Unveiling the Origin of the Scale‐Dependent Conductivity of Ni ₃ (HITP) ₂ Metal–Organic Framework Thin Films

Conductive metal-organic frameworks (MOFs) are crystalline, intrinsically porous materials that combine remarkable electrical conductivity with exceptional structural and chemical versatility. This rare combination makes these materials highly suitable for a wide range of energy-related applications. However, the electrical conductivity in MOF-based devices is often limited by the presence of different types of structural disorder. Here, the electrical transport characteristics of high quality Ni₃(HITP)₂ nanometer-thin films are reported. These findings reveal a tenfold difference in conductivity between the micro- and nano-scale, attributed to poor electrical connection among a limited number of crystalline grains. Average in-plane conductivity values at the micro- (σ_IP,micro = 0.7 ± 0.3 S cm^-1) and nano- (σ_IP,nano = 6 ± 3 S cm^-1) scales is determined, and the value of the inter-grain resistance, R_inter-grain = 40 kΩ is found. Using a 2D resistor network model with a 40 kΩ base resistance and scattered higher resistances, surface potential maps of in-operando MOF-based electrical devices are successfully reproduced. Additionally, a structure-property relationship that links the density and spatial distribution of electrical failures in inter-grain connections to the observed micro-scale conductivity in MOF thin films is established.