Lithium barrier materials for on-chip Si-based microbatteries

Janski, Rafael; Fugger, Michael; Forster, Magdalena; Sorger, Michael; Dunst, Andreas; Hanzu, Ilie; Sternad, Michael; Wilkening, Martin

doi:10.1007/s10854-017-7325-4

Cited by 10 publications

(9 citation statements)

References 23 publications

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“…Second, Li ions escaping the battery or synaptic transistor region would cause an irreversible reduction of the capacity or uncontrolled change of the channel conductance, respectively. Several materials were investigated as possible candidates to act as Li-ion diffusion barriers such as tantalum nitride (TaN) and TiN, whereas the latter offered the best performance. − TiN films manufactured by atomic layer deposition (ALD) demonstrated superior blocking properties showing less than 0.02 Li inserted per TiN formula unit (f.u.) compared to sputtered films. , Furthermore, sputtering does not enable conformal coating of structures with high aspect ratios.…”

Section: Introductionmentioning

confidence: 99%

Surface-Dependent Performance of Ultrathin TiN Films as an Electrically Conducting Li Diffusion Barrier for Li-Ion-Based Devices

Speulmanns

Kia

Kühnel

et al. 2020

ACS Appl. Mater. Interfaces

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An in-depth understanding of lithium (Li) diffusion barriers is a crucial factor for enabling Li-ion-based devices such as three-dimensional (3D) thin-film batteries and synaptic redox transistors integrated on silicon substrates. Diffusion of Li ions into silicon can damage the surrounding components, detach the device itself, lead to battery capacity loss, and cause an uncontrolled change of the transistor channel conductance. In this study, we analyze for the first time ultrathin 10 nm titanium nitride (TiN) films as a bifunctional Li-ion diffusion barrier and current collector. Thermal atomic layer deposition (ALD) and pulsed chemical vapor deposition (pCVD) are employed for manufacturing ultrathin films. The 10 nm ALD films demonstrate excellent blocking capability with an insertion of only 0.03 Li per TiN formula unit exceeding 200 galvanostatic cycles at 3 μA/cm2 between 0.05 and 3 V versus Li/Li+. An ultralow electrical resistivity of 115 μΩ cm is obtained. In contrast, a partial barrier breakdown is observed for 10 nm pCVD films. High surface quality with low contamination is identified as a key factor for the excellent performance of ALD TiN. Conformal deposition of 10 nm ALD TiN in 3D structures with high aspect ratios of up to 20:1 is demonstrated. The measured capacities of the surface area-enhanced samples are in good agreement with the expected values. High-temperature blocking capability is proven for a typical electrode crystallization step. Ultrathin ALD TiN is an ideal candidate for an electrically conducting Li-ion diffusion barrier for Si-integrated devices.

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Section: Introductionmentioning

confidence: 99%

Surface-Dependent Performance of Ultrathin TiN Films as an Electrically Conducting Li Diffusion Barrier for Li-Ion-Based Devices

Speulmanns

Kia

Kühnel

et al. 2020

ACS Appl. Mater. Interfaces

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“…The higher demands with respect to cost, safety, and long-term stability for electric vehicles and storage of intermittently harvested renewable energies 1,2 require further improvements. 3 LIBs combine two Li-ion host electrodes in the rocking chair configuration, i.e., Li + as working ions is moved between a transition-metal oxide with a valence change of Mn III/IV , Co II/III , or Ni II/III and a negative electrode that takes up Li + upon reduction at potentials close to the standard potential of Li|Li + . While graphite has remained the most important material for negative electrodes, 4 silicon is considered as one of the promising alternatives due to its wide abundance, high Li-ion diffusivity in amorphous α-Li x Si, 5 and high theoretical gravimetric capacity of 3579 mAh g −1 .…”

Section: ■ Introductionmentioning

confidence: 99%

Nascent SEI-Surface Films on Single Crystalline Silicon Investigated by Scanning Electrochemical Microscopy

Sardinha

Sternad

Wilkening

et al. 2019

ACS Appl. Energy Mater.

