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Title: Lithium phosphorus oxynitride solid-state thin-film electrolyte deposited and modified by bias sputtering and low temperature annealing

Abstract

Amorphous lithium phosphorus oxynitride (LiPON) solid-state thin-film electrolyte has been deposited and characterized. The thin films were prepared by rf magnetron sputtering under various substrate biases. By fabricating under different substrate biases and applying low temperature annealing (473 K), the properties of the LiPON thin-film electrolytes and the electrolyte/cathode interfaces were modified. The ionic conductivity as high as 9.4x10{sup -4} S m{sup -1} can be obtained by depositing at optimal bias. The performances of the consequently fabricated SnO{sub 2}/LiPON/LiMn{sub 2}O{sub 4} all-solid-state lithium ion thin-film batteries were improved using the bias sputtering technique, due to the enhanced the ionic conductivity and uniform interface.

Authors:
; ; ; ; ; ;  [1];  [2];  [2]
  1. Department of Materials Science and Engineering, Feng Chia University, 100 Wen Hua Road, Taichung, Taiwan (China)
  2. (China)
Publication Date:
OSTI Identifier:
22053724
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Vacuum Science and Technology. A, International Journal Devoted to Vacuum, Surfaces, and Films; Journal Volume: 28; Journal Issue: 4; Other Information: (c) 2010 American Vacuum Society; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ANNEALING; CATHODES; DEPOSITION; ELECTROLYTES; IONIC CONDUCTIVITY; LITHIUM COMPOUNDS; LITHIUM IONS; MAGNETRONS; PHOSPHORUS NITRIDES; SOLIDS; SPUTTERING; TEMPERATURE RANGE 0065-0273 K; THIN FILMS; TIN OXIDES

