Atomic layer deposition (ALD) of silicon nitride (SiNx) is deemed essential for a variety of applications in nanoelectronics, such as gate spacer layers in transistors. In this work an ALD process using bis(tert-butylamino)silane (BTBAS) and N2 plasma was developed and studied. The process exhibited a wide temperature window starting from room temperature up to 500 °C. The material properties and wet-etch rates were investigated as a function of plasma exposure time, plasma pressure, and substrate table temperature. Table temperatures of 300-500 °C yielded a high material quality and a composition close to Si3N4 was obtained at 500 °C (N/Si=1.4±0.1, mass density=2.9±0.1 g/cm3, refractive index=1.96±0.03). Low wet-etch rates of ∼1 nm/min were obtained for films deposited at table temperatures of 400 °C and higher, similar to that achieved in the literature using low-pressure chemical vapor deposition of SiNx at >700 °C. For novel applications requiring significantly lower temperatures, the temperature window from room temperature to 200 °C can be a solution, where relatively high material quality was obtained when operating at low plasma pressures or long plasma exposure times.

Natural fires ignited by lightning strikes following droughts frequently are posited as the ecological mechanism maintaining discontinuous tree cover and grass‐dominated ground layers in savannas. Such fires, however, may not reliably maintain humid savannas. We propose that savanna trees producing pyrogenic shed leaves might engineer fire characteristics, affecting ground‐layer plants in ways that maintain humid savannas. We explored our hypothesis in a high‐rainfall, frequently burned pine savanna in which the dominant tree, longleaf pine (Pinus palustris), produces resinous needles that become highly flammable when shed and dried. We postulated that pyrogenic needles should have much greater influence on fire characteristics at ground level, and hence post‐fire responses of dominant shrubs and grasses, than other abundant fine fuels (shed oak leaves and grass culms). We further reasoned that these effects should increase with amounts of needles. We managed site conditions that affect fuels (time since fire, dominant vegetation), manipulated amounts of needles in ground‐layer plots, prescribed burned the plots, and measured fire characteristics at ground level. We also measured characteristics of ground‐layer oaks and grasses before, then 2 and 8 months after fires. We tested our hypotheses regarding effects of pyrogenic pine fuels on fire characteristics and vegetation regrowth and explored direct and indirect effects of fuels on fire characteristics and vegetation using a structural equation model. Pine needles influenced fire characteristics, elevating maximum temperature increases, durations of heating above 60°C, and fine fuel consumption considerably above measurements when fuels only included other savanna plants. Presence of pine needles depressed post‐fire numbers of oak stems and grass culms, especially in the interior of grass genets, as well as post‐fire flowering of grasses. The structural equation model indicated strong direct and indirect pathways from pine needles to post‐fire responses of oaks and grasses. The experimental field tests of hypotheses, bolstered by structural equation modeling, indicate pyrogenic fine fuels modify characteristics of prescribed fires at ground level, negatively affecting dominant ground‐layer oaks and grasses. Frequent fires fueled by pyrogenic needles should maintain humid savannas and generate spatial pyrodiversity that affects composition and dynamics of pine savanna ground‐layer vegetation.

The authors have been investigating the use of [Al(CH3)2(μ-OiPr)]2 (DMAI) as an alternative Al precursor to [Al(CH3)3] (TMA) for remote plasma-enhanced and thermal ALD over wide temperature ranges of 25–400 and 100–400 °C, respectively. The growth per cycle (GPC) obtained using in situ spectroscopic ellipsometry for plasma-enhanced ALD was 0.7–0.9 Å/cycle, generally lower than the >0.9 Å/cycle afforded by TMA. In contrast, the thermal process gave a higher GPC than TMA above 250 °C, but below this temperature, the GPC decreased rapidly with decreasing temperature. Quadrupole mass spectrometry data confirmed that both CH4 and HOiPr were formed during the DMAI dose for both the plasma-enhanced and thermal processes. CH4 and HOiPr were also formed during the H2O dose but combustion-like products (CO2 and H2O) were observed during the O2 plasma dose. Rutherford backscattering spectrometry showed that, for temperatures >100 °C and >200 °C for plasma-enhanced and thermal ALD, respectively, films from DMAI had an O/Al ratio of 1.5–1.6, a H content of ∼5 at. % and mass densities of 2.7–3.0 g cm−3. The film compositions afforded from DMAI were comparable to those from TMA at deposition temperatures ≥150 °C. At lower temperatures, there were differences in O, H, and C incorporation. 30 nm thick Al2O3 films from the plasma-enhanced ALD of DMAI were found to passivate n- and p-type Si floatzone wafers (∼3.5 and ∼2 Ω cm, respectively) with effective carrier lifetimes comparable to those obtained using TMA. Surface recombination velocities of < 3 and < 6 cm s−1 were obtained for the n- and p-type Si, respectively. Using these results, the film properties obtained using DMAI and TMA are compared and the mechanisms for the plasma-enhanced and thermal ALD using DMAI are discussed.

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The doping efficiency and hence the electrical properties of atomic layer deposited ZnO can be improved by using a novel, safer boron precursor.

Thin films of tungsten carbonitride have been formed on glass by low-pressure chemical vapour deposition (LP)CVD at 550 degrees C from four closely related precursors: [W(mu-N(t)Bu)(N(t)Bu)Cl(2)(H(2)N(t)Bu)](2), [W(N(t)Bu)(2)Cl(2)(TMEDA)] (TMEDA = N,N,N',N'-tetramethylethylenediamine), [W(N(t)Bu)(2)Cl(2)(py)(2)] (py = pyridine) and [W(N(t)Bu)(2)Cl(N{SiMe(3)}(2))]. The grey mirror-like films were grown with a nitrogen or ammonia bleed gas. In all cases the chlorine content of the deposited films was less than 1 at% and the oxygen content of the films was lower for those grown using ammonia. Surprisingly, the use of ammonia did not significantly change the carbon content of the resulting films. Despite the coordination environment around the metal being essentially the same and the materials having a comparable volatility, some differences in film quality were observed. The films were uniform, adhesive, abrasion resistant, conformal and hard, being resistant to scratching with a steel scalpel. X-Ray powder diffraction patterns of all the films showed the formation of beta-WN(x)C(y). As a comparison the aerosol-assisted chemical vapour deposition (AA)CVD of [W(mu-N(t)Bu)(N(t)Bu)Cl(2)(H(2)N(t)Bu)](2) was investigated and amorphous tungsten carbonitride films were deposited.

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