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Surface reactions between LiHMDS, TMA and TMP leading to deposition of amorphous lithium phosphate

(2022) JOURNAL OF MATERIALS CHEMISTRY A. 10(7). p.3543-3551
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Abstract
This work reports on the atomic layer deposition process combining lithium hexamethyl disilazide (LiHMDS) and trimethylphosphate (TMP), and studies the impact of adding a trimethylaluminum (TMA) pulse to this process. When only minute traces of aluminum are incorporated, the deposited layer becomes amorphous instead of crystalline. The TMA-TMP interaction plays a key role in this process and is revealed by time-resolved full-range quadrupole mass spectrometry. It is hypothesized that the interaction of unreacted -OCH3 groups with TMA and the formation of Li4P2O7 units lead to higher growth and structural changes as compared to the phosphate process without TMA. The conformal deposition of lithium-containing phosphates may find applications in modification of electrode-electrolyte interfaces in lithium-ion batteries. This is demonstrated in a half-cell. The amorphous mix of Li4P2O7 and Li3PO4 units in the films grown with TMA benefits the conductive properties of the material: an ionic conductivity of 1.47 +/- 0.09 x 10(-7) S cm(-1) at 30 degrees C is achieved, with an activation energy 0.58 +/- 0.02 eV.
Keywords
General Materials Science, Renewable Energy, Sustainability and the Environment, General Chemistry, ATOMIC LAYER DEPOSITION, SOLID-STATE ELECTROLYTES, NONNEGATIVE MATRIX, THIN-FILMS, CATHODE, CONDUCTIVITYA, LGORITHMS, PRINCIPLES, BATTERIES, DESIGN

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MLA
Werbrouck, Andreas, et al. “Surface Reactions between LiHMDS, TMA and TMP Leading to Deposition of Amorphous Lithium Phosphate.” JOURNAL OF MATERIALS CHEMISTRY A, vol. 10, no. 7, 2022, pp. 3543–51, doi:10.1039/d1ta09500e.
APA
Werbrouck, A., Mattelaer, F., Dhara, A., Nisula, M., Minjauw, M., Munnik, F., … Detavernier, C. (2022). Surface reactions between LiHMDS, TMA and TMP leading to deposition of amorphous lithium phosphate. JOURNAL OF MATERIALS CHEMISTRY A, 10(7), 3543–3551. https://doi.org/10.1039/d1ta09500e
Chicago author-date
Werbrouck, Andreas, Felix Mattelaer, Arpan Dhara, Mikko Nisula, Matthias Minjauw, Frans Munnik, Jolien Dendooven, and Christophe Detavernier. 2022. “Surface Reactions between LiHMDS, TMA and TMP Leading to Deposition of Amorphous Lithium Phosphate.” JOURNAL OF MATERIALS CHEMISTRY A 10 (7): 3543–51. https://doi.org/10.1039/d1ta09500e.
Chicago author-date (all authors)
Werbrouck, Andreas, Felix Mattelaer, Arpan Dhara, Mikko Nisula, Matthias Minjauw, Frans Munnik, Jolien Dendooven, and Christophe Detavernier. 2022. “Surface Reactions between LiHMDS, TMA and TMP Leading to Deposition of Amorphous Lithium Phosphate.” JOURNAL OF MATERIALS CHEMISTRY A 10 (7): 3543–3551. doi:10.1039/d1ta09500e.
Vancouver
1.
Werbrouck A, Mattelaer F, Dhara A, Nisula M, Minjauw M, Munnik F, et al. Surface reactions between LiHMDS, TMA and TMP leading to deposition of amorphous lithium phosphate. JOURNAL OF MATERIALS CHEMISTRY A. 2022;10(7):3543–51.
IEEE
[1]
A. Werbrouck et al., “Surface reactions between LiHMDS, TMA and TMP leading to deposition of amorphous lithium phosphate,” JOURNAL OF MATERIALS CHEMISTRY A, vol. 10, no. 7, pp. 3543–3551, 2022.
@article{8738998,
  abstract     = {{This work reports on the atomic layer deposition process combining lithium hexamethyl disilazide (LiHMDS) and trimethylphosphate (TMP), and studies the impact of adding a trimethylaluminum (TMA) pulse to this process. When only minute traces of aluminum are incorporated, the deposited layer becomes amorphous instead of crystalline. The TMA-TMP interaction plays a key role in this process and is revealed by time-resolved full-range quadrupole mass spectrometry. It is hypothesized that the interaction of unreacted -OCH3 groups with TMA and the formation of Li4P2O7 units lead to higher growth and structural changes as compared to the phosphate process without TMA. The conformal deposition of lithium-containing phosphates may find applications in modification of electrode-electrolyte interfaces in lithium-ion batteries. This is demonstrated in a half-cell. The amorphous mix of Li4P2O7 and Li3PO4 units in the films grown with TMA benefits the conductive properties of the material: an ionic conductivity of 1.47 +/- 0.09 x 10(-7) S cm(-1) at 30 degrees C is achieved, with an activation energy 0.58 +/- 0.02 eV.}},
  author       = {{Werbrouck, Andreas and Mattelaer, Felix and Dhara, Arpan and Nisula, Mikko and Minjauw, Matthias and Munnik, Frans and Dendooven, Jolien and Detavernier, Christophe}},
  issn         = {{2050-7488}},
  journal      = {{JOURNAL OF MATERIALS CHEMISTRY A}},
  keywords     = {{General Materials Science,Renewable Energy,Sustainability and the Environment,General Chemistry,ATOMIC LAYER DEPOSITION,SOLID-STATE ELECTROLYTES,NONNEGATIVE MATRIX,THIN-FILMS,CATHODE,CONDUCTIVITYA,LGORITHMS,PRINCIPLES,BATTERIES,DESIGN}},
  language     = {{eng}},
  number       = {{7}},
  pages        = {{3543--3551}},
  title        = {{Surface reactions between LiHMDS, TMA and TMP leading to deposition of amorphous lithium phosphate}},
  url          = {{http://dx.doi.org/10.1039/d1ta09500e}},
  volume       = {{10}},
  year         = {{2022}},
}

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