Zheshen Li

The Role of Interstitial Sites in the Ti3d Defect State in the Band Gap of Titania

Titanium dioxide (TiO2) has a number of uses in catalysis, photochemistry, and sensing that are linked to the reducibility of the oxide. Usually, bridging oxygen (Obr) vacancies are assumed to cause the Ti3d defect state in the band gap of rutile TiO2(110). From high-resolution scanning tunneling microscopy and photoelectron spectroscopy measurements, we propose that Ti interstitials in the near-surface region may be largely responsible for the defect state in the band gap. We argue that these donor-specific sites play a key role in and may dictate the ensuing surface chemistry, such as providing the electronic charge required for O2 adsorption and dissociation. Specifically, we identified a second O2 dissociation channel that occurs within the Ti troughs in addition to the O2 dissociation channel in Obr vacancies. Comprehensive density functional theory calculations support these experimental observations.

Experimental and theoretical study of oxygen adsorption structures on Ag(111)

The oxidized Ag(111) surface has been studied by a combination of experimental and theoretical methods, scanning tunneling microscopy, x-ray photoelectron spectroscopy, and density functional theory. A large variety of different surface structures is found, depending on the detailed preparation conditions. The observed structures fall into four classes: (a) individually chemisorbed atomic oxygen atoms, (b) three different oxygen overlayer structures, including the well-known p(4x4) phase, formed from the same Ag-6 and Ag-10 building blocks, (c) a c(4x8) structure not previously observed, and (d) at higher oxygen coverages structures characterized by stripes along the high-symmetry directions of the Ag(111) substrate. Our analysis provides a detailed explanation of the atomic-scale geometry of the Ag-6/Ag-10 building block structures and the c(4x8) and stripe structures are discussed in detail. The observation of many different and co-existing structures implies that the O/Ag(111) system is characterized by a significantly larger degree of complexity than previously anticipated, and this will impact our understanding of oxidation catalysis processes on Ag catalysts.

Growth of a stacked silicon nitride/silicon oxide dielectric on Si(100)

We have recently developed processes to grow ultrathin amorphous silicon oxide and amorphous silicon nitride layers on clean Si(111) and Si(100) surfaces exploring the self-limiting nature of the direct oxidation of Si with O2, and the self-limiting nature of the direct nitridation of Si with atomic N produced by microwave dissociation of N2, at processing temperatures around 500°C. In some of today’s microprocessor devices mixed dielectric systems are used as complementary metal oxide semiconductor gate dielectrics. We demonstrate the use of our processes to produce such systems in various structures, and with maximum control, by exposing oxide to N, or nitride to O2 at 500°C. In addition we produce a stacked layer, consisting of 7–8A of SiO2 on top of Si(100), with a layer of varying thickness of Si3N4 grown on top of this structure. The growth of Si3N4 occurs at room temperature in this process. Such structures or thermally postprocessed structures thereof should be further examined as potential stacke...

Direct measurement of electrical conductance through a self-assembled molecular layer.

The self-assembly of organic molecules on surfaces is a promising approach for the development of nanoelectronic devices. Although a variety of strategies have been used to establish stable links between molecules, little is known about the electrical conductance of these links. Extended electronic states, a prerequisite for good conductance, have been observed for molecules adsorbed on metal surfaces. However, direct conductance measurements through a single layer of molecules are only possible if the molecules are adsorbed on a poorly conducting substrate. Here we use a nanoscale four-point probe to measure the conductivity of a self-assembled layer of cobalt phthalocyanine on a silver-terminated silicon surface as a function of thickness. For low thicknesses, the cobalt phthalocyanine molecules lie flat on the substrate, and their main effect is to reduce the conductivity of the substrate. At higher thicknesses, the cobalt phthalocyanine molecules stand up to form stacks and begin to conduct. These results connect the electronic structure and orientation of molecular monolayer and few-layer systems to their transport properties, and should aid in the rational design of future devices.

The effect of reduced dimensionality on a semimetal: the electronic structure of the Bi(110) surface

We have studied the electronic structure of the semimetal surface Bi(110) by high-resolution angle-resolved photoemission using synchrotron radiation. Several surface states are found very close to the Fermi level giving rise to a complex Fermi surface. As a consequence, the surface is a much better metal than the bulk, a fact which could help to explain the observation of superconductivity in granular systems built from small Bi clusters.

Edge reactivity and water-assisted dissociation on cobalt oxide nanoislands

Transition metal oxides show great promise as Earth-abundant catalysts for the oxygen evolution reaction in electrochemical water splitting. However, progress in the development of highly active oxide nanostructures is hampered by a lack of knowledge of the location and nature of the active sites. Here we show, through atom-resolved scanning tunnelling microscopy, X-ray spectroscopy and computational modelling, how hydroxyls form from water dissociation at under coordinated cobalt edge sites of cobalt oxide nanoislands. Surprisingly, we find that an additional water molecule acts to promote all the elementary steps of the dissociation process and subsequent hydrogen migration, revealing the important assisting role of a water molecule in its own dissociation process on a metal oxide. Inspired by the experimental findings, we theoretically model the oxygen evolution reaction activity of cobalt oxide nanoislands and show that the nanoparticle metal edges also display favourable adsorption energetics for water oxidation under electrochemical conditions.

