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Article history: A fully printed carbon nanotube (CNT) based negative temperature coefficient (NTC) thermistor was
Received 19 March 2018 developed for temperature sensing applications. The multi-layer NTC thermistor was fabricated using
Received in revised form 18 May 2018 additive print manufacturing processes on a flexible polyethylene terephthalate (PET) substrate. Two sil-
Accepted 26 May 2018
ver (Ag) electrodes were printed using screen printing process. CNT based active layer was deposited by
Available online 29 May 2018
means of gravure printing. Organic and silver encapsulation layers were deposited using screen printing.
The capability of the fabricated thermistor was investigated by measuring its response towards temper-
Keywords:
atures varying from −40 ◦ C to 100 ◦ C, in steps of 10 ◦ C. As the temperature was increased from −40 ◦ C
Additive print manufacturing processes
Carbon nanotube (CNT)
to 100 ◦ C, the resistive response of the thermistor decreased exponentially with an overall percentage
Flexible thermistor change of 53% with the temperature coefficient of resistance (TCR) of −0.4%/◦ C. The stability of the printed
Gravure printing thermistor towards relative humidity (RH) varying from 20% RH to 70% RH, in steps of 10% RH at two
Screen printing constant temperatures of 30 ◦ C and 50 ◦ C, was also studied. A maximum change of 0.34% and 0.1% was
observed at 30 ◦ C and 50 ◦ C, respectively when compared to its base resistance at 20% RH. In addition, a
response time of ≈300 ms and a recovery time of 4 s were measured for the printed thermistor with an
accuracy of ± 0.5 ◦ C.
© 2018 Elsevier B.V. All rights reserved.
https://doi.org/10.1016/j.sna.2018.05.042
0924-4247/© 2018 Elsevier B.V. All rights reserved.
2 V.S. Turkani et al. / Sensors and Actuators A 279 (2018) 1–9
Fig. 1. TEM micrographs of CNT showing (a) length and (b) diameter.
2. Experimental
2.1. Materials from Sigma-Aldrich Chemical Company, and de-ionized (DI) water
were used as the cleaning solvents for the Ag and CNT inks, respec-
Flexible PET film (MELINEX® ST730) from DuPont Teijin Films tively. d-Limonene from MCM Electronics was used as the cleaning
was used as the substrate. Conductive Ag ink (AG-800) from Applied solvent for the organic encapsulation layer. A flat flexible connector
Ink Solutions was used for the electrodes and for the secondary (FFC) (Model No. 65801-002LF), from Amphenol ICC, was used to
encapsulation layer. CNT (BSI.B16118) and organic encapsulation make electrical connections for the printed thermistor.
(BSI.P16038) inks from Brewer Science Inc. were used as the active
and organic encapsulation layers, respectively. The length and 2.2. Thermistor design
the diameter of the CNT were measured to be in the range of
0.1 m–1 m (Fig. 1(a)) and 10 nm–30 nm (Fig. 1(b)), respectively Fig. 2 shows the schematic of the thermistor design lay-
using transmission electron microscope (JEOL 100 CXII). Acetone, out. It consists of five layers: substrate, electrodes, active layer,
V.S. Turkani et al. / Sensors and Actuators A 279 (2018) 1–9 3
Fig. 2. Thermistor design layout: (a) top-view (b) side-view and (c) 3D exploded view (Not to scale).
and primary and secondary encapsulation layers. The device was Table 1
Measured surface tension (inks) and surface energy (PET and printed layers).
designed with an overall dimension of 8.0 mm × 14.0 mm in Adobe
Illustrator® design software. The dimensions of the electrodes for Layers Material Surface Tension Surface Energy
metallization and the active layer for temperature sensing are (dynes/cm) (dynes/cm)
10.0 mm × 4.0 mm and 3.0 mm × 4.0 mm, respectively. The dimen- Substrate PET N/A 45.39
sion of the primary encapsulation layer to protect the active layer Layer 1 Silver 27.07 41.84
was 6.5 mm × 5.0 mm. The secondary encapsulation layer, which Layer 2 CNT 30.4 46.57
Layer 3 Organic Polymer 27.92 44.98
was used to detect the presence of any pin holes on the primary
Layer 4 Silver 27.07 41.84
encapsulation layer, was designed to be 4.0 mm × 3.0 mm.
