Initial surface reactions of TiO2 atomic layer deposition onto SiO2 surfaces: density functional theory calculations

We present a density functional theory (DFT) study of the initial surface reactions of TiO2 deposition onto a SiO2 substrate using atomic layer deposition (ALD). The precursors for the deposition process were chosen to be TiCl4 and H2O, and several cluster models were used for the SiO2 substrate. We predict the activation barriers, transition states, and reaction pathways of the surface reactions, and we investigate the effect of surface heterogeneity (such as the presence of siloxane bridges) on the reactivity of the SiO2 surface. Our study suggests that the concentration and arrangement of different reactive groups on the substrate will strongly dictate the process of film growth during ALD, including the film morphology and the growth rate.     

The Effect of Surface Terminations on the Initial Stages of TiO2 Deposition on Functionalized Silicon

As atomic layer deposition (ALD) emerges as a method to fabricate architectures with atomic precision, emphasis is placed on understanding surface reactions and nucleation mechanisms. ALD of titanium dioxide with TiCl₄ and water has been used to investigate deposition processes in general, but the effect of surface termination on the initial TiO₂ nucleation lacks needed mechanistic insights. This work examines the adsorption of TiCl₄ on Cl−, H−, and HO− terminated Si(100) and Si(111) surfaces to elucidate the general role of different surface structures and defect types in manipulating surface reactivity of growth and non-growth substrates. The surface sites and their role in the initial stages of deposition are examined by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Density functional theory (DFT) computations of the local functionalized silicon surfaces suggest oxygen-containing defects are primary drivers of selectivity loss on these surfaces.     

Grazing incidence-X-ray fluorescence spectrometry for the compositional analysis of nanometer-thin high-kappa dielectric HfO2 layers.

In future microelectronic devices, SiO2 as a gate dielectric material will be replaced by materials with a higher dielectric constant. One such candidate material is HfO2. Thin layers are typically deposited from ligand-containing precursors in chemical vapor deposition (CVD) processes. In the atomic layer deposition (ALD) of HfO2, these precursors are often HfCl4 and H2O. Obviously, the material properties of the deposited films will be affected by residual ligands from the precursors. In this paper, we evaluate the use of grazing incidence--and total reflection-X-ray fluorescence spectrometry (GI-XRF and TXRF) for Cl trace analysis in nanometer-thin HfO2 films deposited using ALD. First, the results from different X-ray analysis approaches for the determination of Hf coverage are compared with the results from Rutherford backscattering spectrometry (RBS). Next, we discuss the selection of an appropriate X-ray excitation source for the analysis of traces within the high-kappa: layers. Finally, we combine both in a study on the accuracy of Cl determinations in HfO2 layers.     

Diffusion reaction of oxygen in HfO2/SiO2/Si stacks

We study the oxidation mechanism of silicon in the presence of a thin HfO2 layer. We performed a set of annealing in 18O2 atmosphere on HfO2/SiO2/Si stacks observing the 18O distribution in the SiO2 layer with time-of-flight secondary ion mass spectrometry (ToF-SIMS). The 18O distribution in HfO2/SiO2/Si stacks upon 18O2 annealing suggests that what is responsible for SiO2 growth is the molecular O2, whereas no contribution is found of the atomic oxygen to the oxidation. By studying the dependence of the oxidation velocity from oxygen partial pressure and annealing temperature, we demonstrate that the rate-determining step of the oxidation is the oxygen exchange at the HfO2/SiO2 interface. When moisture is chemisorbed in HfO2 films, the oxidation of the underlying silicon substrate becomes extremely fast and its kinetics can be described as a wet silicon oxidation process. The silicon oxidation during O2 annealing of the atomic layer deposited HfO2/Si is fast in its early stage due to chemisorbed moisture and becomes slow after the first 10 s.     

