The well-known synthetic versatility of metal–organic frameworks (MOFs) is rooted in the ability to predict the metal-ion coordination geometry and the vast possibilities to use organic chemistry to modify the linker groups. However, the use of molecules occupying the pores as a component of framework design has been largely ignored. Recent reports show that the presence of these so-called “guests” can have dramatic effects, even when they are a seemingly innocuous species such as water or polar solvents. We term these guests “non-innocent” when their presence alters the MOF in such a way as to create a new material with properties different from the MOF without the guests. Advantages of using guest molecules to impart new properties to MOFs include the relative ease of introducing new functionalities, the ability to modify the material properties at will by removing the guest or inserting different ones, and avoidance of the difficulties associated with synthesizing new frameworks, which can be challenging even when the basic topology remains constant. In this article, we describe the “Guest@MOF” concept and provide examples illustrating its potential as a new MOF design element.

Chlorine-containing precursors are attractive for chemical vapor deposition (CVD) of SiC because they are less hazardous and more economical than silane precursors. The reactivity of HCl, a by-product of these reactions, on SiC is of particular interest because it has been reported that HCl inhibits SiC CVD, but the mechanism for this inhibition has not been identified. In this work the adsorption of HCl on polycrystalline β-SiC was examined with Auger Electron Spectroscopy (AES) and Temperature Programmed Desorption (TPD). HCl adsorbs readily on SiC, with an initial sticking probability of 0.1 at 300 K, and forms a strong bond, with an activation energy for desorption of 64 kcal/mol. The only product detected by TPD is HCl, which desorbs in a peak centered at 1010 K. There are no Si- or C-containing desorption products, demonstrating that HCl does not etch SiC under TPD conditions. These results are consistent with a site-blocking mechanism for HCl inhibition of SiC CVD, but not with an etching mechanism.

Measurements of the decomposition of mixtures of boron trichloride (BCl3), titanium tetrachloride (TiCl4), and hydrogen at elevated temperatures are presented. The decomposition of BCl3 with hydrogen appears to drive the chemistry in this system. The species depositing boron on the surface contains at least 2 chlorine atoms. Once deposited, the surface chlorine is removed by reaction with hydrogen to form HCl and, presumably, surface B-H bonds.

Since NH3 is an important component of TiN chemical vapor deposition (CVD) processes, understanding the NH3/TiN surface interaction is crucial to developing a model for the overall reaction. Temperature programmed desorption experiments show that NH3 adsorbs molecularly on amorphous TiN surfaces. Chemisorption occurs at only ∼5% of the surface sites, with an activation energy for desorption of 24 kcal/mol. The sticking probability into this state is 0.06 at 100 K. In addition, NH3 adsorbs with high probability into a multilayer state with an activation energy for desorption of 7.3 kcal/mol, similar to that found in other systems. NH3 does not dissociate on TiN. Under CVD conditions, however, the reactivity of NH3 on TiN may increase and surface reactions may play a part in film growth.

The kinetics of gas-phase reactions occurring during the CVD of boron nitride (BN) from BCl3 and NH3 are investigated using an elementary reaction mechanism whose rate constants were obtained from theoretical predictions and literature sources. Plug-flow calculations using this mechanism predict that unimolecular decomposition of BCl3 is not significant under typical CVD conditions, but that some NH3 decomposition may occur, especially for deposition occurring at atmospheric pressure. Reaction of BCl3 with NH3 is rapid under CVD conditions and yields species containing both boron and nitrogen. One of these compounds, Cl2BNH2, is predicted to be a key gas-phase precursor to BN.

Methyltrichlorosilane (MTS) is a precursor commonly used in the production of silicon carbide for composites, protective coatings, and structural ceramics. Experiments suggest that MTS decomposes in the gas phase to produce a large number of species whose surface reactivity is expected to vary widely. In this work, we discuss the development of a gas-phase mechanism that describes the decomposition of MTS. Rate coefficients for the reactions were obtained from literature sources, theoretical methods, and comparisons with analogous reaction chemistry. Several unknown reaction rates were fit to experimental measurements of MTS decomposition. The results are used to predict the major reaction paths, identify reactions to which product concentrations are sensitive, and determine the rate-limiting step for MTS decomposition.

Experimental measurements of the decomposition of methyltrichlorosilane (MTS), a common silicon carbide precursor, in a high-temperature flow reactor are presented. Methane, hydrogen chloride, and silicon tetrachloride are observed as products of the decomposition. Trapping experiments with acetylene and ethylene also detected SiCl3 as a decomposition product. Upper limits on the concentrations of any CH3Cl, HSiCl3, H2SiCl2, or H2C=SiCl2 which might form are provided. Quantitative measurements of product branching and MTS decomposition rates are presented. The results suggest a radical-chain mechanism for the decomposition in hydrogen but not in helium.

Experimental measurements of the decomposition of methyltrichlorosilane (MTS), a common silicon carbide precursor, in a high-temperature flow reactor are presented. The results indicate that methane and hydrogen chloride are major products of the decomposition. No chlorinated silane products were observed. Hydrogen carrier gas was found to increase the rate of MTS decomposition. The observations suggest a radical-chain mechanism for the decomposition. The implications for silicon carbide chemical vapor deposition are discussed.

This work explores the reactivity of HCI and methyltrichlorosilane (MTS) with polycrystalline β-silicon carbide (SiC) surfaces using temperature-programmed desorption (TPD) and Auger electron spectroscopy. HCl is a corrosive gas that inhibits SiC deposition. The results show that HCl is adsorbed by SiC, forming a stable surface chloride that could inhibit SiC deposition. TPD shows that chlorine desorbs as HCI or SiCl4, confirming that HCl can etch SiC surfaces. Desorption is rate-limited by the breaking of Si-Cl bonds. MTS is also adsorbed by SiC; its desorption is similar to that of HCI.

Particle-enhanced chemical vapor deposition (PECVD) is capable of producing ceramic films at high deposition rates. A mathematical model of the particle-vapor codeposition process has been developed and has been applied to PECVD processes to predict deposition rate enhancements and deposit properties.

Equilibrium calculations are reported for conditions typical of silicon carbide (SiC) deposition from mixtures of silane and hydrocarbons. Included are 34 molecules containing both silicon and carbon, allowing an assessment to be made of the importance of organosilicon species (and organosilicon radicals in particular) to the deposition process. The results are used to suggest strategies for improved operation of SiC CVD processes.