a CO tip, and density functional and classical computations.

  9. Vapour phase growth and grain boundary structure of molybdenum disulphide atomic layers.

    PubMed

    Najmaei, Sina; Liu, Zheng; Zhou, Wu; Zou, Xiaolong; Shi, Gang; Lei, Sidong; Yakobson, Boris I; Idrobo, Juan-Carlos; Ajayan, Pulickel M; Lou, Jun

    2013-08-01

    Single-layered molybdenum disulphide with a direct bandgap is a promising two-dimensional material that goes beyond graphene for the next generation of nanoelectronics. Here, we report the controlled vapour phase synthesis of molybdenum disulphide atomic layers and elucidate a fundamental mechanism for the nucleation, growth, and grain boundary formation in its crystalline monolayers. Furthermore, a nucleation-controlled strategy is established to systematically promote the formation of large-area, single- and few-layered films. Using high-resolution electron microscopy imaging, the atomic structure and morphology of the grains and their boundaries in the polycrystalline molybdenum disulphide atomic layers are examined, and the primary mechanisms for grain boundary formation are evaluated. Grain boundaries consisting of 5- and 7- member rings are directly observed with atomic resolution, and their energy landscape is investigated via first-principles calculations. The uniformity in thickness, large grain sizes, and excellent electrical performance signify the high quality and scalable synthesis of the molybdenum disulphide atomic layers.

  10. Toward Nanoscale Material Applications: Colloidal Quantum Dot Memory And Multi-Layer Graphene Electronics And Optoelectronics

    NASA Astrophysics Data System (ADS)

    Olac-vaw, Roman

    In this dissertation, the analysis of a possible use of colloidal semiconductor quantum dots (QDs) in memory storage devices is presented. The charging and discharging behaviors of capped cadmium selenide (CdSe) QDs deposited on a sheet of graphite film layers in ambient conditions were analyzed. Individual QDs can be addressed (charged) with the synergistic action of light and the mechanical interaction of a probe of an atomic force microscope (AFM). The probe squeezes the coating layer of QDs helping the photoelectron to tunnel to either the conductive AFM probe or to the substrate. The charge can be induced on individual QDs by locating the QDs with AFM. The charges were stable in ambient conditions (survived up to 24 hours), and even recovered within a minute after their forced neutralization by airflow of negative ions. The analyzed QDs allow recording information at a density up to 1Tb/cm 2. A possibility to attain charging (writing) time down to nanoseconds while keeping discharging (storage) times for more than 100 years is also demonstrated. These results may also be of interest for QDs based sensors, memory, and solar cell applications. Multi-layer heteroepitaxial graphene was successfully formed on 3C-SiC grown on a Si substrate using single gas source molecular beam epitaxy (MBE). The observation of ambipolar behavior, one of the unique properties of graphene, verifies the successful growth of graphene layers. The epitaxial graphene is believed to be unintentionally p-type doped with the Fermi level offset around +0.11˜+0.12 V at the Dirac point. Backgate field-effect transistors using multilayer graphene channel were designed, fabricated and characterized for electronic and optoelectronic applications. Even though some gate leakage current was observed, the experimental results show the device worked as an n-type transistor as well as an infrared detector. The drain saturated current of the graphene channel transistor is on the order of mA/mm. The

  11. Synthesis of Graphene Layers from Metal-Carbon Melts: Nucleation and Growth Kinetics

    NASA Astrophysics Data System (ADS)

    Amini, Shaahin

    A new method for growth of large-area graphene, which can lead to a scalable low-cost high-throughput production technology, was demonstrated. The method is based on growing of graphene films on the surface of metal-carbon melts and involves dissolving carbon in a molten metal at a specified temperature and then allowing the dissolved carbon to nucleate and grow on top of the melt at a lower temperature. The synthesized graphene layers were subjected to detailed microscopic and Raman spectroscopic characterizations. The deconvolution of the Raman 2D band was used to accurately determine the number of atomic planes in the resulting graphene layers and access their quality. The results indicated that the technology can provide bulk graphite films, few-layer graphene as well as high-quality single layer graphene on metals. It was also shown that upon cooling of supersaturated metal-carbon melts; graphite would also grow inside the melt either with flake or sphere morphology, depending on the solidification rate and degree of supersaturation. At small solidification rates, graphite crystals are normally bounded by faceted low index basal and prismatic planes which grow by lateral movement of ledges produced by 2D-nucleation or dislocations. At higher growth rates, however, both interfaces become kinetically rough, and growth becomes limited by diffusion of carbon to the growing interface. The roughening transition from faceted to non-faceted was found to depend on the driving force and nature of growing plane. Due to high number of C-C dangling bonds in prismatic face, its roughening transition occurs at smaller driving forces. At intermediate rates, the prismatic interfaces become rough and grow faster while the basal plane is still faceted, leading to formation of flake graphite. At higher growth rates, both interfaces grow with a relatively similar rate leading to initiation of graphite sphere formation, which later grows by a multi-stage growth mechanism. An

  12. Substrate-Independent Growth of Atomically Precise Chiral Graphene Nanoribbons

    PubMed Central

    2016-01-01

    Contributing to the need for new graphene nanoribbon (GNR) structures that can be synthesized with atomic precision, we have designed a reactant that renders chiral (3,1)-GNRs after a multistep reaction including Ullmann coupling and cyclodehydrogenation. The nanoribbon synthesis has been successfully proven on different coinage metals, and the formation process, together with the fingerprints associated with each reaction step, has been studied by combining scanning tunneling microscopy, core-level spectroscopy, and density functional calculations. In addition to the GNR’s chiral edge structure, the substantial GNR lengths achieved and the low processing temperature required to complete the reaction grant this reactant extremely interesting properties for potential applications. PMID:27548516

  13. Placing single atoms in graphene with a scanning transmission electron microscope

    NASA Astrophysics Data System (ADS)

    Dyck, Ondrej; Kim, Songkil; Kalinin, Sergei V.; Jesse, Stephen

    2017-09-01

    We employ the sub-atomically focused beam of a scanning transmission electron microscope (STEM) to introduce and controllably manipulate individual dopant atoms in a 2D graphene lattice. The electron beam is used to create defects and subsequently sputter adsorbed source materials into the graphene lattice such that individual vacancy defects are controllably passivated by Si substitutional atoms. We further document that Si point defects may be directed through the lattice via e-beam control or modified (as yet, uncontrollably) to form new defects which can incorporate new atoms into the graphene lattice. These studies demonstrate the potential of STEM for atom-by-atom nanofabrication and fundamental studies of chemical reactions in 2D materials on the atomic level.

  14. Fabrication of bi-layer graphene and theoretical simulation for its possible application in thin film solar cell.

    PubMed

    Behura, Sanjay K; Mahala, Pramila; Nayak, Sasmita; Yang, Qiaoqin; Mukhopadhyay, Indrajit; Janil, Omkar

    2014-04-01

    High quality graphene film is fabricated using mechanical exfoliation of highly-oriented pyrolytic graphite. The graphene films on glass substrates are characterized using field-emission scanning electron microscopy, atomic force microscopy, Raman spectroscopy, UV-vis spectroscopy and Fourier transform infrared spectroscopy. A very high intensity ratio of 2D to G-band (to approximately 1.67) and narrow 2D-band full-width at half maximum (to approximately 40 cm(-1)) correspond to the bi-layer graphene formation. The bi-layer graphene/p-GaN/n-InGaN/n-GaN/GaN/sAl2O3 system is studied theoretically using TCAD Silvaco software, in which the properties of exfoliated bi-layer graphene are used as transparent and conductive film, and the device exhibits an efficiency of 15.24% compared to 13.63% for ITO/p-GaN/n-InGaN/n-GaN/GaN/Al2O3 system.

  15. Fabrication of graphene/polyaniline composite multilayer films by electrostatic layer-by-layer assembly

    NASA Astrophysics Data System (ADS)

    Cong, Jiaojiao; Chen, Yuze; Luo, Jing; Liu, Xiaoya

    2014-10-01

    A novel graphene/polyaniline composite multilayer film was fabricated by electrostatic interactions induced layer-by-layer self-assembly technique, using water dispersible and negatively charged chemically converted graphene (CCG) and positively charged polyaniline (PANI) as building blocks. CCG was achieved through partly reduced graphene oxide, which remained carboxyl group on its surface. The remaining carboxyl groups not only retain the dispersibility of CCG, but also allow the growth of the multilayer films via electrostatic interactions between graphene and PANI. The structure and morphology of the obtained CCG/PANI multilayer film are characterized by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, Ultraviolet-visible absorption spectrum (UV-vis), scanning electron microscopy (SEM), Raman spectroscopy and X-Ray Diffraction (XRD). The electrochemical properties of the resulting film are studied using cyclic voltammetry (CV), which showed that the resulting CCG/PANI multilayer film kept electroactivity in neutral solution and showed outstanding cyclic stability up to 100 cycles. Furthermore, the composite film exhibited good electrocatalytic ability toward ascorbic acid (AA) with a linear response from 1×10-4 to 1.2×10-3 M with the detect limit of 5×10-6 M. This study provides a facile and effective strategy to fabricate graphene/PANI nanocomposite film with good electrochemical property, which may find potential applications in electronic devices such as electrochemical sensor.

  16. Nucleation of graphene layers on magnetic oxides: Co3O4(111) and Cr2O3(0001) from theory and experiment

    DOE PAGES

    Beatty, John; Cheng, Tao; Cao, Yuan; ...

    2016-12-14

    We report directly grown strongly adherent graphene on Co3O4(111) by carbon molecular beam epitaxy (C MBE) at 850 K and density functional theory (DFT) findings that the first graphene layer is reconstructed to fit the Co3O4 surface, while subsequent layers retain normal graphene structure. This adherence to the Co3O4 structure results from partial bonding of half the carbons to top oxygens of the substrate. This structure is validated by X-ray photoelectron spectroscopy and low-energy electron diffraction studies, showing layer-by-layer graphene growth with ~0.08 electrons/carbon atom transferred to the oxide from the first graphene layer, in agreement with DFT. In contrast,more » for Cr2O3 DFT finds no strong bonding to the surface and C MBE on Cr2O3(0001) yields only graphite formation at 700 K, with C desorption above 800 K. As a result, strong graphene-to-oxide charge transfer aids nucleation of graphene on incommensurate oxide substrates and may have implications for spintronics.« less

  17. Atomically Precise Bottom-up Fabrication of Graphene Nanoribbons

    NASA Astrophysics Data System (ADS)

    Cai, Jinming

    2011-03-01

    Graphene nanoribbons (GNRs) -- narrow stripes of graphene -- are predicted to exhibit remarkable properties making them suitable for future electronic applications. Contrary to their two-dimensional (2D) parent material graphene, which exhibits semimetallic behavior, GNRs with widths smaller than 10 nm are predicted to be semiconductors due to quantum confinement and edge effects. Despite significant advances in GNR fabrication using chemical, sonochemical and lithographic methods as well as recent reports on the successful unzipping of carbon nanotubes into GNRs, the production of sub-10 nm GNRs with chemical precision remains a major challenge. In this talk, we will present a simple GNR fabrication method that allows for the production of atomically precise GNRs of different topologies and widths. Our bottom-up approach consists in the surface-assisted coupling of suitably designed molecular precursors into linear polyphenylenes and their subsequent cyclodehydrogenation, and results in GNRs whose topology, width and edge periphery are defined by the precursor monomers. By means of STM and Raman characterization, we demonstrate that this fabrication process allows for the atomically precise fabrication of complex GNR topologies. Furthermore, we have developed a reliable procedure to transfer GNRs fabricated on metal surfaces onto other substrates. It will for example be shown that millimeter sized sheets of crosslinked GNRs can be transferred onto silicon wafers, making them available for further processing, e.g. by lithography, prototype device fabrication and characterization. Coauthors: Pascal Ruffieux, Rached Jaafar, Marco Bieri, Thomas Braun, and Stephan Blankenburg, Empa, Swiss Federal Laboratories for Materials Science and Technology, 3602 Thun and 8600 Dübendorf, Switzerland; Matthias Muoth, ETH Zurich, Department of Mechanical and Process Engineering, 8092 Zurich, Switzerland; Ari P. Seitsonen, University of Zurich, Physical Chemistry Institute, 8057

  18. Electronic structure of few-layer epitaxial graphene on Ru(0001).

    PubMed

    Sutter, P; Hybertsen, M S; Sadowski, J T; Sutter, E

    2009-07-01

    The electronic structure of epitaxial monolayer, bilayer, and trilayer graphene on Ru(0001) was determined by selected-area angle-resolved photoelectron spectroscopy (micro-ARPES). Micro-ARPES band maps provide evidence for a strong electronic coupling between monolayer graphene and the adjacent metal, which causes the complete disruption of the graphene pi-bands near the Fermi energy. However, the perturbation by the metal decreases rapidly with the addition of further graphene sheets, and already an epitaxial graphene bilayer on Ru recovers the characteristic Dirac cones of isolated monolayer graphene. A graphene trilayer on Ru behaves like free-standing bilayer graphene. Density-functional theory based calculations show that this decoupling is due to the efficient passivation of metal d-states by the interfacial graphene layer.

  19. High yield production and purification of few layer graphene by Gum Arabic assisted physical sonication

    PubMed Central

    Chabot, Victor; Kim, Brian; Sloper, Brent; Tzoganakis, Costas; Yu, Aiping

    2013-01-01

    Exploiting the emulsification properties of low cost, environmentally safe Gum Arabic we demonstrate a high yield process to produce a few layer graphene with a low defect ratio, maintaining the pristine graphite structure. In addition, we demonstrate the need for and efficacy of an acid hydrolysis treatment to remove the polymer residues to produce 100% pure graphene. The scalable process gives yield of up to 5 wt% graphene based on 10 g starting graphite. The graphene product is compared with reduced graphene oxide produced through Hummer's method using UV-visible spectroscopy, SEM, TEM, and Raman spectroscopy. The two graphene materials show significant difference in these characterizations. Further, the film fabricated from this graphene exhibits 20 times higher electrical conductivity than that of the reduced graphene oxide. Sonication processing of graphite with environmentally approved biopolymers such as Gum Arabic opens up a scalable avenue for production of cheap graphene. PMID:23478744

  20. High stability of few layer graphene nanoplatelets in various solvents

    NASA Astrophysics Data System (ADS)

    Xu, X.; Zhou, J.; lubineau, G.

    2017-04-01

    Dispersion of few-layer graphene nanoplatelets (GNPs) in liquid media is a crucial step for various applications. Here, we highlight a simple, nondestructive method for preparing stable aqueous colloidal solutions with GNP powder quickly dispersed in 5 wt.% sodium-hypochlorite- (NaClO) and sodium-bromide- (NaBr) salted solvent by bath sonication. This method makes it possible to easily prepare a highly concentrated colloidal solution (1 mg·ml-1) of GNPs that can easily be re-dispersed in water (treated GNPs). The aqueous suspension we prepared remained stable for longer than a few weeks. We made similar tests with various solvents and dispersibility appeared to decrease with decreasing polarity. High-concentration suspensions using our facile dispersion method could be of particular interest to the large community using graphene for a diversity of applications.

  1. Extreme ultraviolet induced defects on few-layer graphene

    SciTech Connect

    Gao, A.; Zoethout, E.; Lee, C. J.; Rizo, P. J.; Scaccabarozzi, L.; Banine, V.; Bijkerk, F.

    2013-07-28

    We use Raman spectroscopy to show that exposing few-layer graphene to extreme ultraviolet (EUV, 13.5 nm) radiation, i.e., relatively low photon energy, results in an increasing density of defects. Furthermore, exposure to EUV radiation in a H{sub 2} background increases the graphene dosage sensitivity, due to reactions caused by the EUV induced hydrogen plasma. X-ray photoelectron spectroscopy results show that the sp{sup 2} bonded carbon fraction decreases while the sp{sup 3} bonded carbon and oxide fraction increases with exposure dose. Our experimental results confirm that even in reducing environment oxidation is still one of the main source of inducing defects.