Atomic layer deposition chemistry: recent developments and future challenges

New materials, namely high-k (high-permittivity) dielectrics to replace SiO(2), Cu to replace Al, and barrier materials for Cu, are revolutionizing modern integrated circuits. These materials must be deposited as very thin films on structured surfaces. The self-limiting growth mechanism characteristic to atomic layer deposition (ALD) facilitates the control of film thickness at the atomic level and allows deposition on large and complex surfaces. These features make ALD a very promising technique for future integrated circuits. Recent ALD research has mainly focused on materials required in microelectronics. Chemistry, in particular the selection of suitable precursor combinations, is the key issue in ALD; many interesting results have been obtained by smart chemistry. ALD is also likely to find applications in other areas, such as magnetic recording heads, optics, demanding protective coatings, and micro-electromechanical systems, provided that cost-effective processes can be found for the materials required.     

Bond insertion, complexation, and penetration pathways of vapor-deposited aluminum atoms with HO- and CH(3)O-terminated organic monolayers

The interaction of vapor-deposited Al atoms with self-assembled monolayers (SAMs) of HS-(CH(2))(16)-X (X = -OH and -OCH(3)) chemisorbed at polycrystalline Au[111] surfaces was studied using time-of-flight secondary-ion mass spectrometry, X-ray photoelectron spectroscopy, and infrared reflectance spectroscopy. Whereas quantum chemical theory calculations show that Al insertion into the C-C, C-H, C-O, and O-H bonds is favorable energetically, it is observed that deposited Al inserts only with the OH SAM to form an -O-Al-H product. This reaction appears to cease prior to complete -OH consumption, and is followed by formation of a few overlayers of a nonmetallic type of phase and finally deposition of a metallic film. In contrast, for the OCH(3) SAM, the deposited Al atoms partition along two parallel paths: nucleation and growth of an overlayer metal film, and penetration through the OCH(3) SAM to the monolayer/Au interface region. By considering a previous observation that a CH(3) terminal group favors penetration as the dominant initial process, and using theory calculations of Al-molecule interaction energies, we suggest that the competition between the penetration and overlayer film nucleation channels is regulated by small differences in the Al-SAM terminal group interaction energies. These results demonstrate the highly subtle effects of surface structure and composition on the nucleation and growth of metal films on organic surfaces and point to a new perspective on organometallic and metal-solvent interactions.     

Molecular layer deposition of poly(p-phenylene terephthalamide) films using terephthaloyl chloride and p-phenylenediamine

Ultrathin polymer films can be fabricated using the gas-phase method known as molecular layer deposition. This process typically uses bifunctional monomers in a sequential, self-limiting reaction sequence to grow conformal polymer films with molecular layer control. In this study, terephthaloyl chloride (TC) and p-phenylenediamine (PD) were used as the bifunctional monomers to deposit poly(p-phenylene terephthalamide) (PPTA) thin films. 3-Aminopropyl trimethoxysilane or ethanolamine was used to prepare amine-terminated surfaces prior to the PPTA MLD. The surface chemistry and growth rate during PPTA MLD at 145 degrees C were studied using in situ transmission Fourier transform infrared (FTIR) spectroscopy experiments on high surface area powders of SiO2 particles. PPTA MLD thin film growth at 145 degrees C was also examined using in situ transmission FTIR experiments on flat KBr substrates with an amine-terminated Al2O3 ALD overlayer. The integrated absorbances of the N-H and amide I stretching vibrations were measured and used to estimate the thin film thickness. X-ray reflectivity (XRR) experiments were also employed to measure the film thickness after PPTA MLD at 145 degrees C and 180 degrees C. The experiments revealed that the TC and PD reactions displayed self-limiting surface chemistry. The surface species alternated with sequential TC and PD exposures and the PPTA MLD films grew continuously. However, the growth rates per MLD cycle at 145 degrees C were less than expectations based on the size of the molecules involved in the reaction chemistry and were variable between 0.5 and 4.0 A per TC/PD reaction cycle. The lower growth rates are explained by the growth of a limited number of polymer chains on the substrate. The variability in the growth rate is attributed to the difficulties with the bifunctional monomer precursors. Alternative surface chemistries for polymer MLD are proposed that would avoid the use of bifunctional monomers.     

