In Situ Infrared Absorption Study of Plasma-Enhanced Atomic Layer Deposition of Silicon Nitride.

Despite the success of plasma-enhanced atomic layer deposition (PEALD) in depositing quality silicon nitride films, a fundamental understanding of the growth mechanism has been difficult to obtain because of lack of in situ characterization to probe the surface reactions noninvasively and the complexity of reactions induced/enhanced by the plasma. These challenges have hindered the direct observation of intermediate species formed during the reactions. We address this challenge by examining the interaction of Ar plasma using atomically flat, monohydride-terminated Si(111) as a well-defined model surface and focusing on the initial PEALD with aminosilanes. In situ infrared and X-ray photoelectron spectroscopy reveals that an Ar plasma induces desorption of H atoms from H-Si(111) surfaces, leaving Si dangling bonds, and that the reaction of di-sec-butylaminosilane (DSBAS) with Ar plasma-treated surfaces requires the presence of both active sites (Si dangling bonds) and Si-H; there is no reaction on fully H-terminated or activated surfaces. By contrast, high-quality hydrofluoric acid-etched Si3N4 surfaces readily react with DSBAS, resulting in the formation of O-SiH3. However, the presence of back-bonded oxygen in O-SiH3 inhibits H desorption by Ar or N2 plasma, presumably because of stabilization of H against ion-induced desorption. Consequently, there is no reaction of adsorbed aminosilanes even after extensive Ar or N2 plasma treatments; a thermal process is necessary to partially remove H, thereby promoting the formation of active sites. These observations are consistent with a mechanism requiring the presence of both undercoordinated nitrogen and/or dangling bonds and unreacted surface hydrogen. Because active sites are involved, the PEALD process is found to be sensitive to the duration of the plasma exposure treatment and the purge time, during which passivation of these sites can occur.

Reaction Mechanisms of the Atomic Layer Deposition of Tin Oxide Thin Films Using Tributyltin Ethoxide and Ozone.

Uniform and conformal deposition of tin oxide thin films is important for several applications in electronics, gas sensing, and transparent conducting electrodes. Thermal atomic layer deposition (ALD) is often best suited for these applications, but its implementation requires a mechanistic understanding of the initial nucleation and subsequent ALD processes. To this end, in situ FTIR and ex situ XPS have been used to explore the ALD of tin oxide films using tributyltin ethoxide and ozone on an OH-terminated, SiO2-passivated Si(111) substrate. Direct chemisorption of tributyltin ethoxide on surface OH groups and clear evidence that subsequent ligand exchange are obtained, providing mechanistic insight. Upon ozone pulse, the butyl groups react with ozone, forming surface carbonate and formate. The subsequent tributyltin ethoxide pulse removes the carbonate and formate features with the appearance of the bands for CH stretching and bending modes of the precursor butyl ligands. This ligand-exchange behavior is repeated for subsequent cycles, as is characteristic of ALD processes, and is clearly observed for deposition temperatures of 200 and 300 °C. On the basis of the in situ vibrational data, a reaction mechanism for the ALD process of tributyltin ethoxide and ozone is presented, whereby ligands are fully eliminated. Complementary ex situ XPS depth profiles confirm that the bulk of the films is carbon-free, that is, formate and carbonate are not incorporated into the film during the deposition process, and that good-quality SnOx films are produced. Furthermore, the process was scaled up in a cross-flow reactor at 225 °C, which allowed the determination of the growth rate (0.62 Å/cycle) and confirmed a self-limiting ALD growth at 225 and 268 °C. An analysis of the temperature-dependence data reveals that growth rate increases linearly between 200 and 300 °C.

Surface photochemistry of adsorbed nitrate: the role of adsorbed water in the formation of reduced nitrogen species on α-Fe2O3 particle surfaces.

The surface photochemistry of nitrate, formed from nitric acid adsorption, on hematite (α-Fe2O3) particle surfaces under different environmental conditions is investigated using X-ray photoelectron spectroscopy (XPS). Following exposure of α-Fe2O3 particle surfaces to gas-phase nitric acid, a peak in the N1s region is seen at 407.4 eV; this binding energy is indicative of adsorbed nitrate. Upon broadband irradiation with light (λ > 300 nm), the nitrate peak decreases in intensity as a result of a decrease in adsorbed nitrate on the surface. Concomitant with this decrease in the nitrate coverage, there is the appearance of two lower binding energy peaks in the N1s region at 401.7 and 400.3 eV, due to reduced nitrogen species. The formation as well as the stability of these reduced nitrogen species, identified as NO(-) and N(-), are further investigated as a function of water vapor pressure. Additionally, irradiation of adsorbed nitrate on α-Fe2O3 generates three nitrogen gas-phase products including NO2, NO, and N2O. As shown here, different environmental conditions of water vapor pressure and the presence of molecular oxygen greatly influence the relative photoproduct distribution from nitrate surface photochemistry. The atmospheric implications of these results are discussed.

Sulfur dioxide adsorption and photooxidation on isotopically-labeled titanium dioxide nanoparticle surfaces: roles of surface hydroxyl groups and adsorbed water in the formation and stability of adsorbed sulfite and sulfate.

Transmission FTIR spectroscopy and X-ray photoelectron spectroscopy (XPS) are used to probe the details of sulfur dioxide adsorption and photooxidation on titanium dioxide nanoparticle surfaces. Adsorption sites, surface speciation and photooxidation chemistry have been determined from analysis of FTIR spectra in conjunction with isotope labeling experiments. These data show that surface hydroxyl groups are involved in the adsorption of sulfur dioxide, and in particularly, sulfur dioxide reacts with either one surface O-H group to yield adsorbed bisulfite or two surface O-H groups to yield adsorbed sulfite and water. Using (16)O-H, (16)O-D and (18)O-H labeled surface O-H groups, additional insights into the adsorption mechanism as well as shifts in the vibrational modes of adsorbed sulfite have been determined. Upon irradiation, adsorbed sulfite/bisulfite converts to adsorbed sulfate. The relative stability of adsorbed sulfite to adsorbed sulfate on TiO2 nanoparticle surfaces was also examined in the presence of increasing relative humidity (RH). It is shown here that adsorbed water can more easily displace sulfite compared to sulfate by forming a stable sulfur dioxide water complex in the presence of adsorbed water. These differences in the RH-dependent stability of adsorbed species that form as a result of surface heterogeneous reactions on oxide particles surfaces has important implications in the heterogeneous chemistry of mineral dust aerosol in the atmosphere.

Enhancing the Reactivity of Al/CuO Nanolaminates by Cu Incorporation at the Interfaces.

In situ deposition of a thin (∼5 nm) layer of copper between Al and CuO layers is shown to increase the overall nanolaminate material reactivity. A combination of transmission electron microscopy imaging, in situ infrared spectroscopy, low energy ion scattering measurements, and first-principles calculations reveals that copper spontaneously diffuses into aluminum layers (substantially less in CuO layers). The formation of an interfacial Al:Cu alloy with melting temperature lower than pure Al metal is responsible for the enhanced reactivity, opening a route to controlling the stochiometry of the aluminum layer and increasing the reactivity of the nanoenergetic multilayer systems in general.