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

Eric S. Muckley; Christopher B. Jacobs; Keith Vidal; Nickolay V. Lavrik; Bobby G. Sumpter; Ilia N. Ivanov

doi:10.1038/s41598-017-10401-2

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

Eric S. Muckley, Christopher B. Jacobs, Keith Vidal, Nickolay V. Lavrik, Bobby G. Sumpter, Ilia N. Ivanov

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17 Scopus citations

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. 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.

Original language	English
Article number	9921
Journal	Scientific Reports
Volume	7
Issue number	1
DOIs	https://doi.org/10.1038/s41598-017-10401-2
State	Published - Dec 1 2017

Funding

This research was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. Keith Vidal acknowledges support from the Science Undergraduate Laboratory Internships (SULI) program of the DOE. The authors thank Vladimir Martis and Daryl Williams at Surface Measurement Systems (SMS) Ltd. for their support in development of new testing capability.

Funders	Funder number
U.S. Department of Energy

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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. 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.",

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

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