Effect of reaction mechanism on precursor exposure time in atomic layer deposition of silicon oxide and silicon nitride

Atomic layer deposition (ALD) of highly conformal, silicon-based dielectric thin films has become necessary because of the continuing decrease in feature size in microelectronic devices. The ALD of oxides and nitrides is usually thought to be mechanistically similar, but plasma-enhanced ALD of silicon nitride is found to be problematic, while that of silicon oxide is straightforward. To find why, the ALD of silicon nitride and silicon oxide dielectric films was studied by applying ab initio methods to theoretical models for proposed surface reaction mechanisms. The thermodynamic energies for the elimination of functional groups from different silicon precursors reacting with simple model molecules were calculated using density functional theory (DFT), explaining the lower reactivity of precursors toward the deposition of silicon nitride relative to silicon oxide seen in experiments, but not explaining the trends between precursors. Using more realistic cluster models of amine and hydroxyl covered surfaces, the structures and energies were calculated of reaction pathways for chemisorption of different silicon precursors via functional group elimination, with more success. DFT calculations identified the initial physisorption step as crucial toward deposition and this step was thus used to predict the ALD reactivity of a range of amino-silane precursors, yielding good agreement with experiment. The retention of hydrogen within silicon nitride films but not in silicon oxide observed in FTIR spectra was accounted for by the theoretical calculations and helped verify the application of the model.

Room temperature ferroelectric and magnetic investigations and detailed phase analysis of Aurivillius phase Bi 5Ti 3Fe 0.7Co 0.3O 15 thin films

Aurivillius phase Bi 5Ti 3Fe 0.7Co 0.3O 15 (BTF7C3O) thin films on α-quartz substrates were fabricated by a chemical solution deposition method and the room temperature ferroelectric and magnetic properties of this candidate multiferroic were compared with those of thin films of Mn 3 substituted, Bi 5Ti 3Fe 0.7Mn 0.3O 15 (BTF7M3O). Vertical and lateral piezoresponse force microscopy (PFM) measurements of the films conclusively demonstrate that BTF7C3O and BTF7M3O thin films are piezoelectric and ferroelectric at room temperature, with the major polarization vector in the lateral plane of the films. No net magnetization was observed for the in-plane superconducting quantum interference device (SQUID) magnetometry measurements of BTF7M3O thin films. In contrast, SQUID measurements of the BTF7C3O films clearly demonstrated ferromagnetic behavior, with a remanent magnetization, B r, of 6.37 emu/cm 3 (or 804 memu/g), remanent moment 4.99 × 10 -5 emu. The BTF7C3O films were scrutinized by x-ray diffraction, high resolution transmission electron microscopy, scanning transmission electron microscopy, and energy dispersive x-ray analysis mapping to assess the prospect of the observed multiferroic properties being intrinsic to the main phase. The results of extensive micro-structural phase analysis demonstrated that the BTF7C3O films comprised of a 3.95 Fe/Co-rich spinel phase, likely CoFe 2 - xTi xO 4, which would account for the observed magnetic moment in the films. Additionally, x-ray magnetic circular dichroism photoemission electron microscopy (XMCD-PEEM) imaging confirmed that the majority of magnetic response arises from the Fe sites of Fe/Co-rich spinel phase inclusions. While the magnetic contribution from the main phase could not be determined by the XMCD-PEEM images, these data however imply that the Bi 5Ti 3Fe 0.7Co 0.3O 15 thin films are likely not single phase multiferroics at room temperature. The PFM results presented demonstrate that the naturally 2D nanostructured Bi 5Ti 3Fe 0.7Co 0.3O 15 phase is a novel ferroelectric and has potential commercial applications in high temperature piezoelectric and ferroelectric memory technologies. The implications for the conclusive demonstration of ferroelectric and ferromagnetic properties in single-phase materials of this type are discussed.

