ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
Recently Viewed
You have not visited any articles yet, Please visit some articles to see contents here.
CONTENT TYPES

System Message

The ACS Publications site will be temporarily unavailable for planned maintenance on Friday, Oct. 15 starting at 6:00 pm ET for up to 4 hours. We apologize for this inconvenience.

Quantification of the Interaction Forces between Metals and Graphene by Quantum Chemical Calculations and Dynamic Force Measurements under Ambient Conditions

View Author Information
Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacký University, 771 46 Olomouc, Czech Republic
Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav WiedsVej 14, 8000 Aarhus C, Denmark
§ Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 166 10 Prague 6, Czech Republic
*Address correspondence to [email protected], [email protected]
Cite this: ACS Nano 2013, 7, 2, 1646–1651
Publication Date (Web):January 24, 2013
https://doi.org/10.1021/nn305608a
Copyright © 2013 American Chemical Society
ACS AuthorChoiceACS AuthorChoice
Article Views
3072
Altmetric
-
Citations
LEARN ABOUT THESE METRICS
PDF (2 MB)
Supporting Info (1)»

Abstract

The two-dimensional material graphene has numerous potential applications in nano(opto)electronics, which inevitably involve metal graphene interfaces.Theoretical approaches have been employed to examine metal graphene interfaces, but experimental evidence is currently lacking. Here, we combine atomic force microscopy (AFM) based dynamic force measurements and density functional theory calculations to quantify the interaction between metal-coated AFM tips and graphene under ambient conditions. The results show that copper has the strongest affinity to graphene among the studied metals (Cu, Ag, Au, Pt, Si), which has important implications for the construction of a new generation of electronic devices. Observed differences in the nature of the metal–graphene bonding are well reproduced by the calculations, which included nonlocal Hartree–Fock exchange and van der Waals effects.

Graphene is a two-dimensional material with extraordinary physical properties, (1-4) making it a potentially useful material in nano(opto)electronics applications. (5-10) In this respect, most feasible applications are likely to require metal contacts linking graphene to classical electronic devices. (11, 12) Furthermore, graphene has been suggested as a suitable support for metal catalysts because it is chemically inert and has a large surface area. (13-15) All the above-mentioned challenging applications call for a deeper understanding and quantification of metal binding to graphene.
The interaction of metals with graphene has been the subject of many theoretical studies, (16-19) mostly based on the density functional theory (DFT). (20, 21) The nature of the interaction between metals and graphene involves many phenomena, for example, charge transfer, polarization, London dispersion forces, and relativistic effects, (22-24) which represent a challenge for theoretical calculations. In this respect, DFT calculations may provide very different results, depending on the choice of exchange-correlation (xc) functional and its ability to correctly describe the above-mentioned effects. Unfortunately, to date, experiments have been unable to identify an accurate theoretical approach. Several experimental studies have dealt with graphene/metal contacts. (13, 25, 26) However, so far, no experiment has quantitatively addressed the interaction force between metal and graphene. Therefore, although theoretical methods have advanced in recent years, (27-29) the development is hampered by the absence of benchmark values with which to crosscheck results and evaluate the improvement and accuracy of a particular method. There is no doubt that the experimental quantification of metal–graphene interactions under ambient conditions supported by suitable interaction models possesses a considerable challenge.
Here we present a combined theoretical and experimental study with the aim of quantifying the interaction between various metals and graphene. We employed advanced atomic force microscopy (AFM) to measure dynamic forces under ambient conditions and on a microsecond time scale (30-33) in order to quantify the interaction force between metalized AFM tips and graphene. The results show that Cu exhibits the highest affinity among the studied metals (Cu, Ag, Au, Pt, Si) during the adsorption and peeling processes, whereas Si exhibits the lowest. This finding has important implications with respect to the principal role of copper and silicon in current electronic devices. Moreover, the developed experimental approach is applicable for quantification of interaction forces between graphene and a large number of other metals and elements.

Results and Discussion

ARTICLE SECTIONS
Jump To

The experiments presented in this work were conducted using sharp silicon AFM tips (Figure 1), which were coated with four different metals by thermal evaporation. The probe geometry and coating layer were characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDS). Both the SEM images and EDS plots confirmed the homogeneous coating of all tips without any significant signs of metal oxidation (Figure 1C and Supplementary Figures 1–6). The recently developed dynamic force spectroscopy (30, 31) technique involves scanning the graphene surface with a coated AFM probe (Figure 1) and measurement of the interaction force between metal and graphene as a function of time in the microsecond range. After transformation of the recorded data to force vs separation plots (Figure 2), the adhesion force was extracted, which represents the first exact quantitative information on the interaction force between metal and graphene under ambient conditions.

Figure 1

Figure 1. (A) Schematic of AFM operation in dynamic range force spectroscopy showing a metal-coated probe scanning a graphene sheet on a SiO2 support; (B) atomic level model of metal-coated tip on graphene used in the DFT calculations; (C) SEM image of AFM tip coated by gold (see Supplementary Figure 3 for EDS spectrum); (D) optical image of the graphene substrate on SiO2 used during the experiment. The dashed square indicates the location of the inset of Figure 2A.

Figure 2

Figure 2. Graphene morphology and interaction force curves between metal-coated AFM probe and graphene: (A) AFM morphology images of graphene; (B) typical force vs time curve of Cu-coated probe and graphene; red B and green C dots indicate the adhesion force during approach and withdrawal, respectively; (C) typical force vs separation curves derived from the approach process (Fapp); (D) typical force vs separation curves derived from the withdrawal process (Fw).

Figure 2A shows the morphology of a graphene single layer on a SiO2 substrate, where the AFM experiments were carried out (for details of the experimental setup see also Figure 1A). The coated probe tapped the graphene layer with 2 kHz frequency and one force vs time curve was recorded per cycle. Figure 2B presents the curve obtained with a Cu-coated probe (other typical force vs time curves are shown in Supplementary Figure 7). Two kinds of interaction forces were recorded in one cycle; one during the approach (Figure 2B, letter B) and the other during withdrawal (Figure 2B, letter C). The interaction force during the approach (Figure 2C) corresponds to the adsorption force evaluated in our DFT calculations (Figure 3). On the other hand, the force measured during the withdrawal process (Figure 2D) corresponds to the force needed to peel graphene from the metal surface, which may also involve some surface deformation. (34-36) The calculated interaction energies and forces (Eint, Fint) and experimentally determined interaction forces (Fapp, Fw) of different metals to graphene are summarized in Table 1 and their distributions are shown in the Supporting Information (Supplementary Figures 8 and 9). The data show unambiguously that Cu has the strongest affinity to graphene, whereas Si has the lowest. They also show that the affinity between coinage metals and graphene decreases in the order Cu > Ag > Au (Figure 4).

Figure 3

Figure 3. Calculated interaction energy curves (upper panel) and derived interaction forces (lower panel) between Au tip and graphene. The crosses denote the total energies calculated with various functionals (PBE, PBE+vdW, EE+vdW, and EE+vdW with spin–orbit coupling).

Figure 4

Figure 4. The experimentally derived interaction forces from the approach processes (in blue) are compared with the interaction forces calculated by the EE-vdW method (in red).

Table 1. Interaction Energies Eint and Forces Fint of a Tetrahedral Metal Tip Positioned on Top of One of Carbon Atoms of Graphene Calculated by the EE+vdW Methoda
metalEint(kcal/mol)Fint (nN)Fapp (nN)Fw (nN)
Cu24.61.61.6 ± 0.37.4 ± 1.4
Ag15.81.31.2 ± 0.15.2 ± 0.2
Au16.30.80.8 ± 0.22.0 ± 0.1
Pt16.5 1.2 ± 0.66.2 ± 0.3
Si4.90.30.7 ± 0.21.4 ± 0.1
a

The experimental interaction forces were recorded during both the approach (Fapp) and withdrawal (Fw) processes.

