The mechanism of thermal dry etching of cobalt films is discussed for a thermal process utilizing sequential exposures to chlorine gas and a diketone [either 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (hexafluoroacetylacetone, hfacH) or 2,4-pentanedione (acetylacetone, acacH)]. The process can be optimized experimentally to approach atomic layer etching (ALE); a sequential exposure to Cl 2 and hfacH dry etchants at 140°C is shown to proceed efficiently. The use of acacH as a diketone does not result in ALE with chlorine even at 180°C, but the decrease of surface chlorine concentration and chemical reduction of cobalt is noted. However, thermal desorption analysis suggests that the reaction of chlorinated cobalt surface exposed to the ambient conditions (oxidized) with hfacH does produce volatile Co-containing products within the desired temperature range and the products contain Co 3+. The effect of adsorption of ligands on the energy required to remove surface cobalt atoms is evaluated using the density functional theory.

The use of gas-phase electron-impact activation of metalorganic complexes to facilitate atomic layer depositions (ALD) was tested for the case of (methylcyclopentadienyl)Pt(IV) trimethyl (MeCpPtMe) on silicon oxide films. Uptake enhancements of more than 1 order of magnitude were calculated from X-ray photoelectron spectroscopy (XPS) data. On the basis of the measured C:Pt ratios, the surface species were estimated to mainly consist of MeCpPt moieties, likely because of the prevalent formation of [MeCpPtMe - nH] ions after gas-phase ionization (as determined by mass spectrometry). Counterintuitively, more extensive adsorption was observed on thick SiO films than on the native thin SiO film that forms on Si(100) wafers, despite the former having virtually no surface OH groups. The adsorption of MeCpPt fragments on silicon oxide surfaces was determined by density functional theory (DFT) calculations to be highly exothermic and to favor attachment to Si-O-Si bridge sites.

Amechanism of thermal dry etching process of cobalt thin films by using 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (hexafluoroacetylacetone, hfacH) was investigated. This process, relevant to atomic layer etching (ALE) technology directed towards oxidized cobalt films, requires adsorption of molecular organic precursor, such as hfacH, at moderate temperatures and is often thought of as releasing water and Co(hfac) at elevated temperatures. The reaction was analyzed in situ by temperature-programmed desorption (TPD) and the resulting surface was investigated ex situ by X-ray photoelectron spectroscopy (XPS). The changes in surface morphology during the process were monitored by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The removal of Co(hfac) from the surface was observed above 650 K, a temperature well above commercially desired etching conditions, suggesting that the thermal etching process is more complex than originally envisioned. In addition, the upper limit of thermal treatment is established at 800 K, as the microscopic techniques clearly indicated surface morphology changes above this temperature. In addition, the structure of the surface at the nanoscale is observed to be affected by the presence of surface bound organic ligands even at room temperature. Thus, further mechanistic studies should address the kinetic regime and surface morphology to make inroads into mechanistic understanding of the dry etching process.

Recent advances in preservation of the morphology of ZnO nanostructures during dye sensitization required the use of a two-step preparation procedure. The first step was the key for preserving ZnO materials morphology. It required exposing clean ZnO nanostructures to a gas-phase prop-2-ynoic acid (propiolic acid) in vacuum. This step resulted in the formation of a robust and stable surface-bound carboxylate with ethynyl groups available for further modification, for example, with click chemistry. This paper utilizes spectroscopic and microscopic investigations to answer several questions about this modification and to determine if the process can be performed under medium vacuum conditions instead of high vacuum procedures reported earlier. Comparing the results of the preparation process at medium vacuum of 0.5 Torr base pressure with the previously reported investigations of the same process in high vacuum of 10Torr suggests that both processes lead to the formation of the same surface species, confirming that the proposed modification scheme can be widely applicable for ZnO sensitization procedures and does not require the use of high vacuum. Additional analysis comparing the computationally predicted surface structures with the results of spectroscopic investigations yields the more complete description of the surface species resulting from this approach.

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