Atomic Layer Deposition of the Solid Electrolyte LiPON

Kozen, Alexander C.; Pearse, Alexander J.; Lin, Chuan-Fu; Noked, Malachi; Rubloff, Gary W.

doi:10.1021/acs.chemmater.5b01654

Title: Atomic Layer Deposition of the Solid Electrolyte LiPON

Journal Article · Thu Jul 30 00:00:00 EDT 2015 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.5b01654· OSTI ID:1206791

Kozen, Alexander C. ^[1]; Pearse, Alexander J. ^[1]; Lin, Chuan-Fu ^[1]; Noked, Malachi ^[1]; Rubloff, Gary W. ^[1]

Department of Materials Science & Engineering and ‡Institute for Systems Research, University of Maryland, College Park, Maryland 20742, United States

We demonstrate an atomic layer deposition (ALD) process for the solid electrolyte lithium phosphorousoxynitride (LiPON) using lithium tert-butoxide (LiO^tBu), H₂O, trimethylphosphate (TMP), and plasma N₂ (^PN₂) as precursors. We use in-situ spectroscopic ellipsometry to determine growth rates for process optimization to design a rational, quaternary precursor ALD process where only certain substrate–precursor chemical reactions are favorable. We demonstrate via in-situ XPS tunable nitrogen incorporation into the films by variation of the ^PN₂ dose and find that ALD films over approximately 4.5% nitrogen are amorphous, whereas LiPON ALD films with less than 4.5% nitrogen are polycrystalline. Lastly, we characterize the ionic conductivity of the ALD films as a function of nitrogen content and demonstrate their functionality on a model battery electrode—a Si anode on a Cu current collector.

View Journal Article

Cite

Export

Save

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001160

OSTI ID:: 1206791

Alternate ID(s):: OSTI ID: 1385989

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Vol. 27 Journal Issue: 15; ISSN 0897-4756

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 179 works

Citation information provided by
Web of Science

References (34)