The calculations reveal that the strongest interaction is for the tip positioned on top of one of carbon atoms in the graphene sheet. The order of forces corresponds to the order of measured forces (the interaction is strongest for Cu, followed by Ag, and Au, and weakest for Si, see Table 1). Relativistic effects are very important in the case of Au; according to the scalar relativistic calculation (Supplementary Table 3), the Au tip has the interaction energy of 24.0 kcal/mol, and the respective force is 1.8 nN. The full relativistic calculation including spin–orbit coupling reduces the interaction force to 0.8 nN, which is in excellent agreement with the experimental data (Table 1). Figure 3 displays both the interaction energy and force curves for the Au tip over graphene calculated with various DFT functionals.
To verify our DFT results, additional calculation of the interaction of Cu, Au, Ag dimers with benzene was performed; the small size of such a model system enables a calculation with the multiconfigurational method CASPT2, which is an accurate quantum chemical method utilizing a multireference description of the many-particle wave function and second-order perturbation treatment of the electron correlations. The dimer axis was oriented perpendicular to the benzene ring to mimic the tip–graphene geometry. The CASPT2 results corroborated the order Cu > Au ≈ Ag of the interaction energies, confirming that the apparently strong binding of copper is not an artifact of the EE+vdW method. The different affinities of Cu, Ag, and Au tips arise from a subtle interplay of the size effect (37) and various relativistic effects, which are crucial for the Au tip. It should be noted, that our previous study (38) showed that planar gold and silver tetramers are bound only by weak van der Waals interactions, which would result in lower forces. Therefore, the interaction will also depend on the geometry of the tip; a blunter geometry of the tip may decrease the measured forces.
Theoretical interaction forces agree well with the experimental data only when the EE+vdW method is used (the interaction forces calculated with various xc functionals are displayed in Table 2). The PBE functional gives consistently too low values of interaction force. Its local approach to the xc energy density cannot describe long-ranged van der Waals interactions, which represent an important part of tip-support interaction. Inclusion of the nonlocal vdW correlation to the PBE functional (PBE+vdW) yields better interaction energies, but the forces are still too weak, because this functional does not reproduce well the curvature of the energy around the equilibrium distance. The combination of the vdW correlation with the exact-exchange in the EE+vdW provided accurate interaction forces. It is worth noting that this method is parameter-free and still computationally feasible, which makes it promising for further theoretical calculations of various metals on graphene support.
Table 2. The Interaction Force between M4 and Graphene (Fint in nN) Calculated from the Numerical Derivative of the Calculated Interaction Energy (Obtained by Various Exchange-Correlation Functionals, PBE, PBE+vdW, EE+vdW, for the Preferred Position)a
metalPBEPBE+vdWEE+vdW
Cu1.20.91.6
Ag0.60.51.3
Au0.70.50.8
Au*0.60.71.8
Si0.020.20.3
a

In the case of the Au4 cluster, we also include the results calculated within a scalar relativistic approximation (denoted by an asterisk (∗)).

The order of the calculated Eint remained the same for other high-symmetry positions (above C–C bond, or above hollow site) on the graphene surface (Supplementary Table 1). We further calculated the interaction of the tetrahedral tips when constraining them to a singlet spin state, which may correspond to the paramagnetic state of larger metallic tip structures (Supplementary Table 2). The interaction energies for the top position (23.6, 21.2, 16.0, 25.6, and 5.0 kcal/mol for Cu, Au, Ag, Pt, and Si, respectively) indicate that the order of the metals is preserved, except for Pt. This is because Pt has the largest triplet-singlet energy difference among the studied metals, which promotes its interaction energy in the singlet state above the other metals.
The calculations also revealed interesting spin-crossover when the metals interacted with graphene; although isolated tetrahedrons of Au, Ag, and Cu have a triplet groundstate, they change into singlet spin states as they approach a graphene sheet. This triplet/singlet transition is rather abrupt and occurs when the tip apex atom approaches closer than 2.6 Å to the surface of graphene. The interaction of Pt4 is strongly mediated by its peculiar magnetic properties; the ground-state of Pt4 has a noncollinear arrangement of spin moments due to the spin–orbit coupling. (39) As the spin moments of Pt4 begin to interact with graphene, several magnetic structures appear, leading to the discontinuous curve of the interaction energy. Consequently, it was not possible to extract reliable forces from the calculated data.

Conclusion

ARTICLE SECTIONS
Jump To

For the first time, we have experimentally measured the interaction force between metal and graphene using the recently developed dynamic AFM (30, 31) technique by scanning the graphene surface with metal-coated AFM probes under ambient conditions. The experiments not only allowed quantification of the adhesion force but also provided information on the peeling force between various metals and graphene, which revealed that copper has both the strongest adhesion force and peeling force. Experimental results were corroborated by DFT calculations utilizing a recently introduced vdW+EE method. The order of the calculated interaction energies agreed with the order of measured forces: The interaction was strongest for Cu, followed by Au, Pt, and Ag, and weakest for Si. The interplay of size and relativistic effects can explain the different affinities of Cu, Ag, and Au tips. The calculations also revealed different mechanisms of interaction, including interesting spin-crossover in Cu, Au, and Ag clusters interacting with graphene. In general, the interaction of the graphene surface with the complex electronic structure of metal clusters exhibiting several close-lying spin states creates a subtle energy balance, which can challenge even state-of-the-art theoretical methods. In this respect, the presented experimental data have important implications for the development of theoretical methods. Moreover, the dynamic AFM technique is extremely fast and enables quantification of interaction forces with graphene for other metals that form an adequate coating on the surface of an AFM tip. From this point of view, it seems that the air atmosphere does not have the principal effect on the interaction force as the experimental data recorded in the air correlate well with DFT calculations assuming interaction in a vacuum. One possible main factor is the superhydrophobic properties of graphene, which effectively weaken the capillary force with the coated AFM probe. The identified and quantified superior affinity of copper to graphene is very important with regard to the choice of suitable metal substrate for graphene production as well as for the construction of advanced graphene-based electronic devices.

Methods

ARTICLE SECTIONS
Jump To

Preparation of Graphene Samples

The graphene sheets were deposited by mechanical exfoliation of natural graphite (Alfa Aesar) onto the silicon oxide substrate under ambient conditions. Graphene sheets were located by their contrast under optical microscopy and were further confirmed by Raman spectroscopy (data not shown) and AFM characterization.

SEM Analysis

AFM tips were characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDS). SEM micrographs were taken on a Hitachi 6600 FEG microscope equipped with the Schottky cathode (maximum accelerating voltage of 30 kV; point-to-point resolution in secondary electrons mode (SE) 1.3 nm. Before this measurement, the sample was mounted on an aluminum holder with double-sided adhesive carbon tape. For all measurements, an accelerating voltage of 15 kV, working distance of 7 mm, and SE mode were used. EDS spectra were taken on a NORAN System 7 X-ray Microanalysis system (Thermo Scientific). For all spectra, an accelerating voltage of 15 kV, working distance of 15 mm, and lifetime of 1000 s were used. All spectra were taken from one point on the top of the AFM tips (magnification 90 000×).

AFM Method

All AFM images and force curves were recorded with Peakforce Tapping mode in a commercial Nanoscope VIII MultiMode SPM system (Bruker, Santa Barbara, CA) under ambient conditions (temperature, 24 °C; humidity, 44%). The curves were recorded using ultrasharp silicon tips (triangular, Scanasyst-Air, Bruker) with a standard spring constant of 0.4 nN/nm (the spring constant was calibrated by the Cleveland methods (40) prior to the experiment) and a normal tip radius of 2 nm. The probes were coated with various metals by vacuum evaporation. All force curves were recorded with a 2 kHz speed, and analyzed with offline software NanoScope Analysis (Bruker, Santa Barbara, CA).