  2. Graphene as an efficient interfacial layer for electrochromic devices.

    PubMed

    Lin, Feng; Bult, Justin B; Nanayakkara, Sanjini; Dillon, Anne C; Richards, Ryan M; Blackburn, Jeffrey L; Engtrakul, Chaiwat

    2015-06-03

    This study presents an interfacial modification strategy to improve the performance of electrochromic films that were fabricated by a magnetron sputtering technique. High-quality graphene sheets, synthesized by chemical vapor deposition, were used to modify fluorine-doped tin oxide substrates, followed by the deposition of high-performance nanocomposite nickel oxide electrochromic films. Electrochromic cycling results revealed that a near-complete monolayer graphene interfacial layer improves the electrochromic performance in terms of switching kinetics, activation period, coloration efficiency, and bleached-state transparency, while maintaining ∼100% charge reversibility. The present study offers an alternative route for improving the interfacial properties between electrochromic and transparent conducting oxide films without relying on conventional methods such as nanostructuring or thin film composition control.

  3. Graphene-Dielectric Integration for Graphene Transistors

    PubMed Central

    Liao, Lei; Duan, Xiangfeng

    2010-01-01

    Graphene is emerging as an interesting electronic material for future electronics due to its exceptionally high carrier mobility and single-atomic thickness. Graphene-dielectric integration is of critical importance for the development of graphene transistors and a new generation of graphene based electronics. Deposition of dielectric materials onto graphene is of significant challenge due to the intrinsic material incompatibility between pristine graphene and dielectric oxide materials. Here we review various strategies being researched for graphene-dielectric integration. Physical vapor deposition (PVD) can be used to directly deposit dielectric materials on graphene, but often introduces significant defects into the monolayer of carbon lattice; Atomic layer deposition (ALD) process has also been explored to to deposit high-κ dielectrics on graphene, which however requires functionalization of graphene surface with reactive groups, inevitably leading to a significant degradation in carrier mobilities; Using naturally oxidized thin aluminum or polymer as buffer layer for dielectric deposition can mitigate the damages to graphene lattice and improve the carrier mobility of the resulted top-gated transistors; Lastly, a physical assembly approach has recently been explored to integrate dielectric nanostructures with graphene without introducing any appreciable defects, and enabled top-gated graphene transistors with the highest carrier mobility reported to date. We will conclude with a brief summary and perspective on future opportunities. PMID:21278913

  4. Regulating infrared photoresponses in reduced graphene oxide phototransistors by defect and atomic structure control.

    PubMed

    Chang, Haixin; Sun, Zhenhua; Saito, Mitsuhiro; Yuan, Qinghong; Zhang, Han; Li, Jinhua; Wang, Zhongchang; Fujita, Takeshi; Ding, Feng; Zheng, Zijian; Yan, Feng; Wu, Hongkai; Chen, Mingwei; Ikuhara, Yuichi

    2013-07-23

    Defects play significant roles in properties of graphene and related device performances. Most studies of defects in graphene focus on their influences on electronic or luminescent optical properties, while controlling infrared optoelectronic performance of graphene by defect engineering remains a challenge. In the meantime, pristine graphene has very low infrared photoresponses of ~0.01 A/W due to fast photocarrier dynamics. Here we report regulating infrared photoresponses in reduced graphene oxide phototransistors by defect and atomic structure control for the first time. The infrared optoelectronic transport and photocurrent generation are significantly influenced and well controlled by oxygenous defects and structures in reduced graphene oxide. Moreover, remarkable infrared photoresponses are observed in photoconductor devices based on reduced graphene oxide with an external responsivity of ~0.7 A/W, at least over one order of magnitude higher than that from pristine graphene. External quantum efficiencies of infrared devices reach ultrahigh values of ~97%, which to our knowledge is one of the best efficiencies for infrared photoresponses from nonhybrid, pure graphene or graphene-based derivatives. The flexible infrared photoconductor devices demonstrate no photoresponse degradation even after 1000 bending tests. The results open up new routes to control optoelectronic behaviors of graphene for high-performance devices.

  5. Tailoring nanoporous materials by atomic layer deposition.

    PubMed

    Detavernier, Christophe; Dendooven, Jolien; Sree, Sreeprasanth Pulinthanathu; Ludwig, Karl F; Martens, Johan A

    2011-11-01

    Atomic layer deposition (ALD) is a cyclic process which relies on sequential self-terminating reactions between gas phase precursor molecules and a solid surface. The self-limiting nature of the chemical reactions ensures precise film thickness control and excellent step coverage, even on 3D structures with large aspect ratios. At present, ALD is mainly used in the microelectronics industry, e.g. for growing gate oxides. The excellent conformality that can be achieved with ALD also renders it a promising candidate for coating porous structures, e.g. for functionalization of large surface area substrates for catalysis, fuel cells, batteries, supercapacitors, filtration devices, sensors, membranes etc. This tutorial review focuses on the application of ALD for catalyst design. Examples are discussed where ALD of TiO(2) is used for tailoring the interior surface of nanoporous films with pore sizes of 4-6 nm, resulting in photocatalytic activity. In still narrower pores, the ability to deposit chemical elements can be exploited to generate catalytic sites. In zeolites, ALD of aluminium species enables the generation of acid catalytic activity.

  6. Atomic layer deposition of oxides for microelectronics

    NASA Astrophysics Data System (ADS)

    Wang, Hongtao

    Atomic layer deposition of high-kappa oxides has gained interest due to the wide applications in microelectronics. For gate dielectric application, amorphous oxides are preferred for the structural uniformity at nanometer scale. LaxM2-xO 3 (M = Sc, Lu or Y) films were deposited by ALD with metal amidinate precursors and H2O. Both LaScO3 and LaLuO3 films are amorphous and free of interfacial layers. Besides the structural benefits, both oxides have high dielectric constants (˜23 for LaScO 3 and 28 +/- 1 for LaLuO3), low leakage current density, and very few bulk traps, and are scalable to EOT < 1 nm. La1.23Y 0.77O3 films have polycrystalline structures with moderately high kappa ˜ 17 and low leakage current. The Poole-Frenkel mechanism is verified in the ternary oxide films by studying temperature dependence of the leakage current. For La1.1Al0.9O3/Si, the thermal stability was evaluated by studying the interface structure evolution under different annealing conditions. It concludes that an interfacial layer forms at the temperature above 600°C and the oxygen source resides in the film. For DRAM application, ALD deposition of rutile phase TiO2 is developed for its 70. The substrate, SnO2 and RuO2/Ru, works as both bottom electrodes and templates for rutile TiO2 nucleation. The growth rate is ˜ 0.3 A/cycle and is regardless of phases and crystallinity. The crystallinity strongly depends on the substrates. High quality ruthenium thin films were deposited by ALD with bis( N,N'-di-tert-butylacetamidinato) ruthenium(II) dicarbonyl and O2. The film crystallinity, density, and resistivity strongly depend on the O2 exposure. As EO ≈ Emax, the films have the lowest resistivity, highest density and best crystallinity (˜10 muO·cm, ˜12.3 g/cm3 and grain size comparable to film thickness). When EO > Emax, films peel off from the substrate due to the recombinative desorption of O2. The impurities are mainly O (0.27+/-0.03at.%) and C (0.30+/-0.05at.%). The C is mostly

  7. Density functional theory calculations on alkali and the alkaline Ca atoms adsorbed on graphene monolayers

    NASA Astrophysics Data System (ADS)

    Dimakis, Nicholas; Valdez, Danielle; Flor, Fernando Antonio; Salgado, Andres; Adjibi, Kolade; Vargas, Sarah; Saenz, Justin

    2017-08-01

    The adsorption of the alkali Li, K, and Na and the alkaline Ca on graphene is studied using periodic density functional theory (DFT) under various adatom coverages. The charge transfers between the adatom and the graphene sheet and the almost unchanged densities-of-states spectra in the energy region near and below the Fermi level support an ionic bond pattern between the adatom and the graphene atoms. However, the presence of small orbital overlap between the metal and the nearest graphene atom is indicative of small covalent bonding. Van der Waals interactions are examined through a semiempirical correction in the DFT functional and by comparing adatom-graphene calculations between 3% and 1.4% adatom coverages. Optimized adatom-graphene geometries identify the preferred adatom sites, whereas the adatom-graphene strength is correlated with the adsorption energy and the adatom distance from the graphene plane. Calculated electronic properties and structural parameters are obtained using hybrid functionals and a generalized gradient approximation functional paired with basis sets of various sizes. We found that due to long range electrostatic forces between the alkali/alkaline adatoms and the graphene monolayer, the adatom-graphene structural and electronic properties could be well-described by specific DFT functionals paired with high-quality adatom basis sets. For Li, K, and Na adsorbed on graphene, increased adatom surface coverage weakens the adatom-graphene interaction. However, this statement does not apply for Ca adsorbed on graphene. In this case, the Ca adsorption strength, which is stronger at higher coverages, is opposite to increases in the Ca-4s orbital population.

  8. Immobilizing individual atoms beneath a corrugated single layer of boron nitride.

    PubMed

    Cun, Huanyao; Iannuzzi, Marcella; Hemmi, Adrian; Roth, Silvan; Osterwalder, Jürg; Greber, Thomas

    2013-05-08

    Single atoms, and in particular the least reactive noble gases, are difficult to immobilize at room temperature. Ion implantation into a crystal lattice has this capability, but the randomness of the involved processes does not permit much control over their distribution within the solid. Here we demonstrate that the boron nitride nanomesh, a corrugated single layer of hexagonal boron nitride (h-BN) with a 3.2 nm honeycomb superstructure formed on a Rh(111) surface, can trap individual argon atoms at distinct subsurface sites at room temperature. A kinetic energy window for implantation is identified where the argon ions can penetrate the h-BN layer but not enter the Rh lattice. Scanning tunneling microscopy and photoemission data show the presence of argon atoms at two distinct sites within the nanomesh unit cell, confirmed also by density functional theory calculations. The single atom implants are stable in air. Annealing of implanted structures to 900 K induces the formation of highly regular holes of 2 nm diameter in the h-BN layer with adjacent flakes of the same size found on top of the layer. We explain this "can-opener" effect by the presence of a vacancy defect, generated during the penetration of the Ar ion through the h-BN lattice, and propagating along the rim of a nanomesh pore where the h-BN lattice is highly bent. The reported effects are also observed in graphene on ruthenium and for neon atoms.

  9. Atomic Layer Etching Mechanism of MoS2 for Nanodevices.

    PubMed

    Kim, Ki Seok; Kim, Ki Hyun; Nam, Yeonsig; Jeon, Jaeho; Yim, Soonmin; Singh, Eric; Lee, Jin Yong; Lee, Sung Joo; Jung, Yeon Sik; Yeom, Geun Young; Kim, Dong Woo

    2017-04-05

    Among the layered transition metal dichalcogenides (TMDs) that can form stable two-dimensional crystal structures, molybdenum disulfide (MoS2) has been intensively investigated because of its unique properties in various electronic and optoelectronic applications with different band gap energies from 1.29 to 1.9 eV as the number of layers decreases. To control the MoS2 layers, atomic layer etching (ALE) (which is a cyclic etching consisting of a radical-adsorption step such as Cl adsorption and a reacted-compound-desorption step via a low-energy Ar(+)-ion exposure) can be a highly effective technique to avoid inducing damage and contamination that occur during the reactive steps. Whereas graphene is composed of one-atom-thick layers, MoS2 is composed of three-atom-thick S(top)-Mo(mid)-S(bottom) layers; therefore, the ALE mechanisms of the two structures are significantly different. In this study, for MoS2 ALE, the Cl radical is used as the adsorption species and a low-energy Ar(+) ion is used as the desorption species. A MoS2 ALE mechanism (by which the S(top), Mo(mid), and S(bottom) atoms are sequentially removed from the MoS2 crystal structure due to the trapped Cl atoms between the S(top) layer and the Mo(mid) layer) is reported according to the results of an experiment and a simulation. In addition, the ALE technique shows that a monolayer MoS2 field effect transistor (FET) fabricated after one cycle of ALE is undamaged and exhibits electrical characteristics similar to those of a pristine monolayer MoS2 FET. This technique is also applicable to all layered TMD materials, such as tungsten disulfide (WS2), molybdenum diselenide (MoSe2), and tungsten diselenide (WSe2).

  10. Quantum dynamics of hydrogen atoms on graphene. II. Sticking

    NASA Astrophysics Data System (ADS)

    Bonfanti, Matteo; Jackson, Bret; Hughes, Keith H.; Burghardt, Irene; Martinazzo, Rocco

    2015-09-01

    Following our recent system-bath modeling of the interaction between a hydrogen atom and a graphene surface [Bonfanti et al., J. Chem. Phys. 143, 124703 (2015)], we present the results of converged quantum scattering calculations on the activated sticking dynamics. The focus of this study is the collinear scattering on a surface at zero temperature, which is treated with high-dimensional wavepacket propagations with the multi-configuration time-dependent Hartree method. At low collision energies, barrier-crossing dominates the sticking and any projectile that overcomes the barrier gets trapped in the chemisorption well. However, at high collision energies, energy transfer to the surface is a limiting factor, and fast H atoms hardly dissipate their excess energy and stick on the surface. As a consequence, the sticking coefficient is maximum (˜0.65) at an energy which is about one and half larger than the barrier height. Comparison of the results with classical and quasi-classical calculations shows that quantum fluctuations of the lattice play a primary role in the dynamics. A simple impulsive model describing the collision of a classical projectile with a quantum surface is developed which reproduces the quantum results remarkably well for all but the lowest energies, thereby capturing the essential physics of the activated sticking dynamics investigated.

  11. Quantum dynamics of hydrogen atoms on graphene. II. Sticking

    SciTech Connect

    Bonfanti, Matteo; Jackson, Bret; Hughes, Keith H.; Burghardt, Irene

    2015-09-28

    Following our recent system-bath modeling of the interaction between a hydrogen atom and a graphene surface [Bonfanti et al., J. Chem. Phys. 143, 124703 (2015)], we present the results of converged quantum scattering calculations on the activated sticking dynamics. The focus of this study is the collinear scattering on a surface at zero temperature, which is treated with high-dimensional wavepacket propagations with the multi-configuration time-dependent Hartree method. At low collision energies, barrier-crossing dominates the sticking and any projectile that overcomes the barrier gets trapped in the chemisorption well. However, at high collision energies, energy transfer to the surface is a limiting factor, and fast H atoms hardly dissipate their excess energy and stick on the surface. As a consequence, the sticking coefficient is maximum (∼0.65) at an energy which is about one and half larger than the barrier height. Comparison of the results with classical and quasi-classical calculations shows that quantum fluctuations of the lattice play a primary role in the dynamics. A simple impulsive model describing the collision of a classical projectile with a quantum surface is developed which reproduces the quantum results remarkably well for all but the lowest energies, thereby capturing the essential physics of the activated sticking dynamics investigated.

  12. Quantum dynamics of hydrogen atoms on graphene. II. Sticking.

    PubMed

    Bonfanti, Matteo; Jackson, Bret; Hughes, Keith H; Burghardt, Irene; Martinazzo, Rocco

    2015-09-28

    Following our recent system-bath modeling of the interaction between a hydrogen atom and a graphene surface [Bonfanti et al., J. Chem. Phys. 143, 124703 (2015)], we present the results of converged quantum scattering calculations on the activated sticking dynamics. The focus of this study is the collinear scattering on a surface at zero temperature, which is treated with high-dimensional wavepacket propagations with the multi-configuration time-dependent Hartree method. At low collision energies, barrier-crossing dominates the sticking and any projectile that overcomes the barrier gets trapped in the chemisorption well. However, at high collision energies, energy transfer to the surface is a limiting factor, and fast H atoms hardly dissipate their excess energy and stick on the surface. As a consequence, the sticking coefficient is maximum (∼0.65) at an energy which is about one and half larger than the barrier height. Comparison of the results with classical and quasi-classical calculations shows that quantum fluctuations of the lattice play a primary role in the dynamics. A simple impulsive model describing the collision of a classical projectile with a quantum surface is developed which reproduces the quantum results remarkably well for all but the lowest energies, thereby capturing the essential physics of the activated sticking dynamics investigated.

