Interface layers between reactive and energetic materials in nanolaminates or nanoenergetic materials are believed to play a crucial role in the properties of nanoenergetic systems. Typically, in the case of Metastable Interstitial Composite nanolaminates, the interface layer between the metal and oxide controls the onset reaction temperature, reaction kinetics, and stability at low temperature. So far, the formation of these interfacial layers is not well understood for lack of in situ characterization, leading to a poor control of important properties. We have combined in situ infrared spectroscopy and ex situ X-ray photoelectron spectroscopy, differential scanning calorimetry, and high resolution transmission electron microscopy, in conjunction with first-principles calculations to identify the stable configurations that can occur at the interface and determine the kinetic barriers for their formation. We find that (i) an interface layer formed during physical deposition of aluminum is composed of a mixture of Cu, O, and Al through Al penetration into CuO and constitutes a poor diffusion barrier (i.e., with spurious exothermic reactions at lower temperature), and in contrast, (ii) atomic layer deposition (ALD) of alumina layers using trimethylaluminum (TMA) produces a conformal coating that effectively prevents Al diffusion even for ultrathin layer thicknesses (∼0.5 nm), resulting in better stability at low temperature and reduced reactivity. Importantly, the initial reaction of TMA with CuO leads to the extraction of oxygen from CuO to form an amorphous interfacial layer that is an important component for superior protection properties of the interface and is responsible for the high system stability. Thus, while Al e-beam evaporation and ALD growth of an alumina layer on CuO both lead to CuO reduction, the mechanism for oxygen removal is different, directly affecting the resistance to Al diffusion. This work reveals that it is the nature of the monolayer interface between CuO and alumina/Al rather than the thickness of the alumina layer that controls the kinetics of Al diffusion, underscoring the importance of the chemical bonding at the interface in these energetic materials.
The initial surface chemistry and growth mechanisms of the atomic layer deposition (ALD) of metallic copper on SiO(2) surfaces are investigated using an amidinate precursor (copper(I) di-sec-butylacetamidinate, [Cu((s)Bu-amd)](2)) and molecular hydrogen. Using in situ Fourier transform infrared spectroscopy together with calculations based on density functional theory, we show that the initial surface reaction of [Cu((s)Bu-amd)](2) with hydroxylated SiO(2) takes place by displacement of one of the sec-butylacetamidinate ligands at a surface -OH site, thus forming a Si-O-Cu-((s)Bu-amd) surface species, evident by the stretching vibrations of Si-O-Cu and the chelating -NCN- bonds. Molecular hydrogen exposure during a subsequent pulse dissociates most of the sec-butylacetamidinate ligands bound to surface Cu, which releases free amidine vapor, leaving Cu atoms free to agglomerate on the surface and thus opening more reactive sites for the next [Cu((s)Bu-amd)](2) pulse. Copper agglomeration is evident in the IR absorbance spectra through the partial recovery of the intensity of SiO(2) optical phonon modes upon H(2) reduction, which was lost after the reaction of [Cu((s)Bu-amd)](2) with the initial SiO(2) surface. The thermally activated ligand rearrangement from a bridging to a monodentate structure occurs above 220 degrees C through hydrogenation of the ligand by surface hydroxyl groups after exposure to a [Cu((s)Bu-amd)](2) pulse. As Cu particles grow with further ALD cycles, the activation temperature is lowered to 185 degrees C, and hydrogenation of the ligand takes place after H(2) pulses, catalyzed by Cu particles on the surface. The surface ligand rearranged into a monodentate structure can be removed during subsequent Cu precursor or H(2) pulses. Finally, we postulate that the attachment of dissociated ligands to the SiO(2) surface during the [Cu((s)Bu-amd)](2) pulse can be responsible for carbon contamination at the surface during the initial cycles of growth, where the SiO(2) surface is not yet completely covered by copper metal.