Theoretical Calculations

A tetrahedral M4 metal cluster (Figure 1B) was used as a model of an atomically sharp metalized AFM tip. Recent studies have confirmed that for atomically sharp tips, the maximum attractive force is dominated by the chemical nature of the tip apex atom and the outermost surface atom. (36, 41) All tetrahedrons were positioned tip-down above a 32-atoms periodic supercell representing a graphene sheet (Figure 1B). The geometry of the metal cluster was optimized and fixed throughout the calculation of the interaction energy. The test calculation allowing geometrical relaxation of the metal cluster at an equilibrium distance to the graphene revealed only a minor change of the interaction energy (less than 5%).
The calculations were performed using the Vienna ab Initio Simulation Package (VASP) suite, (42, 43) which makes use of the projector-augmented wave (PAW) construction for the pseudopotential. The energy cutoff for the plane-wave expansion of the eigenfunctions was set to 500 eV. The graphene sheet was modeled using a 4 × 4 supercell (each supercell contained 32 carbon atoms) with a calculated C–C bond length of 1.44 Å. The repeated sheets were separated from each other by 22 Å of vacuum. The shortest in-plane distance between metal atoms was 7 Å. Our test calculations have shown that the 4 × 4 supercell is large enough to prevent the in-plane interaction of repeated tetrahedrons. A dense 5 × 5 × 1 k-point mesh was used to obtain well converged total energies, in particular in the case of exact-exchange calculation. Spin polarization was taken into account in all calculations and spin densities were allowed to relax. The interaction energies (the total energy with respect to the energies of the isolated tetrahedron and graphene sheet) were calculated using the recently developed EE+vdW method, (22) which combines a generalized gradient approximation (GGA) for the exchange functional with a van der Waals functional (vdW-DF) (44, 45) and a fraction of the exact Hartree–Fock exchange. The vdW-DF adds long-range nonlocal electron–electron correlations missing in the GGA functional, and the exact exchange (EE) partly reduces the errors stemming from spurious electron self-interaction in local functionals. (46) The method has been used to obtain very accurate interaction energies of metal adatoms on graphene compared to quantum-chemical coupled-cluster calculations. (22, 38)The forces were calculated from the numerical derivative of the interaction energies (interpolated by a cubic spline). Relativistic effects were included by using a scalar relativistic approximation for Cu, Ag, and Si, whereas a full relativistic description (containing spin–orbit coupling and all relativistic corrections up to order α2, where α is the fine-structure constant) was used for Au and Pt.

Supporting Information

ARTICLE SECTIONS
Jump To

TheSupporting Information contains SEM images and EDS spectra of AFM tips (Supplementary Figures 1–6), interaction energies calculated for various positions on graphene (Supplementary Table 1) and singlet states (Supplementary Table 2) and scalar relativistic Au4 (Supplementary Table 3), typical curves from dynamic AFM measurements (Supplementary Figure 7), and distributions of forces from AFM experiments (Supplementary Figures 8 and 9). This material is available free of charge via the Internet at http://pubs.acs.org.

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

ARTICLE SECTIONS
Jump To

  • Corresponding Authors
    • Mingdong Dong - Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav WiedsVej 14, 8000 Aarhus C, Denmark Email: [email protected] [email protected]
    • Michal Otyepka - Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacký University, 771 46 Olomouc, Czech Republic Email: [email protected] [email protected]
  • Authors
    • Petr Lazar - Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacký University, 771 46 Olomouc, Czech Republic
    • Shuai Zhang - Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav WiedsVej 14, 8000 Aarhus C, Denmark
    • Klára Šafářová - Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacký University, 771 46 Olomouc, Czech Republic
    • Qiang Li - Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav WiedsVej 14, 8000 Aarhus C, Denmark
    • Jens Peter Froning - Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacký University, 771 46 Olomouc, Czech RepublicInterdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav WiedsVej 14, 8000 Aarhus C, Denmark
    • Jaroslav Granatier - Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 166 10 Prague 6, Czech Republic
    • Pavel Hobza - Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacký University, 771 46 Olomouc, Czech RepublicInstitute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 166 10 Prague 6, Czech Republic
    • Radek Zbořil - Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacký University, 771 46 Olomouc, Czech Republic
    • Flemming Besenbacher - Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav WiedsVej 14, 8000 Aarhus C, Denmark
  • Author Contributions

    These authors contributed equally to this work.

  • Notes
    The authors declare no competing financial interest.

Acknowledgment

ARTICLE SECTIONS
Jump To

This work was supported by the Grant Agency of the Czech Republic [P208/12/G016]. This work was also supported by the Operational Program Research and Development for Innovations—European Regional Development Fund (CZ.1.05/2.1.00/03.0058) and European Social Fund (CZ.1.07/2.3.00/20.0017), the Danish National Research Foundation and the Villum Foundation (M.D.) and a student project of Palacký University Olomouc (PrF_2012_028). The support of Praemium Academiae of the Academy of Sciences of the Czech Republic awarded to P.H. in 2007 is also gratefully acknowledged.

References

ARTICLE SECTIONS
Jump To

This article references 46 other publications.