  13. The effect of h-BN buffer layers in bilayer graphene on Co (111)

    NASA Astrophysics Data System (ADS)

    Li, Can; Liu, Yan; Zhang, Bin; Wang, Tao; Guo, Qing; Sheng, Kuang; Yin, You

    2015-05-01

    Understanding of the interface of Co/graphene is essential for applications of graphene-based devices, as well as in the process of graphene synthesis. In this paper, the Co/graphene interface, including five structures of bilayer graphene (BLG) on Co (111) surface with bilayer or monolayer BN buffer sheets, is investigated by using density functional theory calculations. The corresponding atomic and electronic structures and Mulliken charge populations are also analyzed. The bilayer BN sheets are found to be the thinnest insulator for the backside Co metal gate, which shields BLG from Co substrate pining, decreases the charges influenced by the substrate, and improves BLG transport mobility.

  14. Knudsen effusion through polymer-coated three-layer porous graphene membranes.

    PubMed

    Boutilier, Michael S H; Hadjiconstantinou, Nicolas G; Karnik, Rohit

    2017-05-05

    Graphene membranes have the potential to exceed the permeance and selectivity limits of conventional gas separation membranes. Realizing this potential in practical systems relies on overcoming numerous scalability challenges, such as isolating or sealing permeable defects in macroscopic areas of graphene that can compromise performance and developing methods to create high densities of selective pores over large areas. This study focuses on a centimeter-scale membrane design, where leakage is reduced by substrate selection, permeable polymer film coating, and stacking of three independent layers of graphene, while (selective) pores are created by high density ion bombardment. The three-layer graphene provides high resistance to gas flow, which decreases with ion bombardment and results in selectivity consistent with Knudsen effusion. The results suggest that the permeable pores created in three layer graphene were larger than those required for molecular sieving and that designs based on single layer graphene may lend themselves more easily to molecular sieving of gases.

  15. Knudsen effusion through polymer-coated three-layer porous graphene membranes

    NASA Astrophysics Data System (ADS)

    Boutilier, Michael S. H.; Hadjiconstantinou, Nicolas G.; Karnik, Rohit

    2017-05-01

    Graphene membranes have the potential to exceed the permeance and selectivity limits of conventional gas separation membranes. Realizing this potential in practical systems relies on overcoming numerous scalability challenges, such as isolating or sealing permeable defects in macroscopic areas of graphene that can compromise performance and developing methods to create high densities of selective pores over large areas. This study focuses on a centimeter-scale membrane design, where leakage is reduced by substrate selection, permeable polymer film coating, and stacking of three independent layers of graphene, while (selective) pores are created by high density ion bombardment. The three-layer graphene provides high resistance to gas flow, which decreases with ion bombardment and results in selectivity consistent with Knudsen effusion. The results suggest that the permeable pores created in three layer graphene were larger than those required for molecular sieving and that designs based on single layer graphene may lend themselves more easily to molecular sieving of gases.

  16. Benzocyclobutene (BCB) Polymer as Amphibious Buffer Layer for Graphene Field-Effect Transistor.

    PubMed

    Wu, Yun; Zou, Jianjun; Huo, Shuai; Lu, Haiyan; Kong, Yuecan; Chen, Tangshen; Wu, Wei; Xu, Jingxia

    2015-08-01

    Owing to the scattering and trapping effects, the interfaces of dielectric/graphene or substrate/graphene can tailor the performance of field-effect transistor (FET). In this letter, the polymer of benzocyclobutene (BCB) was used as an amphibious buffer layer and located at between the layers of substrate and graphene and between the layers of dielectric and graphene. Interestingly, with the help of nonpolar and hydrophobic BCB buffer layer, the large-scale top-gated, chemical vapor deposited (CVD) graphene transistors was prepared on Si/SiO2 substrate, its cutoff frequency (fT) and the maximum cutoff frequency (fmax) of the graphene field-effect transistor (GFET) can be reached at 12 GHz and 11 GHz, respectively.

  17. Atomic layer deposition of metal sulfide materials.

    PubMed

    Dasgupta, Neil P; Meng, Xiangbo; Elam, Jeffrey W; Martinson, Alex B F

    2015-02-17

    CONSPECTUS: The field of nanoscience is delivering increasingly intricate yet elegant geometric structures incorporating an ever-expanding palette of materials. Atomic layer deposition (ALD) is a powerful driver of this field, providing exceptionally conformal coatings spanning the periodic table and atomic-scale precision independent of substrate geometry. This versatility is intrinsic to ALD and results from sequential and self-limiting surface reactions. This characteristic facilitates digital synthesis, in which the film grows linearly with the number of reaction cycles. While the majority of ALD processes identified to date produce metal oxides, novel applications in areas such as energy storage, catalysis, and nanophotonics are motivating interest in sulfide materials. Recent progress in ALD of sulfides has expanded the diversity of accessible materials as well as a more complete understanding of the unique chalcogenide surface chemistry. ALD of sulfide materials typically uses metalorganic precursors and hydrogen sulfide (H2S). As in oxide ALD, the precursor chemistry is critical to controlling both the film growth and properties including roughness, crystallinity, and impurity levels. By modification of the precursor sequence, multicomponent sulfides have been deposited, although challenges remain because of the higher propensity for cation exchange reactions, greater diffusion rates, and unintentional annealing of this more labile class of materials. A deeper understanding of these surface chemical reactions has been achieved through a combination of in situ studies and quantum-chemical calculations. As this understanding matures, so does our ability to deterministically tailor film properties to new applications and more sophisticated devices. This Account highlights the attributes of ALD chemistry that are unique to metal sulfides and surveys recent applications of these materials in photovoltaics, energy storage, and photonics. Within each application

  18. Atomic layer deposition of metal sulfide materials

    DOE PAGES

    Dasgupta, Neil P.; Meng, Xiangbo; Elam, Jeffrey W.; ...

    2015-01-12

    The field of nanoscience is delivering increasingly intricate yet elegant geometric structures incorporating an ever-expanding palette of materials. Atomic layer deposition (ALD) is a powerful driver of this field, providing exceptionally conformal coatings spanning the periodic table and atomic-scale precision independent of substrate geometry. This versatility is intrinsic to ALD and results from sequential and self-limiting surface reactions. This characteristic facilitates digital synthesis, in which the film grows linearly with the number of reaction cycles. While the majority of ALD processes identified to date produce metal oxides, novel applications in areas such as energy storage, catalysis, and nanophotonics are motivatingmore » interest in sulfide materials. Recent progress in ALD of sulfides has expanded the diversity of accessible materials as well as a more complete understanding of the unique chalcogenide surface chemistry. ALD of sulfide materials typically uses metalorganic precursors and hydrogen sulfide (H2S). As in oxide ALD, the precursor chemistry is critical to controlling both the film growth and properties including roughness, crystallinity, and impurity levels. By modification of the precursor sequence, multicomponent sulfides have been deposited, although challenges remain because of the higher propensity for cation exchange reactions, greater diffusion rates, and unintentional annealing of this more labile class of materials. A deeper understanding of these surface chemical reactions has been achieved through a combination of in situ studies and quantum-chemical calculations. As this understanding matures, so does our ability to deterministically tailor film properties to new applications and more sophisticated devices. This Account highlights the attributes of ALD chemistry that are unique to metal sulfides and surveys recent applications of these materials in photovoltaics, energy storage, and photonics. Within each application space

  19. Modified morphology of graphene sheets by Argon-atom bombardment: molecular dynamics simulations.

    PubMed

    Wei, Xiao-Lin; Zhang, Kai-Wang; Wang, Ru-Zhi; Liu, Wen-Liang; Zhong, Jian-Xin

    2011-12-01

    By a molecular dynamics method, we simulated the process of Argon-atom bombardment on a graphene sheet with 2720 carbon atoms. The results show that, the damage of the bombardment on the graphene sheet depends not only on the incident energy but also on the particle flux density of Argon atoms. To compare and analyze the effect of the incident energy and the particle flux density in the Argon-atom bombardment, we defined the impact factor on graphene sheet by calculating the broken-hole area. The results indicate that, there is an exponential accumulated-damage for the impact of both the incident energy and the particle flux density and there is a critical incident energy ranging from 20-30 eV/atom in Argon-atom bombardment. Different configurations, such as sieve-like and circle-like graphene can be formed by controlling of different particle flux density as the incident energy is more than the critical value. Our results supply a feasible method on fabrication of porous graphene-based materials for gas-storages and molecular sieves, and it also helps to understand the damage mechanism of graphene-based electronic devices under high particle radiation.

  20. Alloyed 2D Metal-Semiconductor Atomic Layer Junctions.

    PubMed

    Kim, Ah Ra; Kim, Yonghun; Nam, Jaewook; Chung, Hee-Suk; Kim, Dong Jae; Kwon, Jung-Dae; Park, Sang Won; Park, Jucheol; Choi, Sun Young; Lee, Byoung Hun; Park, Ji Hyeon; Lee, Kyu Hwan; Kim, Dong-Ho; Choi, Sung Mook; Ajayan, Pulickel M; Hahm, Myung Gwan; Cho, Byungjin

    2016-03-09

    Heterostructures of compositionally and electronically variant two-dimensional (2D) atomic layers are viable building blocks for ultrathin optoelectronic devices. We show that the composition of interfacial transition region between semiconducting WSe2 atomic layer channels and metallic NbSe2 contact layers can be engineered through interfacial doping with Nb atoms. WxNb1-xSe2 interfacial regions considerably lower the potential barrier height of the junction, significantly improving the performance of the corresponding WSe2-based field-effect transistor devices. The creation of such alloyed 2D junctions between dissimilar atomic layer domains could be the most important factor in controlling the electronic properties of 2D junctions and the design and fabrication of 2D atomic layer devices.

  1. Molecular beam epitaxy growth of SrO buffer layers on graphite and graphene for the integration of complex oxides

    DOE PAGES

    Ahmed, Adam S.; Wen, Hua; Ohta, Taisuke; ...

    2016-04-27

    Here, we report the successful growth of high-quality SrO films on highly-ordered pyrolytic graphite (HOPG) and single-layer graphene by molecular beam epitaxy. The SrO layers have (001) orientation as confirmed by X-ray diffraction (XRD) while atomic force microscopy measurements show continuous pinhole-free films having rms surface roughness of <1.5 Å. Moreover, transport measurements of exfoliated graphene, after SrO deposition, show a strong dependence between the Dirac point and Sr oxidation. As a result, the SrO is leveraged as a buffer layer for more complex oxide integration via the demonstration of (001) oriented SrTiO3 grown atop a SrO/HOPG stack.

  2. Molecular beam epitaxy growth of SrO buffer layers on graphite and graphene for the integration of complex oxides

    SciTech Connect

    Ahmed, Adam S.; Wen, Hua; Ohta, Taisuke; Pinchuk, Igor V.; Zhu, Tiancong; Beechem, Thomas; Kawakami, Roland K.

    2016-04-27

    Here, we report the successful growth of high-quality SrO films on highly-ordered pyrolytic graphite (HOPG) and single-layer graphene by molecular beam epitaxy. The SrO layers have (001) orientation as confirmed by X-ray diffraction (XRD) while atomic force microscopy measurements show continuous pinhole-free films having rms surface roughness of <1.5 Å. Moreover, transport measurements of exfoliated graphene, after SrO deposition, show a strong dependence between the Dirac point and Sr oxidation. As a result, the SrO is leveraged as a buffer layer for more complex oxide integration via the demonstration of (001) oriented SrTiO3 grown atop a SrO/HOPG stack.

  3. Molecular beam epitaxy growth of SrO buffer layers on graphite and graphene for the integration of complex oxides

    NASA Astrophysics Data System (ADS)

    Ahmed, Adam S.; Wen, Hua; Ohta, Taisuke; Pinchuk, Igor V.; Zhu, Tiancong; Beechem, Thomas; Kawakami, Roland K.

    2016-08-01

    We report the successful growth of high-quality SrO films on highly-ordered pyrolytic graphite (HOPG) and single-layer graphene by molecular beam epitaxy. The SrO layers have (001) orientation as confirmed by X-ray diffraction (XRD) while atomic force microscopy measurements show continuous pinhole-free films having rms surface roughness of <1.5 Å. Transport measurements of exfoliated graphene after SrO deposition show a strong dependence between the Dirac point and Sr oxidation. Subsequently, the SrO is leveraged as a buffer layer for more complex oxide integration via the demonstration of (001) oriented SrTiO3 grown atop a SrO/HOPG stack.

  4. Monolayer and/or few-layer graphene on metal or metal-coated substrates

    DOEpatents

    Sutter, Peter Werner; Sutter, Eli Anguelova

    2015-04-14

    Disclosed is monolayer and/or few-layer graphene on metal or metal-coated substrates. Embodiments include graphene mirrors. In an example, a mirror includes a substrate that has a surface exhibiting a curvature operable to focus an incident beam onto a focal plane. A graphene layer conformally adheres to the substrate, and is operable to protect the substrate surface from degradation due to the incident beam and an ambient environment.

  5. Study of nanotribological properties of multilayer graphene by calibrated atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Peng, Yitian; Wang, Zhuoqiong; Li, Cong

    2014-08-01

    The nanotribological properties of multilayer graphene oxide (MGO), multilayer reduced graphene oxide (MRGO), and mechanically exfoliated multilayer graphene (MEMG) deposited on SiO2 substrate were comparatively investigated via calibrated atomic force microscopy in ambient conditions. Friction as a function of the applied normal load and sliding velocity was studied. Results show that all three types of multilayer graphene films exhibit good adhesion and friction reduction properties. MEMG exhibits the lowest friction and adhesive force because of its perfect planar lattice. A logarithmic increase in friction was observed at low sliding velocities for all measured graphene films. Friction decreases on MGO and bare SiO2 substrate, whereas it remains approximately constant on MEMG and MRGO, when the sliding velocity exceeds their critical velocities. The possible mechanisms for the experimental results were discussed. Our studies provide a good opportunity to use different types of multilayer graphene films for promising lubricant applications in nanodevices.

  6. A Direct Transfer of Layer-Area Graphene

    DTIC Science & Technology

    2010-01-01

    A direct transfer of layer-area graphene William Regan,1,2 Nasim Alem,1,2,3 Benjamín Alemán,1,2,3 Baisong Geng,1,4 Çağlar Girit,1,2 Lorenzo Maserati... Meyer , Ç. Ö. Girit, M. F. Crommie, and A. Zettl, Appl. Phys. Lett. 92, 123110 2008. 10J. C. Meyer , Ç. Ö. Girit, M. F. Crommie, and A. Zettl, Nature...London 454, 319 2008. 11M. D. Fischbein and M. Drndić, Appl. Phys. Lett. 93, 113107 2008. 12J. C. Meyer , A. K. Geim, M. I. Katsnelson, K. S

  7. Long Spin Diffusion Length in Few-Layer Graphene Flakes

    NASA Astrophysics Data System (ADS)

    Yan, W.; Phillips, L. C.; Barbone, M.; Hämäläinen, S. J.; Lombardo, A.; Ghidini, M.; Moya, X.; Maccherozzi, F.; van Dijken, S.; Dhesi, S. S.; Ferrari, A. C.; Mathur, N. D.

    2016-09-01

    We report a spin valve with a few-layer graphene flake bridging highly spin-polarized La0.67Sr0.33MnO3 electrodes, whose surfaces are kept clean during lithographic definition. Sharp magnetic switching is verified using photoemission electron microscopy with x-ray magnetic circular dichroism contrast. A naturally occurring high interfacial resistance ˜12 M Ω facilitates spin injection, and a large resistive switching (0.8 M Ω at 10 K) implies a 70 - 130 μ m spin diffusion length that exceeds previous values obtained with sharp-switching electrodes.

