The epitaxial sexiphenyl (0 0 1) monolayer on TiO2(1 1 0): A grazing incidence X-ray diffraction study

A para-sexiphenyl monolayer of near up-right standing molecules (nominal thickness of 30 Å) is investigated in-situ by X-ray diffraction using synchrotron radiation and ex-situ by atomic force microscopy. A terrace like morphology is observed, the step height between the terraces is approximately one molecular length. The monolayer terraces, larger than 20 μm in size, are extended along the [0 0 1] direction of the TiO₂(1 1 0) substrate i.e. along the Ti-O rows of the reconstructed substrate surface. The structure of the monolayer and its epitaxial relationship to the substrate is determined by grazing incidence X-ray diffraction. Extremely sharp diffraction peaks reveal high crystalline order within the monolayer, which was found to have the bulk structure of sexiphenyl. The monolayer terraces are epitaxially oriented with the (0 0 1) plane parallel to the substrate surface (out-of-plane order). Four epitaxial relationships are observed. This in-plane alignment is determined by the arrangement of the terminal phenyl rings of the sexiphenyl molecules parallel to the oxygen rows of the substrate.     

Synthesis and Assembly of Zinc Oxide Microcrystals by a Low-Temperature Dissolution–Reprecipitation Process: Lessons Learned About Twin Formation in Heterogeneous Reactions

Cobalt-doped zinc oxide single crystals with the shape of hexagonal platelets were synthesized by thermohydrolysis of zinc acetate, cobalt acetate, and hexamethylenetetramine (HMTA) in mixtures of ethanol and water. The mineralization proceeds by a low-temperature dissolution–reprecipitation process from the liquid phase by the formation of basic cobalt zinc salts as intermediates. The crystal shape as well as twin formation of the resulting oxide phase can be influenced by careful choice of the solvent mixture and the amount of doping. An understanding of the course of the reaction was achieved by comprehensive employment of analytical techniques (i.e., SEM, XRD, IR) including an in-depth HRTEM study of precipitates from various reaction stages. In addition, EPR as well as UV/Vis spectroscopic measurements provide information about the insertion of the cobalt dopant into the zincite lattice. The Langmuir–Blodgett (LB) technique is shown to be suitable for depositing coatings of the platelets on glass substrates functionalized with polyelectrolyte multilayers and hence is applied for the formation of monolayers containing domains with ordered tessellation. No major differences are found between deposits on substrates with anionic or cationic surface modification. The adherence to the substrates is sufficient to determine the absolute orientation of the deposited polar single crystals by piezoresponse force microscopy (PFM) and Kelvin probe force microscopy (KPFM) studies.     

Prebiotic Nucleoside Synthesis: The Selectivity of Simplicity

Ever since the discovery of nucleic acids 150 years ago,^[1] major achievements have been made in understanding and decrypting the fascinating scientific questions of the genetic code.^[2] However, the most fundamental question about the origin and the evolution of the genetic code remains a mystery. How did nature manage to build up such intriguingly complex molecules able to encode structure and function from simple building blocks? What conditions were required? How could the precursors survive the unhostile environment of early Earth? Over the past decades, promising synthetic concepts were proposed providing clarity in the field of prebiotic nucleic acid research. In this Minireview, we show the current status and various approaches to answer these fascinating questions.     

On the Density of Synthetic Glasses in the System Soda Melilite – Gehlenite/Ákermanite

The solid density has been determined at 25°C by hydrostatic weighing along the binary systems Sm–Ge₅₀Åk₅₀ and Sm–Ge₇₀Åk₃₀. The molar volume V decreases linearly with increasing mole fraction of Ge_mÅk_n, x_B, according to δV/δx_B = −5.08 cm³ mol⁻¹ and −4.40 cm³ mol⁻¹ for Ge₅₀Åk₅₀ and Ge₇₀Åk₃₀, respectively. The results enable the molar fraction x_B to be determined from density measurements with an absolute error of ±5 mol%.     

