RESUMO
A simple thermal annealing at 150 °C followed by exposure to air ambient conditions in epitaxial ZnO thin films produces a photoconductivity enhancement and a reduction of the energy gap. The first effect is related to a release of carriers from bulk traps while the second is caused by a gradual adsorption of species on the film surface which increases the band bending, as x-ray photoemission spectroscopy (XPS) shows. An observed drift of the photoconductivity and the energy gap over the days is connected to this adsorption kinetics. These findings have a potential application in ZnO based optoelectronic devices.
RESUMO
We investigated the mechanism of formation and stability of self-assembled monolayers (SAMs) of methaneselenolate on Au(111) prepared by the immersion method in ethanolic solutions of dimethyl diselenide (DMDSe). The adsorbed species were characterized by electrochemical measurements and high-resolution photoelectron spectroscopy (HR-XPS). The importance of the headgroup on formation mechanism and the stability of the SAMs was addressed by comparatively studying methaneselenolate (MSe) and methanethiolate (MT) monolayers. Density Functional Theory (DFT) calculations were performed to identify the elementary reaction steps in the mechanisms of formation and decomposition of the monolayers. Reductive desorption and HR-XPS measurements indicated that a MSe monolayer is formed at short immersion times by the cleavage of the Se-Se bond of DMDSe. However, the monolayer decomposes at long immersion times at room temperature, as evidenced by the appearance of atomic Se on the surface. The decomposition is more pronounced for MSe than for MT monolayers. The MSe monolayer stability can be greatly improved by two modifications in the preparation method: immersion at low temperatures (-20 °C) and the addition of a reducing agent to the forming solution.
Assuntos
Ouro/química , Compostos Organosselênicos/química , Compostos de Sulfidrila/química , Adsorção , Técnicas Eletroquímicas , Etanol/química , Espectroscopia Fotoeletrônica , Teoria Quântica , Soluções , Propriedades de Superfície , TemperaturaRESUMO
High-resolution photoemission spectroscopy is used to characterize adlayers of ethane-, hexane-, and nonanedithiol molecules grown on Au(111) surfaces by the immersion method. The effect of using a reducing agent during and after the immersion to inhibit or eliminate S-S bonds is investigated. Our results demonstrate that immersion 24 h in millimolar dithiol ethanolic solutions gives rise to the formation of multilayers; this effect is more pronounced in the case of ethanedithiol, the shortest molecule. A post-treatment with a disulfide reducing agent is effective to produce monolayers of standing-up molecules; this effect is again more pronounced in the case of ethanedithiol. Finally, the immersion 24 h in a solution containing dithiol and the reducing agent gives an unexpected result: most molecules remain adsorbed in the lying-down configuration; in this case, the almost complete suppression of the standing-up phase occurs equally with the three types of molecules, which suggests that the formation of S-S bonds must be important for the lifting of the molecules.