Koen Schouteden

Synthesis of few-layer graphene via microwave plasma-enhanced chemical vapour deposition

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.

Topological transport and atomic tunnelling–clustering dynamics for aged Cu-doped Bi2Te3 crystals

Enhancing the transport contribution of surface states in topological insulators is vital if they are to be incorporated into practical devices. Such efforts have been limited by the defect behaviour of Bi2Te3 (Se3) topological materials, where the subtle bulk carrier from intrinsic defects is dominant over the surface electrons. Compensating such defect carriers is unexpectedly achieved in (Cu0.1Bi0.9)2Te3.06 crystals. Here we report the suppression of the bulk conductance of the material by four orders of magnitude by intense ageing. The weak antilocalization analysis, Shubnikov–de Haas oscillations and scanning tunnelling spectroscopy corroborate the transport of the topological surface states. Scanning tunnelling microscopy reveals that Cu atoms are initially inside the quintuple layers and migrate to the layer gaps to form Cu clusters during the ageing. In combination with first-principles calculations, an atomic tunnelling–clustering picture across a diffusion barrier of 0.57 eV is proposed.

Towards Passivation of Ge(100) Surfaces by Sulfur Adsorption from a (NH4)2S Solution: A Combined NEXAFS, STM and LEED Study

Using x-ray absorption spectroscopy, scanning tunneling microscopy and low-energy electron diffraction we have studied the surface chemistry and atomic structure of the sulfur passivation layer formed on Ge( 100) surfaces upon treatment in an aqueous (NH 4 ) 2 S solution at room temperature. This treatment was shown to yield incomplete sulfur coverage (<1 monolayer) and residual Ge oxides regardless of the time the substrates are immersed in the solution. Scanning tunneling microscopy images of the surface structure of the passivation layer reveal the coexistence of locally ordered and large disordered areas, attributed to S-Ge and O-Ge bonds, respectively. The passivated surfaces exhibit a pronounced (1×1) electron diffraction pattern. The formation of the passivation layer appears to be dependent on the state of the Ge surface prior to sulfidation, i.e. on the presence of surface oxides, which hamper the formation of a long-range ordered sulfur monolayer.

Dependence of the NaCl/Au(111) interface state on the thickness of the NaCl layer

We investigated the growth and the electronic properties of crystalline NaCl layers on Au(111) surfaces by means of cryogenic scanning tunneling microscopy and spectroscopy under ultra-high vacuum conditions. Deposition of NaCl on Au(111) at room temperature yields bilayer NaCl islands, which can be transformed into trilayer NaCl islands by post-annealing. Upon NaCl adsorption, the Au(111) Shockley surface state becomes an interface state (IS) at the NaCl/Au(111) interface. Using Fourier-transform images of maps of the local density of states, the energy versus wave vector dispersions of the IS and the Au(111) bulk states are determined. The dispersion of both states is found to depend strongly on the thickness of the adsorbed NaCl layer.

Band structure quantization in nanometer sized ZnO clusters

Nanometer sized ZnO clusters are produced in the gas phase and subsequently deposited on clean Au(111) surfaces under ultra-high vacuum conditions. The zinc blende atomic structure of the approximately spherical ZnO clusters is resolved by high resolution scanning transmission electron microscopy. The large band gap and weak n-type conductivity of individual clusters are determined by scanning tunnelling microscopy and spectroscopy at cryogenic temperatures. The conduction band is found to exhibit clear quantization into discrete energy levels, which can be related to finite-size effects reflecting the zero-dimensional confinement. Our findings illustrate that gas phase cluster production may provide unique possibilities for the controlled fabrication of high purity quantum dots and heterostructures that can be size selected prior to deposition on the desired substrate under controlled ultra-high vacuum conditions.

Morphology and electron confinement properties of Co clusters deposited on Au(111)

We present the first measurements of both the morphology and electronic structure of preformed Co nanoclusters in the size range of a few up to several hundreds of atoms by means of low-temperature scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Co clusters are produced in the gas phase and deposited under controlled ultra-high vacuum conditions onto clean Au(111) with low density, well below complete coverage of the Au(111) substrate. We find that smaller clusters, which typically contain less than 20 atoms, exhibit a significant surface mobility with subsequent aggregation, whereas larger clusters turn out to be immobile. From a systematic analysis of the cluster height distribution, we infer that the approximately spherical clusters experience only a restricted flattening and have a multilayered structure, which sometimes is observed to exhibit hexagonal facets, pointing to a truncated octahedral shape. Furthermore, detailed STS measurements on individual Co clusters reveal the presence of various size- and shape-dependent maxima with large energy spacings of the order of 100?meV, as well as an occupied state around ?200?meV that originates from the Co 3d band. Our findings provide direct evidence for the existence of strong electron confinement effects in the Co clusters stemming from delocalized Co valence electrons. Our results provide an original contribution to the understanding of cluster physics and in particular of the specific electronic structure.