  1. 1
    Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric Field Effect in Atomically thin Carbon Films Science 2004, 306, 666 669
  2. 2
    Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Katsnelson, M. I.; Grigorieva, I. V.; Dubonos, S. V.; Firsov, A. A. Two-Dimensional Gas of Massless Dirac Fermions in Graphene Nature 2005, 438, 197 200
  3. 3
    Geim, A. K.; Novoselov, K. S. The Rise of Graphene Nat. Mater. 2007, 6, 183 191
  4. 4
    Gomes, K. K.; Mar, W.; Ko, W.; Guinea, F.; Manoharan, H. C. Designer Dirac Fermions and Topological Phases in Molecular Graphene Nature 2012, 483, 306 310
  5. 5
    Britnell, L.; Gorbachev, R. V.; Jalil, R.; Belle, B. D.; Schedin, F.; Mishchenko, A.; Georgiou, T.; Katsnelson, M. I.; Eaves, L.; Morozov, S. V.et al. Field-Effect Tunneling Transistor Based on Vertical Graphene Heterostructures Science 2012, 335, 947 950
  6. 6
    Tassin, P.; Koschny, T.; Kafesaki, M.; Soukoulis, C. M. A Comparison of Graphene, Superconductors and Metals as Conductors for Metamaterials and Plasmonics Nat. Photon. 2012, 6, 259 264
  7. 7
    Ju, L.; Geng, B. S.; Horng, J.; Girit, C.; Martin, M.; Hao, Z.; Bechtel, H. A.; Liang, X. G.; Zettl, A.; Shen, Y. R.et al. Graphene Plasmonics for Tunable Terahertz Metamaterials Nat. Nanotechnol. 2011, 6, 630 634
  8. 8
    Kim, K.; Choi, J. Y.; Kim, T.; Cho, S. H.; Chung, H. J. A Role for Graphene in Silicon-Based Semiconductor Devices Nature 2011, 479, 338 344
  9. 9
    Bunch, J. S.; van der Zande, A. M.; Verbridge, S. S.; Frank, I. W.; Tanenbaum, D. M.; Parpia, J. M.; Craighead, H. G.; McEuen, P. L. Electromechanical Resonators from Graphene Sheets Science 2007, 315, 490 493
  10. 10
    Kim, K. S.; Zhao, Y.; Jang, H.; Lee, S. Y.; Kim, J. M.; Kim, K. S.; Ahn, J.-H.; Kim, P.; Choi, J.-Y.; Hong, B. H. Large-Scale Pattern Growth of Graphene Films for Stretchable Transparent Electrodes Nature 2009, 457, 706 710
  11. 11
    Leonard, F.; Talin, A. A. Electrical Contacts to One- and Two-Dimensional Nanomaterials Nat. Nanotechnol. 2011, 6, 773 783
  12. 12
    Lee, H.; Heo, K.; Park, J.; Park, Y.; Noh, S.; Kim, K. S.; Lee, C.; Hong, B. H.; Jian, J.; Hong, S. Graphene-nanowire Hybrid Structures for High-Performance Photoconductive Devices J.Mater. Chem. 2012, 22, 8372 8376
  13. 13
    Zan, R.; Bangert, U.; Ramasse, Q.; Novoselov, K. S. Interaction of Metals with Suspended Graphene Observed by Transmission Electron Microscopy J. Phys. Chem. Lett. 2012, 3, 953 958
  14. 14
    Georgakilas, V.; Otyepka, M.; Bourlinos, A. B.; Chandra, V.; Kim, N.; Kemp, K. C.; Hobza, P.; Zboril, R.; Kim, K. S. Functionalization of Graphene: Covalent and Non-covalent Approaches, Derivatives and Applications Chem. Rev. 2012, 112, 6156 6214
  15. 15
    Myung, S.; Yin, P. T.; Kim, C.; Park, J.; Solanki, A.; Reyes, P. I.; Lu, Y. C.; Kim, K. S.; Lee, K. B. Label-free Polypeptide-Based Enzyme Detection Using a Graphene-Nanoparticle Hybrid Sensor Adv. Mater. 2012, 24, 6081 6087
  16. 16
    Chan, K. T.; Neaton, J. B.; Cohen, M. L. First-Principles Study of Metal Adatom Adsorption on Graphene Phys. Rev. B 2008, 77, 235430
  17. 17
    Giovannetti, G.; Khomyakov, P. A.; Brocks, G.; Karpan, V. M.; van den Brink, J.; Kelly, P. J. Doping Graphene with Metal Contacts Phys. Rev. Lett. 2008, 101, 026803
  18. 18
    Johll, H.; Kang, H. C.; Tok, E. S. Density Functional Theory Study of Fe, Co, and Ni Adatoms and Dimers Adsorbed on Graphene Phys. Rev. B 2009, 79, 245416
  19. 19
    Khomyakov, P. A.; Giovannetti, G.; Rusu, P. C.; Brocks, G.; van den Brink, J.; Kelly, P. J. First-Principles Study of the Interaction and Charge Transfer between Graphene and Metals Phys. Rev. B 2009, 79, 195425
  20. 20
    Hohenberg, P.; Kohn, W. Inhomogeneous Electron Gas Phys. Rev. B 1964, 136, B864
  21. 21
    Kohn, W.; Sham, L. J. Self-Consistent Equations Including Exchange and Correlation Effects Phys. Rev. 1965, 140, 1133
  22. 22
    Granatier, J.; Lazar, P.; Otyepka, M.; Hobza, P. The Nature of the Binding of Au, Ag, and Pd to Benzene, Coronene, and Graphene: From Benchmark CCSD(T) Calculations to Plane-Wave DFT Calculations J. Chem. Theory Comput. 2011, 7, 3743 3755
  23. 23
    Vanin, M.; Mortensen, J. J.; Kelkkanen, A. K.; Garcia-Lastra, J. M.; Thygesen, K. S.; Jacobsen, K. W. Graphene on Metals: A van der Waals Density Functional Study Phys. Rev. B 2010, 81, 081408
  24. 24
    Olsen, T.; Yan, J.; Mortensen, J. J.; Thygesen, K. S. Dispersive and Covalent Interactions between Graphene and Metal Surfaces from the Random Phase Approximation Phys. Rev. Lett. 2011, 107, 156401
  25. 25
    Venugopal, A.; Colombo, L.; Vogel, E. M. Contact Resistance in Few and Multilayer Graphene Devices Appl. Phys. Lett. 2010, 96, 013512
  26. 26
    Pi, K.; McCreary, K. M.; Bao, W.; Han, W.; Chiang, Y. F.; Li, Y.; Tsai, S. W.; Lau, C. N.; Kawakami, R. K. Electronic Doping and Scattering by Transition Metals on Graphene Phys. Rev. B 2009, 80, 075406
  27. 27
    Schimka, L.; Harl, J.; Stroppa, A.; Gruneis, A.; Marsman, M.; Mittendorfer, F.; Kresse, G. Accurate Surface and Adsorption Energies from Many-Body Perturbation Theory Nat. Mater. 2010, 9, 741 744
  28. 28
    Grimme, S. Density Functional Theory with London Dispersion Corrections WIREs Comput. Mol. Sci. 2011, 1, 211 228
  29. 29
    Cramer, C. J.; Truhlar, D. G. Density Functional Theory for Transition Metals and Transition Metal Chemistry Phys. Chem. Chem. Phys. 2009, 11, 10757 10816
  30. 30
    Dong, M.; Sahin, O. A Nanomechanical Interface to Rapid Single-Molecule Interactions Nat. Commun. 2011, 2, 247
  31. 31
    Dong, M. D.; Husale, S.; Sahin, O. Determination of Protein Structural Flexibility by Microsecond Force Spectroscopy Nat. Nanotechnol. 2009, 4, 514 517
  32. 32
    Rico, F.; Su, C.; Scheuring, S. Mechanical Mapping of Single Membrane Proteins at Submolecular Resolution Nano Lett. 2011, 11, 3983 3986
  33. 33
    Medalsy, I.; Hensen, U.; Muller, D. J. Imaging and Quantifying Chemical and Physical Properties of Native Proteins at Molecular Resolution by Force-Volume AFM Angew. Chem., Int. Ed. 2011, 50, 12103 12108
  34. 34
    Lantz, M. A.; Hug, H. J.; Hoffmann, R.; van Schendel, P. J. A.; Kappenberger, P.; Martin, S.; Baratoff, A.; Guntherodt, H. J. Quantitative Measurement of Short-Range Chemical Bonding Forces Science 2001, 291, 2580 2583
  35. 35
    Hoffmann, R.; Kantorovich, L. N.; Baratoff, A.; Hug, H. J.; Guntherodt, H. J. Sublattice Identification in Scanning Force Microscopy on Alkali Halide Surfaces Phys. Rev. Lett. 2004, 92, 146103
  36. 36
    Sugimoto, Y.; Pou, P.; Abe, M.; Jelinek, P.; Perez, R.; Morita, S.; Custance, O. Chemical Identification of Individual Surface Atoms by Atomic Force Microscopy Nature 2007, 446, 64 67
  37. 37
    Yi, H.-B.; Diefenbach, M.; Choi, Y. C.; Lee, E. C.; Lee, H. M.; Hong, B. H.; Kim, K. S. Interactions of Neutral and Cationic Transition Metals with the Redox System of Hydroquinone and Quinone: Theoretical Characterization of the Binding Topologies, and Implications for the Formation of Nanomaterials Chem.—Eur. J. 2006, 12, 4885 4892
  38. 38
    Granatier, J.; Lazar, P.; Prucek, R.; Safarova, K.; Zboril, R.; Otyepka, M.; Hobza, P. Interaction of Graphene and Arenes with Noble Metals J. Phys. Chem. C 2012, 116, 14151 14162
  39. 39
    Blonski, P.; Dennler, S.; Hafner, J. Strong Spin-orbit Effects in Small Pt Clusters: Geometric Structure, Magnetic Isomers and Anisotropy J. Chem. Phys. 2011, 134, 034107
  40. 40
    Cleveland, J. P.; Manne, S.; Bocek, D.; Hansma, P. K. A Nondestructive Method for Determining the Spring Constant of Cantilevers for Scanning Force Microscopy Rew. Sci. Instrum. 1993, 64, 403 405
  41. 41
    Pou, P.; Ghasemi, S. A.; Jelinek, P.; Lenosky, T.; Goedecker, S.; Perez, R. Structure and Stability of Semiconductor Tip Apexes for Atomic Force Microscopy Nanotechnology 2009, 20, 264015
  42. 42
    Blochl, P. E. Projector Augmented-Wave Method Phys. Rev. B 1994, 50, 17953 17979
  43. 43
    Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method Phys. Rev. B 1999, 59, 1758 1775
  44. 44
    Dion, M.; Rydberg, H.; Schroder, E.; Langreth, D. C.; Lundqvist, B. I. Van der Waals Density Functional for General Geometries Phys. Rev. Lett. 2004, 92, 246401
  45. 45
    Klimes, J.; Bowler, D. R.; Michaelides, A. Van der Waals Density Functionals Applied to Solids Phys. Rev. B 2011, 83, 195313
  46. 46
    Cohen, A. J.; Mori-Sanchez, P.; Yang, W. T. Challenges for Density Functional Theory Chem. Rev. 2012, 112, 289 320

Cited By


This article is cited by 59 publications.

