Fabien Silly

Tuning the Packing Density of 2D Supramolecular Self-Assemblies at the Solid-Liquid Interface Using Variable Temperature

The two-dimensional (2D) crystal engineering of molecular architectures on surfaces requires controlling various parameters related respectively to the substrate, the chemical structure of the molecules, and the environmental conditions. We investigate here the influence of temperature on the self-assembly of hexakis(n-dodecyl)-peri-hexabenzocoronene (HBC-C(12)) adsorbed on gold using scanning tunneling microscopy (STM) at the liquid/solid interface. We show that the packing density of 2D self-assembled HBC-C(12) can be precisely tuned by adjusting the substrate temperature. Increasing the temperature progressively over the 20-50 degrees C range induces three irreversible phase transitions and a 3-fold increase of the packing density from 0.111 to 0.356 molecule/nm(2). High-resolution STM images reveal that this 2D packing density increase arises from the stepwise desorption of the n-dodecyl chains from the gold surface. Such temperature-controlled irreversible phase transitions are thus a versatile tool that can then be used to adjust the packing density of highly ordered functional materials in view of applications in organic electronic devices.

Long-Range Alignments of Single Fullerenes by Site-Selective Inclusion into a Double-Cavity 2D Open Network

We show by means of STM that C(60) molecules can be trapped into specific sites of a 2D double-cavity open network, thus forming long-range alignments of single molecules. Since only one of the two cavities has the right size to host C(60), the smallest cavity remains empty and is thus available to trap additional species of smaller size. This novel 2D supramolecular network opens new perspectives in the design of multicomponent guest-host architectures with electronic functionalities.

Pairs and heptamers of C70 molecules ordered via PTCDI-melamine supramolecular networks

In this paper, we report on the use of two PTCDI-melamine supramolecular networks on Au(111) to trap C70 molecules. The different supramolecular networks were formed by changing the postannealing temperature after molecular deposition. We observed, using scanning tunneling microscopy, that the deposition of C70 onto a PTCDI melamine network with parallelogram cavities results in the long-range ordering of paired C70, whereas the deposition of C70 molecules onto a PTCDI-melamine honeycomb network results in the trapping of C70 heptamers.

On-Surface Synthesis of Two-Dimensional Covalent Organic Structures versus Halogen-Bonded Self-Assembly: Competing Formation of Organic Nanoarchitectures

The competition between the on-surface synthesis of covalent nanoarchitectures and the self-assembly of star-shaped 1,3,5-Tris(4-iodophenyl)benzene molecules on Au(111) in vacuum is investigated using scanning tunneling microscopy above room temperature. The molecules form covalent polygonal nanoachitectures at the gold surface step edges and at the elbows of the gold reconstruction at low coverage. With coverage increasing two-dimensional halogen-bonded structures appear and grow on the surface terraces. Two different halogen-bonded nanoarchitectures are coexisting on the surface and hybrid covalent-halogen bonded structures are locally observed. At high coverage covalent nanoarchitectures are squeezed at the domain boundary of the halogen-bonded structures. The competitive growth between the covalent and halogen-bonded nanoarchitectures leads to formation of a two-layer film above one monolayer deposition. For this coverage, the covalent nanoarchitectures are propelled on top of the halogen-bonded first layer. These observations open up new opportunities for decoupling covalent nanoarchitectures from catalytically active and metal surfaces in vacuum.

Epitaxial ordering of a perylenetetracarboxylic diimide-melamine supramolecular network driven by the Au(111)-(22×3) reconstruction

Substrate mediated ordering and intermolecular interactions are used to create a long-range supramolecular network of perylenetetracarboxylic diimide and melamine on a reconstructed Au(111)-(22×3) surface. Scanning tunneling microscopy reveals that the network is composed of a succession of double width honeycomb cell rows separated by a more closely packed row of parallelograms. This periodicity of the supramolecular configuration matches that of the reconstructed gold substrate allowing an epitaxial relationship between network and substrate reconstruction.