Atomic layer deposition of TiO2 from TiI4 and H2O onto SiO2 surfaces: ab initio calculations of the initial reaction mechanisms

The initial surface reactions involved in the atomic layer deposition (ALD) of TiO2 from TiI4 and H2O onto a SiO2 substrate have been investigated using electronic structure calculations based on cluster models. The detailed atomic growth mechanisms on different types of functionalities on the SiO2 substrate have been proposed. The effects of quantum tunneling and hindered rotations of adsorbates on the rate of surface reactions have been investigated. The effects of tunneling were found to be negligible for all reactions, because typical ALD temperatures range from 150 to 450 degrees C. However, the rotational contributions to the rate constants must be taken into account in certain cases. All of the three surface functionalities investigated exhibit high chemical reactivity toward TiI4 precursors at typical ALD temperatures. The rate constants of the second half-reactions between Ti intermediates and H2O are 5-8 orders of magnitude smaller than the first half-reactions between TiI4 and the surface functionalities. Although the iodine release reaction has been used to explain previous experimental measurements, it is predicted to be unfavorable (kinetically and thermodynamically) and is unlikely to occur at typical ALD temperatures. Substitution of TiI4 with TiCl4 as the metal precursor can increase the binding energies of the absorbates onto the surface due to the high electronegativity of the Cl ligands. However, the activation barriers are not significantly different between these two metal precursors. More importantly, our calculations predict that TiI4 precursors tend to produce TiO2 films with fewer impurities than the TiCl4 precursors.     

Surface chemistry and electrical properties of germanium nanowires

Germanium nanowires (GeNWs) with p- and n-dopants were synthesized by chemical vapor deposition (CVD) and were used to construct complementary field-effect transistors (FETs). Electrical transport and X-ray photoelectron spectroscopy (XPS) data are correlated to glean the effects of Ge surface chemistry to the electrical characteristics of GeNWs. Large hysteresis due to water molecules strongly bound to GeO(2) on GeNWs is revealed. Different oxidation behavior and hysteresis characteristics and opposite band bending due to Fermi level pinning by interface states between Ge and surface oxides are observed for p- and n-type GeNWs. Vacuum annealing above 400 degrees C is used to remove surface oxides and eliminate hysteresis in GeNW FETs. High-kappa dielectric HfO(2) films grown on clean GeNW surfaces by atomic layer deposition (ALD) using an alkylamide precursor is effective in serving as the first layer of surface passivation. Lastly, the depletion length along the radial direction of nanowires is evaluated. The result suggests that surface effects could be dominant over the "bulk" properties of small diameter wires.     

The application of low energy ion scattering spectroscopy (LEIS) in sub 28‐nm CMOS technology

With the transition to ≤28‐nm CMOS technology nodes, the surface analytical challenges with regard to steadily decreasing dimensions and still growing materials options raise the demand of high performing surface analysis techniques. Characterization of ultrathin films and multilayer stacks, especially in high‐k metal gate stacks, by means of low energy ion scattering spectroscopy (LEIS) with its monolayer sensitivity has been established as a very useful analysis technique next to Auger electron spectroscopy, X‐ray photoelectron spectroscopy , and time‐of‐flight secondary ion mass spectrometry. Questions regarding film nucleation, growth, coverage, and diffusion can be answered, thereby enabling those processes to be controlled appropriately. In this work, growth studies of ALD HfO₂ and TiN are shown, as well as film thickness determination based on surface spectra. PVD aluminum and lanthanum, acting as work function metals on the gate oxide, were deposited, and their film formation and closure were investigated. Further application fields of LEIS have emerged from the characterization of in‐die features on patterned wafers. As presented on test arrays, it is possible to detect material deep in trenches. This is an advantage if residues need to be identified after etch or clean processes.     