Atomic Layer Deposition and in Situ Characterization of Ultraclean Lithium Oxide and Lithium Hydroxide Kozen, Alexander C.; Pearse, Alexander J.; Lin, Chuan-Fu The Journal of Physical Chemistry C, Vol. 118, Issue 48 https://doi.org/10.1021/jp509298r	journal	November 2014
Investigation of the local structure of LiPON thin films to better understand the role of nitrogen on their performance Fleutot, B.; Pecquenard, B.; Martinez, H. Solid State Ionics, Vol. 186, Issue 1 https://doi.org/10.1016/j.ssi.2011.01.006	journal	March 2011
Chemical stability enhancement of lithium conducting solid electrolyte plates using sputtered LiPON thin films West, W. C.; Whitacre, J. F.; Lim, J. R. Journal of Power Sources, Vol. 126, Issue 1-2, p. 134-138 https://doi.org/10.1016/j.jpowsour.2003.08.030	journal	February 2004
Addition of a thin-film inorganic solid electrolyte (Lipon) as a protective film in lithium batteries with a liquid electrolyte Dudney, Nancy J. Journal of Power Sources, Vol. 89, Issue 2, p. 176-179 https://doi.org/10.1016/S0378-7753(00)00427-4	journal	August 2000
Examining the role of hydrogen in the electrical performance of in situ fabricated metal-insulator-metal trilayers using an atomic layer deposited Al ₂ O ₃ dielectric Kozen, Alexander C.; Schroeder, Marshall A.; Osborn, Kevin D. Applied Physics Letters, Vol. 102, Issue 17 https://doi.org/10.1063/1.4801979	journal	April 2013
Mechanistic Study of Lithium Aluminum Oxide Atomic Layer Deposition Comstock, David J.; Elam, Jeffrey W. The Journal of Physical Chemistry C, Vol. 117, Issue 4 https://doi.org/10.1021/jp308828p	journal	January 2013
Atomic subshell photoionization cross sections and asymmetry parameters: 1 ⩽ Z ⩽ 103 Yeh, J. J.; Lindau, I. Atomic Data and Nuclear Data Tables, Vol. 32, Issue 1 https://doi.org/10.1016/0092-640X(85)90016-6	journal	January 1985
Fabrication and characterization of amorphous lithium electrolyte thin films and rechargeable thin-film batteries Bates, J. B.; Dudney, N. J.; Gruzalski, G. R. Journal of Power Sources, Vol. 43, Issue 1-3, p. 103-110 https://doi.org/10.1016/0378-7753(93)80106-Y	journal	March 1993
The influence of the nitrogen-ion flux on structure and ionic conductivity of vapor deposited lithium phosphorus oxynitride films Kim, Yoon Gu; Wadley, H. N. G. Journal of Power Sources, Vol. 196, Issue 3 https://doi.org/10.1016/j.jpowsour.2010.08.115	journal	February 2011
Self-assembled Ni/TiO2 nanocomposite anodes synthesized via electroless plating and atomic layer deposition on biological scaffolds Gerasopoulos, Konstantinos; Chen, Xilin; Culver, James Chemical Communications, Vol. 46, Issue 39 https://doi.org/10.1039/c0cc01689f	journal	January 2010
Inner-orbital photoelectron spectroscopy of the alkali metal halides, perchlorates, phosphates, and pyrophosphates Morgan, Wayne E.; Van Wazer, John R.; Stec, Wojciech J. Journal of the American Chemical Society, Vol. 95, Issue 3 https://doi.org/10.1021/ja00784a018	journal	February 1973
MWCNT/V ₂ O ₅ Core/Shell Sponge for High Areal Capacity and Power Density Li-Ion Cathodes Chen, Xinyi; Zhu, Hongli; Chen, Yu-Chen ACS Nano, Vol. 6, Issue 9 https://doi.org/10.1021/nn302417x	journal	August 2012
Synthesis of ion conducting Li _x Al _y Si _z O thin films by atomic layer deposition Perng, Ya-Chuan; Cho, Jea; Sun, Steven Y. J. Mater. Chem. A, Vol. 2, Issue 25 https://doi.org/10.1039/C3TA14928E	journal	January 2014
An interpretation for the increase of ionic conductivity by nitrogen incorporation in LiPON oxynitride glasses Mascaraque, Nerea; Fierro, José Luis G.; Durán, Alicia Solid State Ionics, Vol. 233 https://doi.org/10.1016/j.ssi.2012.12.017	journal	February 2013
Three-Dimensional Battery Architectures Long, Jeffrey W.; Dunn, Bruce; Rolison, Debra R. Chemical Reviews, Vol. 104, Issue 10, p. 4463-4492 https://doi.org/10.1021/cr020740l	journal	October 2004
Atomic layer deposition for nanostructured Li-ion batteries Knoops, H. C. M.; Donders, M. E.; van de Sanden, M. C. M. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 30, Issue 1 https://doi.org/10.1116/1.3660699	journal	January 2012
Chemical Vapor Deposition of Lithium Phosphate Thin-Films for 3D All-Solid-State Li-Ion Batteries Xie, Jie; Oudenhoven, Jos F. M.; Harks, Peter-Paul R. M. L. Journal of The Electrochemical Society, Vol. 162, Issue 3 https://doi.org/10.1149/2.0091503jes	journal	December 2014
Artificial Solid Electrolyte Interphase To Address the Electrochemical Degradation of Silicon Electrodes Li, Juchuan; Dudney, Nancy J.; Nanda, Jagjit ACS Applied Materials & Interfaces, Vol. 6, Issue 13 https://doi.org/10.1021/am5009419	journal	June 2014
Inorganic solid Li ion conductors: An overview Knauth, Philippe Solid State Ionics, Vol. 180, Issue 14-16, p. 911-916 https://doi.org/10.1016/j.ssi.2009.03.022	journal	June 2009
