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Herein, we report a detailed adsorption process of acetic acid (AA) as a model for the head group of carboxylic acid self-assembled monolayers on Cu and Cu2O (111) surfaces and the effect of diethyl zinc (DEZ) on its adsorption geometry on Cu2O (111) using quantum chemical calculations. The most stable adsorption configurations were obtained considering electrostatic potential compatibility from the molecule and surface. Overall, the adsorption behavior revealed bidentate binding as the most stable configuration. Weak van der Waals interactions are key in AA adsorption on Cu (111), while in Cu2O (111), coordination and hydrogen bonds dominated the interaction. AA adsorption geometry on Cu2O revealed that DEZ has no significative impact on the carbonyl-chemisorbed AA and bidentate adsorption modes. These results highlight the significance of the different adsorption modes for achieving area-selective deposition using atomic layer deposition and soft removal SAM molecules.
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In the present work, we report on a theoretical-computational study of the growth mechanism of the TiO2-Graphene nanohybrid by atomic layer deposition. Hydroxyl groups (OH) are anchoring sites for interacting with the main ALD titanium precursors (Tetrakis (dimethylamino) Titanium, Titanium Tetrachloride, and Titanium Isopropoxide). Results demonstrate that the chemical nature of the precursor directly affects the reaction mechanism in each ALD growth step. Tetrakis(dimethylamino)titanium is the precursor that presents a higher affinity (lower energy barriers for the reaction) to hydroxylated graphene in the growth process. A complete reaction mechanism for each precursor was proposed. The differences between precursors were discussed through the non-covalent interactions index. Finally, the water molecules help reduce the energy barriers and consequently favor the formation of the TiO2-graphene nanohybrid.
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The formation of heterostructures that combine a large surface area with high surface activity has attracted the attention of the scientific community due to the unique properties and applications of these heterostructures. In this work, we describe - at the atomic level - the full reaction mechanisms involved in the atomic layer deposition of a hybrid ZnO/CNT inorganic structure. First, the pristine CNTs are chemically activated with a carboxylic acid, a process unique to carbon materials. Diethylzinc (DEZ) and water are used as gas-phase precursors to form ZnO. Our findings show that DEZ is physically adsorbed on the CNTs during the exposure of the first precursor. The ligand-exchange to generate chemisorbed ethyl zinc on the O side of the COOH group needs to overcome an energy barrier of 0.06 eV. This is a very small energy if compared to the values (0.5-0.6 eV) obtained in previous studies for OH functionalized surfaces. The height of the barrier is associated with the C[double bond, length as m-dash]O side, which mediates the H proton's exchange from the OH group to the C2H5 ligand. Furthermore, upon exposure to the oxidizing agent (H2O), ethyl zinc exchanges its last ligand as ethane, and it accepts a hydroxyl group through a self-limiting reaction with an energy barrier of 0.88 eV. Notice that the energy barrier of the second ligand-exchange is larger than of the first. We have also analyzed the effect in the saturation of the second precursor: as the quantity of water molecules increases, the long-range interactions tend to repel them. However, the energy barrier of the second ligand-exchange decreases from 1.53 eV to 0.88 eV for one and two water molecules, showing a clear dependence on the oxidizing agent. Non-covalent interactions are used as a tool to visualize the driving forces that take place during each partial reaction in real space. Our study points out the importance of using the right functionalization agent to achieve a controlled and conformal ALD growth at the initial steps of the formation of hybrid ZnO/CNT structures, as well as the role played by the oxidizing agent to lower the energy barrier on the second ALD step.
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The design of optoelectronic devices made with ZnO superlattices requires the knowledge of the refractive index, which currently can be done only for films thicker than 30 nm. In this work, we present an effective medium approach to determine the refractive index of ZnO layers as thin as 2 nm. The approach was implemented by determining the refractive index of ZnO layers ranging from 2 nm to 20 nm using spectroscopic ellipsometry measurements in multilayers. For a precise control of morphology and thickness, the superlattices were fabricated with atomic layer deposition (ALD) with alternating layers of 2 nm thick Al2O3 and ZnO, labeled as N ZnO-Al2O3, where N = 10, 20, 30, 50, 75 and 100. The total thickness of all superlattices was kept at 100 nm. The approach was validated by applying it to similar superlattices reported in the literature and fitting the transmittance spectra of the superlattices.