Role of water in the atomic layer deposition of TiO(2) on SiO(2)

Atomic layer deposition (ALD) of TiO(2) on SiO(2) powder using sequential addition of TiCl(4) and H(2)O vapors has been investigated by infrared spectroscopy. In the first cycle, TiCl(4) reacts monofunctionally or bifunctionally with surface silanols forming (Si-O-)(n)Ti-Cl(4)(-)(n) (n = 1, 2) species. Subsequent addition of water vapor leads to the hydrolysis of the (Si-O-)(n)Ti-Cl(4)(-)(n) to form a Ti-O-Ti network, and at the same time, some cleavage of Si-O-Ti bonds occurs, regenerating Si-OH in the process. It is shown that the species formed on the surface in the first TiCl(4) dose are temperature dependent. However, after addition of H(2)O vapor, the amount of TiO(2) deposited in the first complete cycle is independent of reaction temperature. In the second and above cycles, the amount of TiO(2) deposited as a function of ALD cycles strongly correlates with the amount of water on the surface. This, in turn, led to a temperature dependence of the growth rate of the TiO(2) per cycle.     

具有辐射聚合能力的HfO2/SiO2溶胶-凝胶玻璃的制备及其X射线光刻性能研究

采用溶胶-凝胶方法制备了一种新颖的具有辐射聚合能力的HfO2/SiO2凝胶薄膜. 并采用X射线作曝光光源对薄膜进行了曝光, 通过FTIR的测试, 分析了薄膜曝光前后的结构变化. 结果表明, 该材料具有良好的辐射聚合能力. 采用XPS分析了薄膜的成分, 并证实了Hf元素的存在. 用椭偏仪测试了薄膜的折射率, 结果证实, 加入HfO2提高了体系的折射率. 利用其辐射聚合能力, 采用X射线通过掩模板进行曝光, 利用曝光部分与未曝光部分在溶剂中的溶解度差, 在薄膜上制备了高为0.8 μm、周期为1 μm的衍射光栅, 进一步证实了材料具有良好的辐射聚合能力.     

Interaction of Au with thin ZrO2 films: influence of ZrO2 morphology on the adsorption and thermal stability of Au nanoparticles

The model catalysts of ZrO(2)-supported Au nanoparticles have been prepared by deposition of Au atoms onto the surfaces of thin ZrO(2) films with different morphologies. The adsorption and thermal stability of Au nanoparticles on thin ZrO(2) films have been investigated using synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS). The thin ZrO(2) films were prepared by two different methods, giving rise to different morphologies. The first method utilized wet chemical impregnation to synthesize the thin ZrO(2) film through the procedure of first spin-coating a zirconium ethoxide (Zr(OC(2)H(5))(4)) precursor onto a SiO(2)/Si(100) substrate at room temperature followed by calcination at 773 K for 12 h. Scanning electron microscopy (SEM) investigations indicate that highly porous "sponge-like nanostructures" were obtained in this case. The second method was epitaxial growth of a ZrO(2)(111) film through vacuum evaporation of Zr metal onto Pt(111) in 1 × 10(-6) Torr of oxygen at 550 K followed by annealing at 1000 K. The structural analysis with low energy electron diffraction (LEED) of this film exhibits good long-range ordering. It has been found that Au forms smaller particles on the porous ZrO(2) film as compared to those on the ordered ZrO(2)(111) film at a given coverage. Thermal annealing experiments demonstrate that Au particles are more thermally stable on the porous ZrO(2) surface than on the ZrO(2)(111) surface, although on both surfaces, Au particles experience significant sintering at elevated temperatures. In addition, by annealing the surfaces to 1100 K, Au particles desorb completely from ZrO(2)(111) but not from porous ZrO(2). The enhanced thermal stability for Au on porous ZrO(2) can be attributed to the stronger interaction of the adsorbed Au with the defects and the hindered migration or coalescence resulting from the porous structures.     

Change in the interfacial reaction of Hf-silicate film as a function of thickness and stoichiometry

Medium energy ion scattering and high-resolution transmission electron microscopy are used to investigate the depth of the interfacial reaction of Hf-silicate film. The interfacial reaction is critically affected by the film thickness and the mole fraction of HfO(2) in silicate film. The interfacial compressive strain generated at the surface of the Si substrate is dependent on the film thickness during the postannealing process in film with a thickness of approximately 4 nm. Finally, the phase separation phenomenon demonstrates critically different behaviors at different film thicknesses and stoichiometries because the diffusion of Si from interface to surface is dependent on these factors. Moreover, the oxidation by oxygen impurity in the inert ambient causes SiO(2) top formation.     