  8. Surface-plasmons lasing in double-graphene-layer structures

    SciTech Connect

    Dubinov, A. A.; Aleshkin, V. Ya.; Ryzhii, V.; Shur, M. S.; Otsuji, T.

    2014-01-28

    We consider the concept of injection terahertz lasers based on double-graphene-layer (double-GL) structures with metal surface-plasmon waveguide and study the conditions of their operation. The laser under consideration exploits the resonant radiative transitions between GLs. This enables the double-GL laser room temperature operation and the possibility of voltage tuning of the emission spectrum. We compare the characteristics of the double-GL lasers with the metal surface-plasmon waveguides with those of such laser with the metal-metal waveguides.

  9. Synergistic effect of temperature and point defect on the mechanical properties of single layer and bi-layer graphene

    NASA Astrophysics Data System (ADS)

    Debroy, Sanghamitra; Pavan Kumar, V.; Vijaya Sekhar, K.; Acharyya, Swati Ghosh; Acharyya, Amit

    2017-10-01

    The present study reports a comprehensive molecular dynamics simulation of the effect of a) temperature (300-1073 K at intervals of every 100 K) and b) point defect on the mechanical behaviour of single (armchair and zigzag direction) and bilayer layer graphene (AA and AB stacking). Adaptive intermolecular reactive bond order (AIREBO) potential function was used to describe the many-body short-range interatomic interactions for the single layer graphene sheet. Moreover, Lennard Jones model was considered for bilayer graphene to incorporate the van der Waals interactions among the interlayers of graphene. The effect of temperature on the strain energy of single layer and bilayer graphene was studied in order to understand the difference in mechanical behaviour of the two systems. The strength of the pristine single layer graphene was found to be higher as compared to bilayer AA stacked graphene at all temperatures. It was observed at 1073 K and in the presence of vacancy defect the strength for single layer armchair sheet falls by 30% and for bilayer armchair sheet by 33% as compared to the pristine sheets at 300 K. The AB stacked graphene sheet was found to have a two-step rupture process. The strength of pristine AB sheet was found to decrease by 22% on increase of temperature from 300 K to 1073 K.

  10. Large scale atomistic simulation of single-layer graphene growth on Ni(111) surface: molecular dynamics simulation based on a new generation of carbon-metal potential

    NASA Astrophysics Data System (ADS)

    Xu, Ziwei; Yan, Tianying; Liu, Guiwu; Qiao, Guanjun; Ding, Feng

    2015-12-01

    To explore the mechanism of graphene chemical vapor deposition (CVD) growth on a catalyst surface, a molecular dynamics (MD) simulation of carbon atom self-assembly on a Ni(111) surface based on a well-designed empirical reactive bond order potential was performed. We simulated single layer graphene with recorded size (up to 300 atoms per super-cell) and reasonably good quality by MD trajectories up to 15 ns. Detailed processes of graphene CVD growth, such as carbon atom dissolution and precipitation, formation of carbon chains of various lengths, polygons and small graphene domains were observed during the initial process of the MD simulation. The atomistic processes of typical defect healing, such as the transformation from a pentagon into a hexagon and from a pentagon-heptagon pair (5|7) to two adjacent hexagons (6|6), were revealed as well. The study also showed that higher temperature and longer annealing time are essential to form high quality graphene layers, which is in agreement with experimental reports and previous theoretical results.To explore the mechanism of graphene chemical vapor deposition (CVD) growth on a catalyst surface, a molecular dynamics (MD) simulation of carbon atom self-assembly on a Ni(111) surface based on a well-designed empirical reactive bond order potential was performed. We simulated single layer graphene with recorded size (up to 300 atoms per super-cell) and reasonably good quality by MD trajectories up to 15 ns. Detailed processes of graphene CVD growth, such as carbon atom dissolution and precipitation, formation of carbon chains of various lengths, polygons and small graphene domains were observed during the initial process of the MD simulation. The atomistic processes of typical defect healing, such as the transformation from a pentagon into a hexagon and from a pentagon-heptagon pair (5|7) to two adjacent hexagons (6|6), were revealed as well. The study also showed that higher temperature and longer annealing time are

  11. Fabrication of hybrid graphene oxide/polyelectrolyte capsules by means of layer-by-layer assembly on erythrocyte cell templates.

    PubMed

    Irigoyen, Joseba; Politakos, Nikolaos; Diamanti, Eleftheria; Rojas, Elena; Marradi, Marco; Ledezma, Raquel; Arizmendi, Layza; Rodríguez, J Alberto; Ziolo, Ronald F; Moya, Sergio E

    2015-01-01

    A novel and facile method was developed to produce hybrid graphene oxide (GO)-polyelectrolyte (PE) capsules using erythrocyte cells as templates. The capsules are easily produced through the layer-by-layer technique using alternating polyelectrolyte layers and GO sheets. The amount of GO and therefore its coverage in the resulting capsules can be tuned by adjusting the concentration of the GO dispersion during the assembly. The capsules retain the approximate shape and size of the erythrocyte template after the latter is totally removed by oxidation with NaOCl in water. The PE/GO capsules maintain their integrity and can be placed or located on other surfaces such as in a device. When the capsules are dried in air, they collapse to form a film that is approximately twice the thickness of the capsule membrane. AFM images in the present study suggest a film thickness of approx. 30 nm for the capsules in the collapsed state implying a thickness of approx. 15 nm for the layers in the collapsed capsule membrane. The polyelectrolytes used in the present study were polyallylamine hydrochloride (PAH) and polystyrenesulfonate sodium salt (PSS). Capsules where characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light scattering (DLS) and Raman microscopy, the constituent layers by zeta potential and GO by TEM, XRD, and Raman and FTIR spectroscopies.

  12. Fabrication of hybrid graphene oxide/polyelectrolyte capsules by means of layer-by-layer assembly on erythrocyte cell templates

    PubMed Central

    Irigoyen, Joseba; Politakos, Nikolaos; Diamanti, Eleftheria; Rojas, Elena; Marradi, Marco; Ledezma, Raquel; Arizmendi, Layza; Rodríguez, J Alberto; Ziolo, Ronald F

    2015-01-01

    Summary A novel and facile method was developed to produce hybrid graphene oxide (GO)–polyelectrolyte (PE) capsules using erythrocyte cells as templates. The capsules are easily produced through the layer-by-layer technique using alternating polyelectrolyte layers and GO sheets. The amount of GO and therefore its coverage in the resulting capsules can be tuned by adjusting the concentration of the GO dispersion during the assembly. The capsules retain the approximate shape and size of the erythrocyte template after the latter is totally removed by oxidation with NaOCl in water. The PE/GO capsules maintain their integrity and can be placed or located on other surfaces such as in a device. When the capsules are dried in air, they collapse to form a film that is approximately twice the thickness of the capsule membrane. AFM images in the present study suggest a film thickness of approx. 30 nm for the capsules in the collapsed state implying a thickness of approx. 15 nm for the layers in the collapsed capsule membrane. The polyelectrolytes used in the present study were polyallylamine hydrochloride (PAH) and polystyrenesulfonate sodium salt (PSS). Capsules where characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light scattering (DLS) and Raman microscopy, the constituent layers by zeta potential and GO by TEM, XRD, and Raman and FTIR spectroscopies. PMID:26734521

  13. Enhanced memory effect with embedded graphene nanoplatelets in ZnO charge trapping layer

    SciTech Connect

    El-Atab, Nazek; Nayfeh, Ammar; Cimen, Furkan; Alkis, Sabri; Okyay, Ali K.

    2014-07-21

    A charge trapping memory with graphene nanoplatelets embedded in atomic layer deposited ZnO (GNIZ) is demonstrated. The memory shows a large threshold voltage V{sub t} shift (4 V) at low operating voltage (6/−6 V), good retention (>10 yr), and good endurance characteristic (>10{sup 4} cycles). This memory performance is compared to control devices with graphene nanoplatelets (or ZnO) and a thicker tunnel oxide. These structures showed a reduced V{sub t} shift and retention characteristic. The GNIZ structure allows for scaling down the tunnel oxide thickness along with improving the memory window and retention of data. The larger V{sub t} shift indicates that the ZnO adds available trap states and enhances the emission and retention of charges. The charge emission mechanism in the memory structures with graphene nanoplatelets at an electric field E ≥ 5.57 MV/cm is found to be based on Fowler-Nordheim tunneling. The fabrication of this memory device is compatible with current semiconductor processing, therefore, has great potential in low-cost nano-memory applications.

  14. Development of the layer-by-layer biosensor using graphene films: application for cholesterol determination

    NASA Astrophysics Data System (ADS)

    Binh Nguyen, Hai; Chuc Nguyen, Van; Nguyen, Van Tu; Doan Le, Huu; Quynh Nguyen, Van; Thanh Tam Ngo, Thi; Phuc Do, Quan; Nghia Nguyen, Xuan; Phan, Ngoc Minh; Tran, Dai Lam

    2013-03-01

    The preparation and characterization of graphene films for cholesterol determination are described. The graphene films were synthesized by thermal chemical vapor deposition (CVD) method. Methane gas (CH4) and copper tape were used as carbon source and catalyst in the graphene growth process, respectively. The intergrated array was fabricated by using micro-electro-mechanical systems (MEMS) technology in which Fe3O4-doped polyaniline (PANi) film was electropolymerized on Pt/Gr electrodes. The properties of the Pt/Gr/PANi/Fe3O4 films were investigated by field-emission scanning electron microscopy (FE-SEM), Raman spectroscopy and electrochemical techniques. Cholesterol oxidase (ChOx) has been immobilized onto the working electrode with glutaraldehyde agent. The cholesterol electrochemical biosensor shows high sensitivity (74 μA mM-1 cm-2) and fast response time (<5 s). A linear calibration plot was obtained in the wide cholesterol concentration range from 2 to 20 mM and correlation coefficient square (R2) of 0.9986. This new layer-by-layer biosensor based on graphene films promises many practical applications.

  15. Single-Layer Graphene as an Effective Mediator of the Metal-Support Interaction.

    PubMed

    Luo, Wen; Doh, Won Hui; Law, Yeuk T; Aweke, Fitsum; Ksiazek-Sobieszek, Anna; Sobieszek, Andrzej; Salamacha, Leszek; Skrzypiec, Krzysztof; Le Normand, François; Machocki, Andrzej; Zafeiratos, Spyridon

    2014-06-05

    Single-layer chemical vapor deposition (CVD)-grown graphene was transferred onto a ZnO (0001) substrate forming a large-area, low-defect density, protective layer. The quality of the graphene layer and its effect on the interaction between the ZnO support and vapor-deposited cobalt particles was investigated by spectroscopic and microscopic techniques. We demonstrate that the in-between graphene layer influences both the oxidation state and the morphology of cobalt upon annealing in vacuum. In particular, cobalt strongly interacts with the bare ZnO substrate forming flat particles, which are readily oxidized and redispersed upon annealing in ultrahigh vacuum conditions. In contrast, in the presence of the graphene interlayer, cobalt forms highly dispersed nanoparticles, which are resistant to oxidation, but prone to surface diffusion and agglomeration. The graphene layer exhibits remarkable stability upon cobalt deposition and vacuum annealing, while interaction with reactive gases can facilitate the formation of defects.

  16. Atomic-layer deposition of cadmium chalcogenides on silicon

    NASA Astrophysics Data System (ADS)

    Ezhovskii, Yu. K.

    2014-09-01

    The results of studies of the synthesis of ultrafine layers of cadmium selenide and telluride by atomic-layer deposition on the silicon surface of different orientations were summarized. The main tendencies of the chemisorption of the components and conditions of layer growth during the formation of nanostructures of these compounds were determined.

  17. An analysis of electrochemical energy storage using electrodes fabricated from atomically thin 2D structures of MoS2, graphene and MoS2/graphene composites

    NASA Astrophysics Data System (ADS)

    Huffstutler, Jacob D.

    The behavior of 2D materials has become of great interest in the wake of development of electrochemical double-layer capacitors (EDLCs) and the discovery of monolayer graphene by Geim and Novoselov. This study aims to analyze the response variance of 2D electrode materials for EDLCs prepared through the liquid-phase exfoliation method when subjected to differing conditions. Once exfoliated, samples are tested with a series of structural characterization methods, including tunneling electron microscopy, atomic force microscopy, Raman spectroscopy, and x-ray photoelectron spectroscopy. A new ionic liquid for EDLC use, 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate is compared in performance to 6M potassium hydroxide aqueous electrolyte. Devices composed of liquid-phase exfoliated graphene / MoS2 composites are analyzed by concentration for ideal performance. Device performance under cold extreme temperatures for the ionic fluid is presented as well. A brief overview of by-layer analysis of graphene electrode materials is presented as-is. All samples were tested with cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy, with good capacitive results. The evolution of electrochemical behavior through the altered parameters is tracked as well.

  18. Growth of homogeneous single-layer graphene on Ni-Ge binary substrate

    NASA Astrophysics Data System (ADS)

    Wang, Gang; Chen, Da; Lu, Zitong; Guo, Qinglei; Ye, Lin; Wei, Xing; Ding, Guqiao; Zhang, Miao; Di, Zengfeng; Liu, Su

    2014-02-01

    In contrast to the commonly used chemical vapor deposition growth that leads to multilayer graphene formation by carbon segregation from the Ni bulk, we designed a Ni-Ge binary system to directly grow graphene film on Ni-Ge binary substrate, via chemical vapor deposition with methane and hydrogen gas as precursors. Our system fully overcomes the fundamental limitations of Ni and yields homogenous single layer graphene over large areas. The chemical vapor deposition growth of graphene on Ni-Ge binary substrate shows that self limiting monolayer graphene growth can be obtained on these substrate.

  19. Few-layer graphene shells and nonmagnetic encapsulates: a versatile and nontoxic carbon nanomaterial.

    PubMed

    Bachmatiuk, Alicja; Mendes, Rafael G; Hirsch, Cordula; Jähne, Carsten; Lohe, Martin R; Grothe, Julia; Kaskel, Stefan; Fu, Lei; Klingeler, Rüdiger; Eckert, Jürgen; Wick, Peter; Rümmeli, Mark H

    2013-12-23

    In this work a simple and scalable approach to coat nonmagnetic nanoparticles with few-layer graphene is presented. In addition, the easy processing of such nanoparticles to remove their core, leaving only the 3D graphene nanoshell, is demonstrated. The samples are comprehensively characterized, as are their versatility in terms of functionalization and as a material for electrochemical storage. Indeed, these 3D graphene nanostructures are easily functionalized much as is found with carbon nanotubes and planar graphene. Electrochemical investigations indicate these nanostructures are promising for stable long-life battery applications. Finally, initial toxicological investigations suggest no acute health risk from these 3D graphene nanostructures.

  20. Precise Control of the Number of Layers of Graphene by Picosecond Laser Thinning

    PubMed Central

    Lin, Zhe; Ye, Xiaohui; Han, Jinpeng; Chen, Qiao; Fan, Peixun; Zhang, Hongjun; Xie, Dan; Zhu, Hongwei; Zhong, Minlin

    2015-01-01

    The properties of graphene can vary as a function of the number of layers (NOL). Controlling the NOL in large area graphene is still challenging. In this work, we demonstrate a picosecond (ps) laser thinning removal of graphene layers from multi-layered graphene to obtain desired NOL when appropriate pulse threshold energy is adopted. The thinning process is conducted in atmosphere without any coating and it is applicable for graphene films on arbitrary substrates. This method provides many advantages such as one-step process, non-contact operation, substrate and environment-friendly, and patternable, which will enable its potential applications in the manufacturing of graphene-based electronic devices. PMID:26111758

  1. Synthesis and Characterizations of Two-Dimensional Atomic Layers and Their Heterostructures

    NASA Astrophysics Data System (ADS)

    Lee, Yi-Hsien

    2015-03-01

    Monolayers of van der Waals (vdw) materials, including graphene, h-BN, and MoS2, have been highlighted regarding both scientific and industrial aspects due to novel physical phenomenon inherited from the reduced dimensionality. Layered transition metal dichalcogenides (TMD) atomic layers, being considered as the thinnest semiconductor, exhibit great potential for advanced nano-devices. Monolayer in the class of offered a burgeoning field in fundamental physics, energy harvesting, electronics and optoelectronics. Recently, atomically thin heterostructures of TMD monolayer with various geometrical and energy band alignments are expected to be the key materials for next generation flexible optoelectronics. The individual TMD monolayers can be adjoined vertically or laterally to construct diverse heterostructures which are difficult to reach with the laborious pick up-and-transfer method of the exfoliated flakes. The ability to produce copious amounts of high quality layered heterostructures on diverse surfaces is highly desirable but it has remained a challenging issue. Here, we have achieved a direct synthesis of various heterostructures of monolayer TMDs. The synthesis was performed using ambient-pressure CVD with aromatic molecules as seeding promoters. We discuss possible growth behaviors, and we examine the symmetry and the interface of these heterostructures using optical analysis and atomic-resolution scanning TEM. Our method offers a controllable synthesis of to obtain high-quality heterostructures of TMD atomic layers with diverse interface geometry.