Lithium Phosphate Thin Films Grown by Atomic Layer Deposition Hämäläinen, Jani; Holopainen, Jani; Munnik, Frans Journal of The Electrochemical Society, Vol. 159, Issue 3 https://doi.org/10.1149/2.052203jes	journal	January 2012
Characteristics of lithium phosphorous oxynitride thin films deposited by metal-organic chemical vapor deposition technique Kim, Hong Tak; Mun, Taehong; Park, Chinho Journal of Power Sources, Vol. 244 https://doi.org/10.1016/j.jpowsour.2012.12.109	journal	December 2013
25th Anniversary Article: Understanding the Lithiation of Silicon and Other Alloying Anodes for Lithium-Ion Batteries McDowell, Matthew T.; Lee, Seok Woo; Nix, William D. Advanced Materials, Vol. 25, Issue 36 https://doi.org/10.1002/adma.201301795	journal	August 2013
Beam-assisted large elongation of in situ formed Li2O nanowires Zheng, He; Liu, Yang; Mao, Scott X. Scientific Reports, Vol. 2, Issue 1 https://doi.org/10.1038/srep00542	journal	July 2012
A Stable Thin-Film Lithium Electrolyte: Lithium Phosphorus Oxynitride Yu, Xiaohua; Bates, J. B.; Jellison, G. E. Journal of The Electrochemical Society, Vol. 144, Issue 2, p. 524-532 https://doi.org/10.1149/1.1837443	journal	January 1997
Fabrication of 3D Core–Shell Multiwalled Carbon Nanotube@RuO ₂ Lithium-Ion Battery Electrodes through a RuO ₂ Atomic Layer Deposition Process Gregorczyk, Keith E.; Kozen, Alexander C.; Chen, Xinyi ACS Nano, Vol. 9, Issue 1 https://doi.org/10.1021/nn505644q	journal	December 2014
Electrolyte Stability Determines Scaling Limits for Solid-State 3D Li Ion Batteries Ruzmetov, Dmitry; Oleshko, Vladimir P.; Haney, Paul M. Nano Letters, Vol. 12, Issue 1 https://doi.org/10.1021/nl204047z	journal	December 2011
Ultra-thin LiPON films – Fundamental properties and application in solid state thin film model batteries Nowak, Susann; Berkemeier, Frank; Schmitz, Guido Journal of Power Sources, Vol. 275 https://doi.org/10.1016/j.jpowsour.2014.10.202	journal	February 2015
Lanthanum titanate and lithium lanthanum titanate thin films grown by atomic layer deposition Aaltonen, Titta; Alnes, Mari; Nilsen, Ola Journal of Materials Chemistry, Vol. 20, Issue 14 https://doi.org/10.1039/b923490j	journal	January 2010
Nitrogen and fluorine anionic substitution in lithium phosphate glasses Mascaraque, Nerea; Tricot, Gregory; Revel, Bertrand Solid State Ionics, Vol. 254 https://doi.org/10.1016/j.ssi.2013.10.061	journal	January 2014
Synthesis of thin-film electrodes based on LiPON and LiPON-LLTO-LiPON Belous, A. G.; V’yunov, O. I.; Kovalenko, L. L. Russian Journal of Electrochemistry, Vol. 50, Issue 6 https://doi.org/10.1134/S1023193514060020	journal	June 2014
From nanoscience to solutions in electrochemical energy storage Rubloff, Gary W.; Kozen, Alexander C.; Bok Lee, Sang Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 31, Issue 5 https://doi.org/10.1116/1.4816262	journal	September 2013
Atomic Layer Deposition of Li ₂ O–Al ₂ O ₃ Thin Films Aaltonen, Titta; Nilsen, Ola; Magrasó, Anna Chemistry of Materials, Vol. 23, Issue 21 https://doi.org/10.1021/cm200899k	journal	November 2011
An Artificial Solid Electrolyte Interphase Enables the Use of a LiNi _0.5 Mn _1.5 O ₄ 5 V Cathode with Conventional Electrolytes Li, Juchuan; Baggetto, Loïc; Martha, Surendra K. Advanced Energy Materials, Vol. 3, Issue 10 https://doi.org/10.1002/aenm201300378	journal	August 2013
Effects of deposition condition on the ionic conductivity and structure of amorphous lithium phosphorus oxynitrate thin film Roh, Nam-Seok; Lee, Sang-Dong; Kwon, Hyuk-Sang Scripta Materialia, Vol. 42, Issue 1 https://doi.org/10.1016/S1359-6462(99)00307-3	journal	December 1999

Similar Records

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

Journal Article · Mon Apr 10 00:00:00 EDT 2017 · Chemistry of Materials · OSTI ID:1206791

Pearse, Alexander J.; Schmitt, Thomas E.; Fuller, Elliot J.; +7 more

Nanoscale Li, Na, and K ion-conducting polyphosphazenes by atomic layer deposition

Journal Article · Fri Jan 07 00:00:00 EST 2022 · Dalton Transactions · OSTI ID:1206791

Nuwayhid, R. Blake; Fontecha, Daniela; Kozen, Alexander C.; +4 more

Organic-Inorganic Reaction of Li-Containing thin film: Structure of Lithium Propane Dioxide via MLD

Journal Article · Thu Feb 27 00:00:00 EST 2020 · Journal of Physical Chemistry. C · OSTI ID:1206791

Wang, Haotian; Gregorczyk, Keith E.; Lee, Sang Bok; +2 more

Related Subjects

36 MATERIALS SCIENCE
bio-inspired
energy storage (including batteries and capacitors)
defects
charge transport
synthesis (novel materials)
synthesis (self-assembly)
synthesis (scalable processing)

Title: Atomic Layer Deposition of the Solid Electrolyte LiPON

Citation Formats

References (34)

Similar Records

Related Subjects