GaN nanowire functionalized with atomic layer deposition techniques for enhanced immobilization of biomolecules

We report the use of atomic layer deposition (ALD) coating as a nanobiosensor functionalization strategy for enhanced surface immobilization that may enable higher detection sensitivity. Three kinds of ALD coating films, Al(2)O(3), TiO(2), and SiO(2), were grown on the gallium nitride nanowire (GaN NW) surfaces and characterized with high-resolution transmission electron microscopy (HRTEM) and vacuum Fourier transform infrared spectroscopy (FTIR). Results from HRTEM showed that the thicknesses of ALD-Al(2)O(3), ALD-TiO(2) and ALD-SiO(2) coatings were 4-5 nm, 5-6 nm, and 12-14 nm, respectively. Results from FTIR showed that the OH contents of these coatings were, respectively, ～6.9, ～7.4, and ～9.3 times that of piranha-treated GaN NW. Furthermore, to compare protein attachments on the different surfaces, poly(ethylene glycol) (PEG)-biotin was grafted on the OH-functionalized GaN NW surfaces through active Si-Cl functional groups. Streptavidin protein molecules were then attached to the biotin ends via specific binding. The immobilized streptavidin molecules were examined with scanning electron microscopy, HRTEM, and fluorescent imaging. Results from HRTEM and energy-dispersive X-ray revealed that the nitrogen concentrations on the three ALD coatings were significantly higher than that on the piranha-treated surface. Results from fluorescent imaging further showed that the protein attachments on the Al(2)O(3), TiO(2), and SiO(2) ALD coatings were, respectively, 6.4, 7.8, and 9.8 times that of piranha-treated surface. This study demonstrates that ALD coating can be used as a functionalization strategy for nanobiosensors because it is capable of creating functional groups with much higher density compared to widely used acid modifications, and among the three ALD coatings, ALD-SiO(2) yielded the most promising results in OH content and protein attachment.     

Deposition of SiO2-Like Films by HMDSN/O2 Plasmas at Low Pressure in a MMP-DECR Reactor

The effects of process parameters such as O₂/HMDSN (hexamethyldisilazane) ratio, microwave discharge power and deposition pressure on the growth rate, chemical bonding nature, and refractive index of thin films deposited by microwave plasma from HMDSN with oxygen, have been investigated. The plasma was created in a Microwave Multipolar reactor excited by Distributed Electron Cyclotron Resonance. The films were deposited at room temperature and characterized by Fourier Transform Infrared spectroscopy and ellipsometry. Growth rate increased with the discharge power P or the deposition pressure but decreased significantly with increasing O₂/HMDSN ratio. A large change in the film composition was observed when the O₂/HMDSN ratio was varied: films deposited with only HMDSN precursor are polymer-like but as the O₂/HMDSN ratio increased, organic groups decreased. For relative pressure values over 70%, deposited films are SiO₂-like with refractive index values close to those found for thermal silicon dioxide.     

Early Stages of CeO2 Thin-film Nucleation and Growth with Photo Irradiation

In this paper, the early stages of nucleation and photoirradiation growth of CeO₂ thin films have been studied. Cyclic voltammetry, chronoamperometry and scanning electron microscopy were used to analyze the nucleation process of CeO₂ thin films deposited on the anode with photo irradiation. Experimental results show that the anodic deposition process with photo illumination is controlled by diffusion. Compared with the dark state, photo illumination mainly contributed to increase the current density of the three-dimensional nucleation process, because photo illumination is helpful to create active sites and accelerate the nucleation progress on the surface that a thin ceria film has been formed. Two-dimensional nucleation process mainly exists within the initial 2 s, and then only three-dimensional instantaneous nucleation process continues, which may be the main reason why the thickness of the CeO₂ film can continue to grow with photo illumination but not in the dark state. Increasing the deposition overpotential can promote two-dimensional nucleation and growth rate, whilst when the potential exceeds 0.65 V, three-dimensional current density decreases. The li-miting factor at that time may be the diffusion rate of cerium ions in the solution towards the electrode substrate.     

