Atomic Layer Deposition of LiF and Lithium Ion Conducting (AlF3)(LiF)x Alloys Using Trimethylaluminum, Lithium Hexamethyldisilazide and Hydrogen Fluoride

2017 ◽  
Author(s):  
Younghee Lee ◽  
Daniela M. Piper ◽  
Andrew S. Cavanagh ◽  
Matthias J. Young ◽  
Se-Hee Lee ◽  
...  
Keyword(s):  
Lithium Ion ◽  
Atomic Layer ◽  
Mass Gain ◽  
Alloy Film ◽  
Ex Situ ◽  
X Ray ◽  
Layer Deposition ◽  
Ion Conducting ◽  
Good Agreement

<div>Atomic layer deposition (ALD) of LiF and lithium ion conducting (AlF<sub>3</sub>)(LiF)<sub>x</sub> alloys was developed using trimethylaluminum, lithium hexamethyldisilazide (LiHMDS) and hydrogen fluoride derived from HF-pyridine solution. ALD of LiF was studied using in situ quartz crystal microbalance (QCM) and in situ quadrupole mass spectrometer (QMS) at reaction temperatures between 125°C and 250°C. A mass gain per cycle of 12 ng/(cm<sup>2</sup> cycle) was obtained from QCM measurements at 150°C and decreased at higher temperatures. QMS detected FSi(CH<sub>3</sub>)<sub>3</sub> as a reaction byproduct instead of HMDS at 150°C. LiF ALD showed self-limiting behavior. Ex situ measurements using X-ray reflectivity (XRR) and spectroscopic ellipsometry (SE) showed a growth rate of 0.5-0.6 Å/cycle, in good agreement with the in situ QCM measurements.</div><div>ALD of lithium ion conducting (AlF3)(LiF)x alloys was also demonstrated using in situ QCM and in situ QMS at reaction temperatures at 150°C A mass gain per sequence of 22 ng/(cm<sup>2</sup> cycle) was obtained from QCM measurements at 150°C. Ex situ measurements using XRR and SE showed a linear growth rate of 0.9 Å/sequence, in good agreement with the in situ QCM measurements. Stoichiometry between AlF<sub>3</sub> and LiF by QCM experiment was calculated to 1:2.8. XPS showed LiF film consist of lithium and fluorine. XPS also showed (AlF<sub>3</sub>)(LiF)x alloy consists of aluminum, lithium and fluorine. Carbon, oxygen, and nitrogen impurities were both below the detection limit of XPS. Grazing incidence X-ray diffraction (GIXRD) observed that LiF and (AlF<sub>3</sub>)(LiF)<sub>x</sub> alloy film have crystalline structures. Inductively coupled plasma mass spectrometry (ICP-MS) and ionic chromatography revealed atomic ratio of Li:F=1:1.1 and Al:Li:F=1:2.7: 5.4 for (AlF<sub>3</sub>)(LiF)<sub>x</sub> alloy film. These atomic ratios were consistent with the calculation from QCM experiments. Finally, lithium ion conductivity (AlF<sub>3</sub>)(LiF)<sub>x</sub> alloy film was measured as σ = 7.5 × 10<sup>-6</sup> S/cm.</div>

Atomic Layer Deposition of LiF and Lithium Ion Conducting (AlF3)(LiF)x Alloys Using Trimethylaluminum, Lithium Hexamethyldisilazide and Hydrogen Fluoride

2017 ◽  
Author(s):  
Younghee Lee ◽  
Daniela M. Piper ◽  
Andrew S. Cavanagh ◽  
Matthias J. Young ◽  
Se-Hee Lee ◽  
...  
Keyword(s):  
Lithium Ion ◽  
Atomic Layer ◽  
Mass Gain ◽  
Alloy Film ◽  
Ex Situ ◽  
X Ray ◽  
Layer Deposition ◽  
Ion Conducting ◽  
Good Agreement

<div>Atomic layer deposition (ALD) of LiF and lithium ion conducting (AlF<sub>3</sub>)(LiF)<sub>x</sub> alloys was developed using trimethylaluminum, lithium hexamethyldisilazide (LiHMDS) and hydrogen fluoride derived from HF-pyridine solution. ALD of LiF was studied using in situ quartz crystal microbalance (QCM) and in situ quadrupole mass spectrometer (QMS) at reaction temperatures between 125°C and 250°C. A mass gain per cycle of 12 ng/(cm<sup>2</sup> cycle) was obtained from QCM measurements at 150°C and decreased at higher temperatures. QMS detected FSi(CH<sub>3</sub>)<sub>3</sub> as a reaction byproduct instead of HMDS at 150°C. LiF ALD showed self-limiting behavior. Ex situ measurements using X-ray reflectivity (XRR) and spectroscopic ellipsometry (SE) showed a growth rate of 0.5-0.6 Å/cycle, in good agreement with the in situ QCM measurements.</div><div>ALD of lithium ion conducting (AlF3)(LiF)x alloys was also demonstrated using in situ QCM and in situ QMS at reaction temperatures at 150°C A mass gain per sequence of 22 ng/(cm<sup>2</sup> cycle) was obtained from QCM measurements at 150°C. Ex situ measurements using XRR and SE showed a linear growth rate of 0.9 Å/sequence, in good agreement with the in situ QCM measurements. Stoichiometry between AlF<sub>3</sub> and LiF by QCM experiment was calculated to 1:2.8. XPS showed LiF film consist of lithium and fluorine. XPS also showed (AlF<sub>3</sub>)(LiF)x alloy consists of aluminum, lithium and fluorine. Carbon, oxygen, and nitrogen impurities were both below the detection limit of XPS. Grazing incidence X-ray diffraction (GIXRD) observed that LiF and (AlF<sub>3</sub>)(LiF)<sub>x</sub> alloy film have crystalline structures. Inductively coupled plasma mass spectrometry (ICP-MS) and ionic chromatography revealed atomic ratio of Li:F=1:1.1 and Al:Li:F=1:2.7: 5.4 for (AlF<sub>3</sub>)(LiF)<sub>x</sub> alloy film. These atomic ratios were consistent with the calculation from QCM experiments. Finally, lithium ion conductivity (AlF<sub>3</sub>)(LiF)<sub>x</sub> alloy film was measured as σ = 7.5 × 10<sup>-6</sup> S/cm.</div>

Oxygen Vacancies at the γ-Al2O3/STO Heterointerface Grown by Atomic Layer Deposition

2015 ◽  
Vol 1730 ◽  
Author(s):  
Thong Q. Ngo ◽  
Martin D. McDaniel ◽  
Agham Posadas ◽  
Alexander A. Demkov ◽  
John G. Ekerdt
Keyword(s):  
Atomic Layer Deposition ◽  
Photoelectron Spectroscopy ◽  
Oxygen Vacancies ◽  
Atomic Layer ◽  
High Energy ◽  
Ex Situ ◽  
X Ray ◽  
Layer Deposition ◽  
Dimensional Electron Gas

ABSTRACTWe report the epitaxial growth of γ-Al2O3 on SrTiO3 (STO) substrates by atomic layer deposition (ALD). The ALD growth of γ-Al2O3 on STO(001) single crystal substrates was performed at a temperature of 345 °C. Trimethylaluminum and water were used as co-reactants. In-situ reflection high-energy electron diffraction and ex-situ x-ray diffraction were used to determine the crystallinity of the Al2O3 films. In-situ x-ray photoelectron spectroscopy was used to characterize the Al2O3/STO heterointerface. The formation of a Ti3+ feature is observed in the Ti 2p spectrum of STO after the first few ALD cycles of Al2O3 and even after exposure of the STO substrate to trimethylaluminum alone at 345 °C. The presence of a Ti3+ feature is a direct indication of oxygen vacancies at the Al2O3/STO heterointerface, which provide the carriers for the quasi-two dimensional electron gas at the interface.

Atomic Layer Deposition of SrO: Substrate and Temperature Effects

2012 ◽  
Vol 1494 ◽  
pp. 179-183
Author(s):  
Han Wang ◽  
Xiaoqiang Jiang ◽  
Brian G. Willis
Keyword(s):  
Atomic Layer Deposition ◽  
Photoelectron Spectroscopy ◽  
Atomic Layer ◽  
Ex Situ ◽  
Hydroxyl Groups ◽  
Initial Growth ◽  
X Ray ◽  
Steady Growth ◽  
Layer Deposition

ABSTRACTThe atomic layer deposition (ALD) of SrO was conducted on various oxide surfaces by using strontium bis(tri-isopropylcyclopentadienyl) and water at deposition temperatures of 200 and 250°C. The initial and steady growth behaviors were studied by in-situ spectroscopic ellipsometry and ex-situ X-ray photoelectron spectroscopy. For initial growth, the growth per cycle (GPC) of SrO not only depends on the concentration of hydroxyl groups but also the formation of interfacial Sr-O-Si bonds. For the steady growth, in-situ annealing was used to enhance the growth rate and multiple growth regions were identified.