Global surface net-radiation at 5 km from MODIS Terra

Reliable and fine resolution estimates of surface net-radiation are required for estimating latent and sensible heat fluxes between the land surface and the atmosphere. However, currently, fine resolution estimates of net-radiation are not available and consequently it is challenging to develop multi-year estimates of evapotranspiration at scales that can capture land surface heterogeneity and are relevant for policy and decision-making. We developed and evaluated a global net-radiation product at 5 km and 8-day resolution by combining mutually consistent atmosphere and land data from the Moderate Resolution Imaging Spectroradiometer (MODIS) on board Terra. Comparison with net-radiation measurements from 154 globally distributed sites (414 site-years) from the FLUXNET and Surface Radiation budget network (SURFRAD) showed that the net-radiation product agreed well with measurements across seasons and climate types in the extratropics (Wilmott’s index ranged from 0.74 for boreal to 0.63 for Mediterranean sites). Mean absolute deviation between the MODIS and measured net-radiation ranged from 38.0 ± 1.8 W∙m−2 in boreal to 72.0 ± 4.1 W∙m−2 in the tropical climates. The mean bias was small and constituted only 11%, 0.7%, 8.4%, 4.2%, 13.3%, and 5.4% of the mean absolute error in daytime net-radiation in boreal, Mediterranean, temperate-continental, temperate, semi-arid, and tropical climate, respectively. To assess the accuracy of the broader spatiotemporal patterns, we upscaled error-quantified MODIS net-radiation and compared it with the net-radiation estimates from the coarse spatial (1° × 1°) but high temporal resolution gridded net-radiation product from the Clouds and Earth’s Radiant Energy System (CERES). Our estimates agreed closely with the net-radiation estimates from the CERES. Difference between the two was less than 10 W•m−2 in 94% of the total land area. MODIS net-radiation product will be a valuable resource for the science community studying turbulent fluxes and energy budget at the Earth’s surface.

Supercapattery based on binder-free Co3 (PO4)2·8H2O multilayer nano/microflakes on nickel foam

A binder-free cobalt phosphate hydrate (Co3(PO4)2·8H2O) multilayer nano/microflake structure is synthesized on nickel foam (NF) via a facile hydrothermal process. Four different concentrations (2.5, 5, 10, and 20 mM) of Co2+ and PO4–3 were used to obtain different mass loading of cobalt phosphate on the nickel foam. The Co3(PO4)2·8H2O modified NF electrode (2.5 mM) shows a maximum specific capacity of 868.3 C g–1 (capacitance of 1578.7 F g–1) at a current density of 5 mA cm–2 and remains as high as 566.3 C g–1 (1029.5 F g–1) at 50 mA cm–2 in 1 M NaOH. A supercapattery assembled using Co3(PO4)2·8H2O/NF as the positive electrode and activated carbon/NF as the negative electrode delivers a gravimetric capacitance of 111.2 F g–1 (volumetric capacitance of 4.44 F cm–3). Furthermore, the device offers a high specific energy of 29.29 Wh kg–1 (energy density of 1.17 mWh cm–3) and a specific power of 4687 W kg–1 (power density of 187.5 mW cm–3).

Engineering interfacial silicon dioxide for improved metal-insulator-semiconductor silicon photoanode water splitting performance

Silicon photoanodes protected by atomic layer deposited (ALD) TiO2 show promise as components of water splitting devices that may enable the large-scale production of solar fuels and chemicals. Minimizing the resistance of the oxide corrosion protection layer is essential for fabricating efficient devices with good fill factor. Recent literature reports have shown that the interfacial SiO2 layer, interposed between the protective ALD-TiO2 and the Si anode, acts as a tunnel oxide that limits hole conduction from the photoabsorbing substrate to the surface oxygen evolution catalyst. Herein, we report a significant reduction of bilayer resistance, achieved by forming stable, ultrathin (<1.3 nm) SiO2 layers, allowing fabrication of water splitting photoanodes with hole conductances near the maximum achievable with the given catalyst and Si substrate. Three methods for controlling the SiO2 interlayer thickness on the Si(100) surface for ALD-TiO2 protected anodes were employed: (1) TiO2 deposition directly on an HF-etched Si(100) surface, (2) TiO2 deposition after SiO2 atomic layer deposition on an HF-etched Si(100) surface, and (3) oxygen scavenging, post-TiO2 deposition to decompose the SiO2 layer using a Ti overlayer. Each of these methods provides a progressively superior means of reliably thinning the interfacial SiO2 layer, enabling the fabrication of efficient and stable water oxidation silicon anodes.