  2. Prediction of structural and mechanical properties of atom-decorated porous graphene via density functional calculations

    NASA Astrophysics Data System (ADS)

    Ansari, Reza; Ajori, Shahram; Malakpour, Sina

    2016-04-01

    The considerable demand for novel materials with specific properties has motivated the researchers to synthesize supramolecular nanostructures through different methods. Porous graphene is the first two-dimensional hydrocarbon synthesized quite recently. This investigation is aimed at studying the mechanical properties of atom-decorated (functionalized) porous graphene by employing density functional theory (DFT) calculation within both local density approximations (LDA) and generalized gradient approximations (GGA). The atoms are selected from period 3 of periodic table as well as Li and O atom from period 2. The results reveal that metallic atoms and noble gases are adsorbed physically on porous graphene and nonmetallic ones form chemical bonds with carbon atom in porous graphene structure. Also, it is shown that, in general, atom decoration reduces the values of mechanical properties such as Young's, bulk and shear moduli as well as Poisson's ratio, and this reduction is more considerable in the case of nonmetallic atoms (chemical adsorption), especially oxygen atoms, as compared to metallic atoms and noble gases (physical adsorption).

  3. Layer-selective half-metallicity in bilayer graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Jeon, Gi Wan; Lee, Kyu Won; Lee, Cheol Eui

    2015-05-01

    Half-metallicity recently predicted in the zigzag-edge graphene nanoribbons (ZGNRs) and the hydrogenated carbon nanotubes (CNTs) enables fully spin-polarized electric currents, providing a basis for carbon-based spintronics. In both carbon systems, the half-metallicity arises from the edge-localized electron states under an electric field, lowering the critical electric field Dc for the half-metallicity being an issue in recent works on ZGNRs. A properly chosen direction of the electric field alone has been predicted to significantly reduce Dc in the hydrogenated CNTs, which in this work turned out to be the case in narrow bilayer ZGNRs (biZGNRs). Here, our simple model based on the electrostatic potential difference between the edges predicts that for wide biZGNRs of width greater than ~2.0 nm (10 zigzag carbon chains), only one layer of the biZGNRs becomes half-metallic leaving the other layer insulating as confirmed by our density functional theory (DFT) calculations. The electric field-induced switching of the spin-polarized current path is believed to open a new route to graphene-based spintronics applications.

  4. Quantized edge modes in atomic-scale point contacts in graphene

    NASA Astrophysics Data System (ADS)

    Kinikar, Amogh; Phanindra Sai, T.; Bhattacharyya, Semonti; Agarwala, Adhip; Biswas, Tathagata; Sarker, Sanjoy K.; Krishnamurthy, H. R.; Jain, Manish; Shenoy, Vijay B.; Ghosh, Arindam

    2017-07-01

    The zigzag edges of single- or few-layer graphene are perfect one-dimensional conductors owing to a set of gapless states that are topologically protected against backscattering. Direct experimental evidence of these states has been limited so far to their local thermodynamic and magnetic properties, determined by the competing effects of edge topology and electron-electron interaction. However, experimental signatures of edge-bound electrical conduction have remained elusive, primarily due to the lack of graphitic nanostructures with low structural and/or chemical edge disorder. Here, we report the experimental detection of edge-mode electrical transport in suspended atomic-scale constrictions of single and multilayer graphene created during nanomechanical exfoliation of highly oriented pyrolytic graphite. The edge-mode transport leads to the observed quantization of conductance close to multiples of G0 = 2e2/h. At the same time, conductance plateaux at G0/2 and a split zero-bias anomaly in non-equilibrium transport suggest conduction via spin-polarized states in the presence of an electron-electron interaction.

  5. Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns

    NASA Astrophysics Data System (ADS)

    Chang, Tzu-Hsuan; Xiong, Shisheng; Jacobberger, Robert M.; Mikael, Solomon; Suh, Hyo Seon; Liu, Chi-Chun; Geng, Dalong; Wang, Xudong; Arnold, Michael S.; Ma, Zhenqiang; Nealey, Paul F.

    2016-08-01

    Directed self-assembly of block copolymers is a scalable method to fabricate well-ordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Typically, lithographically-defined prepatterns with varying chemical contrast are used to rationally guide the assembly of block copolymers. The directed self-assembly to obtain accurate registration and alignment is largely influenced by the assembly kinetics. Furthermore, a considerably broad processing window is favored for industrial manufacturing. Using an atomically-thin layer of graphene on germanium, after two simple processing steps, we create a novel chemical pattern to direct the assembly of polystyrene-block-poly(methyl methacrylate). Faster assembly kinetics are observed on graphene/germanium chemical patterns than on conventional chemical patterns based on polymer mats and brushes. This new chemical pattern allows for assembly on a wide range of guiding periods and along designed 90° bending structures. We also achieve density multiplication by a factor of 10, greatly enhancing the pattern resolution. The rapid assembly kinetics, minimal topography, and broad processing window demonstrate the advantages of inorganic chemical patterns composed of hard surfaces.

  6. Quantized edge modes in atomic-scale point contacts in graphene.

    PubMed

    Kinikar, Amogh; Phanindra Sai, T; Bhattacharyya, Semonti; Agarwala, Adhip; Biswas, Tathagata; Sarker, Sanjoy K; Krishnamurthy, H R; Jain, Manish; Shenoy, Vijay B; Ghosh, Arindam

    2017-04-03

    The zigzag edges of single- or few-layer graphene are perfect one-dimensional conductors owing to a set of gapless states that are topologically protected against backscattering. Direct experimental evidence of these states has been limited so far to their local thermodynamic and magnetic properties, determined by the competing effects of edge topology and electron-electron interaction. However, experimental signatures of edge-bound electrical conduction have remained elusive, primarily due to the lack of graphitic nanostructures with low structural and/or chemical edge disorder. Here, we report the experimental detection of edge-mode electrical transport in suspended atomic-scale constrictions of single and multilayer graphene created during nanomechanical exfoliation of highly oriented pyrolytic graphite. The edge-mode transport leads to the observed quantization of conductance close to multiples of G0 = 2e(2)/h. At the same time, conductance plateaux at G0/2 and a split zero-bias anomaly in non-equilibrium transport suggest conduction via spin-polarized states in the presence of an electron-electron interaction.

  7. Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns

    PubMed Central

    Chang, Tzu-Hsuan; Xiong, Shisheng; Jacobberger, Robert M.; Mikael, Solomon; Suh, Hyo Seon; Liu, Chi-Chun; Geng, Dalong; Wang, Xudong; Arnold, Michael S.; Ma, Zhenqiang; Nealey, Paul F.

    2016-01-01

    Directed self-assembly of block copolymers is a scalable method to fabricate well-ordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Typically, lithographically-defined prepatterns with varying chemical contrast are used to rationally guide the assembly of block copolymers. The directed self-assembly to obtain accurate registration and alignment is largely influenced by the assembly kinetics. Furthermore, a considerably broad processing window is favored for industrial manufacturing. Using an atomically-thin layer of graphene on germanium, after two simple processing steps, we create a novel chemical pattern to direct the assembly of polystyrene-block-poly(methyl methacrylate). Faster assembly kinetics are observed on graphene/germanium chemical patterns than on conventional chemical patterns based on polymer mats and brushes. This new chemical pattern allows for assembly on a wide range of guiding periods and along designed 90° bending structures. We also achieve density multiplication by a factor of 10, greatly enhancing the pattern resolution. The rapid assembly kinetics, minimal topography, and broad processing window demonstrate the advantages of inorganic chemical patterns composed of hard surfaces. PMID:27528258

  8. Mechanical properties of graphene cantilever from atomic force microscopy and density functional theory.

    PubMed

    Rasuli, R; Iraji Zad, A; Ahadian, M M

    2010-05-07

    We have studied the mechanical properties of a few-layer graphene cantilever (FLGC) using atomic force microscopy (AFM). The mechanical properties of the suspended FLGC over an open hole have been derived from the AFM data. Force displacement curves using the Derjaguin-Müller-Toporov (DMT) and the massless cantilever beam models yield a Young modulus of E(c) approximately 37, E(a) approximately 0.7 TPa and a Hamakar constant of approximately 3 x 10( - 18) J. The threshold force to shear the FLGC was determined from a breaking force and modeling. In addition, we studied a graphene nanoribbon (GNR), which is a system similar to the FLGC; using density functional theory (DFT). The in-plane Young's modulus for the GNRs were calculated from the DFT outcomes approximately 0.82 TPa and the results were compared with the experiment. We found that the Young's modulus and the threshold shearing force are dependent on the direction of applied force and the values are different for zigzag edge and armchair edge GNRs.

  9. USE OF ATOMIC LAYER DEPOSITION OF FUNCTIONALIZATION OF NANOPOROUS BIOMATERIALS

    SciTech Connect

    Brigmon, R.; Narayan, R.; Adiga, S.; Pellin, M.; Curtiss, L.; Stafslien, S.; Chisholm, B.; Monteiro-Riviere, N.; Elam, J.

    2010-02-08

    Due to its chemical stability, uniform pore size, and high pore density, nanoporous alumina is being investigated for use in biosensing, drug delivery, hemodialysis, and other medical applications. In recent work, we have examined the use of atomic layer deposition for coating the surfaces of nanoporous alumina membranes. Zinc oxide coatings were deposited on nanoporous alumina membranes using atomic layer deposition. The zinc oxide-coated nanoporous alumina membranes demonstrated antimicrobial activity against Escherichia coli and Staphylococcus aureus bacteria. These results suggest that atomic layer deposition is an attractive technique for modifying the surfaces of nanoporous alumina membranes and other nanostructured biomaterials.

  10. Slidable atomic layers in van der Waals heterostructures

    NASA Astrophysics Data System (ADS)

    Kobayashi, Yu; Taniguchi, Takashi; Watanabe, Kenji; Maniwa, Yutaka; Miyata, Yasumitsu

    2017-04-01

    We report the preparation and manipulation of slidable atomic layers in clean, incommensurate van der Waals (vdW) heterostructures. Monolayer and multilayer WS2 grains are grown on graphite and hexagonal boron nitride (hBN) via chemical vapor deposition, and these grains can slide smoothly on graphite and hBN surfaces by manipulation with a tip. Furthermore, this sliding process allows the suspension, tearing, stacking, and connection of the atomic layers. These results demonstrate a novel approach for developing a wide variety of atomic-layer heterostructures with tunable interlayer coupling and an ideal system for studying the superlubricity of incommensurate, highly clean vdW contacts.

  11. Measuring graphene adhesion using atomic force microscopy with a microsphere tip

    NASA Astrophysics Data System (ADS)

    Jiang, Tao; Zhu, Yong

    2015-06-01

    Van der Waals adhesion between graphene and various substrates has an important impact on the physical properties, device applications and nanomanufacturing processes of graphene. Here we report a general, high-throughput and reliable method that can measure adhesion energies between ultraflat graphene and a broad range of materials using atomic force microscopy with a microsphere tip. In our experiments, only van der Waals force between the tip and a graphene flake is measured. The Maugis-Dugdale theory is employed to convert the measured adhesion force using AFM to the adhesion energy. The ultraflatness of monolayer graphene on mica eliminates the effect of graphene surface roughness on the adhesion, while roughness of the microsphere tip is addressed by the modified Rumpf model. Adhesion energies of monolayer graphene to SiO2 and Cu are obtained as 0.46 and 0.75 J m-2, respectively. This work provides valuable insight into the mechanism of graphene adhesion and can readily extend to the adhesion measurement for other 2D nanomaterials.Van der Waals adhesion between graphene and various substrates has an important impact on the physical properties, device applications and nanomanufacturing processes of graphene. Here we report a general, high-throughput and reliable method that can measure adhesion energies between ultraflat graphene and a broad range of materials using atomic force microscopy with a microsphere tip. In our experiments, only van der Waals force between the tip and a graphene flake is measured. The Maugis-Dugdale theory is employed to convert the measured adhesion force using AFM to the adhesion energy. The ultraflatness of monolayer graphene on mica eliminates the effect of graphene surface roughness on the adhesion, while roughness of the microsphere tip is addressed by the modified Rumpf model. Adhesion energies of monolayer graphene to SiO2 and Cu are obtained as 0.46 and 0.75 J m-2, respectively. This work provides valuable insight into the

  12. Improved optical sintering efficiency at the contacts of silver nanowires encapsulated by a graphene layer.

    PubMed

    Yang, Seung-Bok; Choi, HongKyw; Lee, Da Som; Choi, Choon-Gi; Choi, Sung-Yool; Kim, Il-Doo

    2015-03-18

    Graphene/silver nanowire (AgNWs) stacked electrodes, i.e., graphene/AgNWs, are fabricated on a glass substrate by air-spray coating of AgNWs followed by subsequent encapsulation via a wet transfer of single-layer graphene (SLG) and multilayer graphene (MLG, reference specimen) sheets. Here, graphene is introduced to improve the optical sintering efficiency of a xenon flash lamp by controlling optical transparency and light absorbing yield in stacked graphene/AgNW electrodes, facilitating the fusion at contacts of AgNWs. Intense pulsed light (IPL) sintering induced ultrafast (<20 ms) welding of AgNW junctions encapsulated by graphene, resulting in approximately a four-fold reduction in the sheet resistance of IPL-treated graphene/AgNWs compared to that of IPL-treated AgNWs. The role of graphene in IPL-treated graphene/AgNWs is further investigated as a passivation layer against thermal oxidation and sulfurization. This work demonstrates that optical sintering is an efficient way to provide fast welding of Ag wire-to-wire junctions in stacked electrodes of graphene/AgNWs, leading to enhanced conductivity as well as superior long-term stability under oxygen and sulfur atmospheres. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. A hybrid Mg-Al layered double hydroxide/graphene nanostructure obtained via hydrothermal synthesis

    NASA Astrophysics Data System (ADS)

    Zhao, Xiaodong; Cao, Jian-Ping; Zhao, Jun; Hu, Guo-Hua; Dang, Zhi-Min

    2014-06-01

    A hybrid Mg-Al layered double hydroxide/graphene (LDH-GR) material nanostructure has been fabricated by employing the hydrothermal treatment at 140 °C for 10 h. Graphene oxide is simultaneously reduced to graphene during the hydrothermal treatment. The LDH and LDH-GR have high degree of crystallinity and assembled layer structure, which is attributed to electrostatic interaction mechanism. The obtained hybrid nanostructure materials can be used as flame retardant or conductor of electricity and heat due to the combination of different properties arising from graphene and LDH.

  14. Scanning tunneling microscopy of a graphene layer placed on a micro structured substrate

    NASA Astrophysics Data System (ADS)

    Ganbarova, T. Sh; Babichev, A. V.; Rykov, S. A.

    2017-03-01

    The features of the surface topography and the local energy spectrum of the graphene layer placed on a two-dimensional array of GaN pyramids are studied using scanning tunneling microscopy and local tunneling spectroscopy. This structure can be used as a test structure for the application of graphene as a flexible conductive transparent electrode in optoelectronics. Sagging of a graphene layer in the space between pyramids is found and the sagging value is estimated to be about 20% of the pyramid height of 1.1 μm. Local energy spectra show the change of the graphene electron energy spectrum due to the mechanical stress at sagging.