Roads to ultrathin silicon oxides

Ultrathin gate dielectrics for complementary metal-oxide-semiconductor (CMOS) devices, with suitable structural and electrical properties, are crucial for the further development of silicon based microelectronics. The effective (SiO2-equivalent) thickness of 10 A or below needed in the next generations of CMOS devices has been found too low to prevent tunneling. and leakage. with current processes for SiO2 based gate insulators. Before abandoning SiO2, completely however. there are good reasons to look for improved procedures or alternative processes to grow or form ultrathin SiO2 films on silicon, and possible improvements through the controlled addition of nitrogen. The present article initially describes an attempt to grow ultrathin oxides in a furnace. but this was limited to 50-Angstrom-thick layers or above. It then unveils some particularly simple. easily controlled, low-thermal budget, low-pressure based processes for thinner oxide layers, which have not been met earlier. These later processes are all done in an ultrahigh vacuum (UHV) based environment, starting from a clean and perfectly ordered Si surface. Thus we formed the thinnest possible (approximate to4 Angstrom) uniformly covering oxide layers on the Si(111) and Si(001) surfaces. They are made very simply from cycles of oxygen adsorption at room temperature and short anneals, and are self-saturating at this thickness. Following these processes we explored isothermal methods in UHV at low temperatures and pressures. Such processes, at low pressures. were found to lead to a universal, self-limiting growth of an approximately 7-Angstrom-thick oxide at a range of temperatures between 300 and 700 degreesC. Further, up to about 10 Angstrom oxides are grown in a series of steps. in each of which a layer of freshly deposited Cs on top of already grown oxide is retaining oxygen on this otherwise passivated surface. The Cs layer also catalyzes oxidation during a subsequent rapid annealing step. Higher thicknesses (up to 50 Angstrom) are obtained by using a precursor layer of Cs-oxide formed in alternating Cs and oxygen dosing processes, which is converted into SiO2, by heating. The present investigations are focused on structural properties of the systems studied with the use of electron spectroscopy, mainly photoemission with synchrotron radiation. in UHV

Comparing Ullmann Coupling on Noble Metal Surfaces: On‐Surface Polymerization of 1,3,6,8‐Tetrabromopyrene on Cu(111) and Au(111)

The on-surface polymerization of 1,3,6,8-tetrabromopyrene (Br4 Py) on Cu(111) and Au(111) surfaces under ultrahigh vacuum conditions was investigated by a combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. Deposition of Br4 Py on Cu(111) held at 300 K resulted in a spontaneous debromination reaction, generating the formation of a branched coordination polymer network stabilized by C-Cu-C bonds. After annealing at 473 K, the C-Cu-C bonds were converted to covalent C-C bonds, leading to the formation of a covalently linked molecular network of short oligomers. In contrast, highly ordered self-assembled two-dimensional (2D) patterns stabilized by both Br-Br halogen and Br-H hydrogen bonds were observed upon deposition of Br4 Py on Au(111) held at 300 K. Subsequent annealing of the sample at 473 K led to a dissociation of the C-Br bonds and the formation of disordered metal-coordinated molecular networks. Further annealing at 573 K resulted in the formation of covalently linked disordered networks. Importantly, we found that the chosen substrate not only plays an important role as catalyst for the Ullmann reaction, but also influences the formation of different types of intermolecular bonds and thus, determines the final polymer network morphology. DFT calculations further support our experimental findings obtained by STM and XPS and add complementary information on the reaction pathway of Br4 Py on the different substrates.

Robust surface doping of Bi2Se3 by rubidium intercalation.

Rubidium adsorption on the surface of the topological insulator Bi(2)Se(3) is found to induce a strong downward band bending, leading to the appearance of a quantum-confined two-dimensional electron gas state (2DEG) in the conduction band. The 2DEG shows a strong Rashba-type spin-orbit splitting, and it has previously been pointed out that this has relevance to nanoscale spintronics devices. The adsorption of Rb atoms, on the other hand, renders the surface very reactive, and exposure to oxygen leads to a rapid degrading of the 2DEG. We show that intercalating the Rb atoms, presumably into the van der Waals gaps in the quintuple layer structure of Bi(2)Se(3), drastically reduces the surface reactivity while not affecting the promising electronic structure. The intercalation process is observed above room temperature and accelerated with increasing initial Rb coverage, an effect that is ascribed to the Coulomb interaction between the charged Rb ions. Coulomb repulsion is also thought to be responsible for a uniform distribution of Rb on the surface.

An ARPEFS study of the structure of an epitaxial VO2 monolayer at the TiO2(110) surface

Abstract In the present communication, we discuss the results of an angle resolved photoemission extended fine structure (ARPEFS) study of a VO 2 monolayer (ML) grown on the TiO 2 (110) surface by successive cycles of sub-ML vanadium metal deposition followed by annealing at 473 K in 2×10 −6 mbar O 2 . The V 3p photoemission peak shows two distinct components chemically shifted by 1.3 eV. While the higher binding energy (BE) component produces a rather flat ARPEFS curve, the lower BE signal, associated with the VO 2 phase, shows well defined intensity modulations whose main features are similar to the ARPEFS scan on the Ti 3p signal of the substrate. This observation demonstrates that the ordered VO 2 phase grows epitaxially to the substrate, with a rutile type structure. However, some oxide is present in a more highly oxidized and less-ordered phase. In order to investigate the actual arrangement of the ML with respect to the question related to the possible formation of an intermixed VO 2 /TiO 2 layer, the ARPEFS data have been interpreted by means of single-scattering spherical wave (SSC-SW) simulations. They are compatible with the hypothesis that the deposited ML evolves toward an intermixed VO 2 /TiO 2 double layer where the vanadium atoms occupy the six-fold oxygen-coordinated sites. In addition, our data are in good agreement with a surface relaxation similar to that found by surface XRD on the stoichiometric TiO 2 (110) surface.