RESUMO
A thorough understanding of native oxides is essential for designing semiconductor devices. Here, we report a study of the rate and mechanisms of spontaneous oxidation of bulk single crystals of ZrSxSe2-x alloys and MoS2. ZrSxSe2-x alloys oxidize rapidly, and the oxidation rate increases with Se content. Oxidation of basal surfaces is initiated by favorable O2 adsorption and proceeds by a mechanism of Zr-O bond switching, that collapses the van der Waals gaps, and is facilitated by progressive redox transitions of the chalcogen. The rate-limiting process is the formation and out-diffusion of SO2. In contrast, MoS2 basal surfaces are stable due to unfavorable oxygen adsorption. Our results provide insight and quantitative guidance for designing and processing semiconductor devices based on ZrSxSe2-x and MoS2 and identify the atomistic-scale mechanisms of bonding and phase transformations in layered materials with competing anions.
RESUMO
Atmospheric and long-term aging effects on electrical properties of WSe2 transistors with various thicknesses are examined. Although countless published studies report electrical properties of transition-metal dichalcogenide materials, many are not attentive to testing environment or to age of samples, which we have found significantly impacts results. Our as-fabricated exfoliated WSe2 pristine devices are predominantly n-type, which is attributed to selenium vacancies. Transfer characteristics of as-fabricated devices measured in air then vacuum reveal physisorbed atmospheric molecules significantly reduced n-type conduction in air. First-principles calculations suggest this short-term reversible atmospheric effect can be attributed primarily to physisorbed H2O on pristine WSe2, which is easily removed from the pristine surface in vacuum due to the low adsorption energy. Devices aged in air for over 300 h demonstrate irreversibly increased p-type conduction and decreased n-type conduction. Additionally, they develop an extended time constant for recovery of the atmospheric adsorbents effect. Short-term atmospheric aging (up to approximately 900 h) is attributed to O2 and H2O molecules physisorbed to selenium vacancies where electron transfer from the bulk and adsorbed binding energies are higher than the H2O-pristine WSe2. The residual/permanent aging component is attributed to electron trapping molecular O2 and isoelectronic O chemisorption at selenium vacancies, which also passivates the near-conduction band gap state, p-doping the material, with very high binding energy. All effects demonstrated have the expected thickness dependence, namely, thinner devices are more sensitive to atmospheric and long-term aging effects.