  1. Geng Chen, Yi Wang, Hanqin Weng, Zhihao Wu, Kebao He, Peng Zhang, Zifang Guo, Mingzhang Lin. Selective Separation of Pd(II) on Pyridine-Functionalized Graphene Oxide Prepared by Radiation-Induced Simultaneous Grafting Polymerization and Reduction. ACS Applied Materials & Interfaces 2019, 11 (27) , 24560-24570. https://doi.org/10.1021/acsami.9b06162
  2. Raman Bekarevich, Masami Toyoda, Kaifeng Zhang, Toshihiko Nakata, Shin-ichi Taniguchi, and Kaori Hirahara . Coalescence of Metal Nanoparticles as the Origin of Nanocapillary Forces in Carbon Nanotubes. The Journal of Physical Chemistry C 2017, 121 (17) , 9606-9611. https://doi.org/10.1021/acs.jpcc.7b01788
  3. Nicolas P. E. Barry, Anaïs Pitto-Barry, Johanna Tran, Simon E. F. Spencer, Adam M. Johansen, Ana M. Sanchez, Andrew P. Dove, Rachel K. O’Reilly, Robert J. Deeth, Richard Beanland, and Peter J. Sadler . Osmium Atoms and Os2 Molecules Move Faster on Selenium-Doped Compared to Sulfur-Doped Boronic Graphenic Surfaces. Chemistry of Materials 2015, 27 (14) , 5100-5105. https://doi.org/10.1021/acs.chemmater.5b01853
  4. Seong Uk Yu, Beomjin Park, Yeonchoo Cho, Seung Hyun, Jin Kon Kim, and Kwang S. Kim . Simultaneous Visualization of Graphene Grain Boundaries and Wrinkles with Structural Information by Gold Deposition. ACS Nano 2014, 8 (8) , 8662-8668. https://doi.org/10.1021/nn503550d
  5. Dan Xia, Shuai Zhang, Jesper Østergaard Hjortdal, Qiang Li, Karen Thomsen, Jacques Chevallier, Flemming Besenbacher, and Mingdong Dong . Hydrated Human Corneal Stroma Revealed by Quantitative Dynamic Atomic Force Microscopy at Nanoscale. ACS Nano 2014, 8 (7) , 6873-6882. https://doi.org/10.1021/nn5015837
  6. Rabeka Alam, Ian V. Lightcap, Christopher J. Karwacki, and Prashant V. Kamat . Sense and Shoot: Simultaneous Detection and Degradation of Low-Level Contaminants Using Graphene-Based Smart Material Assembly. ACS Nano 2014, 8 (7) , 7272-7278. https://doi.org/10.1021/nn502336x
  7. Deliang Zhang, Yuge Zhang, Qiang Li, Mingdong Dong. Origin of friction hysteresis on monolayer graphene. Friction 2021, 17 https://doi.org/10.1007/s40544-021-0517-1
  8. Jiajing Zhu, Yanling Tian, Zuobin Wang, Ying Wang, Wenxiao Zhang, Kaige Qu, Zhankun Weng, Xianping Liu. Investigation of the mechanical effects of targeted drugs on cancerous cells based on atomic force microscopy. Analytical Methods 2021, 13 (28) , 3136-3146. https://doi.org/10.1039/D1AY00649E
  9. Anupam Singha Roy, Aby Cheruvathoor Poulose, Aristides Bakandritsos, Rajender S. Varma, Michal Otyepka. 2D graphene derivatives as heterogeneous catalysts to produce biofuels via esterification and trans-esterification reactions. Applied Materials Today 2021, 23 , 101053. https://doi.org/10.1016/j.apmt.2021.101053
  10. Zhou Huaicheng, Wu Lei, Yu Bingjun, Qin Na, . Revealing Topography Evolution of Glass Surface under Air Pollution by Atomic Force Microscope. Scanning 2021, 2021 , 1-7. https://doi.org/10.1155/2021/6650020
  11. Zezhou Lin, Zheng Wang, Xi Zhang, Dongfeng Diao. Superhydrophobic, photo-sterilize, and reusable mask based on graphene nanosheet-embedded carbon (GNEC) film. Nano Research 2021, 14 (4) , 1110-1115. https://doi.org/10.1007/s12274-020-3158-1
  12. Hao Liu, Ya-nan Qin, Hao-yu Li, Li-xue Gai, Qing-da An, Shang-ru Zhai, Zuo-yi Xiao, Li Cui. Promotional effect of embedded Ni NPs in alginate-based carbon toward Pd NPs efficiency for high-concentration p-nitrophenol reduction. International Journal of Biological Macromolecules 2021, 173 , 160-167. https://doi.org/10.1016/j.ijbiomac.2021.01.111
  13. Periyasami Gnanaprakasam, Aruchamy Gowrisankar, Shanmugam Senthilkumar, Arumugam Murugadoss, Thangavelu Selvaraju, Ramalinga Viswanathan Mangalaraja. One pot in situ synthesis of nano Au–Pd core-shells embedded on reduced graphene oxide for the oxygen reduction reaction. Materials Science and Engineering: B 2021, 264 , 114924. https://doi.org/10.1016/j.mseb.2020.114924
  14. Ming Yang, Yue Liu, Tongxiang Fan, Di Zhang. Metal-graphene interfaces in epitaxial and bulk systems: A review. Progress in Materials Science 2020, 110 , 100652. https://doi.org/10.1016/j.pmatsci.2020.100652
  15. Vito Despoja, Ivan Radović, Antonio Politano, Zoran L. Mišković. Insights on the Excitation Spectrum of Graphene Contacted with a Pt Skin. Nanomaterials 2020, 10 (4) , 703. https://doi.org/10.3390/nano10040703
  16. Carlos Marcuello, Laurence Foulon, Brigitte Chabbert, Veronique Aguié-Béghin, Michael Molinari. Atomic force microscopy reveals how relative humidity impacts the Young’s modulus of lignocellulosic polymers and their adhesion with cellulose nanocrystals at the nanoscale. International Journal of Biological Macromolecules 2020, 147 , 1064-1075. https://doi.org/10.1016/j.ijbiomac.2019.10.074
  17. Eduardo Schiavo, Ana B. Muñoz-García, Pasqualino Maddalena, Orlando Crescenzi, Michele Pavone. Doped graphene and Ag(1 1 1) hybrid material as fuel cell electrode: New insights on interfacial features and oxygen adsorption from dispersion-corrected density functional theory. Computational Materials Science 2019, 169 , 109141. https://doi.org/10.1016/j.commatsci.2019.109141
  18. Xiaolin Jiang, Ke Ma, Cuihua Hu, Mingyan Gao, Jiashuo Zhang, Ying Wang, Yujuan Chen, Zhengxun Song, Zuobin Wang. Evaluation of 5-fluorouracil-treated lung cancer cells by atomic force microscopy. Analytical Methods 2019, 11 (39) , 4977-4982. https://doi.org/10.1039/C9AY01485C
  19. Jing Hu, Jie Jiao, Ying Wang, Mingyan Gao, Zhengcheng Lu, Fan Yang, Cuihua Hu, Zhengxun Song, Yujuan Chen, Zuobin Wang. Effect of extract from ginseng rust rot on the inhibition of human hepatocellular carcinoma cells in vitro. Micron 2019, 124 , 102710. https://doi.org/10.1016/j.micron.2019.102710
  20. K. Rajkumar, R.T. Rajendra Kumar. Gas Sensors Based on Two-Dimensional Materials and Its Mechanisms. 2019,,, 205-258. https://doi.org/10.1016/B978-0-08-102577-2.00006-3
  21. D. Semenova, K. V. Gernaey, Y. E. Silina. Exploring the potential of electroless and electroplated noble metal–semiconductor hybrids within bio- and environmental sensing. The Analyst 2018, 143 (23) , 5646-5669. https://doi.org/10.1039/C8AN01632A
  22. Xueqin Wang, Fang Wang, Chen Bo, Kai Cheng, Junlei Wang, Jiaojing Zhang, Hua Song. Promotion of phenol photodecomposition and the corresponding decomposition mechanism over g-C3N4/TiO2 nanocomposites. Applied Surface Science 2018, 453 , 320-329. https://doi.org/10.1016/j.apsusc.2018.05.082
  23. Scott E. Muller, Raghuram R. Santhapuram, Arun K. Nair. Failure mechanisms in pre-cracked Ni-graphene nanocomposites. Computational Materials Science 2018, 152 , 341-350. https://doi.org/10.1016/j.commatsci.2018.06.013
  24. Nan Li, Zhen Hu, Yudong Huang. Preparation and characterization of nanocomposites of poly( p -phenylene benzobisoxazole) with aminofunctionalized graphene. Polymer Composites 2018, 39 (8) , 2969-2976. https://doi.org/10.1002/pc.24299
  25. Xiao Chang, Lei Zhu, Qingzhong Xue, Xiao Li, Tianchao Guo, Xiaofang Li, Ming Ma. Charge controlled switchable CO2/N2 separation for g-C10N9 membrane: Insights from molecular dynamics simulations. Journal of CO2 Utilization 2018, 26 , 294-301. https://doi.org/10.1016/j.jcou.2018.05.017
  26. Rehana Afrin, Narangerel Ganbaatar, Masashi Aono, H. Cleaves II, Taka-aki Yano, Masahiko Hara. Size-Dependent Affinity of Glycine and Its Short Oligomers to Pyrite Surface: A Model for Prebiotic Accumulation of Amino Acid Oligomers on a Mineral Surface. International Journal of Molecular Sciences 2018, 19 (2) , 365. https://doi.org/10.3390/ijms19020365
  27. Chengli Wang, Yingchun Su, Xiaole Zhao, Shanshan Tong, Xiaojun Han. MoS 2 @HKUST-1 Flower-Like Nanohybrids for Efficient Hydrogen Evolution Reactions. Chemistry - A European Journal 2018, 24 (5) , 1080-1087. https://doi.org/10.1002/chem.201704080
  28. Jinyun Liu, Yingmin Qu, Guoliang Wang, Xinyue Wang, Wenxiao Zhang, Jingmei Li, Zuobin Wang, Dayou Li, Jinlan Jiang. Study of morphological and mechanical features of multinuclear and mononuclear SW480 cells by atomic force microscopy. Microscopy Research and Technique 2018, 81 (1) , 3-12. https://doi.org/10.1002/jemt.22950
  29. Ruby Srivastava. Theoretical studies of optoelectronic, magnetization and heat transport properties of conductive metal adatoms adsorbed on edge chlorinated nanographenes. RSC Advances 2018, 8 (32) , 17723-17731. https://doi.org/10.1039/C8RA02032A
