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:
-
- 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
- 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). 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}
}
Web of Science
Works referenced in this record:
Photoinactivation of bacteria. Use of a cationic water-soluble zinc phthalocyanine to photoinactivate both Gram-negative and Gram-positive bacteria
journal, February 1996
- Minnock, Andrew; Vernon, David I.; Schofield, Jack
- Journal of Photochemistry and Photobiology B: Biology, Vol. 32, Issue 3
Effects of humidity on the electrical properties of thermal inkjet-printed films of copper tetrasulfonated phthalocyanine (CuTsPc) onto paper substrates
journal, December 2014
- Gomes, Tiago Carneiro; de Oliveira, Rafael Furlan; Lopes, Élder Mantovani
- Journal of Materials Science, Vol. 50, Issue 5
Optical absorption studies of copper phthalocyanine thin films
journal, June 2007
- Farag, A. A. M.
- Optics & Laser Technology, Vol. 39, Issue 4
Fluorescence Decay Study of Anisotropic Rotations of Substituted Pyrenes Physisorbed and Chemically Attached to a Fumed Silica Surface
journal, October 2001
- Ivanov, Ilia N.; Dabestani, Reza; Buchanan, A. C.
- The Journal of Physical Chemistry B, Vol. 105, Issue 42
Photochemistry of tetrasulphonated magnesium phthalocyanine in water and DMSO solutions by Raman, femtosecond transient absorption, and stationary absorption spectroscopies
journal, June 2008
- Brożek–Płuska, B.; Czajkowski, W.; Kurczewska, M.
- Journal of Molecular Liquids, Vol. 141, Issue 3
Photochemistry of tetrasulphonated magnesium phthalocyanine in water and DMSO solutions by Raman, femtosecond transient absorption, and stationary absorption spectroscopies
journal, June 2008
- Brożek–Płuska, B.; Czajkowski, W.; Kurczewska, M.
- Journal of Molecular Liquids, Vol. 141, Issue 3
Effects of humidity on the electrical properties of thermal inkjet-printed films of copper tetrasulfonated phthalocyanine (CuTsPc) onto paper substrates
journal, December 2014
- Gomes, Tiago Carneiro; de Oliveira, Rafael Furlan; Lopes, Élder Mantovani
- Journal of Materials Science, Vol. 50, Issue 5
Integration of an M-phthalocyanine layer into solution-processed organic photovoltaic cells for improved spectral coverage
journal, July 2011
- Bamsey, Nathan M.; Yuen, Avery P.; Hor, Ah-Mee
- Solar Energy Materials and Solar Cells, Vol. 95, Issue 7
Photoinactivation of bacteria. Use of a cationic water-soluble zinc phthalocyanine to photoinactivate both Gram-negative and Gram-positive bacteria
journal, February 1996
- Minnock, Andrew; Vernon, David I.; Schofield, Jack
- Journal of Photochemistry and Photobiology B: Biology, Vol. 32, Issue 3
The synthesis and application of thermally stable dyes for ink-jet printed LCD color filters
journal, April 2009
- Kim, Young Do; Kim, Jae Pil; Kwon, Oh Sang
- Dyes and Pigments, Vol. 81, Issue 1
Humidity effect on ammonia sensing properties of substituted and unsubstituted cobalt phthalocyanines
journal, August 2012
- Sizun, Thibaut; Bouvet, Marcel; Suisse, Jean-Moïse
- Talanta, Vol. 97
Viologen Polymer-Coated Impedance Sensors for Midrange Humidity Levels and Other Volatile Organic Compounds
journal, January 1999
- Pfeifer, K. B.
- Journal of The Electrochemical Society, Vol. 146, Issue 2
A Mechanistic Study of O[sub 2] Reduction on Water Soluble Phthalocyanines Adsorbed on Graphite Electrodes
journal, January 1980
- Zagal, J.
