Davy Deduytsche

Atomic layer deposition of TiO2 from tetrakis-dimethyl-amido titanium or Ti isopropoxide precursors and H2O

Atomic layer deposition (ALD) of TiO2 thin films using Ti isopropoxide and tetrakis-dimethyl-amido titanium (TDMAT) as two kinds of Ti precursors and water as another reactant was investigated. TiO2 films with high purity can be grown in a self-limited ALD growth mode by using either Ti isopropoxide or TDMAT as Ti precursors. Different growth behaviors as a function of deposition temperature were observed. A typical growth rate curve-increased growth rate per cycle (GPC) with increasing temperatures was observed for the TiO2 film deposited by Ti isopropoxide and H2O, while surprisingly high GPC was observed at low temperatures for the TiO2 film deposited by TDMAT and H2O. An energetic model was proposed to explain the different growth behaviors with different precursors. Density functional theory (DFT) calculation was made. The GPC in the low temperature region is determined by the reaction energy barrier. From the experimental results and DFT calculation, we found that the intermediate product stability ...

High-temperature degradation of NiSi films: Agglomeration versus NiSi2 nucleation

The thermodynamical and morphological stability of NiSi thin films has been investigated for layers of thickness ranging from 10to60nm formed on either silicon-on-insulator (SOI), polycrystalline silicon, or preannealed polycrystalline silicon substrates. The stability of the films was evaluated using in situ x-ray-diffraction, sheet resistance, and laser light-scattering measurements. For NiSi films that are thinner than 20nm, agglomeration is the main degradation mechanism. For thicker films, the agglomeration of NiSi and nucleation of NiSi2 occur simultaneously, and both degradation mechanisms influence each other. Significant differences were observed in the degradation of the NiSi formed on different substrates. Surprisingly, agglomeration is worse on SOI substrates than on poly-Si substrates, suggesting that the texture of the NiSi film plays an important role in the agglomeration process. As expected, preannealing of the polycrystalline silicon substrate prior to metal deposition results in a signi...

Germanium surface passivation and atomic layer deposition of high-k dielectrics?a tutorial review on Ge-based MOS capacitors

Due to its high intrinsic mobility, germanium (Ge) is a promising candidate as a channel material (offering a mobility gain of approximately??2 for electrons and??4 for holes when compared to conventional Si channels). However, many issues still need to be addressed before Ge can be implemented in high-performance field-effect-transistor (FET) devices. One of the key issues is to provide a high-quality interfacial layer, which does not lead to substantial drive current degradation in both low equivalent oxide thickness and short channel regime. In recent years, a wide range of materials and processes have been investigated to obtain proper interfacial properties, including different methods for Ge surface passivation, various high-k dielectrics and metal gate materials and deposition methods, and different post-deposition annealing treatments. It is observed that each process step can significantly affect the overall metal?oxide?semiconductor (MOS)-FET device performance. In this review, we describe and compare combinations of the most commonly used Ge surface passivation methods (e.g. epi-Si passivation, surface oxidation and/or nitridation, and S-passivation) with various high-k dielectrics. In particular, plasma-based processes for surface passivation in combination with plasma-enhanced atomic layer deposition for high-k depositions are shown to result in high-quality MOS structures. To further improve properties, the gate stack can be annealed after deposition. The effects of annealing temperature and ambient on the electrical properties of the MOS structure are also discussed.

Growth Kinetics and Crystallization Behavior of TiO2 Films Prepared by Plasma Enhanced Atomic Layer Deposition

cSCK-CEN, Boeretang 200, B-2400 Mol, Belgium Atomic layer deposition ALD of TiO2 films from tetrakisdimethylamido titanium TDMAT or titanium tetraisopropoxide TTIP precursors was investigated. The growth kinetics, chemical composition, and crystallization behavior of the TiO2 films were compared for combinations of the two precursors with three different sources of oxygen thermal ALD using H2O and plasma-enhanced ALD PEALD using H2 Oo r O 2 plasma. For TDMAT, the growth rate per cycle GPC decreased with increasing temperature; while for TTIP with either water plasma or O2 plasma, a relatively constant growth rate per cycle was observed as a function of substrate temperature. It was found that the crystallization temperature of the TiO2 films depends both on film thickness and on the deposition conditions. A correlation was observed between the TiO2 crystallization temperature and the C impurity concentration in the film. The TiO2 films grown using a H2O plasma exhibit the lowest crystallization temperature and have no detectable C impurities. In situ X-ray diffraction measurements were used to test the diffusion barrier properties of the TiO2 layers and proved that all TiO2 films grown using either H2 Oo r O2 plasma are dense and continuous.

Semiconductor-metal transition in thin VO2 films grown by ozone based atomic layer deposition

Vanadium dioxide (VO2) has the interesting feature that it undergoes a reversible semiconductor-metal transition (SMT) when the temperature is varied near its transition temperature at 68°C.1 The variation in optical constants makes VO2 useful as a coating material for e.g. thermochromic windows,2 while the associated change in resistivity could be interesting for applications in microelectronics, e.g. for resistive switches and memories.3 Due to aggressive scaling and increasing integration complexity, atomic layer deposition (ALD) is gaining importance for depositing oxides in microelectronics. However, attempts to deposit VO2 by ALD result in most cases in the undesirable V2O5. In the present work, we demonstrate the growth of VO2 by using Tetrakis[EthylMethylAmino]Vanadium and ozone in an ALD process at only 150°C. XPS reveals a 4+ oxidation state for the vanadium, related to VO2. Films deposited on SiO2 are amorphous, but during a thermal treatment in inert gas at 450°C VO2(R) is formed as the first and only crystalline phase. The semiconductor-metal transition has been observed both with in-situ X-ray diffraction and resistivity measurements. Near a temperature of 67°C, the crystal structure changes from VO2(M1) below the transition temperature to VO2(R) above with a hysteresis of 12°C. Correlated to this phase change, the resistivity varies over more than 2 orders of magnitude.

