Reaction Pathways for Atomic Layer Deposition with Lithium Hexamethyl Disilazide, Trimethyl Phosphate, and Oxygen Plasma

Werbrouck, Andreas; Mattelaer, Felix; Minjauw, Matthias; Nisula, Mikko; Julin, Jaakko; Munnik, Frans; Dendooven, Jolien; Detavernier, Christophe

doi:10.1021/acs.jpcc.0c09284

Cited by 5 publications

(11 citation statements)

References 30 publications

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“…However, as we showed in ref. 22, there are no OH groups at the surface in this process (see also Fig. 3a).…”

Section: Resultsmentioning

confidence: 87%

“…As a reference, saturation curves for the LiHMDS–TMP process described in ref. 18 and 22 were also measured and are displayed in Fig. 1d and e.…”

Section: Resultsmentioning

confidence: 99%

“…In another earlier publication, we investigated the reaction pathways for LiHMDS when it is combined with TMP and oxygen plasma in different permutations. 22 Without oxygen plasma, it was concluded that in the absence of surface OH groups, the LiHMDS molecule may bind to the surface via dipole interactions. The interaction between O–Li groups from the surface and the N − –Li + ionic bond from the LiHMDS molecule provides the attractive force required for the LiHMDS to physisorb on the surface.…”

Section: Resultsmentioning

confidence: 99%

“…This confirms the reaction mechanism of LiHMDS as described in our earlier work. 22 A methyl group from the TMP allows the HMDS ligand to desorb, and P–O–Li + bonds are formed. This is as well an indication that the HMDS ligand does not interfere in the TMA reaction mechanism.…”

Section: Resultsmentioning

confidence: 99%

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Surface reactions between LiHMDS, TMA and TMP leading to deposition of amorphous lithium phosphate

et al. 2022

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“…However, as we showed in ref. 22, there are no OH groups at the surface in this process (see also Fig. 3a).…”

Section: Resultsmentioning

confidence: 87%

“…As a reference, saturation curves for the LiHMDS–TMP process described in ref. 18 and 22 were also measured and are displayed in Fig. 1d and e.…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Surface reactions between LiHMDS, TMA and TMP leading to deposition of amorphous lithium phosphate

et al. 2022

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“…The Si incorporation in the film could be precisely controlled by the utilization of plasma-enhanced ALD. [33] However, this mechanism is an undesired side reaction for the here applied thermal ALD. The increased amount of incorporated Si in the deposited film could explain the higher GPCs in process regime III.…”

Section: Ald Process Development Of LI 4 Ti 5 O 12mentioning

confidence: 98%

Atomic Layer Deposition of Textured Li₄Ti₅O₁₂: A High‐Power and Long‐Cycle Life Anode for Lithium‐Ion Thin‐Film Batteries

