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

Abstract

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.

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:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1394448
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Sensors; Sensors and biosensors

Citation Formats

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., 2017. 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. https://doi.org/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. https://doi.org/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},
url = {https://www.osti.gov/biblio/1394448}, journal = {Scientific Reports},
issn = {2045-2322},
number = 1,
volume = 7,
place = {United States},
year = {Wed Aug 30 00:00:00 EDT 2017},
month = {Wed Aug 30 00:00:00 EDT 2017}
}

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Cited by: 13 works
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Works referenced in this record:

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journal, October 2001


Morphology-defined interaction of copper phthalocyanine with O 2 /H 2 O
journal, October 2016


Insights into the modeling of adsorption isotherm systems
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Investigation of gas-sensing properties of copper phthalocyanine films
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Interface between an Au(111) Surface and an Ionic Liquid: The Influence of Water on the Double-Layer Capacitance
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A Mechanistic Study of O[sub 2] Reduction on Water Soluble Phthalocyanines Adsorbed on Graphite Electrodes
journal, January 1980


Characterization of evaporated trivalent and tetravalent phthalocyanines thin films: different degree of organization
journal, June 2005


Integration of an M-phthalocyanine layer into solution-processed organic photovoltaic cells for improved spectral coverage
journal, July 2011


Mechanism and equivalent circuits in electrochemical impedance spectroscopy
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Solubility Properties of Unsubstituted Metal Phthalocyanines in Different Types of Solvents
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New Insights on Electro-Optical Response of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) Film to Humidity
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Works referencing / citing this record:

Temperature and frequency effect on the electrical properties of bulk nickel phthalocyanine octacarboxylic acid (Ni-Pc(COOH)8)
journal, December 2018


Study of Structural, Optical and AC Electrical Properties of Chloroindium Phthalocyanine
journal, August 2019


Multi-modal, ultrasensitive, wide-range humidity sensing with Ti 3 C 2 film
journal, January 2018