Citation Formats

Chiu, K.-F., Chen, C. C., Lin, K. M., Lo, C. C., Lin, H. C., Ho, W.-H., Jiang, C. S., Department of Materials Science and Engineering, National Taiwan University, Taipei, Taiwan, and Taiwan Textile Research Institute, Taipei County, Taiwan. Lithium phosphorus oxynitride solid-state thin-film electrolyte deposited and modified by bias sputtering and low temperature annealing. United States: N. p., 2010. Web. doi:10.1116/1.3435330.
Chiu, K.-F., Chen, C. C., Lin, K. M., Lo, C. C., Lin, H. C., Ho, W.-H., Jiang, C. S., Department of Materials Science and Engineering, National Taiwan University, Taipei, Taiwan, & Taiwan Textile Research Institute, Taipei County, Taiwan. Lithium phosphorus oxynitride solid-state thin-film electrolyte deposited and modified by bias sputtering and low temperature annealing. United States. doi:10.1116/1.3435330.
Chiu, K.-F., Chen, C. C., Lin, K. M., Lo, C. C., Lin, H. C., Ho, W.-H., Jiang, C. S., Department of Materials Science and Engineering, National Taiwan University, Taipei, Taiwan, and Taiwan Textile Research Institute, Taipei County, Taiwan. 2010. "Lithium phosphorus oxynitride solid-state thin-film electrolyte deposited and modified by bias sputtering and low temperature annealing". United States. doi:10.1116/1.3435330.
@article{osti_22053724,
title = {Lithium phosphorus oxynitride solid-state thin-film electrolyte deposited and modified by bias sputtering and low temperature annealing},
author = {Chiu, K.-F. and Chen, C. C. and Lin, K. M. and Lo, C. C. and Lin, H. C. and Ho, W.-H. and Jiang, C. S. and Department of Materials Science and Engineering, National Taiwan University, Taipei, Taiwan and Taiwan Textile Research Institute, Taipei County, Taiwan},
abstractNote = {Amorphous lithium phosphorus oxynitride (LiPON) solid-state thin-film electrolyte has been deposited and characterized. The thin films were prepared by rf magnetron sputtering under various substrate biases. By fabricating under different substrate biases and applying low temperature annealing (473 K), the properties of the LiPON thin-film electrolytes and the electrolyte/cathode interfaces were modified. The ionic conductivity as high as 9.4x10{sup -4} S m{sup -1} can be obtained by depositing at optimal bias. The performances of the consequently fabricated SnO{sub 2}/LiPON/LiMn{sub 2}O{sub 4} all-solid-state lithium ion thin-film batteries were improved using the bias sputtering technique, due to the enhanced the ionic conductivity and uniform interface.},
doi = {10.1116/1.3435330},
journal = {Journal of Vacuum Science and Technology. A, International Journal Devoted to Vacuum, Surfaces, and Films},
number = 4,
volume = 28,
place = {United States},
year = 2010,
month = 7
}
  • The electrochemical and optical properties of lithium phosphorus oxynitride (Lipon) thin films have been studied with an emphasis on the stability window vs. lithium metal and the behavior of the Li/Lipon interface. Impedance measurements made between {minus}26 and 140 C show that Lipon exhibits a single, Li{sup +}-ion conducting phase with an average conductivity of 2.3 ({+-}0.7) {times} 10{sup {minus}6} S/cm at 25 C and an average activation energy of E{sub a} = 0.55 {+-} 0.02 eV. No detectable reaction or degradation was evident at the Li/Lipon interface, and linear sweep voltammetry measurements on three-electrode cells indicated that Lipon ismore » stable from 0 to about 5.5 V with respect to a Li{sup +}/Li reference. The complex refractive index of Lipon was measured by spectroscopic ellipsometry. Optical bandgaps of 3.45 and 3.75 eV were obtained from the ellipsometry data and from optical absorption measurements, respectively.« less
  • The crystallization properties of amorphous silicon (a-Si) thin film deposited by rf magnetron sputter deposition with substrate bias have been thoroughly characterized. The crystallization kinetics for films deposited with substrate bias is enhanced relative to unbiased a-Si by films. The enhanced crystallization for substrate biased a-Si films are attributed to ion enhanced nucleation of crystallites during sputter deposition which subsequently grow during the postdeposition anneal. Conversely films sputter deposited without substrate bias have more intrinsic defects and residual oxygen which enhance nucleation and retard growth, respectively, and lead to a large number of small crystallites.
  • The addition of He to N{sub 2} increases significantly the deposition rate of lithium phosphorus oxynitride thin films by radio frequency magnetron sputtering of Li{sub 3}PO{sub 4} targets. From the correlation with the optical emission intensity, the enhanced rate is attributed to an increase in the N{sup +}{sub 2} ion concentration in the plasma due to Penning ionization. The ionic conductivity of the films deposited at higher rates in He+20{percent} N{sub 2} compares favorably with that of films deposited at lower rates in pure N{sub 2}. {copyright} {ital 1996 American Vacuum Society}
  • Abstract The thin film electrolyte known as Lipon has proven successful for planar thin film battery applications. Here the sputter deposition of the amorphous lithium phosphorous oxynitride electrolyte onto more complex 3D structures is examined. The 3D structures include off-axis alignment of planar substrates and also 10-100 m arrays of pores, columns and grooves. For magnetron sputtering in N2 gas at 2.6 Pa, the Lipon film deposition is not restricted by the line-of-sight to the target, but forms conformal and dense films over the 3D and off-axis substrates. The deposition rate decreases for areas and grooves that are less accessiblemore » for the sputtered flux. The composition varies, but remains within the range that gives sufficient Li+ ionic conductivity, 2 1 S/cm« less
  • The Li[Li{sub 0.2}Mn{sub 0.56}Ni{sub 0.13}Co{sub 0.13}]O{sub 2} thin films were prepared by radio frequency magnetron sputtering on Pt/Ti/SiO{sub 2}/Si substrate with target contained a 5% excess of lithium precursor. Thin films were deposited under various deposition conditions such as working pressure, gas ratio of Ar and O{sub 2}, and the temperature of in-situ annealing treatment. The thin films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The electrochemical property was estimated by a WBC3000 cycler with Li|Li[Li{sub 0.2}Mn{sub 0.54}Ni{sub 0.13}Co{sub 0.13}]O{sub 2} half-type cell at 1C charge/discharge rate. The (0 0 3) andmore » (1 0 4) diffraction peaks which represent layered {alpha}-NaFeO{sub 2} type structure (space group R-3m) were observed. Optimal magnetron sputtering conditions were detected. The 500 Degree-Sign C annealed thin film after deposited at 10 m Torr in Ar:O{sub 2}=3:1 shows a high discharge capacity of around 62 {mu}Ah/cm{sup 2} {mu}m with a high cyclic retention. - Graphical abstract: The Li[Li{sub 0.2}Mn{sub 0.56}Ni{sub 0.13}Co{sub 0.13}]O{sub 2} films is suitable for Lithium thin film battery. The film exhibits great discharge capacity (62 {mu}Ah/cm{sup 2} {mu}m) up to 200 cycles. Highlights: Black-Right-Pointing-Pointer High capacity thin films were deposited by RF magnetron sputtering. Black-Right-Pointing-Pointer Sputtering conditions were optimized by structural and electrochemical analysis. Black-Right-Pointing-Pointer Li[Li{sub 0.2}Mn{sub 0.56}Ni{sub 0.13}Co{sub 0.13}]O{sub 2} thin film shows a high capacity, 62 {mu}Ah/cm{sup 2} {mu}m. Black-Right-Pointing-Pointer The thin film shows an excellent cycling stability up to 200 cycles.« less