The Interaction of Water with Solid Surfaces: Fundamental Aspects Revisited

Unencapsulated, exfoliated black phosphorus (BP) flakes are found to chemically degrade upon exposure to ambient conditions. Atomic force microscopy, electrostatic force microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy are employed to characterize the structure and chemistry of the degradation process, suggesting that O2 saturated H2O irreversibly reacts with BP to form oxidized phosphorus species. This interpretation is further supported by the observation that BP degradation occurs more rapidly on hydrophobic octadecyltrichlorosilane self-assembled monolayers and on H-Si(111) versus hydrophilic SiO2. For unencapsulated BP field-effect transistors, the ambient degradation causes large increases in threshold voltage after 6 h in ambient, followed by a ∼103 decrease in FET current on/off ratio and mobility after 48 h. Atomic layer deposited AlOx overlayers effectively suppress ambient degradation, allowing encapsulated BP FETs to ma...

Effective Passivation of Exfoliated Black Phosphorus Transistors against Ambient Degradation

The outstanding properties of SiO2, which include high resistivity, excellent dielectric strength, a large band gap, a high melting point, and a native, low defect density interface with Si, are in large part responsible for enabling the microelectronics revolution. The Si/SiO2 interface, which forms the heart of the modern metal–oxide–semiconductor field effect transistor, the building block of the integrated circuit, is arguably the worlds most economically and technologically important materials interface. This article summarizes recent progress and current scientific understanding of ultrathin (<4 nm) SiO2 and Si–O–N (silicon oxynitride) gate dielectrics on Si based devices. We will emphasize an understanding of the limits of these gate dielectrics, i.e., how their continuously shrinking thickness, dictated by integrated circuit device scaling, results in physical and electrical property changes that impose limits on their usefulness. We observe, in conclusion, that although Si microelectronic devices...

Ultrathin (<4 nm) SiO2 and Si-O-N gate dielectric layers for silicon microelectronics: Understanding the processing, structure, and physical and electrical limits

Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments / Albert Rimola;Dominique Costa;Mariona Sodupe;Jean-François Lambert;Piero Ugliengo. In: CHEMICAL REVIEWS. ISSN 0009-2665. STAMPA. 113:6(2013), pp. 4216-4313. Original Citation: Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

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Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

Parameters important to the self-assembly of 3-(aminopropyl)triethoxysilane (APTES) on chemically grown silicon oxide (SiO2) to form an aminopropyl silane (APS) film have been investigated using in situ infrared (IR) absorption spectroscopy. Preannealing to ∼70 °C produces significant improvements in the quality of the film: the APS film is denser, and the Si−O−Si bonds between the molecules and the SiO2 surface are more structured and ordered with only a limited number of remaining unreacted ethoxy groups. In contrast, post-annealing the functionalized SiO2 samples after room temperature reaction with APTES (i.e., ex situ annealing) does not lead to any spectral change, suggesting that post-annealing has no strong effect on the horizontal polymerization as suggested earlier. Both IR and ellipsometry data show that the higher the solution temperature, the denser and thinner the APS layer is for a given immersion time. Finally, the APS layer obtained by preannealing the solution at 70 °C exhibits a better ...

Attachment of 3-(Aminopropyl)triethoxysilane on Silicon Oxide Surfaces: Dependence on Solution Temperature

The nature of the silicon oxide transition region in the vicinity of the Si/SiO2 interface is probed by infrared and x-ray photoelectron spectroscopies. The layer-by-layer composition of the interface is evaluated by uniformly thinning thermal oxide films from 31 A down to 6 A. We find that the thickness dependence of the frequencies of the transverse optical and longitudinal optical phonons of the oxide film cannot be reconciled by consideration of simple homogeneous processes such as image charge effects or stress near the interface. Rather, by applying the Bruggeman effective medium approximation, we show that film inhomogeneity in the form of substoichiometric silicon oxide species accounts for the observed spectral changes as the interface is approached. The presence of such substoichiometric oxide species is supported by the thickness dependence of the integrated Si suboxide signal in companion x-ray photoelectron spectra.

Infrared spectroscopic analysis of the Si/SiO2 interface structure of thermally oxidized silicon

The dissociation of NH3 on Si(100)-(2x1) is investigated by a combination of infrared absorption spectroscopy and density functional cluster calculations, revealing that this reaction is governed by a complex set of interdimer interactions involving both bare and adsorbate-covered Si dimers. We propose that such adsorbate-induced changes in the electronic structure of neighboring dimers may have general implications for controlling the two-dimensional ordering of reactions on the dimerized Si(100) surface.

Role of Interdimer Interactions in NH3 Dissociation on Si(100)-(2×1)

Surface infrared spectroscopy and density functional cluster calculations are used to study the thermal and atomic hydrogen-induced decomposition of water molecules on the clean Si(100)-(2×1) surface. We report the first observation of the Si–H bending modes associated with the initial insertion of oxygen into the dimer and backbonds of a silicon dimer. We find that, while one and two oxygen-containing dimers are formed almost simultaneously during the thermal decomposition of water on this surface, atomic H can be used to drive the preferential formation of the singly oxidized dimer. This work highlights the sensitivity of Si–H bending modes to the details of local chemical structure in an inhomogeneous system, suggesting that the combined experimental and theoretical approach demonstrated herein may be extremely useful in studying even more complex systems such as the hydrogenation of defects in SiO2 films.

Si–H bending modes as a probe of local chemical structure: Thermal and chemical routes to decomposition of H2O on Si(100)-(2×1)

The microscopic mechanism of the formation of ultrathin oxides on Si(100) has been investigated using a combination of infrared spectroscopy and ab initio quantum chemical cluster calculations. The 0→2 monolayer oxide films are grown sequentially from the “bottom-up” using repeated water exposures and annealing cycles, with the partial pressure of water ranging from 10−10 to 10 Torr. The resultant films were then compared to the equivalent thicknesses of thermal and native oxide films. In this way, we obtain unprecedented insight into the essential chemical structures formed during the initial oxidation and subsequent layer growth of these technologically relevant films.

K. T. Queeney

Papers

Infrared spectroscopic analysis of the Si/SiO2 interface structure of thermally oxidized silicon

Role of Interdimer Interactions in NH3 Dissociation on Si(100)-(2×1)

Si–H bending modes as a probe of local chemical structure: Thermal and chemical routes to decomposition of H2O on Si(100)-(2×1)

Mechanistic studies of silicon oxidation

Silicon Oxidation and Ultra-Thin Oxide Formation on Silicon Studied by Infrared Absorption Spectroscopy