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We report the adsorption of diethylzinc on hydroxyl functionalized carbon nanotubes. This study intends to understand, at the atomic level, the initial stages of ZnO formation by atomic layer deposition. Our study begins with the molecule physisorbed on the nanotube (initial state of the reaction). The final state of this reaction is when the H atom of the hydroxyl group is abstracted and migrates to one ethyl group of diethylzinc. The oxygen atom relaxes towards the nanotube and forms a strong bond with a carbon atom, while the remaining part of the molecule forms a bond with the H atom and physisorbs on top of the ZnO unit. The probability for this process to happen is very high since the energy to desorb the diethylzinc molecule is higher than the energy needed to break down the O-H bond. Non-covalent interactions and charge density distributions are plotted to confirm the break-down, formation of bonds, and repulsion during the reaction pathway.
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This is a report of a study of the nonlinear optical properties of samples based on multiple Al2O3/ZnO bilayers fabricated by atomic layer deposition (ALD) in silica. The multi-layer configuration for samples consists of alternated layers of constant thickness of Al2O3 (Δx) and ZnO (Δy) nanolaminates with a total thickness of â¼ 500 nm. The physical properties of the samples were characterized by means of TEM, spectrophotometry and variable angle spectroscopic ellipsometry. The absorptive and refractive contributions to the nonlinearity of the samples were studied by means of z-scan technique using a 100 fs at 800 nm. The nonlinear parameters, ß and n2, are studied using different values of the layers thickness, Δx and Δy, in the nanolaminated stack. The possible applications in optical signal processing system are discussed by means of the figures of merit W and T.
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Carbon Nanotubes (CNTs) are coated by an insulator (Al2O3) shell using the atomic layer deposition (ALD) technique. This is achieved in large quantities (tens of milligrams per batch) for electrical wiring purposes. Here we present a transmission electron microscopy (TEM) characterization together with a detailed high resolution elemental analysis by in-column energy dispersive X-ray spectroscopy (EDXS). An excellent conformality of the insulator around the CNTs is obtained. Moreover, the elemental maps show the composition of the shell while the line scan analyses demonstrate an abrupt shell-CNT interface achieved by our ALD approach.
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Multifuncionality in polycrystalline multiferroic ceramics can be improved using an advanced synthesis process. In this work, core-shell design is being proposed to enhance the transport properties of biferroic YCrO3. The atomic layer deposition (ALD) thin-film growth technique was used for the YCrO3/Al2O3 (Y@Al) nanocomposite fabrication. A continuous, amorphous, and uniform Al2O3 shell, a few nanometers thick, was obtained and characterized by X-ray photoelectron spectroscopy, X-ray diffraction, and high-resolution transmission electron microscopy. The transport properties of biferroic YCrO3 coated with 50, 500, and 1000 ALD cycles of insulating Al2O3 were investigated using magnetization and AC conductivity measurements. It is observed that the values of the magnetic coercive field and the magnetization are affected by the amorphous and partially crystallized Al2O3 shell. Additionally, the Y@Al nanocomposite experiments show a notorious decreasing in the loss tangent and the electrical conductivity. Accordingly, hysteresis loops in the polarization versus electric energy data confirm the decrease of the leakage current as a consequence of the Al2O3 shell acting as a barrier layer. The results shown here confirm that the core-shell architecture is a promising alternative for improvement of the magnetic and ferroelectric properties in bulk multiferroics.
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Synthetic methodology and physicochemical characterization of multi-wall carbon nanotubes (MWCNTs) functionalized with a crown ether molecule is reported. The MWCNTs were synthesized by spray pyrolysis technique using toluene as carbon source and ferrocene as catalyst. The nanotubes were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Oxidation of MWCNTs was carried out by 8 h of sonication in a mixture of sulfuric and nitric acid (3:1). The MWCNT-COOH was amidated with 4-aminobenzo-15-crown-5 under mild reaction conditions using N,N'-dicyclohexylcarbodiimide and dimethylaminopyridine as catalyst and dimethylformamide as solvent, at room temperature for 24 h. The amidation product was characterized by scanning electron microscopy, infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy and a mass spectrometry study to determine the fragmentation pattern being m/z 309, 177 and 149 the most important ions.