The ability of the substrate to wet the ink plays an important role
in promoting the adhesion of the printed layer. Both surface energy press. A stainless steel screen, fabricated at Microscreen® , with
of the substrate and the surface tension of the ink collectively deter- 325 mesh count, wire diameter of 28 m, mesh angle of 22.5◦ and
mine the ability of the substrate to wet the ink and consequently 12.7 m thick MS-22 emulsion was used for screen printing. An
affects adhesion. Due to the multilayer configuration of the ther- electromechanically engraved gravure plate, from IR Engraving LLC,
mistor, it becomes important to measure the surface energy of each with 200-line screen (LS) and 45◦ cell angle was used for gravure
printed layer and to verify its compatibility with the surface tension printing.
of the subsequent ink being deposited on it for proper adhesion of Fig. 3(a) shows the steps involved in the fabrication of the ther-
the printed layers. In order to obtain good print compatibility and mistor. Initially, two Ag electrodes were screen printed on the PET
adhesion properties between the printed layers, the surface energy substrate and were cured at 130 ◦ C for 6 min in a VWR 1320 temper-
of the corresponding substrate layer should be greater than the sur- ature controlled oven. Then, the CNT based active layer was gravure
face tension of the ink to be printed [42,43]. The surface energy of printed on the Ag electrodes and was cured at 110 ◦ C for 3 min in
the substrates (PET and printed layers) and surface tension of the the VWR 1320 oven. Following this, the organic encapsulation layer
inks were measured with a goniometer (First Ten Angstroms FTA- was screen printed and cured in two stages. During the first stage,
200) using Owens Wendt method [44] and pendant drop method the printed encapsulation layer was cured at 150 ◦ C for 5 min in
[45], respectively (Table 1). The surface energy for PET, Ag, CNT and the VWR 1320 oven. In the second stage, to improve the adhesion,
organic polymer is 18.32, 11.44, 18.65 and 17.91 units, greater than the printed layer was subjected to UV curing in a LC6B benchtop
the corresponding surface tension of the inks to be printed. It was UV conveyor from Fusion UV Systems, Inc. with a belt speed of 40
thus evident that the layers are print compatible with each other. feet per second (fps) and two passes. To obtain a thicker encap-
sulation layer and to eliminate pinholes, an additional layer of the
2.4. Sensor fabrication organic encapsulant was again deposited and cured, thus protect-
ing the active layer. Finally, the secondary Ag encapsulation layer
The fabrication of the thermistor was performed using a was screen printed on the organic encapsulation layer and cured
semi-automatic screen printer (AMI MSP 485) from Affiliated Man- at 130 ◦ C for 6 min in the VWR 1320 oven. A photograph of the
ufacturers Inc. and K-Printing Proofer, a laboratory scale gravure fabricated thermistor is shown in Fig. 3(b).
4 V.S. Turkani et al. / Sensors and Actuators A 279 (2018) 1–9
Fig. 3. (a) Fabrication steps of the printed thermistor (b) photograph of the printed sensor.
2.5. Surface characterization of the printed layers stability of the thermistor towards varying RH values ranging from
20% RH to 70% RH, in steps of 10% RH. During both stages of the
A Bruker CounterGT-K vertical scanning interferometer was experiment, an Agilent E4980 A precision LCR meter, controlled by
used to characterize the thickness and roughness of all the a custom-built LabVIEWTM program on the PC, was used to record
printed layers (Fig. 4). Average thickness (Z) of 4.99 ± 0.06 m, the resistive response of the thermistor at an operating frequency
0.09 ± 0.02 m, 8.39 ± 0.08 m and 4.66 ± 0.09 m, and aver- of 1 kHz and an applied voltage of 1 V.
age surface roughness (Sa) of 0.68 ± 0.02 m, 0.05 ± 0.01 m,
0.39 ± 0.03 m and 0.78 ± 0.01 m was obtained for the Ag elec-
trode, CNT active layer, organic encapsulation and Ag encapsulation
layer, respectively. 3. Results and discussion
Fig. 4. 3D output of the vertical scanning interferometry showing thickness and roughness of (a, e) silver electrodes (b, f) CNT layer (c, g) organic encapsulation layer and (d,
h) silver encapsulation layer.