  30. Guangshun Wu, Lichun Ma, Hua Jiang, Li Liu, Yudong Huang. Improving the interfacial strength of silicone resin composites by chemically grafting silica nanoparticles on carbon fiber. Composites Science and Technology 2017, 153 , 160-167. https://doi.org/10.1016/j.compscitech.2017.10.020
  31. Akshay V. Singhal, Hemant Charaya, Indranil Lahiri. Noble Metal Decorated Graphene-Based Gas Sensors and Their Fabrication: A Review. Critical Reviews in Solid State and Materials Sciences 2017, 42 (6) , 499-526. https://doi.org/10.1080/10408436.2016.1244656
  32. Somayeh Taghavi, Alireza Asghari, Ahmad Tavasoli. Enhancement of performance and stability of Graphene nano sheets supported cobalt catalyst in Fischer–Tropsch synthesis using Graphene functionalization. Chemical Engineering Research and Design 2017, 119 , 198-208. https://doi.org/10.1016/j.cherd.2017.01.021
  33. Diego Mateo, Iván Esteve-Adell, Josep Albero, Ana Primo, Hermenegildo García. Oriented 2.0.0 Cu2O nanoplatelets supported on few-layers graphene as efficient visible light photocatalyst for overall water splitting. Applied Catalysis B: Environmental 2017, 201 , 582-590. https://doi.org/10.1016/j.apcatb.2016.08.033
  34. Jens P. Froning, Petr Lazar, Martin Pykal, Qiang Li, Mingdong Dong, Radek Zbořil, Michal Otyepka. Direct mapping of chemical oxidation of individual graphene sheets through dynamic force measurements at the nanoscale. Nanoscale 2017, 9 (1) , 119-127. https://doi.org/10.1039/C6NR05799C
  35. Cai Xia Wu, Shi Zheng Wen, Li Kai Yan, Min Zhang, Teng Ying Ma, Yu He Kan, Zhong Min Su. Conductive metal adatoms adsorbed on graphene nanoribbons: a first-principles study of electronic structures, magnetization and transport properties. Journal of Materials Chemistry C 2017, 5 (16) , 4053-4062. https://doi.org/10.1039/C6TC05545A
  36. Yue Liu, Yuhong Zhang, Lanlan Duan, Weili Zhang, Mingji Su, Zhengguang Sun, Peixin He. Polystyrene/graphene oxide nanocomposites synthesized via Pickering polymerization. Progress in Organic Coatings 2016, 99 , 23-31. https://doi.org/10.1016/j.porgcoat.2016.04.034
  37. Yakang Jin, Qingzhong Xue, Lei Zhu, Xiaofang Li, Xinglong Pan, Jianqiang Zhang, Wei Xing, Tiantian Wu, Zilong Liu. Self-Assembly of Hydrofluorinated Janus Graphene Monolayer: A Versatile Route for Designing Novel Janus Nanoscrolls. Scientific Reports 2016, 6 (1) https://doi.org/10.1038/srep26914
  38. Juan José Gamboa-Carballo, Kenia Melchor-Rodríguez, Daniel Hernández-Valdés, Carlos Enriquez‐Victorero, Ana Lilian Montero-Alejo, Sarra Gaspard, Ulises Javier Jáuregui-Haza. Theoretical study of chlordecone and surface groups interaction in an activated carbon model under acidic and neutral conditions. Journal of Molecular Graphics and Modelling 2016, 65 , 83-93. https://doi.org/10.1016/j.jmgm.2016.02.008
  39. Myunghee Jung, Jin-San Moon, Won-Hwa Park. Observation of a scrolled graphene nanoribbons with gap-plasmonic system. Applied Physics Letters 2016, 108 (13) , 133101. https://doi.org/10.1063/1.4944895
  40. A. Politano, I. Radović, D. Borka, Z.L. Mišković, G. Chiarello. Interband plasmons in supported graphene on metal substrates: Theory and experiments. Carbon 2016, 96 , 91-97. https://doi.org/10.1016/j.carbon.2015.09.053
  41. Josep Albero, Hermenegildo Garcia. Doped graphenes in catalysis. Journal of Molecular Catalysis A: Chemical 2015, 408 , 296-309. https://doi.org/10.1016/j.molcata.2015.06.011
  42. María Pilar de Lara-Castells, Alexander O. Mitrushchenkov, Hermann Stoll. Combining density functional and incremental post-Hartree-Fock approaches for van der Waals dominated adsorbate-surface interactions: Ag 2 /graphene. The Journal of Chemical Physics 2015, 143 (10) , 102804. https://doi.org/10.1063/1.4919397
  43. Daniel Hernández-Valdés, Carlos Enriquez-Victorero, Luis Pizarro-Lou, David Turiño-Pérez, Luis Ducat-Pagés, Melvin Arias, Ulises Jáuregui-Haza. Interaction of paracetamol and 125I-paracetamol with surface groups of activated carbon: theoretical and experimental study. Journal of Radioanalytical and Nuclear Chemistry 2015, 305 (2) , 609-622. https://doi.org/10.1007/s10967-015-4022-8
  44. M. Althaf Hussain, A. Subha Mahadevi, G. Narahari Sastry. Estimating the binding ability of onium ions with CO 2 and π systems: a computational investigation. Physical Chemistry Chemical Physics 2015, 17 (3) , 1763-1775. https://doi.org/10.1039/C4CP03434A
  45. Jacco Hoekstra, Andrew M. Beale, Fouad Soulimani, Marjan Versluijs-Helder, John W. Geus, Leonardus W. Jenneskens. Shell decoration of hydrothermally obtained colloidal carbon spheres with base metal nanoparticles. New Journal of Chemistry 2015, 39 (8) , 6593-6601. https://doi.org/10.1039/C5NJ00804B
  46. Mikhail V. Polynski, Valentine P. Ananikov. Computational Modeling of Graphene Systems Containing Transition Metal Atoms and Clusters. 2014,,, 321-374. https://doi.org/10.1002/9783527678211.ch11
  47. Nicolas P. E. Barry, Anaïs Pitto-Barry, Ana M. Sanchez, Andrew P. Dove, Richard J. Procter, Joan J. Soldevila-Barreda, Nigel Kirby, Ian Hands-Portman, Corinne J. Smith, Rachel K. O’Reilly, Richard Beanland, Peter J. Sadler. Fabrication of crystals from single metal atoms. Nature Communications 2014, 5 (1) https://doi.org/10.1038/ncomms4851
  48. Zi Wen, Jinsong Luo, Yongfu Zhu, Qing Jiang. Cohesive-Energy-Resolved Bandgap of Nanoscale Graphene Derivatives. ChemPhysChem 2014, 15 (12) , 2563-2568. https://doi.org/10.1002/cphc.201402125
  49. Siyavash Kazemi Movahed, Minoo Dabiri, Ayoob Bazgir. A one-step method for preparation of [email protected] nanoparticles on reduced graphene oxide and their catalytic activities in N-arylation of N-heterocycles. Applied Catalysis A: General 2014, 481 , 79-88. https://doi.org/10.1016/j.apcata.2014.04.023
  50. Petr Lazar, Eva Otyepková, Pavel Banáš, Ariana Fargašová, Klára Šafářová, Lubomír Lapčík, Jiří Pechoušek, Radek Zbořil, Michal Otyepka. The nature of high surface energy sites in graphene and graphite. Carbon 2014, 73 , 448-453. https://doi.org/10.1016/j.carbon.2014.03.010
  51. Carlos Enriquez-Victorero, Daniel Hernández-Valdés, Ana Lilian Montero-Alejo, Axelle Durimel, Sarra Gaspard, Ulises Jáuregui-Haza. Theoretical study of γ-hexachlorocyclohexane and β-hexachlorocyclohexane isomers interaction with surface groups of activated carbon model. Journal of Molecular Graphics and Modelling 2014, 51 , 137-148. https://doi.org/10.1016/j.jmgm.2014.05.004
  52. Yongfu Zhu, Jianshe Lian, Qing Jiang. Role of Edge Geometry and Magnetic Interaction in Opening Bandgap of Low-Dimensional Graphene. ChemPhysChem 2014, 15 (5) , 958-965. https://doi.org/10.1002/cphc.201301127
  53. Zhanghui Chen, Jingbo Li, Shushen Li, Linwang Wang. Approximate Hessian for accelerating ab initio structure relaxation by force fitting. Physical Review B 2014, 89 (14) https://doi.org/10.1103/PhysRevB.89.144110
  54. Zaixing Jiang, Jun Li, Hüsnü Aslan, Qiang Li, Yue Li, Menglin Chen, Yudong Huang, Jens Peter Froning, Michal Otyepka, Radek Zbořil, Flemming Besenbacher, Mingdong Dong. A high efficiency H 2 S gas sensor material: paper like Fe 2 O 3 /graphene nanosheets and structural alignment dependency of device efficiency. J. Mater. Chem. A 2014, 2 (19) , 6714-6717. https://doi.org/10.1039/C3TA15180H
  55. Petr Lazar, Jaroslav Granatier, Jiří Klimeš, Pavel Hobza, Michal Otyepka. The nature of bonding and electronic properties of graphene and benzene with iridium adatoms. Phys. Chem. Chem. Phys. 2014, 16 (38) , 20818-20827. https://doi.org/10.1039/C4CP02608J
  56. Shuai Zhang, Hüsnü Aslan, Flemming Besenbacher, Mingdong Dong. Quantitative biomolecular imaging by dynamic nanomechanical mapping. Chem. Soc. Rev. 2014, 43 (21) , 7412-7429. https://doi.org/10.1039/C4CS00176A
  57. Nick Clark, Antonios Oikonomou, Aravind Vijayaraghavan. Ultrafast quantitative nanomechanical mapping of suspended graphene. physica status solidi (b) 2013, 250 (12) , 2672-2677. https://doi.org/10.1002/pssb.201300137
  58. Patanachai Janthon, Francesc Viñes, Sergey M. Kozlov, Jumras Limtrakul, Francesc Illas. Theoretical assessment of graphene-metal contacts. The Journal of Chemical Physics 2013, 138 (24) , 244701. https://doi.org/10.1063/1.4807855
  59. Lei Chen, Zhen Hu, Li Liu, Yudong Huang. A facile method to prepare multifunctional PBO fibers: simultaneously enhanced interfacial properties and UV resistance. RSC Advances 2013, 3 (46) , 24664. https://doi.org/10.1039/c3ra44876b
  • Abstract