Mechanisms of atomic layer deposition (ALD) growth of lanthanum oxide on H-terminated Si(111) using lanthanum tris(N,N′-diisopropylacetamidinate) (La( i Pr-MeAMD) 3 ) are investigated using infrared (IR) absorption spectroscopy. The reactivity of this amidinate precursor is high, with almost all surface Si-H bonds consumed after 5 ALD cycles at 300°C. Gas phase IR spectra show that, although most of the precursor (La( i Pr-MeAMD) 3 ) remains intact, a strong feature at 1665 cm -1 , characteristic of a hydrogenated and dissociated free ligand with localized electrons in the N-CdN bonds, is present. Such partial precursor dissociation in the gas phase is due to hydrolysis by traces of water vapor remaining in the reactor, even after purging. As a result, some Si-O-La bonds are formed upon reaction with the surface during the first La( i PrMeAMD) 3 pulse, prior to any water pulse. During film growth, acetate/carbonate and hydroxyl impurities are incorporated into the film. Annealing to 500°C in dry N 2 removes these impurities but fosters the growth of interfacial SiO 2 . Deposition at 300°C leads to decomposition of adsorbed ligands, as evidenced by the formation of cyanamide or carbodiimide vibrational bands (or both) at 1990 and 2110 cm -1 , respectively. Despite this decomposition, ideal self-limited ALD growth is maintained because the decomposed ligands are removed by the subsequent water pulse. Growth of pure lanthanum oxide films is often characterized by nonuniform film thickness if purging is not complete because of reversible absorption of water by the La 2 O 3 film. Uniform ALD growth can be maintained without a rigorous dry purge by introducing alternating trimethylaluminum (TMA)/D 2 O ALD cycles between La/D 2 O cycles.
Tertbutylallylcobalttricarbonyl (tBu-AllylCo(CO)3) is shown to have strong substrate selectivity during atomic layer deposition of metallic cobalt. The interaction of tBu-AllylCo(CO)3 with SiO2 surfaces, where hydroxyl groups would normally provide more active reaction sites for nucleation during typical ALD processes, is thermodynamically disfavored, resulting in no chemical reaction on the surface at a deposition temperature of 140 °C. On the other hand, the precursor reacts strongly with H-terminated Si surfaces (H/Si), depositing ∼1 ML of cobalt after the first pulse by forming Si–Co metallic bonds. This remarkable substrate selectivity of tBu-AllylCo(CO)3 is due to an ALD nucleation reaction process paralleling a catalytic hydrogenation, which requires a coreactant that acts as a hydrogen donor rather than a source of bare protons. The chemical specificity demonstrated in this work suggests a new paradigm for developing selective ALD precursors. Namely, selectivity can be achieved by tailoring the ligands in the coordination sphere to obtain structural analogues to reaction intermediates for catalytic transformations that exhibit the desired chemical discrimination.
In situ FTIR studies of O3 interacting with TMA-derived Al2O3 surfaces reveal that O incorporation into the surface results in a stable formate intermediate. DFT calculations provide conclusive band assignments, identifying the surface species. These results have broad implications for understanding the high-κ dielectric ALD process using an O3 precursor
Passivation of semiconductor surfaces is conveniently realized by terminating surface dangling bonds with a monovalent atom such as hydrogen using a simple wet chemical process (for example, HF treatment for silicon). However, the real potential of surface chemical passivation lies in the ability to replace surface hydrogen by multivalent atoms to form surfaces with tailored properties. Although some progress has been made to attach organic layers on top of H-terminated surfaces, it has been more challenging to understand and control the incorporation of multivalent atoms, such as oxygen and nitrogen, within the top surface layer of H-terminated surfaces. The difficulty arises partly because such processes are dominated by defect sites. Here, we report mechanistic pathways involved in the nitridation of H-terminated silicon surfaces using ammonia vapour. Surface infrared spectroscopy and first-principles calculations clearly show that the initial interaction is dominated by the details of the surface morphology (defect structure) and that NH and NH(2) are precursors to N insertion into Si-Si bonds. For the dihydride-stepped Si(111) surface, a unique reaction pathway is identified leading to selective silazane step-edge formation at the lowest reaction temperatures.
We demonstrate that interfacial SiO2, usually formed during high-κ oxide growth on silicon using ozone (O3), is suppressed during Al2O3 atomic layer deposition (ALD) by decreasing the O3 flow rate. First-principles calculations indicate that oxygen introduced by the first low-dose O3 exposure is inserted into the surface nucleation layer rather than the Si lattice. Subsequent Al2O3 deposition further passivates the surface against substrate oxidation. Aluminum methoxy [–Al(OCH3)2] and surface Al–O–Al linkages formed after O3 pulses are suggested as the reaction sites for trimethylaluminum during ALD of Al2O3.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.