6 V.S. Turkani et al. / Sensors and Actuators A 279 (2018) 1–9
RT
i
ln R
Tf
ˇ Ti = (2)
Tf ( T1 ) − ( T1 )
i f
where RTi and RTf are the resistance values obtained at initial tem-
perature Ti and final temperature Tf . An average ␣ and  of −0.4%/◦ C
and 474.13◦ K was calculated for the fabricated thermistor. The
results demonstrated a 300% increase in the TCR value when com-
pared to that of a printed thermistor reported by Sibinski et al. [16].
In addition, the TCR value of the printed thermistor is better than
several other CNT based thermistors [15–19] and a comparison is
shown in Table 2. The higher TCR value for the printed thermis-
tor can be attributed to the relatively shorter length of the CNT
used in this work. This is consistent with the results reported by
Todri-Sanial [46] and Naeemi et al. [47], who investigated the effect
of varying diameter and length of CNT on TCR by electro-thermal
modelling, and concluded that a higher negative TCR is achieved as
the length of the CNT decreases as compared to the neutral length
(length at which TCR is 0) of the CNT. Todri-Sanial reported that the
neutral length for a 10 nm and 50 nm diameter CNT were calculated
to be 2.4 m and 20.7 m, respectively [46].
The accuracy of the printed thermistor was determined using
Steinhart’s equation which is mathematically given by Eq. (3) [48].
1
= A + B ln R + C (lnR)3 (3)
T
where, T is the temperature in Kelvin, R is the resistance at temper-
ature T. A, B and C are the Steinhart coefficients which are used
to calibrate the thermistor for better accuracy with the help of
three experimentally measured resistance values at precise tem-
peratures. The Steinhart coefficients are calculated using Eq. (4).
⎛ ⎞
⎛ ⎞ 1
1 ln(R1 ) ln (R1 ) ⎛ ⎞ ⎜ ⎟
3
T1
⎜ ⎟ A ⎜ ⎟
⎜ 1 ln(R2 ) ln3 (R2 ) ⎟ ⎝ B ⎠ = ⎜ ⎟
Fig. 6. (a) Dynamic and (b) static response of the printed thermistor.
1
⎝ ⎠ ⎜T ⎟ (4)
⎜ 2 ⎟
TCR and material constant of a thermistor is mathematically given 3
1 ln(R ) ln (R )
C ⎝ 1 ⎠
3 3
using Eqs. (1) and (2), respectively [6]. T3
(R − R ) For the printed thermistor, Steinhart’s coefficients of
1 Ti Tf
˛= (1) A = 1.04 × 10−1 , B = −1.25 × 10−2 and C = 2.76 × 10−5 were calcu-
(RTi ) (Ti − Tf )
lated at three operating temperatures of −40 ◦ C (T1 = 233.15 K),
V.S. Turkani et al. / Sensors and Actuators A 279 (2018) 1–9 7
Table 2
Comparison of TCR between the printed thermistor and other reported CNT based thermistors.
Fig. 8. Stability of the printed thermistor towards (a) varying humidity and (b) over
Fig. 7. (a) Response time and (b) accuracy of the printed thermistor. time.
