electrode 8ABSTRACT: We demonstrate the fabrication of high-quality electrochemically active organic 9 lithium electrode thin films by the currently strongly emerging combined atomic/molecular layer 10 deposition (ALD/MLD) technique using lithium terephthalate, a recently found anode material for 11 lithium-ion battery (LIB), as a proof-of-the-concept material. Our deposition process for terephthalate is shown to well comply with the basic principles of ALD-type growth including the 13 sequential self-saturated surface reactions, a necessity when aiming at micro-LIB devices with 3D 14 architectures. The as-deposited films are found crystalline across the deposition temperature range 15 of 200 -280 °C, which is a trait highly desired for an electrode material but rather unusual for 16 hybrid organic-inorganic thin films. Excellent rate capability is ascertained for the Li-terephthalate 17 films with no conductive additives required. The electrode performance can be further enhanced 18 by depositing a thin protective LiPON solid-state electrolyte layer on top of Li-terephthalate; this

An atomic layer deposition (ALD) process is successfully developed for fabricating high-quality lithium phosphorus oxynitride (LiPON) thin films for a potential use as a conformal solid-state electrolyte coating in 3D Li-ion microbattery technology. In our ALD process the challenge of simultaneously incorporating phosphorus and nitrogen in the films is overcome by using a novel nitrogen-containing phosphorus precursor, diethyl phosphoramidate, together with lithium hexamethyldisilazide as the lithium precursor. A temperature window is found around 270−310°C, where homogeneous films are realized and the film growth is controlled in a digital manner by the number of ALD cycles at a rate of ∼0.7 Å/cycle. The process allows for a high N-to-P ratio in the films, which is beneficial for achieving the required high ionic conductivity. For a film deposited at 330°C with a composition of Li 0.95 PO 3.00 N 0.60 according to RBS/NRA analysis, an ionic conductivity value as high as 6.6 × 10 −7 S cm −1 is measured at 25°C.

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Organic electrode materials are promising next-generation battery materials. Combining them with a solid-state electrolyte, and fabricating the materials using atomic/molecular layer deposition provides us a unique platform to study the interactions.

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.

We demonstrate that the high-capacity organic electrode material, p-benzoquinone, is able to sustain ultrahigh redox reaction rates without any conductive additives when applied as ultrathin layers in an all-solid-state thin-film battery setup, viable for e.g. high-performance power sources in microelectronic devices.

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.

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.