Conversion of self-assembled monolayers into nanocrystalline graphene: Structure and electric transport

Graphene-based materials have been suggested for applications ranging from nanoelectronics to nanobiotechnology. However, the realization of graphene-based technologies will require large quantities of free-standing two-dimensional (2D) carbon materials with tuneable physical and chemical properties. Bottom-up approaches via molecular self-assembly have great potential to fulfil this demand. Here, we report on the fabrication and characterization of graphene made by electron-radiation induced cross-linking of aromatic self-assembled monolayers (SAMs) and their subsequent annealing. In this process, the SAM is converted into a nanocrystalline graphene sheet with well defined thickness and arbitrary dimensions. Electric transport data demonstrate that this transformation is accompanied by an insulator to metal transition that can be utilized to control electrical properties such as conductivity, electron mobility and ambipolar electric field effect of the fabricated graphene sheets. The suggested route opens broad prospects towards the engineering of free-standing 2D carbon materials with tuneable properties on various solid substrates and on holey substrates as suspended membranes.Comment: 30 pages, 5 figure

Structural Investigation of 1,1 '-Biphenyl-4-thiol Self-Assembled Monolayers on Au(111) by Scanning Tunneling Microscopy and Low-Energy Electron Diffraction

Matei D, Muzik H, Gölzhäuser A, Turchanin A. Structural Investigation of 1,1 '-Biphenyl-4-thiol Self-Assembled Monolayers on Au(111) by Scanning Tunneling Microscopy and Low-Energy Electron Diffraction. Langmuir. 2012;28(39):13905-13911.Self-assembled monolayers (SAMs) of 1,1'-biphenyl-4-thiol (H-(C6H4)(2)-SH) on Au(111) were prepared from solution or via vapor deposition in ultrahigh vacuum and characterized by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and X-ray photoelectron spectroscopy (XPS). In contrast to the typically observed for densely packed alkane-thiol SAMs on Au(111) (root 3 x root 3)R30 degrees structure, the densely packed aromatic biphenylthiol SAMs prepared by both methods exhibit an unusual hexagonal (2 x 2) structure. Upon annealing at 100 degrees C, this structure evolves into the (2 x 7 root 3) structure resulting in the formation of highly ordered pinstripes oriented along the directions. Lower density SAMs, prepared by vapor deposition in vacuum, show mixed structures comprising the hexagonal (2 x 2) structure and two rectangular arrangements with the unit cells of (3 root 3 x 9) and (2 root 3 x 8). An extinction of the (3 root 3 x 9) structure in the favor of the (2 root 3 x 8) structure is observed upon annealing at temperatures of similar to 100 degrees C

X-ray holographic microscopy with zone plates applied to biological samples in the water window using 3rd harmonic radiation from the free-electron laser FLASH

The imaging of hydrated biological samples - especially in the energy window of 284-540 eV, where water does not obscure the signal of soft organic matter and biologically relevant elements - is of tremendous interest for life sciences. Free-electron lasers can provide highly intense and coherent pulses, which allow single pulse imaging to overcome resolution limits set by radiation damage. One current challenge is to match both the desired energy and the intensity of the light source. We present the first images of dehydrated biological material acquired with 3rd harmonic radiation from FLASH by digital in-line zone plate holography as one step towards the vision of imaging hydrated biological material with photons in the water window. We also demonstrate the first application of ultrathin molecular sheets as suitable substrates for future free-electron laser experiments with biological samples in the form of a rat fibroblast cell and marine biofouling bacteria Cobetia marina

A Universal Scheme to Convert Aromatic Molecular Monolayers into Functional Carbon Nanomembranes

Angelova P, Vieker H, Weber N-E, et al. A Universal Scheme to Convert Aromatic Molecular Monolayers into Functional Carbon Nanomembranes. Acs Nano. 2013;7(8):6489-6497.Free-standing nanomembranes with molecular or atomic thickness are currently explored for separation technologies, electronics, and sensing. Their engineering with well-defined structural and functional properties is a challenge for materials research. Here we present a broadly applicable scheme to create mechanically stable carbon nanomembranes (CNMs) with a thickness of similar to 0.5 to similar to 3 nm. Monolayers of polyaromatic molecules (oligophenyls, hexaphenylbenzene, and polycyclic aromatic hydrocarbons) were assembled and exposed to electrons that cross-link them into CNMs; subsequent pyrolysis converts the CNMs into graphene sheets. In this transformation the thickness, porosity, and surface functionality of the nanomembranes are determined by the monolayers, and structural and functional features are passed on from the molecules through their monolayers to the CNMs and finally on to the graphene. Our procedure is scalable to large areas and allows the engineering of ultrathin nanomembranes by controlling the composition and structure of precursor molecules and their monolayers

Molecular Mechanisms of Electron-Induced Cross-Linking in Aromatic SAMs

Turchanin A, Käfer D, El-Desawy M, Wöll C, Witte G, Gölzhäuser A. Molecular Mechanisms of Electron-Induced Cross-Linking in Aromatic SAMs. LANGMUIR. 2009;25(13):7342-7352.When aromatic self-assembled monolayers (SAMs) are electron-irradiated, intermolecular cross-links are formed and the SAMs transform into carbon nanosheets with molecular thickness. These nanosheets have a very high mechanical stability and can withstand temperatures above 1000 K. In this report, we investigate the electron induced cross-linking of 1,1'-biphenyl-4-thiol (BPT) SAMs on gold by combining X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (NEXAFS), thermal desorption spectroscopy (TDS), and UV photoelectron spectroscopy (UPS). The experimental data were acquired as a function of electron dose and temperature and compared with quantum chemical calculations. Details of the intermolecular cross-linking, the microstructure of cross-linked films, and their structural transformations upon heating were obtained to derive a view of the mechanisms involved. Our analysis shows that room-temperature electron irradiation causes a lateral cross-linking via the formation of C-C linked phenyl species as well as a new 2 sulfur species. The thermal stability of the BPT films increases with the electron dose and saturates at similar to 50 mC/cm(2). Nevertheless, nonlinked fragments in the thermal desorption spectra indicate an incomplete cross-linking even at high doses, which can be attributed to steric reasons and quenching due to the reduced band gap of partially linked molecules. At temperatures above 800 K, all sulfur species are thermally desorbed, while the remaining film reveals an onset of carbonization

Graphene oxide : structural analysis and application as a highly transparent support for electron microscopy

We report on the structural analysis of graphene oxide (GO) by transmission electron microscopy (TEM). Electron diffraction shows that on average the underlying carbon lattice maintains the order and lattice-spacings of graphene; a structure that is clearly resolved in 80 kV aberration-corrected atomic resolution TEM images. These results also reveal that single GO sheets are highly electron transparent and stable in the electron beam, and hence ideal support films for the study of nanoparticles and macromolecules by TEM. We demonstrate this through the structural analysis of physiological ferritin, an iron-storage protein