Modeling the Conformality of Atomic Layer Deposition: The Effect of Sticking Probability

The key advantage of atomic layer deposition (ALD) is undoubtedly the excellent step coverage, which allows for conformal deposition of thin films in high-aspect-ratio structures. In this paper, a model is proposed to predict the deposited film thickness as a function of depth inside a hole. The main model parameters are the gas pressure, the deposition temperature, and the initial sticking probability of the precursor molecules. Earlier work by Gordon et al. assumed a sticking probability of 0/100% for molecules hitting a covered/uncovered section of the wall of the hole, thus resulting in a stepwise film-thickness profile. In this work, the sticking probability is related to the surface coverage θ by Langmuirs equation s(θ) = s 0 (1 - θ), whereby the initial sticking probability s 0 is now an adjustable model parameter. For s 0 ≅ 100%, the model predicts a steplike profile, in agreement with Gordon et al., while for smaller values of s 0 , a gradual decreasing coverage profile is predicted. Furthermore, experiments were performed to quantify the conformality for the trimethylaluminum (TMA)/H 2 O ALD process using macroscopic test structures. It is shown that the experimental data and the simulation results follow the same trends.

Formation and morphological stability of NiSi in the presence of W, Ti, and Ta alloying elements

The formation and degradation of NiSi films has been studied when elements with a high melting point (W, Ta, and Ti) were added to pure Ni films as an alloying element. In situ techniques were used to characterize the phase stability and the morphological stability of the NiSi layers. Depending on the concentration of the alloying element, two distinct regimes could be distinguished. First, the addition of a small quantity of an alloying element (e.g., y) could be observed prior to NiSi formation. Furthermore, a significant increase was observed of the apparent activation energy for NiSi formation.

Conformality of Al2O3 and AlN Deposited by Plasma-Enhanced Atomic Layer Deposition

This paper focuses on the conformality of the plasma-enhanced atomic layer deposition (PE-ALD) of Al2O3 using trimethylaluminum [Al(CH3)(3); (TMA)] as a precursor and O-2 plasma as an oxidant source. The conformality was quantified by measuring the deposited film thickness as a function of depth into macroscopic test structures with aspect ratios of similar to 5, 10, and 22. A comparison with the thermal TMA/H2O process indicates that the conformality of the plasma based process is more limited due to the surface recombination of radicals during the plasma step. The conformality can slightly be improved by raising the gas pressure or the radio-frequency power. Prolonging the plasma exposure time results in further improvement of the conformality. Furthermore, there are indications that the H2O produced during the plasma step in the PE-ALD process for Al2O3 contributes to the observed conformality through a secondary thermal ALD reaction. The conformality of Al2O3 is also compared to the conformality of AlN deposited by PE-ALD from TMA and NH3 plasma. For the same exposure, O-2 plasma results in better conformality compared to NH3 plasma, suggesting a faster recombination of the radicals in the NH3 plasma.

Comparison of Thermal and Plasma-Enhanced ALD/CVD of Vanadium Pentoxide

Vanadium pentoxide was deposited by atomic layer deposition (ALD) from vanadyl-tri-isopropoxide (VTIP). Water or oxygen was used as a reactive gas in thermal and plasma-enhanced (PE) processes. For PE ALD, there was a wide ALD temperature window from 50 to 200°C. Above 200°C, VTIP decomposed thermally, resulting in the chemical vapor deposition (CVD) of vanadium pentoxide. The PE ALD reactions saturated much faster than during thermal ALD, leading to a growth rate of approximately 0.7 A/cycle during PE ALD using H 2 O or O 2 . Optical emission spectroscopy showed combustion-like reactions during the plasma step. X-ray diffraction was performed to determine the crystallinity of the films after deposition and after postannealing under He or O 2 atmosphere. Films grown with CVD at 300°C and PE O 2 ALD at 150°C were (001)-oriented V 2 O 5 as deposited, while thermal and PE H 2 O ALD films grown at 150°C were amorphous as deposited. The crystallinity of the PE O 2 ALD could be correlated to its high purity, while the other films had significant carbon contamination, as shown by X-ray photoelectron spectroscopy. Annealing under He led to oxygen-deficient films, while all samples eventually crystallized into V 2 O 5 under O 2 .

Reactor concepts for atomic layer deposition on agitated particles: A review

The number of possible applications for nanoparticles has strongly increased in the last decade. For many applications, nanoparticles with different surface and bulk properties are necessary. A popular surface modification technique is coating the particle surface with a nanometer thick layer. Atomic layer deposition (ALD) is known as a reliable method for depositing ultrathin and conformal coatings. In this article, agitation or fluidization of the particles is necessary for performing ALD on (nano)particles. The principles of gas fluidization of particles will be outlined, and a classification of the gas fluidization behavior of particles based on their size and density will be given. Following different reactor concepts that have been designed to conformally coat (nano)particles with ALD will be described, and a concise overview will be presented of the work that has been performed with each of them ending with a concept reactor for performing spatial ALD on fluidized particles.