Lanthanum titanate and lithium lanthanum titanate thin films grown by atomic layer deposition

Aaltonen, Titta; Alnes, Mari; Nilsen, Ola; Costelle, Leila; Fjellvåg, Helmer

doi:10.1039/b923490j

Cited by 95 publications

(102 citation statements)

References 15 publications

(22 reference statements)

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“…8 However, work on lithium-containing solid-state electrolytes and electrode materials is still very exploratory. Even though several lithium-containing compounds have recently been prepared by ALD, 9,10 no reports of electrochemical investigations are available to date. An overview of Li-containing compounds prepared by ALD is presented in Table I.…”

mentioning

confidence: 99%

Atomic Layer Deposition of LiCoO₂Thin-Film Electrodes for All-Solid-State Li-Ion Micro-Batteries

Donders

Arnoldbik

Knoops

et al. 2013

J. Electrochem. Soc.

102

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One of the remaining challenges in the field of portable electronics is the miniaturization of lithium-ion batteries. To prepare all-solid-state batteries with a sufficient high storage capacity it is vital to prepare high quality thin films for battery stacks on 3D-structured substrates. A remote plasma atomic layer deposition (ALD) process has therefore been developed for LiCoO2 which can serve as a cathode material. A combination of CoCp2 as cobalt precursor, LiOtBu as lithium precursor and O2 plasma as oxidant source was used to create super-cycles to deposit LiCoO2 from Co3O4 and Li2CO3 cycles. The thin films were deposited at a temperature of 325°C and showed linear growth with a rate of 0.06 nm/cycle. After annealing the samples at 700°C for 6 minutes high temperature phase LiCoO2 was obtained, as was demonstrated by XRD and Raman spectroscopy. A new procedure was proposed to obtain the composition of all three chemical elements in the LiCoO2 films. Elastic Backscattering Spectroscopy (EBS) measurements turned out to be very convenient and reliable to obtain the quantities of all chemical elements, including lithium. Moreover, the ALD-deposited LiCoO2 thin film electrodes were electrochemically characterized, revealing good electrochemical performance. To the best of our knowledge this paper provides the first evidence that electrochemically active LiCoO2 can be deposited by ALD.

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confidence: 99%

Atomic Layer Deposition of LiCoO₂Thin-Film Electrodes for All-Solid-State Li-Ion Micro-Batteries

Donders

Arnoldbik

Knoops

et al. 2013

J. Electrochem. Soc.

102

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“…1). Here the previously described remote plasma ALD process for Co 3 O 4 is combined with a novel ALD process using a lithium precursor reported recently for the deposition of LLT and Li 2 CO 3 (13,14). In both processes a precursor dosing time of 2 s is applied combined with an O 2 plasma at 100 W for 5 s at a pressure of 0.01 Torr.…”

Section: Film Preparationmentioning

confidence: 99%

“…Due to the surface chemistry controlled deposition process, ALD is chosen in this work and provides an excellent conformality and thickness control at the atomic level, even in challenging high-aspectratio structures. Several lithium compounds have recently been deposited using ALD in the form of LiOH, Li 2 CO 3 and lithium lanthanum titanate [(Li, La) x Ti y O z (LLT)] films (13,14), however no reports of electrochemical analysis of ALD deposited lithium containing materials are available to date. An overview of Li-based materials deposited by ALD as reported in the literature is shown in Table I.…”

Section: Introductionmentioning

confidence: 99%

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Remote Plasma Atomic Layer Deposition of Thin Films of Electrochemically Active LiCoO₂

et al. 2011

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One of the remaining challenges in the field of portable electronics is the miniaturization of lithium-ion batteries without decreasing their storage capacity. To tackle this challenge and to effectively integrate battery technology in even a wider variety of applications, it is essential to produce high quality thin films for all-solid-state batteries. A remote plasma ALD process for the positive electrode material LiCoO2 was developed using the combination of CoCp2 as the cobalt precursor, LiOtBu as the lithium precursor and O2 plasma as the oxidant source. The thin films were deposited at a temperature of 325 °C with a virtually linear growth rate of 0.06 nm/cycle. After annealing the samples at 700 °C for 6 minutes the high temperature phase LiCoO2 was obtained, as demonstrated by XRD and Raman spectroscopy measurements. Electrochemical charge/discharge cycling showed good electrochemical activity with a promising storage capacity.