  15. Kapitza Resistance between Few-Layer Graphene and Water: Liquid Layering Effects.

    PubMed

    Alexeev, Dmitry; Chen, Jie; Walther, Jens H; Giapis, Konstantinos P; Angelikopoulos, Panagiotis; Koumoutsakos, Petros

    2015-09-09

    The Kapitza resistance (RK) between few-layer graphene (FLG) and water was studied using molecular dynamics simulations. The RK was found to depend on the number of the layers in the FLG though, surprisingly, not on the water block thickness. This distinct size dependence is attributed to the large difference in the phonon mean free path between the FLG and water. Remarkably, RK is strongly dependent on the layering of water adjacent to the FLG, exhibiting an inverse proportionality relationship to the peak density of the first water layer, which is consistent with better acoustic phonon matching between FLG and water. These findings suggest novel ways to engineer the thermal transport properties of solid-liquid interfaces by controlling and regulating the liquid layering at the interface.

  16. Designing nanoscale constructs from atomic thin sheets of graphene, boron nitride and gold nanoparticles for advanced material applications

    NASA Astrophysics Data System (ADS)

    Jasuja, Kabeer

    2011-12-01

    ' interaction with graphene, and applied to address the challenge of dispersing bare-surfaced GNPs for efficient liquid-phase catalysis. We also revisited the functionalization of graphene and present a non-invasive surface introduction of interfaceable moieties. Isostructural to graphene, ultrathin BN sheet is another atomic-thick nanomaterial possessing a highly diverse set of properties inconceivable from graphene. Exfoliating UTBNSs has been challenging due to their exceptional intersheet-bonding and chemical-inertness. To develop applications of BN monolayers and evolve research, a facile lab-scale approach was desired that can produce processable dispersions of BN monolayers. We demonstrated a novel chlorosulfonic acid based treatment that resulted in protonation assisted layer-by-layer exfoliation of BN monolayers with highest reported yields till date. Further, the BN monolayers exhibited extensively protonated N centers, which are utilized for chemically interfacing GNPs, demonstrating their ability to act as excellent nano-templates. The scientific details obtained from the research shown here will significantly support current research activities and greatly impact their future applications. Our research findings have been published in ACS Nano, Small, Journal of Physical Chemistry Letters, MRS Proceedings and have gathered >45 citations.

  17. Low-frequency phonons of few-layer graphene within a tight-binding model

    NASA Astrophysics Data System (ADS)

    Popov, Valentin N.; Van Alsenoy, Christian

    2014-12-01

    Few-layer graphene is a layered carbon material with covalent bonding in the layers and weak van der Waals interactions between the layers. The interlayer energy is more than two orders of magnitude smaller than the intralayer one, which hinders the description of the static and dynamic properties within electron band structure models. We overcome this difficulty by introducing two sets of matrix elements—one set for the covalent bonds in the graphene layers and another one for the van der Waals interactions between adjacent graphene layers in a tight-binding model of the band structure. Both sets of matrix elements are derived from an ab initio study on carbon dimers. The matrix elements are applied in the calculation of the phonon dispersion of graphite and few-layer graphene with AB and ABC layer stacking. The results for few-layer graphene with AB stacking agree well with the available experimental data, which justifies the application of the matrix elements to other layered carbon structures with van der Waals interactions such as few-layer graphene nanoribbons, multiwall carbon nanotubes, and carbon onions.

  18. Atomically Thin Interfacial Suboxide Key to Hydrogen Storage Performance Enhancements of Magnesium Nanoparticles Encapsulated in Reduced Graphene Oxide.

    PubMed

    Wan, Liwen F; Liu, Yi-Sheng; Cho, Eun Seon; Forster, Jason D; Jeong, Sohee; Wang, Hsiao-Tsu; Urban, Jeffrey J; Guo, Jinghua; Prendergast, David

    2017-09-13

    As a model system for hydrogen storage, magnesium hydride exhibits high hydrogen storage density, yet its practical usage is hindered by necessarily high temperatures and slow kinetics for hydrogenation-dehydrogenation cycling. Decreasing particle size has been proposed to simultaneously improve the kinetics and decrease the sorption enthalpies. However, the associated increase in surface reactivity due to increased active surface area makes the material more susceptible to surface oxidation or other side reactions, which would hinder the overall hydrogenation-dehydrogenation process and diminish the capacity. Previous work has shown that the chemical stability of Mg nanoparticles can be greatly enhanced by using reduced graphene oxide as a protecting agent. Although no bulklike crystalline MgO layer has been clearly identified in this graphene-encapsulated/Mg nanocomposite, we propose that an atomically thin layer of honeycomb suboxide exists, based on first-principles interpretation of Mg K-edge X-ray absorption spectra. Density functional theory calculations reveal that in contrast to conventional expectations for thick oxides this interfacial oxidation layer permits H2 dissociation to the same degree as pristine Mg metal with the added benefit of enhancing the binding between reduced graphene oxide and the Mg nanoparticle, contributing to improved mechanical and chemical stability of the functioning nanocomposite.

  19. Semiconducting properties of bilayer graphene modulated by an electric field for next-generation atomic-film electronics

    NASA Astrophysics Data System (ADS)

    Tsukagoshi, K.; Li, S.-L.; Miyazaki, H.; Aparecido-Ferreira, A.; Nakaharai, S.

    2014-03-01

    A practical wide bandgap was induced in bilayer graphene using a perpendicular electric field. A self-assembled gate insulator was used to apply a large electric field. The wide bandgap allows the operation of fundamental logic gates composed of bilayer graphene transistors. The results reviewed here indicate the potential for graphene electronics to be realized as emerging transistors with an atomically thin semiconductor.

  20. Structure stability and magnetism in graphene impurity complexes with embedded V and Nb atoms

    NASA Astrophysics Data System (ADS)

    Thakur, Jyoti; Kashyap, Manish K.; Taya, Ankur; Rani, Priti; Saini, Hardev S.; Reshak, A. H.

    2017-07-01

    The appearance of vacancy defects could produce appropriate magnetic moment in graphene and the sensitivity to absorb atoms/molecules also increases with this. In this direction, a DFT study of embedding V and Nb atom in graphene containing monovacancies (MV) and divacancies (DV) is reported. Complete/almost complete spin polarization is detected for V/Nb embedding. The origin of magnetism has been identified via interaction of 3d-states of embedded atom with C-p states present in the vicinity of embedded site. The band structures have been analyzed to counter the observed semiconducting nature of graphene in minority spin on embedding V/Nb atom. The isosurface analysis also confirms the induced magnetism of present nanosystems. The present results reveal that these nanosystems have the potential for futuristic applications like spintronics and energy resources.

  1. Electrical Double Layer Capacitance in a Graphene-embedded Al2O3 Gate Dielectric.

    PubMed

    Ki Min, Bok; Kim, Seong K; Jun Kim, Seong; Ho Kim, Sung; Kang, Min-A; Park, Chong-Yun; Song, Wooseok; Myung, Sung; Lim, Jongsun; An, Ki-Seok

    2015-11-04

    Graphene heterostructures are of considerable interest as a new class of electronic devices with exceptional performance in a broad range of applications has been realized. Here, we propose a graphene-embedded Al2O3 gate dielectric with a relatively high dielectric constant of 15.5, which is about 2 times that of Al2O3, having a low leakage current with insertion of tri-layer graphene. In this system, the enhanced capacitance of the hybrid structure can be understood by the formation of a space charge layer at the graphene/Al2O3 interface. The electrical properties of the interface can be further explained by the electrical double layer (EDL) model dominated by the diffuse layer.

  2. Electrical Double Layer Capacitance in a Graphene-embedded Al2O3 Gate Dielectric

    PubMed Central

    Ki Min, Bok; Kim, Seong K.; Jun Kim, Seong; Ho Kim, Sung; Kang, Min-A; Park, Chong-Yun; Song, Wooseok; Myung, Sung; Lim, Jongsun; An, Ki-Seok

    2015-01-01

    Graphene heterostructures are of considerable interest as a new class of electronic devices with exceptional performance in a broad range of applications has been realized. Here, we propose a graphene-embedded Al2O3 gate dielectric with a relatively high dielectric constant of 15.5, which is about 2 times that of Al2O3, having a low leakage current with insertion of tri-layer graphene. In this system, the enhanced capacitance of the hybrid structure can be understood by the formation of a space charge layer at the graphene/Al2O3 interface. The electrical properties of the interface can be further explained by the electrical double layer (EDL) model dominated by the diffuse layer. PMID:26530817

  3. Fabrication and properties of silicene and silicene-graphene layered structures on Ir (111)

    NASA Astrophysics Data System (ADS)

    Meng, Lei; Wang, Ye-Liang; Zhang, Li-Zhi; Du, Shi-Xuan; Gao, Hong-Jun

    2015-08-01

    Silicene, a two-dimensional (2D) honeycomb structure similar to graphene, has been successfully fabricated on various substrates. This work will mainly review the syntheses and the corresponding properties of silicene and silicene-graphene layered structures on Ir (111) substrates. For silicene on Ir (111), the buckled silicene/ Ir (111) configuration and its electronic structure are fully discussed. For silicene-graphene layered structures, silicene layer can be constructed underneath graphene layer by an intercalation method. These results indicate the possibility of integrating silicene with graphene and may link up with potential applications in nanoelectronics and related areas. Project supported by the National Basic Research Program of China (Grant Nos. 2013CBA01600 and 2011CB932700), the National Natural Science Foundation of China (Grant Nos. 61222112, 61390501, 51325204, 11334006, and 61306114), the Science Fund from Chinese Academy of Sciences (Grant Nos. 1731300500015 and XDB07030100), and the Fundamental Research Funds for the Central Universities, China.

  4. Enhanced ultra-low-frequency interlayer shear modes in folded graphene layers

    NASA Astrophysics Data System (ADS)

    Cong, Chunxiao; Yu, Ting

    2014-08-01

    Few-layer graphene has attracted tremendous attention owing to its exceptional electronic properties inherited from single-layer graphene and new features led by introducing extra freedoms such as interlayer stacking sequences or rotations. Effectively probing interlayer shear modes are critical for unravelling mechanical and electrical properties of few-layer graphene and further developing its practical potential. Unfortunately, shear modes are extremely weak and almost fully blocked by a Rayleigh rejecter in Raman measurements. This greatly hinders investigations of shear modes in few-layer graphene. Here, we demonstrate enhancing of shear modes by properly folding few-layer graphene. As a direct benefit of the strong signal, enhancement mechanism, vibrational symmetry, anharmonicity and electron-phonon coupling of the shear modes are uncovered through studies of Raman mapping, polarization- and temperature-dependent Raman spectroscopy. This work complements Raman studies of graphene layers, and paves an efficient way to exploit low-frequency shear modes of few-layer graphene and other two-dimensional layered materials.

  5. Graphene-like two-dimensional layered nanomaterials: applications in biosensors and nanomedicine

    NASA Astrophysics Data System (ADS)

    Yang, Guohai; Zhu, Chengzhou; Du, Dan; Zhu, Junjie; Lin, Yuehe

    2015-08-01

    The development of nanotechnology provides promising opportunities for various important applications. The recent discovery of atomically-thick two-dimensional (2D) nanomaterials can offer manifold perspectives to construct versatile devices with high-performance to satisfy multiple requirements. Many studies directed at graphene have stimulated renewed interest on graphene-like 2D layered nanomaterials (GLNs). GLNs including boron nitride nanosheets, graphitic-carbon nitride nanosheets and transition metal dichalcogenides (e.g. MoS2 and WS2) have attracted significant interest in numerous research fields from physics and chemistry to biology and engineering, which has led to numerous interdisciplinary advances in nano science. Benefiting from the unique physical and chemical properties (e.g. strong mechanical strength, high surface area, unparalleled thermal conductivity, remarkable biocompatibility and ease of functionalization), these 2D layered nanomaterials have shown great potential in biochemistry and biomedicine. This review summarizes recent advances of GLNs in applications of biosensors and nanomedicine, including electrochemical biosensors, optical biosensors, bioimaging, drug delivery and cancer therapy. Current challenges and future perspectives in these rapidly developing areas are also outlined. It is expected that they will have great practical foundation in biomedical applications with future efforts.

  6. Graphene-like two-dimensional layered nanomaterials: applications in biosensors and nanomedicine.

    PubMed

    Yang, Guohai; Zhu, Chengzhou; Du, Dan; Zhu, Junjie; Lin, Yuehe

    2015-09-14

    The development of nanotechnology provides promising opportunities for various important applications. The recent discovery of atomically-thick two-dimensional (2D) nanomaterials can offer manifold perspectives to construct versatile devices with high-performance to satisfy multiple requirements. Many studies directed at graphene have stimulated renewed interest on graphene-like 2D layered nanomaterials (GLNs). GLNs including boron nitride nanosheets, graphitic-carbon nitride nanosheets and transition metal dichalcogenides (e.g. MoS2 and WS2) have attracted significant interest in numerous research fields from physics and chemistry to biology and engineering, which has led to numerous interdisciplinary advances in nano science. Benefiting from the unique physical and chemical properties (e.g. strong mechanical strength, high surface area, unparalleled thermal conductivity, remarkable biocompatibility and ease of functionalization), these 2D layered nanomaterials have shown great potential in biochemistry and biomedicine. This review summarizes recent advances of GLNs in applications of biosensors and nanomedicine, including electrochemical biosensors, optical biosensors, bioimaging, drug delivery and cancer therapy. Current challenges and future perspectives in these rapidly developing areas are also outlined. It is expected that they will have great practical foundation in biomedical applications with future efforts.

  7. Nanoprocessing of layered crystalline materials by atomic force microscopy.

    PubMed

    Miyake, Shojiro; Wang, Mei

    2015-01-01

    By taking advantage of the mechanical anisotropy of crystalline materials, processing at a single-layer level can be realized for layered crystalline materials with periodically weak bonds. Mica (muscovite), graphite, molybdenum disulfide (MoS2), and boron nitride have layered structures, and there is little interaction between the cleavage planes existing in the basal planes of these materials. Moreover, it is easy to image the atoms on the basal plane, where the processed shape can be observed on the atomic level. This study reviews research evaluating the nanometer-scale wear and friction as well as the nanometer-scale mechanical processing of muscovite using atomic force microscopy (AFM). It also summarizes recent AFM results obtained by our research group regarding the atomic-scale mechanical processing of layered materials including mica, graphite, MoS2, and highly oriented pyrolytic graphite.

  8. Graphene as a transparent conducting and surface field layer in planar Si solar cells.

    PubMed

    Kumar, Rakesh; Mehta, Bodh R; Bhatnagar, Mehar; S, Ravi; Mahapatra, Silika; Salkalachen, Saji; Jhawar, Pratha

    2014-01-01

    This work presents an experimental and finite difference time domain (FDTD) simulation-based study on the application of graphene as a transparent conducting layer on a planar and untextured crystalline p-n silicon solar cell. A high-quality monolayer graphene with 97% transparency and 350 Ω/□ sheet resistance grown by atmospheric pressure chemical vapor deposition method was transferred onto planar Si cells. An increase in efficiency from 5.38% to 7.85% was observed upon deposition of graphene onto Si cells, which further increases to 8.94% upon SiO2 deposition onto the graphene/Si structure. A large increase in photon conversion efficiency as a result of graphene deposition shows that the electronic interaction and the presence of an electric field at the graphene/Si interface together play an important role in this improvement and additionally lead to a reduction in series resistance due to the conducting nature of graphene.

  9. Ionic liquid-assisted exfoliation and dispersion: stripping graphene and its two-dimensional layered inorganic counterparts of their inhibitions.

