CO<sub>2</sub>‐Laser Flash Evaporation as Novel CVD Precursor Delivery System for Functional Thin Film Growth

Loho, Christoph; Darbandi, Azad J.; Djenadic, Ruzica; Clemens, Oliver; Hahn, Horst

doi:10.1002/cvde.201307089

Cited by 11 publications

(11 citation statements)

References 30 publications

(35 reference statements)

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“…Formation of this compound was already observed in systems other than LLZO deposited by LA-CVD at elevated temperatures. 16 In an earlier study, 16 two ways to suppress the Li 2 PtO 3 phase formation in LA-CVD of LiCoO 2 were investigated, based on the reaction scheme:…”

Section: Resultsmentioning

confidence: 99%

“…16 The only modification made to the setup described in Loho et al 16 is that a porous stainless steel microsieve R200 (Tridelta Siperm GmbH) was used in front of the sample holder to achieve a more uniform gas flow and hence deposition. As precursor materials for the LLZO thin film deposition, 2,2,6,6-tetramethyl-3,5-heptanedionato lithium (LiC 11 4 , Sigma Aldrich, 98%) were premixed inside an Ar-filled glove box (MBraun GmbH) with O 2 -and H 2 Olevels <1 ppm.…”

Section: Methodsmentioning

confidence: 99%

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Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

Loho

Djenadic

Bruns

et al. 2016

J. Electrochem. Soc.

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111

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The detailed characterization of garnet-type Li-ion conducting Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte thin films grown by novel CO 2 -laser assisted chemical vapor deposition (LA-CVD) is reported. A deposition process parameter study reveals that an optimal combination of deposition temperature and oxygen partial pressure is essential to obtain high quality tetragonal LLZO thin films. The polycrystalline tetragonal LLZO films grown on platinum have a dense and homogeneous microstructure and are free of cracks. A total lithium ion conductivity of 4.2 · 10 −6 S · cm −1 at room temperature, with an activation energy of 0.50 eV, is achieved. This is the highest total lithium ion conductivity value reported for tetragonal LLZO thin films so far, being about one order of magnitude higher than previously reported values for tetragonal LLZO thin films prepared by sputtering and pulsed laser deposition. The results of this study suggest that the tetragonal LLZO thin films grown by LA-CVD are applicable for the use in all-solid-state thin film lithium ion batteries. Over the last decades a progressive miniaturization of electronic components took place. As a result there is an increasing demand for micro-sized power sources that drives the current research on thin film batteries. Possible applications range from sensors and radiofrequency identification tags to implantable medical devices. For these applications an all-solid-state thin film Li-ion battery is desirable due to considerable advantages such as excellent safety properties and easy integration in microelectronics. Furthermore, the energy density of such an all-solid-state cell can be increased compared to a cell with conventional liquid electrolyte, if the chosen solid electrolyte material is stable toward high voltage cathode materials as well as toward a lithium metal anode. The garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 (LLZO), first reported in 2007 by Murugan et al., 1 is a material that combines those properties with reasonably high lithium ion conductivity of up to 2.3 · 10 −5 S · cm −1 in its tetragonal 2 and up to 1.2 · 10 −3S · cm −1 in its cubic 3 modification. However, these high conductivity values have so far only been achieved for bulk ceramics, but not for thin films. Apparently, over the last years researchers have focused on the optimization of the lithium ion conductivity in bulk ceramics, e.g. by stabilization of the cubic LLZO phase via doping, 4,5 while only a few publications have addressed LLZO thin film deposition at all. 6-12The advantage of thin films is that their lithium ion conductivity for the use in an all-solid-state battery does not need to be as high as compared to bulk solid electrolytes, taking into account the electrolyte resistance R:where A is the contact area, l is the thickness and σ is the Li-ion conductivity of the solid electrolyte, respectively. For example, in their recent study Liu et al. 13 report on a functioning bulk all-solid-state battery using cubic LLZO as solid electrolyte with ∼ 1 mm thickn...

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

Loho

Djenadic

Bruns

et al. 2016

J. Electrochem. Soc.

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111

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“…Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZTO) thin films were deposited by LASER-assisted chemical vapor deposition (LA-CVD) on Si wafers (CrysTec GmbH, Berlin Germany) with an orientation of (100). For a detailed description of the deposition setup please see previous publications of our group [ 18 ]. As precursors, 2,2,6,6-tetramethyl-3,5-heptanedionato lithium (LiC 11 H 19 O 2 , STREM Chemicals GmbH, Kehl, Germany, 98%), lanthanum(III) acetylacetonate hydrate (La(C 5 H 7 O 2 ) 3 ·4H 2 O, abcr GmbH, Karlsruhe, Germany, 99.9%), tantalum(V) tetraethoxyacetylacetonate (TaC 13 H 27 O 6 , STREM Chemicals GmbH, Kehl, Germany, 99.99%), and zirconium(IV) acetylacetonate (Zr(C 5 H 7 O 2 ) 4 , STREM Chemicals GmbH, Kehl, Germany, 98%) were mixed in stoichiometric ratio, with a 50 wt % excess of Li.…”