Ex-situ X-ray diffraction analysis of electrode strain at TiO2 atomic layer deposition/α-MoO3 interface in a novel aqueous potassium ion battery

2016 ◽  
Vol 316 ◽  
pp. 160-169 ◽  
Author(s):  
Nicholas David Schuppert ◽  
Santanu Mukherjee ◽  
Alex M. Bates ◽  
Eun-Jin Son ◽  
Moon Jong Choi ◽  
...  
Keyword(s):  
Atomic Layer Deposition ◽  
Diffraction Analysis ◽  
Atomic Layer ◽  
Potassium Ion ◽  
Ex Situ ◽  
X Ray Diffraction ◽  
X Ray ◽  
Layer Deposition

scholarly journals Atomic Layer Deposition of Lithium–Nickel–Silicon Oxide Cathode Material for Thin-Film Lithium-Ion Batteries

Energies ◽  
2020 ◽  
Vol 13 (9) ◽  
pp. 2345
Author(s):  
Maxim Maximov ◽  
Denis Nazarov ◽  
Aleksander Rumyantsev ◽  
Yury Koshtyal ◽  
Ilya Ezhov ◽  
...  
Keyword(s):  
Thin Film ◽  
Electron Microscopy ◽  
Atomic Layer Deposition ◽  
Lithium Ion Batteries ◽  
Silicon Oxide ◽  
Lithium Ion ◽  
Atomic Layer ◽  
X Ray ◽  
Layer Deposition ◽  
Nickel Silicon

Lithium nickelate (LiNiO2) and materials based on it are attractive positive electrode materials for lithium-ion batteries, owing to their large capacity. In this paper, the results of atomic layer deposition (ALD) of lithium–nickel–silicon oxide thin films using lithium hexamethyldisilazide (LiHMDS) and bis(cyclopentadienyl) nickel (II) (NiCp2) as precursors and remote oxygen plasma as a counter-reagent are reported. Two approaches were studied: ALD using supercycles and ALD of the multilayered structure of lithium oxide, lithium nickel oxide, and nickel oxides followed by annealing. The prepared films were studied by scanning electron microscopy, spectral ellipsometry, X-ray diffraction, X-ray reflectivity, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and selected-area electron diffraction. The pulse ratio of LiHMDS/Ni(Cp)2 precursors in one supercycle ranged from 1/1 to 1/10. Silicon was observed in the deposited films, and after annealing, crystalline Li2SiO3 and Li2Si2O5 were formed at 800 °C. Annealing of the multilayered sample caused the partial formation of LiNiO2. The obtained cathode materials possessed electrochemical activity comparable with the results for other thin-film cathodes.

A Combined Experimental and Theoretical Study of Lithiation Mechanism in ZnFe2O4 Anode Materials

MRS Advances ◽  
2018 ◽  
Vol 3 (14) ◽  
pp. 773-778 ◽  
Author(s):  
Lei Wang ◽  
Alison McCarthy ◽  
Kenneth J. Takeuchi ◽  
Esther S. Takeuchi ◽  
Amy C. Marschilok
Keyword(s):  
Early Stage ◽  
Deep Understanding ◽  
Lithium Ion ◽  
Oxidation Products ◽  
Ex Situ ◽  
Theoretical Modelling ◽  
X Ray Diffraction ◽  
X Ray ◽  
X Ray Absorption

ABSTRACTZnFe2O4 (ZFO) represents a promising anode material for lithium ion batteries, but there is still a lack of deep understanding of the fundamental reduction mechanism associated with this material. In this paper, the complete visualization of reduction/oxidation products irrespective of their crystallinity was achieved experimentally through a compilation of in situ X-ray diffraction, synchrotron based powder diffraction, and ex-situ X-ray absorption fine structure data. Complementary theoretical modelling study further shed light upon the fundamental understanding of the lithiation mechanism, especially at the early stage from ZnFe2O4 up to LixZnFe2O4 (x = 2).

scholarly journals Atomic Layer Deposition of NiO to Produce Active Material for Thin-Film Lithium-Ion Batteries