- Journal of The Electrochemical Society, Vol. 127, Issue 7
Characterization of evaporated trivalent and tetravalent phthalocyanines thin films: different degree of organization
journal, June 2005
- Del Caño, T.; Parra, V.; Rodríguez-Méndez, M. L.
- Applied Surface Science, Vol. 246, Issue 4
High dielectric constant response of modified copper phthalocyanine
journal, November 2014
- Hamam, Khalil J.; Al-Amar, Mohammad M.; Mezei, Gellert
- Journal of Molecular Liquids, Vol. 199
Adsorption of Cu(II) and Pb(II) onto a grafted silica: isotherms and kinetic models
journal, July 2003
- Chiron, Nathalie; Guilet, Richard; Deydier, Eric
- Water Research, Vol. 37, Issue 13
Water Confined in Films of Sulphonated Phthalocyanines
journal, November 2011
- Jarota, Arkadiusz; Brozek-Pluska, Beata; Czajkowski, Wojciech
- The Journal of Physical Chemistry C, Vol. 115, Issue 50
Ellipsometry of thin films of copper phthalocyanine
journal, August 1975
- Barrett, M. A.; Borkowska, Z.; Humphreys, M. W.
- Thin Solid Films, Vol. 28, Issue 2
Solubility Properties of Unsubstituted Metal Phthalocyanines in Different Types of Solvents
journal, December 2011
- Ghani, Fatemeh; Kristen, Juliane; Riegler, Hans
- Journal of Chemical & Engineering Data, Vol. 57, Issue 2
On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells
journal, April 2001
- Kreuer, K. D.
- Journal of Membrane Science, Vol. 185, Issue 1, p. 29-39
New Insights on Electro-Optical Response of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) Film to Humidity
journal, April 2017
- Muckley, Eric S.; Jacobs, Christopher B.; Vidal, Keith
- ACS Applied Materials & Interfaces, Vol. 9, Issue 18
The synthesis and application of thermally stable dyes for ink-jet printed LCD color filters
journal, April 2009
- Kim, Young Do; Kim, Jae Pil; Kwon, Oh Sang
- Dyes and Pigments, Vol. 81, Issue 1
Spectra of porphyrins
journal, January 1961
- Gouterman, Martin
- Journal of Molecular Spectroscopy, Vol. 6
Ellipsometry of thin films of copper phthalocyanine
journal, August 1975
- Barrett, M. A.; Borkowska, Z.; Humphreys, M. W.
- Thin Solid Films, Vol. 28, Issue 2
Interface between an Au(111) Surface and an Ionic Liquid: The Influence of Water on the Double-Layer Capacitance
journal, October 2016
- Friedl, Jochen; Markovits, Iulius I. E.; Herpich, Max
- ChemElectroChem, Vol. 4, Issue 1
Fluorescence Decay Study of Anisotropic Rotations of Substituted Pyrenes Physisorbed and Chemically Attached to a Fumed Silica Surface
journal, October 2001
- Ivanov, Ilia N.; Dabestani, Reza; Buchanan, A. C.
- The Journal of Physical Chemistry B, Vol. 105, Issue 42
Enhanced photocurrent and stability of organic solar cells using solution-based TS-CuPc interfacial layer
journal, October 2016
- Raïssi, M.; Leroy-Lhez, S.; Ratier, B.
- Organic Electronics, Vol. 37
Morphology-defined interaction of copper phthalocyanine with O 2 /H 2 O
journal, October 2016
- Muckley, Eric S.; Miller, Nicholas; Jacobs, Christopher B.
- Journal of Photonics for Energy, Vol. 6, Issue 4
The kinetics of sorption of divalent metal ions onto sphagnum moss peat
journal, February 2000
- Ho, Y.
- Water Research, Vol. 34, Issue 3
Insights into the modeling of adsorption isotherm systems
journal, January 2010
- Foo, K. Y.; Hameed, B. H.