    PubMed

    Ravula, Sudhir; Baker, Sheila N; Kamath, Ganesh; Baker, Gary A

    2015-03-14

    Research on graphene-monolayers of carbon atoms arranged in a honeycomb lattice-is proceeding at a relentless pace as scientists of both experimental and theoretical bents seek to explore and exploit its superlative attributes, including giant intrinsic charge mobility, record-setting thermal conductivity, and high fracture strength and Young's modulus. Of course, fully exploiting the remarkable properties of graphene requires reliable, large-scale production methods which are non-oxidative and introduce minimal defects, criteria not fully satisfied by current approaches. A major advance in this direction is ionic liquid-assisted exfoliation and dispersion of graphite, leading to the isolation of few- and single-layered graphene sheets with yields two orders of magnitude higher than the earlier liquid-assisted exfoliation approaches using surface energy-matched solvents such as N-methyl-2-pyrrolidone (NMP). In this Minireview, we discuss the emerging use of ionic liquids for the practical exfoliation, dispersion, and modification of graphene nanosheets. These developments lay the foundation for strategies seeking to overcome the many challenges faced by current liquid-phase exfoliation approaches. Early computational and experimental results clearly indicate that these same approaches can readily be extended to inorganic graphene analogues (e.g., BN, MoX2 (X = S, Se, Te), WS2, TaSe2, NbSe2, NiTe2, and Bi2Te3) as well.

  10. Ionic liquid-assisted exfoliation and dispersion: stripping graphene and its two-dimensional layered inorganic counterparts of their inhibitions

    NASA Astrophysics Data System (ADS)

    Ravula, Sudhir; Baker, Sheila N.; Kamath, Ganesh; Baker, Gary A.

    2015-02-01

    Research on graphene--monolayers of carbon atoms arranged in a honeycomb lattice--is proceeding at a relentless pace as scientists of both experimental and theoretical bents seek to explore and exploit its superlative attributes, including giant intrinsic charge mobility, record-setting thermal conductivity, and high fracture strength and Young's modulus. Of course, fully exploiting the remarkable properties of graphene requires reliable, large-scale production methods which are non-oxidative and introduce minimal defects, criteria not fully satisfied by current approaches. A major advance in this direction is ionic liquid-assisted exfoliation and dispersion of graphite, leading to the isolation of few- and single-layered graphene sheets with yields two orders of magnitude higher than the earlier liquid-assisted exfoliation approaches using surface energy-matched solvents such as N-methyl-2-pyrrolidone (NMP). In this Minireview, we discuss the emerging use of ionic liquids for the practical exfoliation, dispersion, and modification of graphene nanosheets. These developments lay the foundation for strategies seeking to overcome the many challenges faced by current liquid-phase exfoliation approaches. Early computational and experimental results clearly indicate that these same approaches can readily be extended to inorganic graphene analogues (e.g., BN, MoX2 (X = S, Se, Te), WS2, TaSe2, NbSe2, NiTe2, and Bi2Te3) as well.

  11. Plasma assisted fabrication of multi-layer graphene/nickel hybrid film as enhanced micro-supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Ding, Q.; Li, W. L.; Zhao, W. L.; Wang, J. Y.; Xing, Y. P.; Li, X.; Xue, T.; Qi, W.; Zhang, K. L.; Yang, Z. C.; Zhao, J. S.

    2017-03-01

    A facile synthesis strategy has been developed for fabricating multi-layer graphene/nickel hybrid film as micro-supercapacitor electrodes by using plasma enhanced chemical vapor deposition. The as-presented method is advantageous for rapid graphene growth at relatively low temperature of 650 °C. In addition, after pre-treating for the as-deposited nickel film by using argon plasma bombardment, the surface-to-volume ratio of graphene film on the treated nickel substrate is effectively increased by the increasing of surface roughness. This is demonstrated by the characterization results from transmission electron microscopy, scanning electron microscope and atomic force microscopy. Moreover, the electrochemical performance of the resultant graphene/nickel hybrid film as micro-supercapacitor working electrode was investigated by cyclic voltammetry and galvanostatic charge/discharge measurements. It was found that the increase of the surface-to-volume ratio of graphene/nickel hybrid film improved the specific capacitance of 10 times as the working electrode of micro-supercapacitor. Finally, by using comb columnar shadow mask pattern, the micro-supercapacitor full cell device was fabricated. The electrochemical performance measurements of the micro-supercapacitor devices indicate that the method presented in this study provides an effective way to fabricate micro-supercapacitor device with enhanced energy storage property.

  12. Determination of the geometric corrugation of graphene on SiC(0001) by grazing incidence fast atom diffraction

    SciTech Connect

    Zugarramurdi, A.; Debiossac, M.; Lunca-Popa, P.; Mayne, A. J.; Borisov, A. G.; Mu, Z.; Roncin, P.; Khemliche, H.; Momeni, A.

    2015-03-09

    We present a grazing incidence fast atom diffraction (GIFAD) study of monolayer graphene on 6H-SiC(0001). This system shows a Moiré-like 13 × 13 superlattice above the reconstructed carbon buffer layer. The averaging property of GIFAD results in electronic and geometric corrugations that are well decoupled; the graphene honeycomb corrugation is only observed with the incident beam parallel to the zigzag direction while the geometric corrugation arising from the superlattice is revealed along the armchair direction. Full-quantum calculations of the diffraction patterns show the very high GIFAD sensitivity to the amplitude of the surface corrugation. The best agreement between the calculated and measured diffraction intensities yields a corrugation height of 0.27 ± 0.03 Å.

  13. Spin and valley resolved Landau level crossing in tri-layer ABA stacked graphene

    NASA Astrophysics Data System (ADS)

    Datta, Biswajit; Gupta, Vishakha; Borah, Abhinandan; Watanabe, Kenji; Taniguchi, Takashi; Deshmukh, Mandar

    We present quantum Hall measurements on a high quality encapsulated tri-layer graphene device. Low temperature field effect mobility of this device is around 500,000 cm2/Vs and we see SdH oscillations at a magnetic field as low as 0.3 T. Quantum Hall measurements confirm that the chosen tri layer graphene is Bernal (ABA) stacked. Due to the presence of both mass-less monolayer like Dirac fermions and massive bi-layer like Dirac fermions in Bernal stacked tri-layer graphene, there are Landau level crossings between monolayer and bi-layer bands in quantum Hall regime. Although most of the Landau Level crossings are predominantly present on the electron sides, we also observe signatures of the crossings on the hole side. This behaviour is consistent with the asymmetry of electron and hole in ABA tri-layer graphene. We observe a series of crossings of the spin and valley resolved Landau Levels.

  14. Graphene-silicon layered structures on single-crystalline Ir(111) thin films

    SciTech Connect

    Que, Yande D.; Tao, Jing; Zhang, Yong; Wang, Yeliang L.; Wu, Lijun J.; Zhu, Yimei M.; Kim, Kisslinger; Weinl, Michael; Schreck, Matthias; Shen, Chengmin M.; Du, Shixuan X.; Liu, Yunqi Q.; Gao, H. -J.; Huang, Li; Xu, Wenyan Y.

    2015-01-20

    Epitaxial growth of graphene on transition metal crystals, such as Ru,⁽¹⁻³⁾ Ir,⁽⁴⁻⁶⁾ and Ni,⁽⁷⁾ provides large-area, uniform graphene layers with controllable defect density, which is crucial for practical applications in future devices. To decrease the high cost of single-crystalline metal bulks, single-crystalline metal films are strongly suggested as the substrates for epitaxial growth large-scale high-quality graphene.⁽⁸⁻¹⁰⁾ Moreover, in order to weaken the interactions of graphene with its metal host, which may result in a suppression of the intrinsic properties of graphene,⁽¹¹ ¹²⁾ the method of element intercalation of semiconductors at the interface between an epitaxial graphene layer and a transition metal substrate has been successfully realized.⁽¹³⁻¹⁶⁾

  15. Robust adhesion of flower-like few-layer graphene nanoclusters

    PubMed Central

    Tian, Shibing; Li, Lin; Sun, Wangning; Xia, Xiaoxiang; Han, Dong; Li, Junjie; Gu, Changzhi

    2012-01-01

    Nanostructured surface possessing ultrahigh adhesion like “gecko foot” or “rose petal” can offer more opportunities for bionic application. We grow flower-like few-layer graphene on silicon nanocone arrays to form graphene nanoclusters, showing robust adhesion. Their contact angle (CA) is 164° with a hysteresis CA of 155° and adhesive force for a 5 μL water droplet is about 254 μN that is far larger than present reported results. We bring experimental evidences that this great adhesion depends on large-area plentiful edges of graphene nanosheets tuned by conical nanostructure and intrinsic wetting features of graphene. Such new hierarchical few-layer graphene nanostructure provides a feasible strategy to understand the ultra-adhesive mechanism of the “gecko effect” or “rose effect” and enhance the wettability of graphene for many practical applications. PMID:22803004

  16. Robust adhesion of flower-like few-layer graphene nanoclusters

    NASA Astrophysics Data System (ADS)

    Tian, Shibing; Li, Lin; Sun, Wangning; Xia, Xiaoxiang; Han, Dong; Li, Junjie; Gu, Changzhi

    2012-07-01

    Nanostructured surface possessing ultrahigh adhesion like ``gecko foot'' or ``rose petal'' can offer more opportunities for bionic application. We grow flower-like few-layer graphene on silicon nanocone arrays to form graphene nanoclusters, showing robust adhesion. Their contact angle (CA) is 164° with a hysteresis CA of 155° and adhesive force for a 5 μL water droplet is about 254 μN that is far larger than present reported results. We bring experimental evidences that this great adhesion depends on large-area plentiful edges of graphene nanosheets tuned by conical nanostructure and intrinsic wetting features of graphene. Such new hierarchical few-layer graphene nanostructure provides a feasible strategy to understand the ultra-adhesive mechanism of the ``gecko effect'' or ``rose effect'' and enhance the wettability of graphene for many practical applications.

  17. Thermoacoustic and photoacoustic characterizations of few-layer graphene by pulsed excitations

    SciTech Connect

    Wang, Xiong; Witte, Russell S.; Xin, Hao

    2016-04-04

    We characterized the thermoacoustic and photoacoustic properties of large-area, few-layer graphene by pulsed microwave and optical excitations. Due to its high electric conductivity and low heat capacity per unit area, graphene lends itself to excellent microwave and optical energy absorption and acoustic signal emanation due to the thermoacoustic effect. When exposed to pulsed microwave or optical radiation, distinct thermoacoustic and photoacoustic signals generated by the few-layer graphene are obtained due to microwave and laser absorption of the graphene, respectively. Clear thermoacoustic and photoacoustic images of large-area graphene sample are achieved. A numerical model is developed and the simulated results are in good accordance with the measured ones. This characterization work may find applications in ultrasound generator and detectors for microwave and optical radiation. It may also become an alternative characterization approach for graphene and other types of two-dimensional materials.

  18. Graphene-silicon layered structures on single-crystalline Ir(111) thin films

    DOE PAGES

    Que, Yande D.; Tao, Jing; Zhang, Yong; ...

    2015-01-20

    Epitaxial growth of graphene on transition metal crystals, such as Ru,⁽¹⁻³⁾ Ir,⁽⁴⁻⁶⁾ and Ni,⁽⁷⁾ provides large-area, uniform graphene layers with controllable defect density, which is crucial for practical applications in future devices. To decrease the high cost of single-crystalline metal bulks, single-crystalline metal films are strongly suggested as the substrates for epitaxial growth large-scale high-quality graphene.⁽⁸⁻¹⁰⁾ Moreover, in order to weaken the interactions of graphene with its metal host, which may result in a suppression of the intrinsic properties of graphene,⁽¹¹ ¹²⁾ the method of element intercalation of semiconductors at the interface between an epitaxial graphene layer and a transitionmore » metal substrate has been successfully realized.⁽¹³⁻¹⁶⁾« less

  19. Determining charge state of graphene vacancy by noncontact atomic force microscopy and first-principles calculations.

    PubMed

    Liu, Y; Weinert, M; Li, L

    2015-01-21

    Graphene vacancies are engineered for novel functionalities, however, the charge state of these defects, the key parameter that is vital to charge transfer during chemical reactions and carrier scattering, is generally unknown. Here, we carried out atomic resolution imaging of graphene vacancy defects created by Ar plasma using noncontact atomic force microscopy, and made the first determination of their charge state by local contact potential difference measurements. Combined with density functional theory calculations, we show that graphene vacancies are typically positively charged, with size-dependent charge states that are not necessarily integer-valued. These findings provide new insights into carrier scattering by vacancy defects in graphene, as well as its functionalization for chemical sensing and catalysis, and underline the tunability of these functions by controlling the size of vacancy defect.

  20. Atomically precise edge chlorination of nanographenes and its application in graphene nanoribbons

    PubMed Central

    Tan, Yuan-Zhi; Yang, Bo; Parvez, Khaled; Narita, Akimitsu; Osella, Silvio; Beljonne, David; Feng, Xinliang; Müllen, Klaus

    2013-01-01

    Chemical functionalization is one of the most powerful and widely used strategies to control the properties of nanomaterials, particularly in the field of graphene. However, the ill-defined structure of the present functionalized graphene inhibits atomically precise structural characterization and structure-correlated property modulation. Here we present a general edge chlorination protocol for atomically precise functionalization of nanographenes at different scales from 1.2 to 3.4 nm and its application in graphene nanoribbons. The well-defined edge chlorination is unambiguously confirmed by X-ray single-crystal analysis, which also discloses the characteristic non-planar molecular shape and detailed bond lengths of chlorinated nanographenes. Chlorinated nanographenes and graphene nanoribbons manifest enhanced solution processability associated with decreases in the optical band gap and frontier molecular orbital energy levels, exemplifying the structure-correlated property modulation by precise edge chlorination. PMID:24212200

  1. Ab initio simulation and design of graphene-based transistors at the atomic scale

    NASA Astrophysics Data System (ADS)

    Lu, Wenchang; Bernholc, Jerry

    2015-03-01

    Two-dimensional materials, such as graphene and molybdenum disulfide, have attracted much attention because of their unique properties. Graphene's high mobility make it a very promising material for next generation electronics, but its zero band gap is a big hurdle for digital transistors. However, graphene nanoribbons can exhibit band gaps due to quantum confinement, and their electronic properties differ depending on the structures of their edges. Based on the real space multigrid method and the non-equilibrium Green functions technique for multi-probe systems, we have developed massively parallel DFT-based software to calculate quantum transport properties with several thousands atoms. We present results for transport properties of graphene-based transistors with different atomic structures and study the effects of nanoribbon length, width and gate structure.

  2. Quantum-confined electronic states in atomically well-defined graphene nanostructures.

    PubMed

    Hämäläinen, Sampsa K; Sun, Zhixiang; Boneschanscher, Mark P; Uppstu, Andreas; Ijäs, Mari; Harju, Ari; Vanmaekelbergh, Daniël; Liljeroth, Peter

    2011-12-02

    Despite the enormous interest in the properties of graphene and the potential of graphene nanostructures in electronic applications, the study of quantum-confined states in atomically well-defined graphene nanostructures remains an experimental challenge. Here, we study graphene quantum dots (GQDs) with well-defined edges in the zigzag direction, grown by chemical vapor deposition on an Ir(111) substrate by low-temperature scanning tunneling microscopy and spectroscopy. We measure the atomic structure and local density of states of individual GQDs as a function of their size and shape in the range from a couple of nanometers up to ca. 20 nm. The results can be quantitatively modeled by a relativistic wave equation and atomistic tight-binding calculations. The observed states are analogous to the solutions of the textbook "particle-in-a-box" problem applied to relativistic massless fermions.

  3. Cutting forces related with lattice orientations of graphene using an atomic force microscopy based nanorobot

    NASA Astrophysics Data System (ADS)

    Zhang, Yu; Gao, Yang; Liu, Lianqing; Xi, Ning; Wang, Yuechao; Ma, Laipeng; Dong, Zaili; Wejinya, Uchechukwu C.