30 ◦ C (T2 = 303.15 K) and 100 ◦ C (T2 = 373.15 K), respectively. Using CNTs, which have holes as the majority charge carriers, typi-
the calculated Steinhart’s coefficients, the accuracy of the printed cally exhibit p-type semiconducting characteristics when exposed
thermistor was calculated to be ± 0.5 ◦ C and is shown in Fig. 7(b) to gases or vapors [49]. When CNTs are exposed to humidity, water
over a temperature of −40 ◦ C–100 ◦ C. The accuracy of the printed molecules adsorb on its surface, and transfer of electrons occur
thermistor is comparable to commercially available thermistors thereby resulting in the depletion of the holes [10]. This in turn
with typical accuracies ranging from ±0.001 ◦ C–0.1 ◦ C [6]. causes a decrease in the electrical conductivity of the CNTs, which is
The response time was recorded by introducing the printed not desirable for temperature sensing applications [50]. The printed
thermistor, from room temperature, into hot water that was organic encapsulant layer, in the printed thermistor, provides pro-
maintained at 100 ◦ C. Fig. 7(a) shows the response curve of the ther- tection from humidity variations in the test environment. Fig. 8(a)
mistor. A resistance change of 28% was obtained when compared shows the resistive response of the thermistor towards varying rel-
to the normalized base resistance at room temperature. A response ative humidity ranging from 20% RH to 70% RH, in steps of 10% RH at
time of ≈300 ms was recorded when the thermistor was introduced two constant temperatures of 30 ◦ C and 50 ◦ C. Average percentage
from room temperature into the hot water. In addition, a recovery change, in resistance, of 0.11%, 0.14%, 0.25%, 0.25% and 0.34% were
time of 4 s was measured when the thermistor was removed from obtained at 30 ◦ C for the 30% RH, 40% RH, 50% RH, 60% RH and 70%
the hot water. The measured response time for the printed thermis- RH, respectively when compared to the average base resistance of
tor is comparable with the performance of conventional thermistor 519 ± 3 k at 20% RH. Similarly, an average percentage change, in
which typically range from 100 ms to 1 s [6]. resistance, of 0.08%, 0.1%, 0.09%, 0.08% and 0.02% were obtained
8 V.S. Turkani et al. / Sensors and Actuators A 279 (2018) 1–9
at 50 ◦ C when compared to the average base resistance of 466 ± 4 [8] J.A. Becker, C.B. Green, G. Pearson, Properties and uses of
k at 20% RH. A maximum percentage drift in the resistance was thermistors—thermally sensitive resistors, Bell Labs Tech. J. 26 (1) (1946)
711–725.
0.34% and 0.1% at 30 ◦ C and 50 ◦ C, respectively. The measured values [9] S.D. Wood, B.W. Mangum, J.J. Filliben, S.B. Tillett, An investigation of the
show that the effect of humidity on the response of the thermistor stability of thermistors, J. Res. Natl. Bur Stand. 83 (1978) 247–263.
is minimal, at a constant temperature. [10] L. Liu, X. Ye, K. Wu, R. Han, Z. Zhou, T. Cui, Humidity sensitivity of
multi-walled carbon nanotube networks deposited by dielectrophoresis,
The stability of the thermistor over time was investigated Sensors 9 (3) (2009) 1714–1721.
by recording the resistive response of the thermistor at −20 ◦ C [11] T. Yamada, Y. Hayamizu, Y. Yamamoto, Y. Yomogida, A. Izadi-Najafabadi, D.N.
and + 20 ◦ C, over a period of 60 min each (Fig. 8(b)). An average Futaba, K. Hata, A stretchable carbon nanotube strain sensor for
human-motion detection, Nat. Nanotechnol. 6 (2011) 296.
resistance of 734 ± 0.8 k was measured at −20 ◦ C resulting in an
[12] D. Maddipatla, B.B. Narakathu, M.M. Ali, A.A. Chlaihawi, M.Z. Atashbar,
average drift of ± 0.1%. When the temperature of the chamber was Development of a novel carbon nanotube based printed and flexible pressure
raised to + 20 ◦ C, a drift of ± 0.2% was observed over the 60 min sensor, in: Proc. IEEE Sensors Applications Symposium (SAS), 2017, pp. 1–4.
[13] S. Iijima, Helical microtubules of graphitic carbon, Nature 354 (1991) 56.
duration with an average resistance of 590 ± 1.2 k, thus showing
[14] M.Z. Atashbar, B.E. Bejcek, S. Singamaneni, Carbon nanotube network-based
a stable resistive response towards temperature. It was observed biomolecule detection, IEEE Sens. J. 6 (3) (2006) 524–528.
that the printed thermistor was capable of sensing a broad range [15] H.C. Neitzert, L. Vertuccio, A. Sorrentino, Epoxy/MWCNT composite as
of temperatures (−40 ◦ C to 100 ◦ C) while demonstrating stability temperature sensor and electrical heating element, IEEE Trans. Nanotechnol.