- Chemical Engineering Journal, Vol. 156, Issue 1
Layer-by-layer deposition films of copper phthalocyanine derivative; their photoelectrochemical properties and application to solution-processed thin-film organic solar cells
journal, January 2009
- Benten, Hiroaki; Kudo, Naomi; Ohkita, Hideo
- Thin Solid Films, Vol. 517, Issue 6
Layer-by-layer deposition films of copper phthalocyanine derivative; their photoelectrochemical properties and application to solution-processed thin-film organic solar cells
journal, January 2009
- Benten, Hiroaki; Kudo, Naomi; Ohkita, Hideo
- Thin Solid Films, Vol. 517, Issue 6
Investigation of gas-sensing properties of copper phthalocyanine films
journal, April 2009
- Basova, T.; Tsargorodskaya, A.; Nabok, A.
- Materials Science and Engineering: C, Vol. 29, Issue 3
Ammonium Removal from Aqueous Solutions by Clinoptilolite: Determination of Isotherm and Thermodynamic Parameters and Comparison of Kinetics by the Double Exponential Model and Conventional Kinetic Models
journal, March 2012
- Tosun, İsmail
- International Journal of Environmental Research and Public Health, Vol. 9, Issue 3
Interface between an Au(111) Surface and an Ionic Liquid: The Influence of Water on the Double-Layer Capacitance
journal, October 2016
- Friedl, Jochen; Markovits, Iulius I. E.; Herpich, Max
- ChemElectroChem, Vol. 4, Issue 1
Enhanced photocurrent and stability of organic solar cells using solution-based TS-CuPc interfacial layer
journal, October 2016
- Raïssi, M.; Leroy-Lhez, S.; Ratier, B.
- Organic Electronics, Vol. 37
Kinetics of Solute Adsorption at Solid/Solution Interfaces: A Theoretical Development of the Empirical Pseudo-First and Pseudo-Second Order Kinetic Rate Equations, Based on Applying the Statistical Rate Theory of Interfacial Transport
journal, August 2006
- Rudzinski, Wladyslaw; Plazinski, Wojciech
- The Journal of Physical Chemistry B, Vol. 110, Issue 33
Investigation of gas-sensing properties of copper phthalocyanine films
journal, April 2009
- Basova, T.; Tsargorodskaya, A.; Nabok, A.
- Materials Science and Engineering: C, Vol. 29, Issue 3
Spectra of porphyrins
journal, January 1961
- Gouterman, Martin
- Journal of Molecular Spectroscopy, Vol. 6
Phthalocyanines: From outstanding electronic properties to emerging applications
journal, January 2008
- Claessens, Christian G.; Hahn, Uwe; Torres, Tomás
- The Chemical Record, Vol. 8, Issue 2
PEDOT:PSS/QCM-based multimodal humidity and pressure sensor
journal, November 2016
- Muckley, Eric S.; Lynch, James; Kumar, Rajeev
- Sensors and Actuators B: Chemical, Vol. 236
A Mechanistic Study of O[sub 2] Reduction on Water Soluble Phthalocyanines Adsorbed on Graphite Electrodes
journal, January 1980
- Zagal, J.
- Journal of The Electrochemical Society, Vol. 127, Issue 7
Characterization of evaporated trivalent and tetravalent phthalocyanines thin films: different degree of organization
journal, June 2005
- Del Caño, T.; Parra, V.; Rodríguez-Méndez, M. L.
- Applied Surface Science, Vol. 246, Issue 4
Integration of an M-phthalocyanine layer into solution-processed organic photovoltaic cells for improved spectral coverage
journal, July 2011
- Bamsey, Nathan M.; Yuen, Avery P.; Hor, Ah-Mee
- Solar Energy Materials and Solar Cells, Vol. 95, Issue 7
Mechanism and equivalent circuits in electrochemical impedance spectroscopy
journal, September 2011
- Harrington, David A.; van den Driessche, P.
- Electrochimica Acta, Vol. 56, Issue 23
Adsorption kinetics of optochemical NH3 gas sensing with semiconductor polyaniline films
journal, February 2002
- Hu, H.; Trejo, M.; Nicho, M. E.