Tailoring two-dimensional PTCDA-melamine self-assembled architectures at room temperature by tuning molecular ratio

Engineering and tuning multi-component supramolecular self-assemblies on surfaces is one of the challenges of nanotechnology. We use scanning tunneling microscopy to investigate the influence of molecular ratio on the self-assembly of PTCDA-melamine structures on Au(111)-(22 x complex square root of 3). Our observations reveal that three different chiral supramolecular networks having a PTCDA:melamine ratio of 3:2, 1:2, 1:4 can be selectively created by tuning the ratio of molecules deposited on the surface. The 1:2 ratio network having melamine in excess has been observed previously but the 1:4 network has not yet been reported. In comparison, the multi-component 3:2 network having PTCDA in excess is a completely new structure.

Coverage-dependent self-organization: from individual adatoms to adatom superlattices

The coverage-dependent self-organization of Ce-adatoms on a Ag(111) surface is studied by scanning tunnelling microscopy at temperatures ranging from 3.9 to 10 K. At a coverage of 0.03% of a Ce monolayer individual Ce-adatoms and Ce dimers are observed, the mutual interatomic distances of which are clearly related to multiples of the Fermi wavelength λF/2, reflecting surface-state-mediated electronic interactions. At a coverage of 0.2% the formation of chains and small islands with hexagonal structure prevails. At a coverage of 1% a hexagonal superlattice with a periodicity of 3.2 nm is observed. At a coverage of 2% the superlattice of Ce-adatoms is found to be compressed, showing an interatomic distance of 2.2 nm. At higher coverage the number of dimers increases considerably and the superlattice collapses into compact islands. An increase in the temperature towards about 10 K at a coverage of 1% also causes the collapse of the hexagonal Ce superlattice. These experimental findings are rationalized within the electron scattering model of Hyldgard and Persson, which specifically takes into account the electronic surface-state on Ag(111). The experimentally derived two-body interaction potential is able to account for the observed phenomena as a function of concentration and temperature.

Controlled surface ordering of endohedral fullerenes with a SrTiO3 template

The ability to select the way in which atoms and molecules self-organize on a surface is important for synthesizing nanometre scale devices. Here we show how endohedral fullerenes (Er(3)N@C(80)) can be assembled into four distinctive arrangements on a strontium titanate surface template. Each template pattern correlates to a particular reconstruction on n-doped SrTiO(3)(001), made in whole or in part by self-assembled arrays of non-stoichiometric oxide nanostructures. Close-packed assemblies of Er(3)N@C(80) molecules are formed, as well as one-dimensional chains and two-dimensional grids. This method of template-assisted molecular ordering provides a new platform for the development of experimental schemes of classical and quantum information processing at the molecular level.

Formation of single-domain anatase TiO2(001)‐(1×4) islands on SrTiO3(001) after thermal annealing

Scanning tunneling microscopy is used to investigate the appearance of nanoscale islands on the SrTiO3(001) surface following cycles of repetitive annealing. Atomic-resolution images reveal that the surface of the islands is covered by features typical of the anatase TiO2(001) surface reconstruction. Small islands display a mixed (1x4) and (1x5) reconstruction, whereas only the single-domain (1x4) reconstruction is observed on large islands. These results reveal a simple process for the creation of single-domain anatase nanoislands.

Growth of Ag icosahedral nanocrystals on a SrTiO3(001) support

We have investigated the structure and morphology of self-assembled silver nanocrystals supported on a SrTiO3(001)−(2×1) substrate using scanning tunneling microscopy. Ag forms nanocrystals with five-fold symmetry which have an icosahedral shape. Nanocrystals with point, edge, and face orientation (five-fold, two-fold, and three-fold symmetry, respectively) have been studied. The images of these nanocrystals allow a crystallographic identification of the supported shape of the icosahedral form.