Speulmanns

Kia

Bönhardt

et al. 2021

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autonomous sensors, wearable devices, and medical implants will grow up to 100 billion USD. [1,2] The shrinking device sizes of portable electronics require microsized on-chip energy storage solutions with high-energy and high-power capability. These demands are beyond the abilities of liquid lithium (Li)-ion batteries due to limited miniaturization potential and inherent risks of the liquid electrolyte such as flammability and leakage.TFBs with solid-state electrolytes and binder-free electrodes are a promising alternative. In general, interfaces are more pronounced in thin-film devices, which remains challenging in all-solid-state batteries. [3] TFBs provide high-power density, long cycle life, low self-discharge, high-temperature and chemical stability, on-chip integration, and miniaturization. [4] These properties pave the way for future replacement of standard on-chip supercapacitors. [5] However, the small form factor and short Li diffusion length of TFBs come at the cost of low energy density. So-called 3D TFBs can partially compensate this by increasing energy density per footprint area. Thereby the battery layer stack is coated over a microstructured substrate with an enhanced surface area. [6] A first functional full cell 3D TFB was recently demonstrated by Pearse et al. [7] Moitzheim et al. reported an extensive overview of the current state, challenges, and outlooks of 3D TFBs. [8] ALD is the ideal technique enabling the required conformal, pinhole-free deposition and stoichiometric control of nanometer-thin films on highly structured surfaces. The vapor-phase technique based on sequential, self-limiting surface reactions is well understood and an industrial standard in integrated circuit manufacturing. [9] However, the deposition of Li metal is not possible and Li compounds remain challenging. [10,11] Functional ALD films of cathode materials such as LiMn 2 O 4 [12] or LiCoO 2 [13] and solid-state electrolytes such as LiPON [14] or Li x Al y Si z O [15] were demonstrated. However, Li-containing anode materials directly fabricated by ALD were not yet electrochemically evaluated. Only closely related ALD TiO 2 anodes were successfully investigated and optimized. [16,17] Spinel Li 4 Ti 5 O 12 (LTO) is a well-suited anode for 3D TFBs. The material undergoes a phase transition to the rocksalt-like structure during lithiation by rearranging the Li atoms with minimal volume change below 0.1%. [18] This so-called "zero-strain"The "zero-strain" Li 4 Ti 5 O 12 is an attractive anode material for 3D solid-state thin-film batteries (TFB) to power upcoming autonomous sensor systems. Herein, Li 4 Ti 5 O 12 thin films fabricated by atomic layer deposition (ALD) are electrochemically evaluated for the first time. The developed ALD process with a growth per cycle of 0.6 Å cycle −1 at 300 °C enables high-quality and dense spinel films with superior adhesion after annealing. The short lithiumion diffusion pathways of the nanostructured 30 nm films result in excellent electrochemical properties. Planar films reveal 9...

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Atomic and Molecular Layer Deposition of Alkali Metal Based Thin Films

Madadi

Heiska

Multia

et al. 2021

ACS Appl. Mater. Interfaces

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Atomic layer deposition (ALD) is the fastest growing thin-film technology in microelectronics, but it is also recognized as a promising fabrication strategy for various alkali-metal-based thin films in emerging energy technologies, the spearhead application being the Li-ion battery. Since the pioneering work in 2009 for Li-containing thin films, the field has been rapidly growing and also widened from lithium to other alkali metals. Moreover, alkali-metal-based metal–organic thin films have been successfully grown by combining molecular layer deposition (MLD) cycles of the organic molecules with the ALD cycles of the alkali metal precursor. The current literature describes already around 100 ALD and ALD/MLD processes for alkali-metal-bearing materials. Interestingly, some of these materials cannot even be made by any other synthesis route. In this review, our intention is to present the current state of research in the field by (i) summarizing the ALD and ALD/MLD processes so far developed for the different alkali metals, (ii) highlighting the most intriguing thin-film materials obtained thereof, and (iii) addressing both the advantages and limitations of ALD and MLD in the application space of these materials. Finally, (iv) a brief outlook for the future perspectives and challenges of the field is given.

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Reaction Pathways for Atomic Layer Deposition with Lithium Hexamethyl Disilazide, Trimethyl Phosphate, and Oxygen Plasma

Cited by 5 publications

References 30 publications

Surface reactions between LiHMDS, TMA and TMP leading to deposition of amorphous lithium phosphate

Surface reactions between LiHMDS, TMA and TMP leading to deposition of amorphous lithium phosphate

Atomic Layer Deposition of Textured Li₄Ti₅O₁₂: A High‐Power and Long‐Cycle Life Anode for Lithium‐Ion Thin‐Film Batteries

Atomic and Molecular Layer Deposition of Alkali Metal Based Thin Films

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Reaction Pathways for Atomic Layer Deposition with Lithium Hexamethyl Disilazide, Trimethyl Phosphate, and Oxygen Plasma

Cited by 5 publications

References 30 publications

Surface reactions between LiHMDS, TMA and TMP leading to deposition of amorphous lithium phosphate

Surface reactions between LiHMDS, TMA and TMP leading to deposition of amorphous lithium phosphate

Atomic Layer Deposition of Textured Li4Ti5O12: A High‐Power and Long‐Cycle Life Anode for Lithium‐Ion Thin‐Film Batteries

Atomic and Molecular Layer Deposition of Alkali Metal Based Thin Films

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Product

Resources

About

Atomic Layer Deposition of Textured Li₄Ti₅O₁₂: A High‐Power and Long‐Cycle Life Anode for Lithium‐Ion Thin‐Film Batteries