    Figure 1

    Figure 1. (A) Schematic of AFM operation in dynamic range force spectroscopy showing a metal-coated probe scanning a graphene sheet on a SiO2 support; (B) atomic level model of metal-coated tip on graphene used in the DFT calculations; (C) SEM image of AFM tip coated by gold (see Supplementary Figure 3 for EDS spectrum); (D) optical image of the graphene substrate on SiO2 used during the experiment. The dashed square indicates the location of the inset of Figure 2A.

    Figure 2

    Figure 2. Graphene morphology and interaction force curves between metal-coated AFM probe and graphene: (A) AFM morphology images of graphene; (B) typical force vs time curve of Cu-coated probe and graphene; red B and green C dots indicate the adhesion force during approach and withdrawal, respectively; (C) typical force vs separation curves derived from the approach process (Fapp); (D) typical force vs separation curves derived from the withdrawal process (Fw).

    Figure 3

    Figure 3. Calculated interaction energy curves (upper panel) and derived interaction forces (lower panel) between Au tip and graphene. The crosses denote the total energies calculated with various functionals (PBE, PBE+vdW, EE+vdW, and EE+vdW with spin–orbit coupling).

    Figure 4

    Figure 4. The experimentally derived interaction forces from the approach processes (in blue) are compared with the interaction forces calculated by the EE-vdW method (in red).

  • References

    ARTICLE SECTIONS
    Jump To

    This article references 46 other publications.