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Silicon is a promising high-capacity host material for negative electrodes in lithium-ion batteries with low potential for the lithiation/delithiation reaction that is outside the stability window of organic carbonate electrolytes. Thus, the use of such electrodes critically depends on the formation of a protective solid electrolyte interphase (SEI) from the decomposition products of electrolyte components. Due to the large volume change upon charging, exposure of the electrode material to the electrolyte must be expected, and facile reformation of SEI is a scope for improving the stabilities of such electrodes. Here, we report the formation of incipient SEI layers on monocrystalline silicon by in situ imaging of their passivating properties using scanning electrochemical microscopy after potentiodynamic charging to different final potentials. The images show a local initiation of the SEI growth at potentials of around 1.0 V vs Li/Li+ in 1 M LiClO4 in propylene carbonate.

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“…The diffusion of small cations and anions plays an important role in many devices such as sensors − and batteries. − Although for some applications, e.g., in the semiconductor industry or in the development of breeding materials − for fusion reactor blankets, diffusion is unwanted, in other branches, materials with extremely high diffusion coefficients are desired. − Finding the right material and tailoring its dynamic properties further requires an in-depth understanding of the origins that determine fast ion dynamics. − …”

Section: Introductionmentioning

confidence: 99%

Rapid Low-Dimensional Li⁺ Ion Hopping Processes in Synthetic Hectorite-Type Li_0.5[Mg_2.5Li_0.5]Si₄O₁₀F₂

et al. 2020

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Understanding the origins of fast ion transport in solids is important to develop new ionic conductors for batteries and sensors. Nature offers a rich assortment of rather inspiring structures to elucidate these origins. In particular, layer-structured materials are prone to show facile Li + transport along their inner surfaces. Here, synthetic hectorite-type Li 0.5 [Mg 2.5 Li 0.5 ]Si 4 O 10 F 2 , being a phyllosilicate, served as a model substance to investigate Li + translational ion dynamics by both broadband conductivity spectroscopy and diffusion-induced 7 Li nuclear magnetic resonance (NMR) spin–lattice relaxation experiments. It turned out that conductivity spectroscopy, electric modulus data, and NMR are indeed able to detect a rapid 2D Li + exchange process governed by an activation energy as low as 0.35 eV. At room temperature, the bulk conductivity turned out to be in the order of 0.1 mS cm –1 . Thus, the silicate represents a promising starting point for further improvements by crystal chemical engineering. To the best of our knowledge, such a high Li + ionic conductivity has not been observed for any silicate yet.

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Lithium barrier materials for on-chip Si-based microbatteries

Cited by 10 publications

References 23 publications

Surface-Dependent Performance of Ultrathin TiN Films as an Electrically Conducting Li Diffusion Barrier for Li-Ion-Based Devices

Surface-Dependent Performance of Ultrathin TiN Films as an Electrically Conducting Li Diffusion Barrier for Li-Ion-Based Devices

Nascent SEI-Surface Films on Single Crystalline Silicon Investigated by Scanning Electrochemical Microscopy

Rapid Low-Dimensional Li⁺ Ion Hopping Processes in Synthetic Hectorite-Type Li_0.5[Mg_2.5Li_0.5]Si₄O₁₀F₂

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Lithium barrier materials for on-chip Si-based microbatteries

Cited by 10 publications

References 23 publications

Surface-Dependent Performance of Ultrathin TiN Films as an Electrically Conducting Li Diffusion Barrier for Li-Ion-Based Devices

Surface-Dependent Performance of Ultrathin TiN Films as an Electrically Conducting Li Diffusion Barrier for Li-Ion-Based Devices

Nascent SEI-Surface Films on Single Crystalline Silicon Investigated by Scanning Electrochemical Microscopy

Rapid Low-Dimensional Li+ Ion Hopping Processes in Synthetic Hectorite-Type Li0.5[Mg2.5Li0.5]Si4O10F2

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Rapid Low-Dimensional Li⁺ Ion Hopping Processes in Synthetic Hectorite-Type Li_0.5[Mg_2.5Li_0.5]Si₄O₁₀F₂