Ambient-processable high capacitance hafnia-organic self-assembled nanodielectrics

Ken Everaerts, Jonathan D. Emery, Deep Jariwala, Hunter J. Karmel, Vinod K. Sangwan, Pradyumna L. Prabhumirashi, Michael L. Geier, Julian J. McMorrow, Michael J. Bedzyk, Antonio Facchetti, Mark C Hersam, Tobin J Marks

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

Ambient and solution-processable, low-leakage, high capacitance gate dielectrics are of great interest for advances in low-cost, flexible, thin-film transistor circuitry. Here we report a new hafnium oxide-organic self-assembled nanodielectric (Hf-SAND) material consisting of regular, alternating π-electron layers of 4-[[4-[bis(2-hydroxyethyl)amino]phenyl]diazenyl]-1-[4- (diethoxyphosphoryl) benzyl]pyridinium bromide) (PAE) and HfO2 nanolayers. These Hf-SAND multilayers are grown from solution in ambient with processing temperatures ≤150 C and are characterized by AFM, XPS, X-ray reflectivity (2.3 nm repeat spacing), X-ray fluorescence, cross-sectional TEM, and capacitance measurements. The latter yield the largest capacitance to date (1.1 μF/cm2) for a solid-state solution-processed hybrid inorganic-organic gate dielectric, with effective oxide thickness values as low as 3.1 nm and have gate leakage -7 A/cm2 at ±2 MV/cm using photolithographically patterned contacts (0.04 mm 2). The sizable Hf-SAND capacitances are attributed to relatively large PAE coverages on the HfO2 layers, confirmed by X-ray reflectivity and X-ray fluorescence. Random network semiconductor-enriched single-walled carbon nanotube transistors were used to test Hf-SAND utility in electronics and afforded record on-state transconductances (5.5 mS) at large on:off current ratios (ION:IOFF) of ∼105 with steep 150 mV/dec subthreshold swings and intrinsic field-effect mobilities up to 137 cm2/(V s). Large-area devices (>0.2 mm2) on Hf-SAND (6.5 nm thick) achieve mA on currents at ultralow gate voltages (-6 A/cm 2 at ±2 V) and enhances Hf-SAND multilayer capacitance densities to nearly 1 μF/cm2, demonstrating excellent compatibility with device postprocessing methodologies. These results represent a significant advance in hybrid organic-inorganic dielectric materials and suggest synthetic routes to even higher capacitance materials useful for unconventional electronics.

Original languageEnglish
Pages (from-to)8926-8939
Number of pages14
JournalJournal of the American Chemical Society
Volume135
Issue number24
DOIs
Publication statusPublished - Jun 19 2013

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Hafnia
Hafnium oxides
Capacitance
X-Rays
X rays
Gate dielectrics
Multilayers
Electronic equipment
Fluorescence
Equipment and Supplies
Semiconductors
Carbon Nanotubes
Capacitance measurement
Leakage (fluid)
Transconductance
Single-walled carbon nanotubes (SWCN)
Thin film transistors
Bromides
Oxides
hafnium oxide

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Everaerts, K., Emery, J. D., Jariwala, D., Karmel, H. J., Sangwan, V. K., Prabhumirashi, P. L., ... Marks, T. J. (2013). Ambient-processable high capacitance hafnia-organic self-assembled nanodielectrics. Journal of the American Chemical Society, 135(24), 8926-8939. https://doi.org/10.1021/ja4019429

Ambient-processable high capacitance hafnia-organic self-assembled nanodielectrics. / Everaerts, Ken; Emery, Jonathan D.; Jariwala, Deep; Karmel, Hunter J.; Sangwan, Vinod K.; Prabhumirashi, Pradyumna L.; Geier, Michael L.; McMorrow, Julian J.; Bedzyk, Michael J.; Facchetti, Antonio; Hersam, Mark C; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 135, No. 24, 19.06.2013, p. 8926-8939.

Research output: Contribution to journalArticle

Everaerts, K, Emery, JD, Jariwala, D, Karmel, HJ, Sangwan, VK, Prabhumirashi, PL, Geier, ML, McMorrow, JJ, Bedzyk, MJ, Facchetti, A, Hersam, MC & Marks, TJ 2013, 'Ambient-processable high capacitance hafnia-organic self-assembled nanodielectrics', Journal of the American Chemical Society, vol. 135, no. 24, pp. 8926-8939. https://doi.org/10.1021/ja4019429
Everaerts K, Emery JD, Jariwala D, Karmel HJ, Sangwan VK, Prabhumirashi PL et al. Ambient-processable high capacitance hafnia-organic self-assembled nanodielectrics. Journal of the American Chemical Society. 2013 Jun 19;135(24):8926-8939. https://doi.org/10.1021/ja4019429
Everaerts, Ken ; Emery, Jonathan D. ; Jariwala, Deep ; Karmel, Hunter J. ; Sangwan, Vinod K. ; Prabhumirashi, Pradyumna L. ; Geier, Michael L. ; McMorrow, Julian J. ; Bedzyk, Michael J. ; Facchetti, Antonio ; Hersam, Mark C ; Marks, Tobin J. / Ambient-processable high capacitance hafnia-organic self-assembled nanodielectrics. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 24. pp. 8926-8939.
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