4-NO2 and 4-Br benzenediazonium salts have been
electrochemically reduced on H-terminated Si(111)
electrodes. Electrochemical measurements evidence that the
reaction results in a robust modification of Si(111) surfaces. XPS shows that organic films are monolayer thick
and that covalent ≡SiAr bonding occurs,
with no oxide at the interface. In the case of the Br salt,
quantitative RBS measurements suggest that layers
are (2×1) close-packed and assess their stability against several
rinsing procedures including exposure to
40% HF. A mechanism of grafting is discussed.
The reactions taking place during voltametric cycling of manganese oxides can be determined using in situ Raman spectroscopy. The main difficulty for the oxide identification is to obtain relevant Raman reference spectra because of the many possible compounds and, for some of these compounds, of their instability in the laser beam. As a consequence, several modifications of different tetra-, tri-and divalent manganese oxides and oxyhydroxides were carefully studied. The electrochromic behavior of three types of manganese oxides, two prepared by thermal oxidations and the other by electrochemical deposition, were then compared. The presence of nonstoichiometry in the pristine material was necessary to obtain a reversible electrochromic effect. The reaction during eleetrochromic cycling is more complicated than a simple passage from Mn02 to MnOOH.
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