In situ detection of potassium atoms in high-temperature coal-combustion systems using near-infrared-diode lasers

Direct tunable diode laser absorption spectroscopy at 769.9 and 767.5 nm was used to measure potassium (K) atom concentrations in situ in the high temperature (up to 1650 K) flue gas of two different pulverized coal dust combustion systems (atmospheric or pressurized (12 bar)). Two laser types (Fabry-Pérot (FP) and vertical-cavity surface-emitting lasers (VCSEL)) were used for the spectrometer and characterized with respect to the magnitude and linearity of their static and dynamic wavelength tuning properties. The wide continuous current-induced tuning range of the VCSEL of 20 cm(-1) (compared to 1 cm(-1) for the FP) make this laser ideal for species monitoring in high pressure processes. Two VCSELs were time-multiplexed to realize the simultaneous detection of the potassium D1 and D2 lines. Several oxygen absorption lines in the A-band, which are in close spectral vicinity of the K lines, were detected simultaneously, showing the possibility of multi-species detection with one laser. Using the FP-DL for the atmospheric process and the VCSEL for the high pressure process, the pressure-dependent coefficients for spectral broadening as well as a shift of the K line in the flue gas were determined to be (0.18 +/- 0.01) and (-0.060 +/- 0.003) cm(-1) per atm (at 1540 K and 11.2 bar). The total width and shift of the D1 line (11.2 bar/1540 K) were 60 and -20 GHz, respectively. The K atom concentration was determined continuously for several days in both plants under various operation conditions. Typical concentrations in the atmospheric plant were around 2 microg m(-3) with a range of 50 ng m(-3)-30 microg m(-3). Averaging 100 scans for each concentration value, we achieved a time resolution of 1.7 s and a detection limit of 10 ng m(-3), which corresponds to a fractional absorption in the 10(-3)-10(-4) range. A strong anti-correlation with the oxygen concentration could be verified. At the 12 bar plant, the concentration was again typically around 2 microg m(-3) but K levels up to 60 microg m(-3) were observed. Here, a strong dependence of the K-signal on the type of fuel could be verified.     

Atomic structure of a (2 x 1) reconstructed NiSi2/Si(001) interface

Nickel disilicide/silicon (001) interfaces were investigated by aberration corrected scanning transmission electron microscopy (STEM). The atomic structure was derived directly from the high spatial resolution high angle annular dark field STEM images without recourse to image simulation. It comprises fivefold coordinated silicon and sevenfold coordinated nickel sites at the interface and shows a 2 x 1 reconstruction. The proposed structure has not been experimentally observed before but has been recently predicted theoretically by others to be energetically favored.     

Self-organized semiconductor surfaces as templates for nanostructured magnetic thin films

Spontaneous pattern formation during epitaxial growth or ion erosion of semiconductor wafers offers an elegant route towards large-area nanostructured surfaces. In homoepitaxy, kinetics may result in rather uniform three-dimensional islands. In the case of semiconductor heteroepitaxy, strain relief leads to the formation of nanofaceted three-dimensional crystallites, which may self-organize into quasiperiodic arrays. By tuning substrate miscut and film thickness, or growing superlattices, a variety of patterns with different symmetries can be obtained, as will be summarized for the model system of SiGe on Si(001). Since these self-organized nanostructure arrays cover the entire wafer on which they are grown, they can serve as large-area nanopatterned substrates for subsequent deposition of magnetic thin films. It will be demonstrated that such templates allow the study of correlations between magnetic and chemical interfacial roughness, as well as the influence of pattern symmetry on the magnetic anisotropy of thin Co films. Furthermore, shadow deposition of magnetic material onto specially faceted nanostructure arrays allows the fabrication of nanomagnet arrays and the study of their magnetic properties. Received: 31 July 2002 / Accepted: 2 October 2002 / Published online: 5 February 2003 RID="*" ID="*"Corresponding author. Fax: +43-3842/402-760, E-mail: teichert@unileoben.ac.at