    1. 1
      Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric Field Effect in Atomically thin Carbon Films Science 2004, 306, 666 669
    2. 2
      Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Katsnelson, M. I.; Grigorieva, I. V.; Dubonos, S. V.; Firsov, A. A. Two-Dimensional Gas of Massless Dirac Fermions in Graphene Nature 2005, 438, 197 200
    3. 3
      Geim, A. K.; Novoselov, K. S. The Rise of Graphene Nat. Mater. 2007, 6, 183 191
    4. 4
      Gomes, K. K.; Mar, W.; Ko, W.; Guinea, F.; Manoharan, H. C. Designer Dirac Fermions and Topological Phases in Molecular Graphene Nature 2012, 483, 306 310
    5. 5
      Britnell, L.; Gorbachev, R. V.; Jalil, R.; Belle, B. D.; Schedin, F.; Mishchenko, A.; Georgiou, T.; Katsnelson, M. I.; Eaves, L.; Morozov, S. V.et al. Field-Effect Tunneling Transistor Based on Vertical Graphene Heterostructures Science 2012, 335, 947 950
    6. 6
      Tassin, P.; Koschny, T.; Kafesaki, M.; Soukoulis, C. M. A Comparison of Graphene, Superconductors and Metals as Conductors for Metamaterials and Plasmonics Nat. Photon. 2012, 6, 259 264
    7. 7
      Ju, L.; Geng, B. S.; Horng, J.; Girit, C.; Martin, M.; Hao, Z.; Bechtel, H. A.; Liang, X. G.; Zettl, A.; Shen, Y. R.et al. Graphene Plasmonics for Tunable Terahertz Metamaterials Nat. Nanotechnol. 2011, 6, 630 634
    8. 8
      Kim, K.; Choi, J. Y.; Kim, T.; Cho, S. H.; Chung, H. J. A Role for Graphene in Silicon-Based Semiconductor Devices Nature 2011, 479, 338 344
    9. 9
      Bunch, J. S.; van der Zande, A. M.; Verbridge, S. S.; Frank, I. W.; Tanenbaum, D. M.; Parpia, J. M.; Craighead, H. G.; McEuen, P. L. Electromechanical Resonators from Graphene Sheets Science 2007, 315, 490 493
    10. 10
      Kim, K. S.; Zhao, Y.; Jang, H.; Lee, S. Y.; Kim, J. M.; Kim, K. S.; Ahn, J.-H.; Kim, P.; Choi, J.-Y.; Hong, B. H. Large-Scale Pattern Growth of Graphene Films for Stretchable Transparent Electrodes Nature 2009, 457, 706 710
    11. 11
      Leonard, F.; Talin, A. A. Electrical Contacts to One- and Two-Dimensional Nanomaterials Nat. Nanotechnol. 2011, 6, 773 783
    12. 12
      Lee, H.; Heo, K.; Park, J.; Park, Y.; Noh, S.; Kim, K. S.; Lee, C.; Hong, B. H.; Jian, J.; Hong, S. Graphene-nanowire Hybrid Structures for High-Performance Photoconductive Devices J.Mater. Chem. 2012, 22, 8372 8376
    13. 13
      Zan, R.; Bangert, U.; Ramasse, Q.; Novoselov, K. S. Interaction of Metals with Suspended Graphene Observed by Transmission Electron Microscopy J. Phys. Chem. Lett. 2012, 3, 953 958
    14. 14
      Georgakilas, V.; Otyepka, M.; Bourlinos, A. B.; Chandra, V.; Kim, N.; Kemp, K. C.; Hobza, P.; Zboril, R.; Kim, K. S. Functionalization of Graphene: Covalent and Non-covalent Approaches, Derivatives and Applications Chem. Rev. 2012, 112, 6156 6214
    15. 15
      Myung, S.; Yin, P. T.; Kim, C.; Park, J.; Solanki, A.; Reyes, P. I.; Lu, Y. C.; Kim, K. S.; Lee, K. B. Label-free Polypeptide-Based Enzyme Detection Using a Graphene-Nanoparticle Hybrid Sensor Adv. Mater. 2012, 24, 6081 6087
    16. 16
      Chan, K. T.; Neaton, J. B.; Cohen, M. L. First-Principles Study of Metal Adatom Adsorption on Graphene Phys. Rev. B 2008, 77, 235430
    17. 17
      Giovannetti, G.; Khomyakov, P. A.; Brocks, G.; Karpan, V. M.; van den Brink, J.; Kelly, P. J. Doping Graphene with Metal Contacts Phys. Rev. Lett. 2008, 101, 026803
    18. 18
      Johll, H.; Kang, H. C.; Tok, E. S. Density Functional Theory Study of Fe, Co, and Ni Adatoms and Dimers Adsorbed on Graphene Phys. Rev. B 2009, 79, 245416
    19. 19
      Khomyakov, P. A.; Giovannetti, G.; Rusu, P. C.; Brocks, G.; van den Brink, J.; Kelly, P. J. First-Principles Study of the Interaction and Charge Transfer between Graphene and Metals Phys. Rev. B 2009, 79, 195425
    20. 20
      Hohenberg, P.; Kohn, W. Inhomogeneous Electron Gas Phys. Rev. B 1964, 136, B864
    21. 21
      Kohn, W.; Sham, L. J. Self-Consistent Equations Including Exchange and Correlation Effects Phys. Rev. 1965, 140, 1133
    22. 22
      Granatier, J.; Lazar, P.; Otyepka, M.; Hobza, P. The Nature of the Binding of Au, Ag, and Pd to Benzene, Coronene, and Graphene: From Benchmark CCSD(T) Calculations to Plane-Wave DFT Calculations J. Chem. Theory Comput. 2011, 7, 3743 3755
    23. 23
      Vanin, M.; Mortensen, J. J.; Kelkkanen, A. K.; Garcia-Lastra, J. M.; Thygesen, K. S.; Jacobsen, K. W. Graphene on Metals: A van der Waals Density Functional Study Phys. Rev. B 2010, 81, 081408
    24. 24
      Olsen, T.; Yan, J.; Mortensen, J. J.; Thygesen, K. S. Dispersive and Covalent Interactions between Graphene and Metal Surfaces from the Random Phase Approximation Phys. Rev. Lett. 2011, 107, 156401
    25. 25
      Venugopal, A.; Colombo, L.; Vogel, E. M. Contact Resistance in Few and Multilayer Graphene Devices Appl. Phys. Lett. 2010, 96, 013512
    26. 26
      Pi, K.; McCreary, K. M.; Bao, W.; Han, W.; Chiang, Y. F.; Li, Y.; Tsai, S. W.; Lau, C. N.; Kawakami, R. K. Electronic Doping and Scattering by Transition Metals on Graphene Phys. Rev. B 2009, 80, 075406
    27. 27
      Schimka, L.; Harl, J.; Stroppa, A.; Gruneis, A.; Marsman, M.; Mittendorfer, F.; Kresse, G. Accurate Surface and Adsorption Energies from Many-Body Perturbation Theory Nat. Mater. 2010, 9, 741 744
    28. 28
      Grimme, S. Density Functional Theory with London Dispersion Corrections WIREs Comput. Mol. Sci. 2011, 1, 211 228
    29. 29
      Cramer, C. J.; Truhlar, D. G. Density Functional Theory for Transition Metals and Transition Metal Chemistry Phys. Chem. Chem. Phys. 2009, 11, 10757 10816
    30. 30
      Dong, M.; Sahin, O. A Nanomechanical Interface to Rapid Single-Molecule Interactions Nat. Commun. 2011, 2, 247
    31. 31
      Dong, M. D.; Husale, S.; Sahin, O. Determination of Protein Structural Flexibility by Microsecond Force Spectroscopy Nat. Nanotechnol. 2009, 4, 514 517
    32. 32
      Rico, F.; Su, C.; Scheuring, S. Mechanical Mapping of Single Membrane Proteins at Submolecular Resolution Nano Lett. 2011, 11, 3983 3986
    33. 33
      Medalsy, I.; Hensen, U.; Muller, D. J. Imaging and Quantifying Chemical and Physical Properties of Native Proteins at Molecular Resolution by Force-Volume AFM Angew. Chem., Int. Ed. 2011, 50, 12103 12108
    34. 34
      Lantz, M. A.; Hug, H. J.; Hoffmann, R.; van Schendel, P. J. A.; Kappenberger, P.; Martin, S.; Baratoff, A.; Guntherodt, H. J. Quantitative Measurement of Short-Range Chemical Bonding Forces Science 2001, 291, 2580 2583
    35. 35
      Hoffmann, R.; Kantorovich, L. N.; Baratoff, A.; Hug, H. J.; Guntherodt, H. J. Sublattice Identification in Scanning Force Microscopy on Alkali Halide Surfaces Phys. Rev. Lett. 2004, 92, 146103
    36. 36
      Sugimoto, Y.; Pou, P.; Abe, M.; Jelinek, P.; Perez, R.; Morita, S.; Custance, O. Chemical Identification of Individual Surface Atoms by Atomic Force Microscopy Nature 2007, 446, 64 67
    37. 37
      Yi, H.-B.; Diefenbach, M.; Choi, Y. C.; Lee, E. C.; Lee, H. M.; Hong, B. H.; Kim, K. S. Interactions of Neutral and Cationic Transition Metals with the Redox System of Hydroquinone and Quinone: Theoretical Characterization of the Binding Topologies, and Implications for the Formation of Nanomaterials Chem.—Eur. J. 2006, 12, 4885 4892
    38. 38
      Granatier, J.; Lazar, P.; Prucek, R.; Safarova, K.; Zboril, R.; Otyepka, M.; Hobza, P. Interaction of Graphene and Arenes with Noble Metals J. Phys. Chem. C 2012, 116, 14151 14162
    39. 39
      Blonski, P.; Dennler, S.; Hafner, J. Strong Spin-orbit Effects in Small Pt Clusters: Geometric Structure, Magnetic Isomers and Anisotropy J. Chem. Phys. 2011, 134, 034107
    40. 40
      Cleveland, J. P.; Manne, S.; Bocek, D.; Hansma, P. K. A Nondestructive Method for Determining the Spring Constant of Cantilevers for Scanning Force Microscopy Rew. Sci. Instrum. 1993, 64, 403 405
    41. 41
      Pou, P.; Ghasemi, S. A.; Jelinek, P.; Lenosky, T.; Goedecker, S.; Perez, R. Structure and Stability of Semiconductor Tip Apexes for Atomic Force Microscopy Nanotechnology 2009, 20, 264015
    42. 42
      Blochl, P. E. Projector Augmented-Wave Method Phys. Rev. B 1994, 50, 17953 17979
    43. 43
      Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method Phys. Rev. B 1999, 59, 1758 1775
    44. 44
      Dion, M.; Rydberg, H.; Schroder, E.; Langreth, D. C.; Lundqvist, B. I. Van der Waals Density Functional for General Geometries Phys. Rev. Lett. 2004, 92, 246401
    45. 45
      Klimes, J.; Bowler, D. R.; Michaelides, A. Van der Waals Density Functionals Applied to Solids Phys. Rev. B 2011, 83, 195313
    46. 46
      Cohen, A. J.; Mori-Sanchez, P.; Yang, W. T. Challenges for Density Functional Theory Chem. Rev. 2012, 112, 289 320
  • Supporting Information

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    TheSupporting Information contains SEM images and EDS spectra of AFM tips (Supplementary Figures 1–6), interaction energies calculated for various positions on graphene (Supplementary Table 1) and singlet states (Supplementary Table 2) and scalar relativistic Au4 (Supplementary Table 3), typical curves from dynamic AFM measurements (Supplementary Figure 7), and distributions of forces from AFM experiments (Supplementary Figures 8 and 9). This material is available free of charge via the Internet at http://pubs.acs.org.


    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect

This website uses cookies to improve your user experience. By continuing to use the site, you are accepting our use of cookies. Read the ACS privacy policy.

CONTINUE