- Sensors and Actuators B: Chemical, Vol. 82, Issue 1
Ammonium Removal from Aqueous Solutions by Clinoptilolite: Determination of Isotherm and Thermodynamic Parameters and Comparison of Kinetics by the Double Exponential Model and Conventional Kinetic Models
journal, March 2012
- Tosun, İsmail
- International Journal of Environmental Research and Public Health, Vol. 9, Issue 3
Phthalocyanines: From outstanding electronic properties to emerging applications
journal, January 2008
- Claessens, Christian G.; Hahn, Uwe; Torres, Tomás
- The Chemical Record, Vol. 8, Issue 2
Solubility Properties of Unsubstituted Metal Phthalocyanines in Different Types of Solvents
journal, December 2011
- Ghani, Fatemeh; Kristen, Juliane; Riegler, Hans
- Journal of Chemical & Engineering Data, Vol. 57, Issue 2
Investigation of Optical and Humidity-Sensing Properties of Vanadyl Phthalocyanine-Derivative Thin Films
journal, November 2012
- Aziz, F.; Sulaiman, K.; Karimov, K. S.
- Molecular Crystals and Liquid Crystals, Vol. 566, Issue 1
New Insights on Electro-Optical Response of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) Film to Humidity
journal, April 2017
- Muckley, Eric S.; Jacobs, Christopher B.; Vidal, Keith
- ACS Applied Materials & Interfaces, Vol. 9, Issue 18
Kinetics of Solute Adsorption at Solid/Solution Interfaces: A Theoretical Development of the Empirical Pseudo-First and Pseudo-Second Order Kinetic Rate Equations, Based on Applying the Statistical Rate Theory of Interfacial Transport
journal, August 2006
- Rudzinski, Wladyslaw; Plazinski, Wojciech
- The Journal of Physical Chemistry B, Vol. 110, Issue 33
Verwendung von Schwingquarzen zur W�gung d�nner Schichten und zur Mikrow�gung
journal, April 1959
- Sauerbrey, G�nter
- Zeitschrift f�r Physik, Vol. 155, Issue 2
High dielectric constant response of modified copper phthalocyanine
journal, November 2014
- Hamam, Khalil J.; Al-Amar, Mohammad M.; Mezei, Gellert
- Journal of Molecular Liquids, Vol. 199
Electrical Properties and Gas Response in Alternate Layer-by-Layer Films of Copper Phthalocyanine Dyes
journal, April 2004
- Kato, Keizo; Watanabe, Naoki; Katagiri, Shigenobu
- Japanese Journal of Applied Physics, Vol. 43, Issue 4S
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
- Hamam, Khalil J.; Mezei, Gellert; Khattari, Ziad
- Applied Physics A, Vol. 125, Issue 1
Machine Learning‐Enabled Correlation and Modeling of Multimodal Response of Thin Film to Environment on Macro and Nanoscale Using “Lab‐on‐a‐Crystal”
journal, January 2020
- Muckley, Eric S.; Collins, Liam; Srijanto, Bernadeta R.
- Advanced Functional Materials, Vol. 30, Issue 10
Non-covalent functionalization of CNTs with polycarbazole: a chemiresistive humidity sensor with tunable chemo-electric attributes at room temperature
journal, January 2018
- Das, Madhurima; Ghosh, Saptarshi; Roy, Somenath
- New Journal of Chemistry, Vol. 42, Issue 9
Study of Structural, Optical and AC Electrical Properties of Chloroindium Phthalocyanine
journal, August 2019
- Mahmoudi, Samaneh; Azim Araghi, Mohammad Esmaeil
- Journal of Electronic Materials, Vol. 48, Issue 11
Multi-modal, ultrasensitive, wide-range humidity sensing with Ti 3 C 2 film
journal, January 2018
- Muckley, Eric S.; Naguib, Michael; Ivanov, Ilia N.
- Nanoscale, Vol. 10, Issue 46