Molecular Layer Deposition of Zeolitic Imidazolate Framework‑8 Films [Dataset]

24 pages. -- Methods. -- Summary of some of the reported vapor-phase processes for the layer-by-layer deposition of MOFs6. -- Synchrotron GIXRD reciprocal space maps of direct ZIF-8 MLD show crystallinity even at a very low number of cycles. -- Vapor pressure determination of 2-methylimidazole (HmIM) via thermogravimetry: Knudsen effusion method. -- Direct ZIF-8 MLD linker exposure times. -- Direct ZIF-8 MLD films on Si are pinhole-free. -- AFM image of a MOF-CVD ZIF-8 “layer”, i.e., scattered crystallites. -- Photograph of a 200 mm wafer with 30 MLD ZIF-8 cycles and the corresponding 100-point ellipsometry thickness mapping. -- Film characterization of direct ZIF-8 MLD with a missing water pulse. -- Effect of no water pulses in direct ZIF-8 MLD. -- Direct ZIF-8 MLD with water completely or partially substituted by methanol. -- Humidified conditions HmIM post-deposition treatment of direct ZIF-8 MLD. -- HAXPES survey scans. -- HAXPES peak fitting. -- Study of aging effect due to exposure to atmospheric gasses. -- Direct ZIF-8 MLD on (100) oriented supercrystals. -- ZIF-67 crystals powder characterization. -- SEM images ZIF-67. -- Direct ZIF-8 MLD schematic representation of the protocol. -- Two-step ZIF-8 MLD schematic representation of the protocol. -- The optimized temperature gradient in the MOF-MLD reactor. -- MOF-MLD optimization of the temperature gradient. -- Ellipsometry of HmIM post-deposition treatment and activation in two-step ZIF-8 MLD. -- Ellipsometric porosimetry as a function of time. -- Supporting Information References.Vapor-phase film deposition of metal–organic frameworks (MOFs) would facilitate the integration of these materials into electronic devices. We studied the vapor-phase layer-by-layer deposition of zeolitic imidazolate framework 8 (ZIF-8) by consecutive, self-saturating reactions of diethyl zinc, water, and 2-methylimidazole on a substrate. Two approaches were compared: (1) Direct ZIF-8 “molecular layer deposition” (MLD), which enables a nanometer-resolution thickness control and employs only self-saturating reactions, resulting in smooth films that are crystalline as-deposited, and (2) two-step ZIF-8 MLD, in which crystallization occurs during a postdeposition treatment with additional linker vapor. The latter approach resulted in a reduced deposition time and an improved MOF quality, i.e., increased crystallinity and probe molecule uptake, although the smoothness and thickness control were partially lost. Both approaches were developed in a modified atomic layer deposition reactor to ensure cleanroom compatibility.Peer reviewe

The current status of MOF and COF applications

The amalgamation of different disciplines is at the heart of reticular chemistry and has broadened the boundaries of chemistry by opening up an infinite space of chemical composition, structure, and material properties. Reticular design has enabled the precise prediction of crystalline framework structures, tunability of chemical composition, incorporation of various functionalities onto the framework backbone, and as a consequence, fine-tuning of metal-organic framework (MOF) and covalent organic framework (COF) properties beyond that of any other material class. Leveraging the unique properties of reticular materials has resulted in significant advances from both a fundamental and an applied perspective. Here, we wish to review the milestones in MOF and COF research and give a critical view on progress in their real-world applications. Finally, we briefly discuss the major challenges in the field that need to be addressed to pave the way for industrial applications

Chemical Vapor Deposition and High-Resolution Patterning of a Highly Conductive Two-Dimensional Coordination Polymer Film

Crystalline coordination polymers with high electrical conductivities and charge carrier mobilities might open new opportunities for electronic devices. However, current solvent-based synthesis methods hinder compatibility with microfabrication standards. Here, we describe a solvent-free chemical vapor deposition method to prepare high-quality films of the two-dimensional conjugated coordination polymer Cu-BHT (BHT = benzenehexanothiolate). This approach involves the conversion of a metal oxide precursor into Cu-BHT nanofilms with a controllable thickness (20–85 nm) and low roughness (<10 nm) through exposure to the vaporized organic linker. Moreover, the restricted metal ion mobility during the vapor–solid reaction enables high-resolution patterning via both bottom-up lithography, including the fabrication of micron-sized Hall bar and electrode patterns to accurately evaluate the conductivity and mobility values of the Cu-BHT films

Molecular layer deposition of zeolitic imidazolate framework-8 films

Vapor-phase film deposition of metal–organic frameworks (MOFs) would facilitate the integration of these materials into electronic devices. We studied the vapor-phase layer-by-layer deposition of zeolitic imidazolate framework 8 (ZIF-8) by consecutive, self-saturating reactions of diethyl zinc, water, and 2-methylimidazole on a substrate. Two approaches were compared: (1) Direct ZIF-8 “molecular layer deposition” (MLD), which enables a nanometer-resolution thickness control and employs only self-saturating reactions, resulting in smooth films that are crystalline as-deposited, and (2) two-step ZIF-8 MLD, in which crystallization occurs during a postdeposition treatment with additional linker vapor. The latter approach resulted in a reduced deposition time and an improved MOF quality, i.e., increased crystallinity and probe molecule uptake, although the smoothness and thickness control were partially lost. Both approaches were developed in a modified atomic layer deposition reactor to ensure cleanroom compatibility