Coatings ◽  
2019 ◽  
Vol 9 (5) ◽  
pp. 301 ◽  
Author(s):  
Yury Koshtyal ◽  
Denis Nazarov ◽  
Ilya Ezhov ◽  
Ilya Mitrofanov ◽  
Artem Kim ◽  
...  
Keyword(s):  
Thin Film ◽  
Atomic Layer Deposition ◽  
Oxygen Plasma ◽  
Active Material ◽  
Specific Capacity ◽  
Lithium Ion ◽  
Atomic Layer ◽  
Cyclic Voltammograms ◽  
X Ray ◽  
Layer Deposition

Atomic layer deposition (ALD) provides a promising route for depositing uniform thin-film electrodes for Li-ion batteries. In this work, bis(methylcyclopentadienyl) nickel(II) (Ni(MeCp)2) and bis(cyclopentadienyl) nickel(II) (NiCp2) were used as precursors for NiO ALD. Oxygen plasma was used as a counter-reactant. The films were studied by spectroscopic ellipsometry, scanning electron microscopy, atomic force microscopy, X-ray diffraction, X-ray reflectometry, and X-ray photoelectron spectroscopy. The results show that the optimal temperature for the deposition for NiCp2 was 200–300 °C, but the optimal Ni(MeCp)2 growth per ALD cycle was 0.011–0.012 nm for both precursors at 250–300 °C. The films deposited using NiCp2 and oxygen plasma at 300 °C using optimal ALD condition consisted mainly of stoichiometric polycrystalline NiO with high density (6.6 g/cm3) and low roughness (0.34 nm). However, the films contain carbon impurities. The NiO films (thickness 28–30 nm) deposited on stainless steel showed a specific capacity above 1300 mAh/g, which is significantly more than the theoretical capacity of bulk NiO (718 mAh/g) because it includes the capacity of the NiO film and the pseudo-capacity of the gel-like solid electrolyte interface film. The presence of pseudo-capacity and its increase during cycling is discussed based on a detailed analysis of cyclic voltammograms and charge–discharge curves (U(C)).

In-Situ Synchrotron X-Ray Scattering Study of Thin Film Growth by Atomic Layer Deposition

2011 ◽  
Vol 11 (2) ◽  
pp. 1577-1580 ◽  
Author(s):  
Yong Jun Park ◽  
Dong Ryeol Lee ◽  
Hyun Hwi Lee ◽  
Han-Bo-Ram Lee ◽  
Hyungjun Kim ◽  
...  
Keyword(s):  
Thin Film ◽  
Atomic Layer Deposition ◽  
Film Growth ◽  
Atomic Layer ◽  
Thin Film Growth ◽  
X Ray ◽  
X Ray Scattering ◽  
Layer Deposition ◽  
Scattering Study

scholarly journals Selective Growth of Al2O3 on Size-Selected Platinum Clusters by Atomic Layer Deposition

2019 ◽  
Author(s):  
Timothy J. Gorey ◽  
Yang Dai ◽  
Scott Anderson ◽  
Sungsik Lee ◽  
Sungwon Lee ◽  
...  
Keyword(s):  
Atomic Layer Deposition ◽  
Photoelectron Spectroscopy ◽  
High Vacuum ◽  
Atomic Layer ◽  
Ultra High Vacuum ◽  
Ex Situ ◽  
Dimensional Structure ◽  
Alumina Layer ◽  
X Ray ◽  
Layer Deposition

In heterogeneous catalysis, atomic layer deposition (ALD) has been developed as a tool to stabilize and reduce carbon deposition on supported nanoparticles. Here, we discuss use of high vacuum ALD to deposit alumina films on size-selected, sub-nanometer Pt/SiO2 model catalysts. Mass-selected Pt24 clusters were deposited on oxidized Si(100), to form model Pt24/SiO2 catalysts with particles shown to be just under 1 nm, with multilayer three dimensional structure. Alternating exposures to trimethylaluminum and water vapor in an ultra-high vacuum chamber were used to grow alumina on the samples without exposing them to air. The samples were probed in situ using X-ray photoelectron spectroscopy (XPS), low-energy ion scattering spectroscopy (ISS), and CO temperature-programmed desorption (TPD). Additional samples were prepared for ex situ experiments using grazing incidence small angle x-ray scattering spectroscopy (GISAXS). Alumina growth is found to initiate at least 60 times more efficiently at the Pt24 cluster sites, compared to bare SiO2/Si, with a single ALD cycle depositing a full alumina layer on top of the clusters, with substantial additional alumina growth initiating on SiO2 sites surrounding the clusters. As a result, the clusters were completely passivated, with no exposed Pt binding sites.

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