Integrating metal-organic frameworks (MOFs) in microelectronics has disruptive potential because of the unique properties of these microporous crystalline materials. Nanoscale patterning is a fundamental step in the implementation of MOFs in miniaturised solid-state devices. Conventional MOF patterning methods suffer from a low resolution and poorly defined pattern edges. Here, we demonstrate for the first time resist-free, direct X-ray and e-beam lithography of MOFs. This process avoids etching damage and contamination, and leaves the porosity and crystallinity of the patterned MOFs intact. The resulting highquality patterns have a record sub-50 nm resolution, far beyond the state of the art in MOF patterning and approaching the mesopore regime. The excellent compatibility of X-ray and e-beam lithography with existing microfabrication processes, both in research and production facilities, provides an avenue to explore the integration of MOFs in microelectronics further. This approach is the first example of direct lithography of any type of microporous crystalline network solid, and marks an important milestone in the processing of such materials.

The performance of modern chips is strongly related to the multi-layer interconnect structure that interfaces the semiconductor layer with the outside world. The resulting demand to continuously reduce the k-value of the dielectric in these interconnects creates multiple integration challenges and encourages the search for novel materials. Here we report a strategy for the integration of metal-organic frameworks (MOFs) as gap-filling low-k dielectrics in advanced on-chip interconnects. The method relies on the selective conversion of purpose-grown or native metal-oxide films on the metal interconnect lines into MOFs by exposure to organic linker vapor. The proposed strategy is validated for thin films of the zeolitic imidazolate frameworks ZIF-8 and ZIF-67, formed in 2-methylimidazole vapor from ALD ZnO and native CoO x , respectively. Both materials show a Young’s modulus and dielectric constant comparable to state-of-the-art porous organosilica dielectrics. Moreover, the fast nucleation and volume expansion accompanying the oxide-to-MOF conversion enable uniform growth and gap-filling of narrow trenches, as demonstrated for 45 nm half-pitch fork-fork capacitors.

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.