Jan Musschoot

Bio: Jan Musschoot is an academic researcher from Ghent University. The author has contributed to research in topics: Atomic layer deposition & Thin film. The author has an hindex of 15, co-authored 25 publications receiving 905 citations.

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

Abstract: 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.

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

Abstract: 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 Langmuir's 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.

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

Abstract: 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.

The Chemistry and Applications of Metal-Organic Frameworks

Abstract: Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

Applications of metal–organic frameworks in heterogeneous supramolecular catalysis

Abstract: This review summarizes the use of metal–organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal–organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.

Crystallinity of inorganic films grown by atomic layer deposition: Overview and general trends

Abstract: Atomic layer deposition (ALD) is gaining attention as a thin film deposition method, uniquely suitable for depositing uniform and conformal films on complex three-dimensional topographies. The deposition of a film of a given material by ALD relies on the successive, separated, and self-terminating gas–solid reactions of typically two gaseous reactants. Hundreds of ALD chemistries have been found for depositing a variety of materials during the past decades, mostly for inorganic materials but lately also for organic and inorganic–organic hybrid compounds. One factor that often dictates the properties of ALD films in actual applications is the crystallinity of the grown film: Is the material amorphous or, if it is crystalline, which phase(s) is (are) present. In this thematic review, we first describe the basics of ALD, summarize the two-reactant ALD processes to grow inorganic materials developed to-date, updating the information of an earlier review on ALD [R. L. Puurunen, J. Appl. Phys. 97, 121301 (2005)], and give an overview of the status of processing ternary compounds by ALD. We then proceed to analyze the published experimental data for information on the crystallinity and phase of inorganic materials deposited by ALD from different reactants at different temperatures. The data are collected for films in their as-deposited state and tabulated for easy reference. Case studies are presented to illustrate the effect of different process parameters on crystallinity for representative materials: aluminium oxide, zirconium oxide, zinc oxide, titanium nitride, zinc zulfide, and ruthenium. Finally, we discuss the general trends in the development of film crystallinity as function of ALD process parameters. The authors hope that this review will help newcomers to ALD to familiarize themselves with the complex world of crystalline ALD films and, at the same time, serve for the expert as a handbook-type reference source on ALD processes and film crystallinity.

Metal–organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations

Abstract: Novel catalytic materials are highly demanded to perform a variety of catalytic organic reactions. MOFs combine the benefits of heterogeneous catalysis like easy post reaction separation, catalyst reusability, high stability and homogeneous catalysis such as high efficiency, selectivity, controllability and mild reaction conditions. The possible organization of active centers like metallic nodes, organic linkers, and their chemical synthetic functionalization on the nanoscale shows potential to build up MOFs particularly modified for catalytic challenges. In this review, we have summarized the recent research progress in heterogeneous catalysis by MOFs and their catalytic behavior in various organic reactions, highlighting the key features of MOFs as catalysts based on the active sites in the framework. Examples of their post functionalization, inclusion of active guest species and metal nanoparticles have been discussed. Finally, the use of MOFs as catalysts for asymmetric heterogeneous catalysis and stability of MOFs has been presented as separate sections.

Defect‐Engineered Metal–Organic Frameworks

Abstract: Defect engineering in metal–organic frameworks (MOFs) is an exciting concept for tailoring material properties, which opens up novel opportunities not only in sorption and catalysis, but also in controlling more challenging physical characteristics such as band gap as well as magnetic and electrical/conductive properties. It is challenging to structurally characterize the inherent or intentionally created defects of various types, and there have so far been few efforts to comprehensively discuss these issues. Based on selected reports spanning the last decades, this Review closes that gap by providing both a concise overview of defects in MOFs, or more broadly coordination network compounds (CNCs), including their classification and characterization, together with the (potential) applications of defective CNCs/MOFs. Moreover, we will highlight important aspects of “defect-engineering” concepts applied for CNCs, also in comparison with relevant solid materials such as zeolites or COFs. Finally, we discuss the future potential of defect-engineered CNCs.