Electron probe and auger electron microprobe characterization of modified Cu-based amorphous alloys.

Changes in morphology and local chemical composition due to various methods of modification of surfaces of Cu-Zr, Cu-Hf, and Cu-Ti amorphous alloys (caused by aging in air/dry corrosion or hydrogen charging) were investigated. These modification/activation procedures transform the original amorphous ribbons of low surface area into efficient and stable catalysts, due to the segregation of a distinct amount of Cu and the development of a large specific surface area of Cu on a ZrO x or HfO x support. It was found that aging in air resulted in the formation of a bilayer of rough copper (containing small Cu particles indispensable for catalysis) on top of a rather smooth oxide underlayer (ZrO x, HfO x ). Careful examination of the cross sections of the modified Cu-based ribbons revealed that, even after prolonged aging in air, only the first few microns of the surface layer was modified. Cu-Ti alloy was stable in air and did not undergo the expected modification. Hydrogenation followed by air exposure resulted in a disintegration of the ribbons into small pieces. Each piece was covered with many small Cu clusters 0.1-0.5 microm in diameter formed on an oxide underlayer. High-energy resolution Auger spectroscopy allowed identification of the underlayers (ZrO2, HfO2, or TiO x ), identification of small Cu clusters, determination of the degree of surface oxidation of them, and mapping of the surface to identify the Cu-covered and "naked" heavy metal.     

ALD resist formed by vapor-deposited self-assembled monolayers

A new process of applying molecular resists to block HfO2 and Pt atomic layer deposition has been investigated. Monolayer films are formed from octadecyltrichlorosilane (ODTS) or tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane (FOTS) and water vapor on native silicon oxide surfaces and from 1-octadecene on hydrogen-passivated silicon surfaces through a low-pressure chemical vapor deposition process. X-ray photoelectron spectroscopy data indicates that surfaces blocked by these monolayer resists can prevent atomic layer deposition of both HfO2 and Pt successfully. Time-dependent studies show that the ODTS monolayers continue to improve in blocking ability for as long as 48 h of formation time, and infrared spectroscopy measurements confirm an evolution of packing order over these time scales.     

CO gas sensing by ultrathin tin oxide films grown by atomic layer deposition using transmission FTIR spectroscopy

Ultrathin tin oxide films were deposited on SiO2 nanoparticles using atomic layer deposition (ALD) techniques with SnCl4 and H2O2 as the reactants. These SnO(x) films were then exposed to O2 and CO gas pressure at 300 degrees C to measure and understand their ability to serve as CO gas sensors. In situ transmission Fourier transform infrared (FTIR) spectroscopy was used to monitor both the charge conduction in the SnO(x) films and the gas-phase species. The background infrared absorbance measured the electrical conductivity of the SnO(x) films based on Drude-Zener theory. O2 pressure was observed to decrease the SnO(x) film conductivity. Addition of CO pressure then increased the SnO(x) film conductivity. Static experiments also monitored the buildup of gas-phase CO2 reaction products as the CO reacted with oxygen species. These results were consistent with both ionosorption and oxygen-vacancy models for chemiresistant semiconductor gas sensors. Additional experiments demonstrated that O2 pressure was not necessary for the SnO(x) films to detect CO pressure. The background infrared absorbance increased with CO pressure in the absence of O2 pressure. These results indicate that CO can produce oxygen vacancies on the SnO(x) surface that ionize and release electrons that increase the SnO(x) film conductivity, as suggested by the oxygen-vacancy model. The time scale of the response of the SnO(x) films to O2 and CO pressure was also measured by using transient experiments. The ultrathin SnO(x) ALD films with a thickness of approximately 10 A were able to respond to O2 within approximately 100 s and to CO within approximately 10 s. These in situ transmission FTIR spectroscopy help confirm the mechanisms for chemiresistant semiconductor gas sensors.