Atomic layer deposition (ALD) is a thin film synthesis technique that can provide exquisite accuracy and precision in film thickness and composition even on complex, large area substrates. Based on self-limiting surface chemistry, ALD can be insensitive to process conditions and reactor designs, allowing an ALD process developed in one lab to be easily reproduced in other labs. In practice, however, ALD is sometimes difficult to reproduce or replicate, and the results can vary substantially between ALD reactors and between labs. This is exemplified by large deviations in reports on the growth of, e.g., Al2O3, FeOx, and TiO2 given the same precursors under similar conditions. Furthermore, the problem of irreproducibility seems to be growing as ALD is adopted by more researchers and integrated into new applications. In this article, the authors highlight some of the major sources of variations and errors and common misconceptions related to ALD. In particular, the authors focus on issues related to precursors, substrates, and deposition tools. The authors illustrate these problems through examples from the literature, and they present results from numerical simulations that describe how nonidealities would manifest in thickness profiles in a typical cross-flow reactor. They also describe how reproducibility in ALD is linked to consistent experimental practice and reporting between labs. The authors’ hope is that by educating newcomers to ALD and advocating for consistent reporting of deposition conditions, they can minimize irreproducibility and enable ALD practitioners to realize the full potential afforded by self-limiting surface chemistry.

Insight to the crystallization process of functional materials deposited as thin films in an amorphous state is essential when phase pure samples of specific polymorphs are sought for utilization of performance aspects or fundamental studies. In this work, we report on controlled crystallization of α- and β-MoO₃ polymorphs from amorphous MoO₃ thin films produced by atomic layer deposition (ALD). The MoO₃ films are amorphous as deposited. Our experiments show that β-MoO₃ starts to crystallize from amorphous MoO₃ at a surprisingly low temperature of 185 °C, only 20 °C above the adopted ALD deposition temperature. Thin films of the β-MoO₃ polymorph start slowly to convert into α-MoO₃ at temperatures above 300 °C; however, long holding times are required to obtain phase pure products. High-quality thin film samples (electrodes) were characterized by electrochemical cycling towards lithium, demonstrating that α- and β-MoO₃ transfers into the same chemical state during cycling and that amorphous MoO₃ undergoes less change upon cycling.

As traditional silicon technology is moving fast towards its fundamental limits, all-oxide electronics is emerging as a challenger offering principally different electronic behavior and switching mechanisms. This technology can be utilized to fabricate devices with enhanced and exotic functionality. One of the challenges for integration of complex oxides in electronics is the availability of appreciable low-temperature synthesis routes. Herein we provide a fundamental extension of the materials toolbox for oxide electronics by reporting a facile route for deposition of highly electrically conductive thin films of LaNiO₃ by atomic layer deposition at low temperatures. The films grow epitaxial on SrTiO₃ and LaAlO₃ as deposited at 225 °C, with no annealing required to obtain the attractive electronic properties. The films exhibit resistivity below 100 µΩ cm with carrier densities as high as 3.6 · 10²² cm⁻³. This marks an important step in the realization of all-oxide electronics for emerging technological devices.

Thin films of sodium and potassium oxides have for the first time been deposited using atomic layer deposition. Sodium and potassium complexes of tert-butanol, trimethylsilanol and hexamethyldisilazide have been evaluated as precursors by characterising their thermal properties as well as tested in applications for thin film depositions. Out of these, sodium and potassium tert-butoxide and sodium trimethylsilanolate and hexamethyldisilazide were further tested as precursors together with the Al(CH₃)₃ + H₂O/O₃ process to form aluminates and together with ozone to form silicates. Sodium and potassium tert-butoxide and sodium trimethylsilanolate showed self-limiting growth and proved useable at deposition temperatures from 225 to 375 or 300 °C, respectively. The crystal structures of NaO^tBu and KO^tBu were determined by single crystal diffraction revealing hexamer- and tetramer structures, respectively. The current work demonstrates the suitability of the ALD technique to deposit thin films containing alkaline elements even at 8′′ wafer scale.

Alkali metal containing materials have become increasingly attractive in a world hunting for sustainable energy materials and green functional devices. Lithium- and sodium battery technology, lead-free piezo- and ferroelectric devices, and record-breaking alkali doped tandem perovskite solar cells are among the applications where alkali metal-containing thin films get increasing attention. Atomic layer deposition (ALD) is one of the enabling thin film deposition techniques that offer chemical and geometrical versatility to realize the implementation of such thin films on an applicable scale. The drawback has until recently been a lack of available precursor chemistry that offers self-limiting growth that is fundamental to ALD. The alkali metal tert-butoxides have been shown to exhibit the necessary properties to facilitate saturating growth for Li-, Na-, K-, and Rb-containing compounds. However, the behavior of the tert-butoxides in ALD-growth has been considered difficult to unravel, with processes exhibiting limited control and low reproducibility. Very little has been reported on trends in reaction mechanisms as the mass of the alkali metal increases. Herein, we summarize the existing literature on the use of alkali metal tert-butoxides as precursors in ALD. We consider differences in the structure and behavior of the tert-butoxides as the alkali metal cation becomes heavier. In addition, we present precursor synthesis routes and key information on precursor structure, stability, and mechanistic behavior. Finally, we provide the first ever report of Cs-containing films by ALD to complement previous work on its lighter counterparts.