We present novel atomic/molecular layer deposition (ALD/MLD) processes for the fabrication of crystalline inorganic-organic coordination network thin films with different s-block elements. Terephthalic acid is employed as the organic precursor. Such thin films could enable for example, next-generation battery, sensor and gas-storage technologies. The deposition processes fulfill the basic principles of ALD/MLD-type growth including the sequential self-saturated gas-surface reactions and atomic/molecular-level control for the film thickness, and yield crystalline thin films in a wide deposition temperature range. Structural characterization of the films is performed by grazing incidence X-ray diffraction (GIXRD) and Fourier-transform infrared (FTIR) spectroscopy. The data do not unambiguously prove but also do not rule out the crystal structures previously reported for the corresponding bulk samples. We moreover demonstrate the growth of crystalline thin films of a new terephthalate material with La as the metal component. Upon humidity treatments the Li, Na, K, Ba, and La terephthalate films remain unaffected while the Mg, Ca, and Sr terephthalate films reversibly absorb water molecules forming well-defined crystalline water-derivative phases.
The combined atomic and molecular layer deposition (ALD/MLD) technique offers a unique way to build—both known and previously unknown—crystalline coordination polymer materials directly from gaseous precursors in a high‐quality thin‐film form. Here, we demonstrate the ALD/MLD of crystalline Li‐, Na‐, and K‐based 3,5‐pyridinedicarboxylate (3,5‐PDC) thin films; the Li2‐3,5‐PDC films are of the known Li‐ULMOF‐4 crystal structure whereas the other as‐deposited crystalline films possess structures not previously reported. Another exciting possibility offered by ALD/MLD is the deposition of well‐defined but amorphous metal–organic thin films, such as our Mg‐, Ca‐, Sr‐, and Ba‐based 3,5‐PDC films, which can then be crystallized into water‐containing structures through a post‐deposition humidity treatment. All together, the new metal–organic structures realized in this study through ALD/MLD comprise a majority of the (anhydrous and water‐containing) members of the s‐block metal 3,5‐pyridinedicarboxylate family.
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