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Title: Multi-mode humidity sensing with water-soluble copper phthalocyanine for increased sensitivity and dynamic range

Aqueous solubility of copper phthalocyanine-3,4',4',4"'-tetrasulfonic acid tetrasodium salt (CuPcTs) enables fabrication of flexible electronic devices by low cost inkjet printing. We (1) investigate water adsorption kinetics on CuPcTs for better understanding the effects of relative humidity (RH) on hydrophilic phthalocyanines, and (2) assess CuPcTs as a humidity-sensing material. Reaction models show that H 2O undergoes 2-site adsorption which can be represented by a pair of sequentially-occurring pseudo-first order reactions. Using high frequency (300–700 THz) and low frequency (1–8 MHz) dielectric spectroscopy combined with gravimetric measurements and principal component analysis, we observe that significant opto-electrical changes in CuPcTs occur at RH ≈ 60%. The results suggest that rapid H 2O adsorption takes place at hydrophilic sulfonyl/salt groups on domain surfaces at low RH, while slow adsorption and diffusion of H 2O into CuPcTs crystallites leads to a mixed CuPcTs-H 2O phase at RH > 60%, resulting in high frequency dielectric screening of the film by water and dissociation of Na+ from CuPc(SO 3-) 4 ions. Lastly, the CuPcTs-H 2O interaction can be tracked using a combination of gravimetric, optical, and electrical sensing modes, enabling accurate ( ± 2.5%) sensing in the ~0–95% RH range with a detection limit of less thanmore » 0.1% RH.« less
Authors:
ORCiD logo [1] ; ORCiD logo [2] ;  [2] ; ORCiD logo [2] ; ORCiD logo [3] ; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Univ. of Tennessee, Knoxville, TN (United States). Bredesen Center
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Computer Science and Mathematics Division
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Sensors; Sensors and biosensors
OSTI Identifier:
1394448

Muckley, Eric S., Jacobs, Christopher B., Vidal, Keith, Lavrik, Nickolay V., Sumpter, Bobby G., and Ivanov, Ilia N.. Multi-mode humidity sensing with water-soluble copper phthalocyanine for increased sensitivity and dynamic range. United States: N. p., Web. doi:10.1038/s41598-017-10401-2.
Muckley, Eric S., Jacobs, Christopher B., Vidal, Keith, Lavrik, Nickolay V., Sumpter, Bobby G., & Ivanov, Ilia N.. Multi-mode humidity sensing with water-soluble copper phthalocyanine for increased sensitivity and dynamic range. United States. doi:10.1038/s41598-017-10401-2.
Muckley, Eric S., Jacobs, Christopher B., Vidal, Keith, Lavrik, Nickolay V., Sumpter, Bobby G., and Ivanov, Ilia N.. 2017. "Multi-mode humidity sensing with water-soluble copper phthalocyanine for increased sensitivity and dynamic range". United States. doi:10.1038/s41598-017-10401-2. https://www.osti.gov/servlets/purl/1394448.
@article{osti_1394448,
title = {Multi-mode humidity sensing with water-soluble copper phthalocyanine for increased sensitivity and dynamic range},
author = {Muckley, Eric S. and Jacobs, Christopher B. and Vidal, Keith and Lavrik, Nickolay V. and Sumpter, Bobby G. and Ivanov, Ilia N.},
abstractNote = {Aqueous solubility of copper phthalocyanine-3,4',4',4"'-tetrasulfonic acid tetrasodium salt (CuPcTs) enables fabrication of flexible electronic devices by low cost inkjet printing. We (1) investigate water adsorption kinetics on CuPcTs for better understanding the effects of relative humidity (RH) on hydrophilic phthalocyanines, and (2) assess CuPcTs as a humidity-sensing material. Reaction models show that H2O undergoes 2-site adsorption which can be represented by a pair of sequentially-occurring pseudo-first order reactions. Using high frequency (300–700 THz) and low frequency (1–8 MHz) dielectric spectroscopy combined with gravimetric measurements and principal component analysis, we observe that significant opto-electrical changes in CuPcTs occur at RH ≈ 60%. The results suggest that rapid H2O adsorption takes place at hydrophilic sulfonyl/salt groups on domain surfaces at low RH, while slow adsorption and diffusion of H2O into CuPcTs crystallites leads to a mixed CuPcTs-H2O phase at RH > 60%, resulting in high frequency dielectric screening of the film by water and dissociation of Na+ from CuPc(SO3-)4 ions. Lastly, the CuPcTs-H2O interaction can be tracked using a combination of gravimetric, optical, and electrical sensing modes, enabling accurate ( ± 2.5%) sensing in the ~0–95% RH range with a detection limit of less than 0.1% RH.},
doi = {10.1038/s41598-017-10401-2},
journal = {Scientific Reports},
number = 1,
volume = 7,
place = {United States},
year = {2017},
month = {8}
}

Works referenced in this record:

On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells
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