Journal of Vacuum Science & Technology A publishes reports of original research, letters, and review articles that focus on fundamental scientific understanding of interfaces, surfaces, plasmas and thin films and on using this understanding to advance the state-of-the-art in various technological applications.
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Thermal atomic layer etching (ALE) of crystalline aluminum nitride (AlN) films was demonstrated using sequential, self-limiting reactions with hydrogen fluoride (HF) and tin(II) acetylacetonate [Sn(acac)2] as the reactants. Film thicknesses were monitored versus number of ALE reaction cycles at 275 °C using in situ spectroscopic ellipsometry (SE). A low etch rate of ∼0.07 Å/cycle was measured during etching of the first 40 Å of the film. This small etch rate corresponded with the AlOxNy layer on the AlN film. The etch rate then increased to ∼0.36 Å/cycle for the pure AlN films. In situ SE experiments established the HF and Sn(acac)2 exposures that were necessary for self-limiting surface reactions. In the proposed reaction mechanism for thermal AlN ALE, HF fluorinates the AlN film and produces an AlF3 layer on the surface. The metal precursor, Sn(acac)2, then accepts fluorine from the AlF3 layer and transfers an acac ligand to the AlF3 layer in a ligand-exchange reaction. The possible volatile etch products are SnF(acac) and either Al(acac)3 or AlF(acac)2. Adding a H2 plasma exposure after each Sn(acac)2 exposure dramatically increased the AlN etch rate from 0.36 to 1.96 Å/cycle. This enhanced etch rate is believed to result from the ability of the H2 plasma to remove acac surface species that may limit the AlN etch rate. The active agent from the H2 plasma is either hydrogen radicals or radiation. Adding an Ar plasma exposure after each Sn(acac)2 exposure increased the AlN etch rate from 0.36 to 0.66 Å/cycle. This enhanced etch rate is attributed to either ions or radiation from the Ar plasma that may also lead to the desorption of acac surface species.
Epitaxial growth of (BaxSr1− x)SnO3 films with 0 ≤ x ≤ 1 using molecular beam epitaxy is reported. It is shown that SrSnO3 films can be grown coherently strained on closely lattice and symmetry matched PrScO3 substrates. The evolution of the optical band gap as a function of composition is determined by spectroscopic ellipsometry. The direct band gap monotonously decreases with x from to 4.46 eV (x = 0) to 3.36 eV (x = 1). A large Burnstein-Moss shift is observed with La-doping of BaSnO3 films. The shift corresponds approximately to the increase in Fermi level and is consistent with the low conduction band mass.
The solar system contains large quantities of organic compounds that can form complex molecular structures. The processing of organic compounds by biological systems leads to molecules with distinctive structural characteristics; thus, the detection and characterization of organic materials could lead to a high degree of confidence in the existence of extra-terrestrial life. Given the nature of the surface of most planetary bodies in the solar system, evidence of life is more likely to be found in the subsurface where conditions are more hospitable. Basalt is a common rock throughout the solar system and the primary rock type on Mars and Earth. Basalt is therefore a rock type that subsurface life might exploit and as such a suitable material for the study of methods required to detect and analyze organic material in rock. Telluric basalts from Earth represent an analog for extra-terrestrial rocks where the indigenous organic matter could be analyzed for molecular biosignatures. This study focuses on organic matter in the basalt with the use of surface analysis techniques utilizing Ar gas cluster ion beams (GCIB); time of flight secondary ion mass spectrometry (ToF-SIMS), and x-ray photoelectron spectroscopy (XPS), to characterize organic molecules. Tetramethylammonium hydroxide (TMAH) thermochemolysis was also used to support the data obtained using the surface analysis techniques. The authors demonstrate that organic molecules were found to be heterogeneously distributed within rock textures. A positive correlation was observed to exist between the presence of microtubule textures in the basalt and the organic compounds detected. From the results herein, the authors propose that ToF-SIMS with an Ar GCIB is effective at detecting organic materials in such geological samples, and ToF-SIMS combined with XPS and TMAH thermochemolysis may be a useful approach in the study of extra-terrestrial organic material and life.
Angstrom-level plasma etching precision is required for semiconductor manufacturing of sub-10 nm critical dimension features. Atomic layer etching (ALE), achieved by a series of self-limited cycles, can precisely control etching depths by limiting the amount of chemical reactant available at the surface. Recently, SiO2 ALE has been achieved by deposition of a thin (several Angstroms) reactive fluorocarbon (FC) layer on the material surface using controlled FC precursor flow and subsequent low energy Ar+ ion bombardment in a cyclic fashion. Low energy ion bombardment is used to remove the FC layer along with a limited amount of SiO2 from the surface. In the present article, the authors describe controlled etching of Si3N4 and SiO2 layers of one to several Angstroms using this cyclic ALE approach. Si3N4 etching and etching selectivity of SiO2 over Si3N4 were studied and evaluated with regard to the dependence on maximum ion energy, etching step length (ESL), FC surface coverage, and precursor selection. Surface chemistries of Si3N4 were investigated by x-ray photoelectron spectroscopy (XPS) after vacuum transfer at each stage of the ALE process. Since Si3N4 has a lower physical sputtering energy threshold than SiO2, Si3N4 physical sputtering can take place after removal of chemical etchant at the end of each cycle for relatively high ion energies. Si3N4 to SiO2 ALE etching selectivity was observed for these FC depleted conditions. By optimization of the ALE process parameters, e.g., low ion energies, short ESLs, and/or high FC film deposition per cycle, highly selective SiO2 to Si3N4 etching can be achieved for FC accumulation conditions, where FC can be selectively accumulated on Si3N4 surfaces. This highly selective etching is explained by a lower carbon consumption of Si3N4 as compared to SiO2. The comparison of C4F8 and CHF3 only showed a difference in etching selectivity for FC depleted conditions. For FC accumulation conditions, precursor chemistry has a weak impact on etching selectivity. Surface chemistry analysis shows that surface fluorination and FC reduction take place during a single ALE cycle for FC depleted conditions. A fluorine rich carbon layer was observed on the Si3