Probing Magnetism in 2D Molecular Networks after in Situ Metalation by Transition Metal Atoms

Metalated molecules are the ideal building blocks for the bottom-up fabrication of, e.g., two-dimensional arrays of magnetic particles for spintronics applications. Compared to chemical synthesis, metalation after network formation by an atom beam can yield a higher degree of control and flexibility and allows for mixing of different types of magnetic atoms. We report on successful metalation of tetrapyridyl-porphyrins (TPyP) by Co and Cr atoms, as demonstrated by scanning tunneling microscopy experiments. For the metalation, large periodic networks formed by the TPyP molecules on a Ag(111) substrate are exposed in situ to an atom beam. Voltage-induced dehydrogenation experiments support the conclusion that the porphyrin macrocycle of the TPyP molecule incorporates one transition metal atom. The newly synthesized Co-TPyP and Cr-TPyP complexes exhibit striking differences in their electronic behavior, leading to a magnetic character for Cr-TPyP only as evidenced by Kondo resonance measurements.

Size-Dependent Penetration of Gold Nanoclusters through a Defect-Free, Nonporous NaCl Membrane

Membranes and their size-selective filtering properties are universal in nature and their behavior is exploited to design artificial membranes suited for, e.g., molecule or nanoparticle filtering and separation. Exploring and understanding penetration and transmission mechanisms of nanoparticles in thin-film systems may provide new opportunities for size selective deposition or embedding of the nanoparticles. Here, we demonstrate an unexpected finding that the sieving of metal nanoparticles through atomically thin nonporous alkali halide films on a metal support is size dependent and that this sieving effect can be tuned via the film thickness. Specifically, relying on scanning tunneling microscopy and spectroscopy techniques, combined with density functional theory calculations, we find that defect-free NaCl films on a Au(111) support act as size-dependent membranes for deposited Au nanoclusters. The observed sieving ability is found to originate from a driving force toward the metal support and from the dynamics of both the nanoparticles and the alkali halide films.

Chemically modified STM tips for atomic-resolution imaging of ultrathin NaCl films

Cl-functionalized scanning tunneling microscopy (STM) tips are fabricated by modifying a tungsten STM tip in situ on islands of ultrathin NaCl(100) films on Au(111) surfaces. The functionalized tips are used to achieve clear atomicresolution imaging of NaCl(100) islands. In comparison with bare metal tips, the chemically modified tips yield drastically enhanced spatial resolution as well as contrast reversal in STM topographs, implying that Na atoms, rather than Cl atoms, are imaged as protrusions. STM simulations based on a Green’s function formalism reveal that the experimentally observed contrast reversal in the STM topographs is due to the highly localized character of the Cl-pz states at the tip apex. An additional remarkable characteristic of the modified tips is that in dI/dV maps, a Na atom appears as a ring with a diameter that depends crucially on the tip-sample distance.

Noninvasive embedding of single Co atoms in Ge(111)2x1 surfaces

We report on a combined scanning tunneling microscopy (STM) and density functional theory (DFT) based investigation of Co atoms on Ge(111)2x1 surfaces. When deposited on cold surfaces, individual Co atoms have a limited diffusivity on the atomically flat areas and apparently reside on top of the upper pi-bonded chain rows exclusively. Voltage-dependent STM imaging reveals a highly anisotropic electronic perturbation of the Ge surface surrounding these Co atoms and pronounced one-dimensional confinement along the pi-bonded chains. DFT calculations reveal that the individual Co atoms are in fact embedded in the Ge surface, where they occupy a quasi-stationary position within the big 7-member Ge ring in between the 3rd and 4th atomic Ge layer. The energy needed for the Co atoms to overcome the potential barrier for penetration in the Ge surface is provided by the kinetic energy resulting from the deposition process. DFT calculations further demonstrate that the embedded Co atoms form four covalent Co-Ge bonds, resulting in a Co4+ valence state and a 3d5 electronic configuration. Calculated STM images are in perfect agreement with the experimental atomic resolution STM images for the broad range of applied tunneling voltages.