10 (2011) 688–693.
against varying humidity (20% RH to 70% RH). From the results [16] M. Sibinski, M. Jakubowska, M. Sloma, Flexible temperature sensors on fibers,
obtained, it is evident that the fabricated thermistor using additive Sensors 10 (9) (2010) 7934–7946.
print manufacturing processes has the capability to be employed [17] A. Di Bartolomeo, et al., Multiwalled carbon nanotube films as small-sized
temperature sensors, J. Appl. Phys. 105 (2009) 064518.
for temperature sensing applications in biomedical, automotive, [18] C.Y. Kuo, C.L. Chan, C. Gau, C.W. Liu, S.H. Shiau, J.H. Ting, Nano temperature
robotics, food and agricultural industries. In addition, the flexibil- sensor using selective lateral growth of carbon nanotube between electrodes,
ity and conformability of the miniaturized, fully printed thermistor IEEE Trans. Nanotechnol. 6 (2007) 63–69.
[19] C.K. Fung, W.J. Li, Ultra-low-power polymer thin film encapsulated carbon
makes it viable for smart wearable applications. nanotube thermal sensors, in: Proc. 4th IEEE Conference on Nanotechnology,
2004, pp. 158–160.
[20] B.F. Monea, E.I. Ionete, S.I. Spiridon, A. Leca, A. Stanciu, E. Petre, A. Vaseashta,
4. Conclusion Single wall carbon nanotubes based cryogenic temperature sensor platforms,
Sensors 17 (2017) 2071.
[21] G. Matzeu, A. Pucci, S. Savi, M. Romanelli, F. Di Francesco, A temperature
In this work, a fully printed CNT based thermistor was suc- sensor based on a MWCNT/SEBS nanocomposite, Sens. Actuators A Phys. 178
cessfully fabricated on flexible PET substrate using additive print (2012) 94–99.
manufacturing processes. The silver electrodes, organic and sil- [22] V.T. Wong, W.J. Li, Bulk carbon nanotube as thermal sensing and electronic
circuit elements, Proc. of the International Symposium on Circuits and
ver based encapsulation layers were screen printed and the CNT Systems 4 (2003), IV-IV.
active layer was gravure printed. Surface morphology of the various [23] S. Chatterjee, K. Sengupta, H.S. Maiti, A miniature PTC thermistor based sensor
printed layers of the thermistor were characterized. The resistive element fabricated by tape casting technique, Sens. Actuators B Chem. 60
(1999) 155–160.
response of the thermistor towards varying temperatures rang- [24] R. Schmidt, A. Basu, A.W. Brinkman, Production of NTCR thermistor devices
ing from −40 ◦ C to 100 ◦ C was investigated. An overall percentage based on NiMn2 O4+␦ , J. Eur. Ceram. Soc. 24 (2004) 1233–1236.
change in resistance of 53% was recorded with a TCR of −0.4%/◦ C. [25] J. Gao, J. Siden, H. Nilsson, M. Gulliksson, Printed humidity sensor with
memory functionality for passive RFID tags, IEEE J. Sens. 13 (5) (2013)
The stability of the thermistor was demonstrated by measuring 1824–1834.
its response towards varying humidity which resulted in a max- [26] V. Sanchez-Romaguera, et al., Inkjet printed paper based frequency selective
imum change in resistance of 0.34% and 0.1% at 30 ◦ C and 50 ◦ C, surfaces and skin mounted RFID tags: the interrelation between silver
nanoparticle ink, paper substrate and low temperature sintering technique, J.
respectively at 20% RH. A response time of ≈300 ms and a recov-
Mater. Chem. C 3 (9) (2015) 2132–2140.
ery time of 4 s were measured for the printed thermistor with an [27] T. Vuorinen, M.M. Laurila, R. Mangayil, M. Karp, M. Mäntysalo, High resolution
accuracy of ±0.5 ◦ C. This work has demonstrated that thermistors e-jet printed temperature sensor on artificial skin, Proc. In EMBEC & NBC
(2017) 839–842.
fabricated using additive print manufacturing processes have a sig-
[28] S. Yao, Y. Zhu, Wearable multifunctional sensors using printed stretchable
nificant potential in flexible and wearable electronics where light conductors made of silver nanowires, Nanoscale 6 (4) (2014) 2345–2352.
weight, conformability with large scale manufacturing capabili- [29] A.S.G. Reddy, B.B. Narakathu, M.Z. Atashbar, M. Rebros, E. Rebrosova, B.J.