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“…Amorphous LLTO thin films have been synthesized by pulsed laser deposition (PLD), RF magnetron sputtering, E-beam evaporation, atomic layer deposition, chemical solution deposition and sol-gel synthesis. [15][16][17][18][19][20][21][22][23][24] Furusawa et al demonstrated amorphous LLTO thin films deposited via PLD with higher ionic conductivity (8.98 × 10 −4 * Electrochemical Society Student Member. * * Electrochemical Society Member.…”

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confidence: 99%

Amorphous Lithium Lanthanum Titanate for Solid-State Microbatteries

Lee

Wang

Xin

et al. 2016

J. Electrochem. Soc.

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Lithium lanthanum titanate (LLTO) is a promising solid state electrolyte for solid state batteries due to its demonstrated high bulk ionic conductivity. However, crystalline LLTO has a relatively low grain boundary conductivity, limiting the overall material conductivity. In this work, we investigate amorphous LLTO (a-LLTO) thin films grown by pulsed laser deposition (PLD). By controlling the background pressure and temperature we are able to optimize the ionic conductivity to 3 × 10 −4 S/cm and electronic conductivity to 5 × 10 −11 S/cm. XRD, TEM, and STEM/EELS analysis confirm that the films are amorphous and indicate that oxygen background gas is necessary during the PLD process to decrease the oxygen vacancy concentration, decreasing the electrical conductivity. Amorphous LLTO is deposited onto high voltage LiNi 0. Next generation lithium-ion batteries will require a broad range of energies to meet the challenges of portable electronic storage from electric vehicles to microelectromechanical systems (MEMS). The cost per Watt-hour of commercial batteries have shown incremental improvement due to better manufacturing design, but drastic increases in energy and power density are needed to satisfy projected demand. 1 Solid-state electrolytes are researched heavily because they have the potential to improve capacity loss, cycle lifetime, operation temperature, and safety. Lithium Phosphorous Oxynitride (LiPON) based thin-film solid-state batteries have excellent cycle life and are currently commercialized.2,3 However, LiPON has a relatively low ionic conductivity (1 × 10 −6 S/cm) and other solid electrolytes have demonstrated conductivity several orders of magnitude higher. 4,5 Lithium lanthanum titanate (LLTO) is a promising solid-state electrolyte due to its high bulk ionic conductivity (∼10 −3 S/cm) at room temperature, negligible electronic conductivity, and high voltage, atmospheric, and temperature stabilities.6-8 Extensive fundamental studies have been carried out to demonstrate this high ionic conductivity, elucidate the crystal structure, and determine the mechanism of lithium ion conduction.9-12 However, there are fundamental impediments to the implementation of crystalline LLTO into an actual device. One key issue is that crystalline LLTO has a relatively low grain boundary ionic conductivity (<10 −5 S/cm), lowering the effective material ionic conductivity. 6 In addition, crystalline LLTO is unstable in contact with lithium metal because lithium will easily insert reducing Ti 4+ to Ti 3+ , thus increasing electronic conductivity. 13,14Fortunately, amorphous LLTO has not only been shown to overcome these barriers, the lower energy constraints of fabricating amorphous LLTO opens up numerous thin film synthesis techniques. Amorphous LLTO thin films have been synthesized by pulsed laser deposition (PLD), RF magnetron sputtering, E-beam evaporation, atomic layer deposition, chemical solution deposition and sol-gel synthesis. [15][16][17][18][19][20][21][22][23][24] Furusawa et al. demonstrated amorphous LL...

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Lanthanum titanate and lithium lanthanum titanate thin films grown by atomic layer deposition

Cited by 95 publications

References 15 publications

Atomic Layer Deposition of LiCoO₂Thin-Film Electrodes for All-Solid-State Li-Ion Micro-Batteries

Atomic Layer Deposition of LiCoO₂Thin-Film Electrodes for All-Solid-State Li-Ion Micro-Batteries

Remote Plasma Atomic Layer Deposition of Thin Films of Electrochemically Active LiCoO₂

Amorphous Lithium Lanthanum Titanate for Solid-State Microbatteries

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Lanthanum titanate and lithium lanthanum titanate thin films grown by atomic layer deposition

Cited by 95 publications

References 15 publications

Atomic Layer Deposition of LiCoO2Thin-Film Electrodes for All-Solid-State Li-Ion Micro-Batteries

Atomic Layer Deposition of LiCoO2Thin-Film Electrodes for All-Solid-State Li-Ion Micro-Batteries

Remote Plasma Atomic Layer Deposition of Thin Films of Electrochemically Active LiCoO2

Amorphous Lithium Lanthanum Titanate for Solid-State Microbatteries

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Atomic Layer Deposition of LiCoO₂Thin-Film Electrodes for All-Solid-State Li-Ion Micro-Batteries

Atomic Layer Deposition of LiCoO₂Thin-Film Electrodes for All-Solid-State Li-Ion Micro-Batteries

Remote Plasma Atomic Layer Deposition of Thin Films of Electrochemically Active LiCoO₂