    2012-11-01

    The relationship between cutting forces and lattice orientations of monolayer graphene is investigated by using an atomic force microscopy (AFM) based nanorobot. In the beginning, the atomic resolution image of the graphene lattice is obtained by using an AFM. Then, graphene cutting experiments are performed with sample rotation method, which gets rid of the tip effect completely. The experimental results show that the cutting force along the armchair orientation is larger than the force along the zigzag orientation, and the cutting forces are almost identical every 60°, which corresponds well with the 60° symmetry in graphene honeycomb lattice structure. By using Poisson analysis method, the single cutting force along zigzag orientation is 3.9 nN, and the force along armchair is 20.5 nN. This work lays the experimental foundation to build a close-loop fabrication strategy with real-time force as a feedback sensor to control the cutting direction.

  4. Photodetection in Hybrid Single-Layer Graphene/Fully Coherent Germanium Island Nanostructures Selectively Grown on Silicon Nanotip Patterns.

    PubMed

    Niu, Gang; Capellini, Giovanni; Lupina, Grzegorz; Niermann, Tore; Salvalaglio, Marco; Marzegalli, Anna; Schubert, Markus Andreas; Zaumseil, Peter; Krause, Hans-Michael; Skibitzki, Oliver; Lehmann, Michael; Montalenti, Francesco; Xie, Ya-Hong; Schroeder, Thomas

    2016-01-27

    Dislocation networks are one of the most principle sources deteriorating the performances of devices based on lattice-mismatched heteroepitaxial systems. We demonstrate here a technique enabling fully coherent germanium (Ge) islands selectively grown on nanotip-patterned Si(001) substrates. The silicon (Si)-tip-patterned substrate, fabricated by complementary metal oxide semiconductor compatible nanotechnology, features ∼50-nm-wide Si areas emerging from a SiO2 matrix and arranged in an ordered lattice. Molecular beam epitaxy growths result in Ge nanoislands with high selectivity and having homogeneous shape and size. The ∼850 °C growth temperature required for ensuring selective growth has been shown to lead to the formation of Ge islands of high crystalline quality without extensive Si intermixing (with 91 atom % Ge). Nanotip-patterned wafers result in geometric, kinetic-diffusion-barrier intermixing hindrance, confining the major intermixing to the pedestal region of Ge islands, where kinetic diffusion barriers are, however, high. Theoretical calculations suggest that the thin Si/Ge layer at the interface plays, nevertheless, a significant role in realizing our fully coherent Ge nanoislands free from extended defects especially dislocations. Single-layer graphene/Ge/Si-tip Schottky junctions were fabricated, and thanks to the absence of extended defects in Ge islands, they demonstrate high-performance photodetection characteristics with responsivity of ∼45 mA W(-1) and an Ion/Ioff ratio of ∼10(3).

  5. Unraveling the 3D Atomic Structure of a Suspended Graphene/hBN van der Waals Heterostructure

    NASA Astrophysics Data System (ADS)

    Argentero, Giacomo; Mittelberger, Andreas; Reza Ahmadpour Monazam, Mohammad; Cao, Yang; Pennycook, Timothy J.; Mangler, Clemens; Kramberger, Christian; Kotakoski, Jani; Geim, A. K.; Meyer, Jannik C.

    2017-03-01

    In this work we demonstrate that a free-standing van der Waals heterostructure, usually regarded as a flat object, can exhibit an intrinsic buckled atomic structure resulting from the interaction between two layers with a small lattice mismatch. We studied a freely suspended membrane of well aligned graphene on a hexagonal boron nitride (hBN) monolayer by transmission electron microscopy (TEM) and scanning TEM (STEM). We developed a detection method in the STEM that is capable of recording the direction of the scattered electron beam and that is extremely sensitive to the local stacking of atoms. Comparison between experimental data and simulated models shows that the heterostructure effectively bends in the out-of-plane direction, producing an undulated structure having a periodicity that matches the moir\\'e wavelength. We attribute this rippling to the interlayer interaction and also show how this affects the intralayer strain in each layer.

  6. Unraveling the 3D Atomic Structure of a Suspended Graphene/hBN van der Waals Heterostructure.

    PubMed

    Argentero, Giacomo; Mittelberger, Andreas; Reza Ahmadpour Monazam, Mohammad; Cao, Yang; Pennycook, Timothy J; Mangler, Clemens; Kramberger, Christian; Kotakoski, Jani; Geim, A K; Meyer, Jannik C

    2017-03-08

    In this work we demonstrate that a free-standing van der Waals heterostructure, usually regarded as a flat object, can exhibit an intrinsic buckled atomic structure resulting from the interaction between two layers with a small lattice mismatch. We studied a freely suspended membrane of well-aligned graphene on a hexagonal boron nitride (hBN) monolayer by transmission electron microscopy (TEM) and scanning TEM (STEM). We developed a detection method in the STEM that is capable of recording the direction of the scattered electron beam and that is extremely sensitive to the local stacking of atoms. A comparison between experimental data and simulated models shows that the heterostructure effectively bends in the out-of-plane direction, producing an undulated structure having a periodicity that matches the moiré wavelength. We attribute this rippling to the interlayer interaction and also show how this affects the intralayer strain in each layer.

  7. Unraveling the 3D Atomic Structure of a Suspended Graphene/hBN van der Waals Heterostructure

    PubMed Central

    2017-01-01

    In this work we demonstrate that a free-standing van der Waals heterostructure, usually regarded as a flat object, can exhibit an intrinsic buckled atomic structure resulting from the interaction between two layers with a small lattice mismatch. We studied a freely suspended membrane of well-aligned graphene on a hexagonal boron nitride (hBN) monolayer by transmission electron microscopy (TEM) and scanning TEM (STEM). We developed a detection method in the STEM that is capable of recording the direction of the scattered electron beam and that is extremely sensitive to the local stacking of atoms. A comparison between experimental data and simulated models shows that the heterostructure effectively bends in the out-of-plane direction, producing an undulated structure having a periodicity that matches the moiré wavelength. We attribute this rippling to the interlayer interaction and also show how this affects the intralayer strain in each layer. PMID:28140602

  8. Programmable hydrogenation of graphene for novel nanocages

    NASA Astrophysics Data System (ADS)

    Zhang, Liuyang; Zeng, Xiaowei; Wang, Xianqiao

    2013-11-01

    Folded graphene has exhibited novel electrical and mechanical properties unmatched by pristine graphene, which implies that morphology of graphene adds the dimensionality of design space to tailor its properties. However, how to overcome the energy barrier of the folding process to fold the graphene with the specific morphology remains unexplored. Here we propose a programmable chemical functionalization by doping a pristine graphene sheet in a certain pattern with hydrogen atoms to precisely control its folding morphology. Molecular dynamics simulation has been performed to create a cross-shaped cubic graphene nanocage encapsulating a biomolecule by warping the top graphene layer downward and the bottom graphene layer upward to mimic the drug delivery vehicle. Such a paradigm, programmable enabled graphene nanocage, opens up a new avenue to control the 3D architecture of folded graphene and therefore provides a feasible way to exploit and fabricate the graphene-based unconventional nanomaterials and nanodevices for drug delivery.

  9. Formulation of atomic positions and carbon-carbon bond length in armchair graphene nanoribbons: an ab initio study

    NASA Astrophysics Data System (ADS)

    Balarastaghi, Mehran; Ahmadi, Vahid

    2017-09-01

    In this paper, we investigate the atomic positions of single layer armchair graphene nanoribbon for two cases, with and without hydrogen-passivate edges, accurately and propose a formula which either removes the need of structural relaxation generally or decreases its time extremely (up to seven times). We also propose a general pattern (hyperbolic) for these positions. On the other hand, we show that edge effect influences several atoms near the edge not just one. These results can be used in software, which compute atomic positions and can increase their efficiency. In addition, we prove that the C-C bond distance depends on dimer number and differs in length and width directions, especially for narrow AGNRs. The maximum value of these differences is about 0.017 Å.

  10. Symmetry breaking in graphene layers on SiC-substrate—an ab-initio study

    NASA Astrophysics Data System (ADS)

    Agrawal, B. K.; Agrawal, S.

    2013-05-01

    A comprehensive detailed ab-initio study of the electronic structure of 1-7 graphene layers on the polar SiC (0 0 0 1) substrate systems has been performed for the first time. We observe a symmetry-breaking in all the graphene-SiC (0 0 0 1) substrate systems leading to an opening of band gap in contrast to the existence of zero band gap seen in the isolated graphene layer. The planar lattice parameter in graphene-SiC system decreases with the number of graphene layers from 3.051 Å to 2.948 Å showing an overall decrease of 3.5% and it approaches toward the bulk graphite. The electronic structure of the graphene layer-SiC system depends crucially on the planar lattice parameter and both the band gap and the location of the Dirac point are affected drastically. The band gap and the depth of the Dirac point below the Fermi level decrease with the number of graphene layers in conformity with the recent ARPES experiments of Zhou et al. The present results in some graphene-SiC systems are seen to be different from the earlier theoretical results reported in the literature.

  11. Strain engineering of Kapitza resistance in few-layer graphene.

    PubMed

    Chen, Jie; Walther, Jens H; Koumoutsakos, Petros

    2014-02-12

    We demonstrate through molecular dynamics simulations that the Kapitza resistance in few-layer graphene (FLG) can be controlled by applying mechanical strain. For unstrained FLG, the Kapitza resistance decreases with the increase of thickness and reaches an asymptotic value of 6 × 10(-10) m(2)K/W at a thickness about 16 nm. Uniaxial cross-plane strain is found to increase the Kapitza resistance in FLG monotonically, when the applied strain varies from compressive to tensile. Moreover, uniaxial strain couples the in-plane and out-of-plane strain/stress when the surface of FLG is buckled. We find that with a compressive cross-plane stress of 2 GPa, the Kapitza resistance is reduced by about 50%. On the other hand it is almost tripled with a tensile cross-plane stress of 1 GPa. Remarkably, compressive in-plane strain can either increase or reduce the Kapitza resistance, depending on the specific way it is applied. Our study suggests that graphene can be exploited for both heat dissipation and insulation through strain engineering.

  12. Layer-by-layer assembly of functionalized reduced graphene oxide for direct electrochemistry and glucose detection.

    PubMed

    Mascagni, Daniela Branco Tavares; Miyazaki, Celina Massumi; da Cruz, Nilson Cristino; de Moraes, Marli Leite; Riul, Antonio; Ferreira, Marystela

    2016-11-01

    We report an electrochemical glucose biosensor made with layer-by-layer (LbL) films of functionalized reduced graphene oxide (rGO) and glucose oxidase (GOx). The LbL assembly using positively and negatively charged rGO multilayers represents a simple approach to develop enzymatic biosensors. The electron transport properties of graphene were combined with the specificity provided by the enzyme. rGO was obtained and functionalized using chemical methods, being positively charged with poly(diallyldimethylammonium chloride) to form GPDDA, and negatively charged with poly(styrene sulfonate) to form GPSS. Stable aqueous dispersions of GPDDA and GPSS are easily obtained, enabling the growth of LbL films on various solid supports. The use of graphene in the immobilization of GOx promoted Direct Electron Transfer, which was evaluated by Cyclic Voltammetry. Amperometric measurements indicated a detection limit of 13.4μmol·L(-1) and sensitivity of 2.47μA·cm(-2)·mmol(-1)·L for glucose with the (GPDDA/GPSS)1/(GPDDA/GOx)2 architecture, whose thickness was 19.80±0.28nm, as determined by Surface Plasmon Resonance (SPR). The sensor may be useful for clinical analysis since glucose could be detected even in the presence of typical interfering agents and in real samples of a lactose-free milk and an electrolyte solution to prevent dehydration.

  13. Sprayable, Paintable Layer-by-Layer Polyaniline Nanofiber/Graphene Electrodes for Electrochemical Energy Storage

    NASA Astrophysics Data System (ADS)

    Kwon, Se Ra; Jeon, Ju-Won; Lutkenhus, Jodie

    2015-03-01

    Sprayable batteries are growing in interest for applications in structural energy storage and power or flexible power. Spray-assisted layer-by-layer (LbL) assembly, in which complementary species are alternately sprayed onto a surface, is particularly amenable toward this application. Here, we report on the fabrication of composite films containing polyaniline nanofibers (PANI NF) and graphene oxide (GO) sheets fabricated via spray-assisted LbL assembly. The resulting films are electrochemical reduced to yield PANI NF/electrochemically reduced graphene (ERGO) electrodes for use as a cathode in non-aqueous energy storage systems. Through the spray-assisted LbL process, the hybrid electrodes could be fabricated 74 times faster than competing dip-assisted LbL assembly. The resulting electrodes are highly porous (0.72 void fraction), and are comprised of 67 wt% PANI NF and 33 wt% ERGO. The sprayed electrodes showed better rate capability, higher specific power, as well as more stable cycle life than dip-assisted LbL electrodes. It is shown here that the spray-assisted LbL approach is well-suited towards the fabrication of paintable electrodes containing polyaniline nanofibers and electrochemically reduced graphene oxide sheets.

  14. Optical control of graphene plasmon using liquid crystal layer 29K New One

    DTIC Science & Technology

    2017-03-01

    excitation because there is a huge wave vector mismatch between the graphene plasmonic wave and the incident electromagnetic wave. In graphene structures the... electromagnetic wave. In graphene structures the resonant plasmon frequency depends on the dielectric properties of layers placed above and below the...of prof. V. Yu. Reshetnyak for participation in 9th International Congress on Advanced Electromagnetic Materials in Microwaves and Optics, Oxford

  15. Temperature-dependent dielectric functions in atomically thin graphene, silicene, and arsenene

    SciTech Connect

    Yang, J. Y.; Liu, L. H.

    2015-08-31

    The dielectric functions of atomically thin graphene, silicene, and arsenene have been investigated as a function of temperature. With zero energy gap, more carriers in graphene and silicene are thermally excited as temperature increases and intraband transition strengthens, resulting in the strengthened absorption peak. Yet with large energy gap, interband transition dominates optical absorption of arsenene but it reduces as lattice vibration enhances, inducing the redshift and decreased absorption peak. To validate the theoretical method, the calculated optical constants of isolated graphene are compared with ellipsometry results and demonstrate good agreement.

  16. In Situ Transmission Electron Microscopy Characterization and Manipulation of Two-Dimensional Layered Materials beyond Graphene.

    PubMed

    Luo, Chen; Wang, Chaolun; Wu, Xing; Zhang, Jian; Chu, Junhao

    2017-08-07

    Two-dimensional (2D) ultra-thin materials beyond graphene with rich physical properties and unique layered structures are promising for applications in electronics, chemistry, energy, and bioscience, etc. The interaction mechanisms among the structures, chemical compositions and physical properties of 2D layered materials are critical for fundamental nanosciences and the practical fabrication of next-generation nanodevices. Transmission electron microscopy (TEM), with its high spatial resolution and versatile external fields, is undoubtedly a powerful tool for the static characterization and dynamic manipulation of nanomaterials and nanodevices at the atomic scale. The rapid development of thin-film and precision microelectromechanical systems (MEMS) techniques allows 2D layered materials and nanodevices to be probed and engineered inside TEM under external stimuli such as thermal, electrical, mechanical, liquid/gas environmental, optical, and magnetic fields at the nanoscale. Such advanced technologies leverage the traditional static TEM characterization into an in situ and interactive manipulation of 2D layered materials without sacrificing the resolution or the high vacuum chamber environment, facilitating exploration of the intrinsic structure-property relationship of 2D layered materials. In this Review, the dynamic properties tailored and observed by the most advanced and unprecedented in situ TEM technology are introduced. The challenges in spatial, time and energy resolution are discussed also. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Size-controlled InGaN/GaN nanorod LEDs with an ITO/graphene transparent layer

    NASA Astrophysics Data System (ADS)

    Shim, Jae-Phil; Seong, Won-Seok; Min, Jung-Hong; Kong, Duk-Jo; Seo, Dong-Ju; Kim, Hyung-jun; Lee, Dong-Seon

    2016-11-01

    We introduce ITO on graphene as a current-spreading layer for separated InGaN/GaN nanorod LEDs for the purpose of passivation-free and high light-extraction efficiency. Transferred graphene on InGaN/GaN nanorods effect