ties are paramount for improved user-device interactions. Further Bazuin, M.K. Joyce, P.D. Fleming, A. Pekarovicova, Printed capacitive based
humidity sensors on flexible substrates, Sens. Lett. 9 (2) (2011) 869–871.
research is underway to investigate the effects of parameters, such [30] S. Emamian, B.B. Narakathu, A.A. Chlaihawi, B.J. Bazuin, M.Z. Atashbar, Screen
as flexibility and ageing, to implement the printed thermistor into printing of flexible piezoelectric based device on polyethylene terephthalate
a field deployable sensing system. (PET) and paper for touch and force sensing applications, Sens. Actuators A
Phys. 263 (2017) 639–647.
[31] A.A. Chlaihawi, et al., A screen printed and flexible piezoelectric based AC
magnetic field sensor, Sens. Actuators A Phys. 268 (2017) 1–8.
References [32] S.G.R. Avuthu, et al., A screen printed phenanthroline based flexible
electrochemical sensor for selective detection of toxic heavy metal ions, IEEE
[1] G.L. Coté, R.M. Lec, M.V. Pishko, Emerging biomedical sensing technologies Sens. J. 16 (2016) 8678–8684.
and their applications, IEEE Sens. J. 3 (2003) 251–266. [33] B.B. Narakathu, A.S.G. Reddy, A. Eshkeiti, S. Emamian, M.Z. Atashbar,
[2] J. Riegel, H. Neumann, H.M. Wiedenmann, Exhaust gas sensors for automotive Development of a microfluidic sensing platform by integrating PCB
emission control, Solid State Ionics 152 (2002) 783–800. technology and inkjet printing process, IEEE Sens. J. 15 (11) (2015)
[3] N. Wang, N. Zhang, M. Wang, Wireless sensors in agriculture and food 6374–6380.
industry-recent development and future perspective, Comput. Electron. Agric. [34] S. Emamian, A. Eshkeiti, A.S.G. Reddy, B.B. Narakathu, M.Z. Atashbar, Gravure
1 (2006) 1–14. printed flexible surface enhanced Raman spectroscopy (SERS) substrate for
[4] V.J. Hodge, S. O’Keefe, M. Weeks, A. Moulds, Wireless sensor networks for detection of 2,4-dinitrotoluene (DNT) vapor, Sens. Actuators B Chem. 217 (1)
condition monitoring in the railway industry: a survey, IEEE Trans. Intell. (2015) 129–135.
Transp. Syst. 16 (2015) 1088–1106. [35] B.B. Narakathu, et al., Novel fully screen printed flexible electrochemical
[5] R. Linares, G. Vergara, R. Gutiérrez, C. Fernández, V. Villamayor, L. Gómez, M. sensor for the investigation of electron transfer between thiol functionalized
González-Camino, A. Baldasano, G. Castro, R. Arias, Y. Lapido, Laser beam viologen and gold clusters, Sens. Actuators B Chem. 176 (2013) 768–774.
welding quality monitoring system based in high-speed (10 kHz) uncooled [36] A. Eshkeiti, B.B. Narakathu, A.S.G. Reddy, A. Moorthi, M.Z. Atashbar, Detection
MWIR imaging sensors, Proc. of SPIE 9485 (2015) 948514. of toxic heavy metals using a novel inkjet printed surface enhanced Raman
[6] A. Feteira, Negative temperature coefficient resistance (NTCR) ceramic spectroscopy (SERS) substrate, Sens. Actuators B Chem. 171 (2012) 705–711.
thermistors: an industrial perspective, J. Am. Ceram. Soc. 192 (2009) 967–983. [37] G.A. dos Reis Benatto, et al., Roll-to-roll printed silver nanowires for increased
[7] P. Ouyang, H. Zhang, Y. Zhang, J. Wang, Z. Li, Zr-substituted SnO2 -based NTC stability of flexible ITO-free organic solar cell modules, Nanoscale 8 (2016)
thermistors with wide application temperature range and high property 318–326.
stability, J. Mater. Sci. Mater. Electron. 26 (2015) 6163–6169.
V.S. Turkani et al. / Sensors and Actuators A 279 (2018) 1–9 9