Section: Methodsmentioning

confidence: 99%

On the Surface Modification of LLZTO with LiF via a Gas-Phase Approach and the Characterization of the Interfaces of LiF with LLZTO as Well as PEO+LiTFSI

et al. 2022

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In this study we present gas-phase fluorination as a method to create a thin LiF layer on Li6.5La3Zr1.5Ta0.5O12 (LLZTO). We compared these fluorinated films with LiF films produced by RF-magnetron sputtering, where we investigated the interface between the LLZTO and the deposited LiF showing no formation of a reaction layer. Furthermore, we investigated the ability of this LiF layer as a protection layer against Li2CO3 formation in ambient air. By this, we show that Li2CO3 formation is absent at the LLZTO surface after 24 h in ambient air, supporting the protective character of the formed LiF films, and hence potentially enhancing the handling of LLZTO in air for battery production. With respect to the use within hybrid electrolytes consisting of LLZTO and a mixture of polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), we also investigated the interface between the formed LiF films and a mixture of PEO+LiTFSI by X-ray photoelectron spectroscopy (XPS), showing decomposition of the LiTFSI at the interface.

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“…Different types of battery materials were shown to be successfully protected by applying thin layers using various modifications of CVD method, namely metal‐organic CVD, [ 174 ] laser flash evaporation CVD, [ 175 ] electron cyclotron resonance CVD. [ 176 ] CVD techniques have particular popularity in the context of all‐solid‐state LIBs, where the large polarization at the interface between Li metal anode and oxide‐based (garnet) solid electrolyte is a main challenge.…”

Section: Production Methods—advantages Challenges and Effectivenessmentioning

confidence: 99%

Molecular Engineering Approaches to Fabricate Artificial Solid‐Electrolyte Interphases on Anodes for Li‐Ion Batteries: A Critical Review

Fedorov

Maletti

Heubner

et al. 2021

Advanced Energy Materials

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in further markets, such as electromobility and large-scale grid storage. Although LIBs offer high energy density and have reached a high level of maturity, there are still many technological challenges to meet established user habits and increasing demands. [1] Among the remaining challenges of LIBs, one of the most crucial issues is the electrochemical instability of anodes toward electrolytes. When using anode materials with favorably low electrode potentials close to Li/Li + , common liquid electrolytes are decomposed. Ideally, this leads to the formation of a stable so-called solid-electrolyte interphase (SEI), preventing further electrolyte decomposition and leading to stable cycling performance. Furthermore, the SEI has decisive influence on the charge/discharge kinetics of the battery, as this is where the Li-ions overcome the interface between the electrolyte and the electrode. Accordingly, the SEI is a key component that determines the performance of LIBs. The "natural SEI" that forms at the anode/electrolyte interface during initial cycling represents a thin layer made of salts, oxides, polymers. [2] The conceptual model of SEI was introduced by Peled in 1979 [3] and further developed by other groups. [4][5][6][7][8][9][10][11][12] According to this model, natural SEIs possess only ionic conductivity, while serving as a barrier to electron transfer. In this regard, the thickness and conformity of SEI An intrinsic challenge of Li-ion batteries is the instability of electrolytes against anode materials. For anodes with a favorably low operating potential, a solid-electrolyte interphase (SEI) formed during initial cycles provides stability, traded off for capacity consumption. The SEI is mainly determined by the anode material, electrolyte composition, and formation conditions. Its properties are typically adjusted by changing the liquid electrolyte's composition. Artificial SEIs (Art-SEIs) offer much more freedom to address and tune specific properties, such as chemical composition, impedance, thickness, and elasticity. Art-SEIs for intercalation, alloying, conversion and Li metal anodes have to fulfil varying requirements. In all cases, sufficient transport properties for Li-ions and (electro-)chemical stability must be guaranteed. Several approaches for Art-SEIs preparation have been reported: from simple casting and coating techniques to elaborated Phys-Chem modifications and deposition processes. This review critically reports on the promising approaches for Art-SEIs formation on different type of anode materials, focusing on methodological aspects. The specific requirements for each approach and material class, as well as the most effective strategies for Art-SEI coating, are discussed and a roadmap for further developments towards next-generation stable anodes are provided.

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CO₂‐Laser Flash Evaporation as Novel CVD Precursor Delivery System for Functional Thin Film Growth

Cited by 11 publications

References 30 publications

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

On the Surface Modification of LLZTO with LiF via a Gas-Phase Approach and the Characterization of the Interfaces of LiF with LLZTO as Well as PEO+LiTFSI

Molecular Engineering Approaches to Fabricate Artificial Solid‐Electrolyte Interphases on Anodes for Li‐Ion Batteries: A Critical Review

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CO2‐Laser Flash Evaporation as Novel CVD Precursor Delivery System for Functional Thin Film Growth

Cited by 11 publications

References 30 publications

Garnet-Type Li7La3Zr2O12Solid Electrolyte Thin Films Grown by CO2-Laser Assisted CVD for All-Solid-State Batteries

Garnet-Type Li7La3Zr2O12Solid Electrolyte Thin Films Grown by CO2-Laser Assisted CVD for All-Solid-State Batteries

On the Surface Modification of LLZTO with LiF via a Gas-Phase Approach and the Characterization of the Interfaces of LiF with LLZTO as Well as PEO+LiTFSI

Molecular Engineering Approaches to Fabricate Artificial Solid‐Electrolyte Interphases on Anodes for Li‐Ion Batteries: A Critical Review

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CO₂‐Laser Flash Evaporation as Novel CVD Precursor Delivery System for Functional Thin Film Growth

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries