Lithium Aryloxide Thin Films with Guest‐Induced Structural Transformation by ALD/MLD

Abstract

Crystalline Li–organic thin films are grown with the atomic/molecular layer deposition (ALD/MLD) technique from lithium hexamethyldisilazide and hydroquinone. The as‐deposited films are found to undergo a reversible structural transformation upon exposure to ambient humid air. According to density functional theory calculations, the guest‐induced transformation may be related to an unsaturated Li site in the crystal structure.

Atomic/molecular layer deposition and electrochemical performance of dilithium 2-aminoterephthalate

“…The Gaussian Type Orbital basis sets have been derived from Karlsruhe basis sets 60 and adapted for solid-state calculations. 13,61 For all low-energy structures, we applied a k-mesh of 3 × 5 × 3 for the reciprocal space sampling. The structures were optimized with the default optimization convergence criteria in CRYSTAL17 and the lowest-energy structures were confirmed to be true local minima by means of harmonic frequency calculations.…”

“…12 The recent developments in the field of ALD/MLD have opened new avenues towards new interesting metal-organic materials. 8,[13][14][15][16][17][18] Here we extend the ALD/MLD material repertoire to dilithium 2-aminoterephthalate (Li 2 TP-NH 2 ), which then allows us to evaluate the role of the electron-donating amino group on the redox potential of the terephthalate skeleton, with the anticipation that the somewhat high redox potential of Li 2 TP could be decreased by introducing the additional amino group (Fig. 1).…”

New s‐Block Metal Pyridinedicarboxylate Network Structures through Gas‐Phase Thin‐Film Synthesis

“…New ALD/MLD processes have been actively developed for a decade, but up until a few years ago it seemed that the technique was only capable to yield amorphous metal–organic thin films . Initially, efforts were made to apply different post‐deposition treatments to crystallize CP‐type metal–organic structures from amorphous as‐deposited films, but three years ago we succeeded in growing the first in situ crystalline ALD/MLD metal–organic thin films . In particular and most relevant to the present work, we recently fabricated a series of crystalline s‐block metal‐based terephthalate thin films with “sheet‐like” ordered structures through ALD/MLD, and investigated their water‐intercalation characteristics .…”

“…[29,30] Initially,e fforts were made to apply different post-deposition treatments to crystallize CP-type metal-organic structures from amorphous as-deposited films, [33][34][35] but three years ago we succeeded in growing the first in situ crystalline ALD/MLD metal-organic thin films. [36][37][38][39][40][41][42][43][44] In particular and most relevantt ot he present work, we recently fabricated a series of crystalline s-block metal-based terephthalate thin films with "sheet-like" ordered structures through ALD/MLD, and investigated their water-intercalation characteristics. [36,38,41,42] Now in the presentw ork, we challenge for the first time s-blockm etal-PDC materials with the anticipation to discover novel CP-types tructures.…”

Atomic/Molecular Layer Deposition of s‐Block Metal Carboxylate Coordination Network Thin Films

“…Hybrid inorganic–organic thin films of aromatic carboxylic acid precursors have indeed been deposited by ALD/MLD, but the majority of the films have been amorphous . Very recently, we succeeded in growing the first in situ crystalline ALD/MLD thin films . In these crystalline hybrid thin films the metal constituents were copper, calcium, lithium and sodium, and in the first three cases the organic precursor was terephthalic acid.…”