Though generally considered insulating, recent progress on the discovery of conductive porous metal-organic frameworks (MOFs) offers new opportunities for their integration as electroactive components in electronic devices. Compared to classical semiconductors, these metal-organic hybrids combine the crystallinity of inorganic materials with easier chemical functionalization and processability. Still, future development depends on the ability to produce high-quality films with fine control over their orientation, crystallinity, homogeneity, and thickness. Here self-assembled monolayer substrate modification and bottom-up techniques are used to produce preferentially oriented, ultrathin, conductive films of Cu-CAT-1. The approach permits to fabricate and study the electrical response of MOF-based devices incorporating the thinnest MOF film reported thus far (10 nm thick).

This review aims to reassess the progress, issues and opportunities in the path towards integrating conductive and magnetically bistable coordination polymers and metal–organic frameworks as active components in electronic devices.

Robust and scalable thin film deposition methods are key to realize the potential of metal-organic frameworks (MOFs) in electronic devices. Here, we report the first integration of the chemical vapor deposition (CVD) of MOF coatings in a custom reactor within a cleanroom setting. As a test case, the MOF-CVD conditions for ZIF-8 are optimized to enable smooth, pinhole-free, and uniform thin films on full 200 mm wafers under mild conditions. The single-chamber MOF-CVD process and the impact of the deposition parameters are elucidated via a combination of in situ monitoring and ex situ characterization. The resulting process guidelines will pave the way for new MOF-CVD formulations and a plethora of MOF-based devices. Apart from their applications in catalysis, 1 gas storage, 2 and separation processes, 3 metal-organic frameworks (MOFs), with their unprecedented specific surface areas and chemical modularity, show tremendous potential for integration in microelectronics. 4,5 As sensor coatings, their tunable composition and crystalline structure can be exploited for the selective adsorption of target molecules. 6-9 The low dielectric constant resulting from their porosity makes MOFs prime candidates for high-performance insulators in future logic processors. 10,11 To capitalize on the 10-6 cm 2 , were estimated using a CCD camera. All instruments were controlled using custom software. The generated current density (J) histograms were fitted using Gaussian functions for determining the peak center and width.

Conductive metal–organic frameworks are opening new perspectives for the use of these porous materials for applications traditionally limited to more classical inorganic materials, such as their integration into electronic devices. This has enabled the development of chemiresistive sensors capable of transducing the presence of specific guests into an electrical response with good selectivity and sensitivity. By combining experimental data with computational modelling, a possible origin for the underlying mechanism of this phenomenon in ultrathin films (ca. 30 nm) of Cu‐CAT‐1 is described.

Film thickness and microstructure critically affect the spin crossover transition of a 2D coordination polymer.

Currently available methodologies arguably lack the exquisite control required for producing metal-organic framework (MOF) thin films of sufficient quality for electronic applications. By directing MOF transfer with self-assembled monolayers (SAMs), we achieve very smooth, homogeneous, highly oriented, ultrathin films across millimeter-scale areas that display moderate conductivity likely due to electron hopping. Here, the SAM is key for directing the transfer thereby enlarging the number and nature of the substrates of choice. We have exploited this versatility to evolve from deposition onto standard Si and Au to nonconventional substrates such as ferromagnetic Permalloy. We believe that this strategy might be useful for the integration of MOFs as active interfaces in electronic devices.

Integration of the ON-OFF cooperative spin crossover (SCO) properties of Fe II coordination polymers as components of electronic and/or spintronic devices is currently an area of great interest for potential applications. This requires the selection and growth of thin films of the appropriate material onto selected substrates. In this context, two new series of cooperative SCO two-dimensional Fe II coordination polymers of the Hofmann-type formulated {Fe II (Pym)2[M II (CN)4]•xH2O}n and {Fe II (Isoq)2[M II (CN)4]}n (Pym = pyrimidine, Isoq = isoquinoline; M II = Ni, Pd, Pt) have been synthesized, characterized and the corresponding Pt derivatives selected for fabrication of thin films by liquid-phase epitaxy (LPE). At ambient pressure, variable-temperature single-crystal, magnetic and calorimetric studies of the Pt and Pd microcrystalline materials of both series display strong cooperative thermal induced SCO properties. In contrast, this property is only observed for higher pressures in the Ni derivatives. The SCO behavior of the {Fe II (L)2[Pt II (CN)4]}n thin films (L = Pym, Isoq) were monitored by magnetization measurements in a SQUID magnetometer and compared with the homologous samples of the previously reported isostructural {Fe II (Py)2[Pt II (CN)4]}n (Py = pyridine). Application of the theory of regular solutions to the SCO of the three derivatives allowed us to evaluate the effect on the characteristic SCO temperatures and the hysteresis, as well as the associated thermodynamic parameters when moving from microcrystalline bulk solids to nanometric thin films.

The landscape of possible polymorphs for some metal–organic frameworks (MOFs) can pose a challenge for controlling the outcome of their syntheses. Demonstrated here is the use of a template to control in the vapor‐assisted formation of zeolitic imidazolate framework (ZIF) powders and thin films. Introducing a small amount of either ethanol or dimethylformamide vapor during the reaction between ZnO and 4,5‐dichloroimidazole vapor results in the formation of the porous ZIF‐71 phase, whereas other conditions lead to the formation of the dense ZIF‐72 phase or amorphous materials. Time‐resolved in situ small‐angle X‐ray scattering reveals that the porous phase is metastable and can be transformed into its dense polymorph. This transformation is avoided through the introduction of template vapor. The porosity of the resulting ZIF powders and films was studied by N2 and Kr physisorption, as well as positron annihilation lifetime spectroscopy. The templating principle was demonstrated for other members of the ZIF family as well, including the ZIF‐7 series, ZIF‐8_Cl, and ZIF‐8_Br.