Crosslinked tannic acid/polyethyleneimine for high-performance

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flexible humidity sensors enabled with porous interdigitated

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electrode created by direct laser writing carbonization

Hongyan He, Yanbo Yao, Tao Liu

College of Chemistry, Chemical Engineering and Materials Science, Soochow University,

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Soochow 215123, PR China

Email: tliu@suda.edu.cn; ybyao@suda.edu.cn

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Abstract
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For their advantages of flexibility in nature, low cost, and ease of processing, polymers and
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polymer composites are considered to be ideal candidatesfor the development of wearable and

flexible humidity sensors. Nevertheless, the commonly adopted polymer-based humidity sensing

materials are usually subjected to long-term stability issue, due to a lack of chemically
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crosslinked network structure. Herein, we rely on the robust Michael addition reaction between

polyethyleneimine (PEI) and tannic acid (TA) in aqueous solution for fabricating the chemically
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crosslinked TA-x-PEI based humidity sensors through a simple spray coating process. With

assistance of direct laser writing carbonization (DLWc) technique, we manifest that the
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combination of TA-x-PEI with porous carbon interdigitated electrode (PC-IDE) allow for facile

fabrication of high-performance flexible humidity sensors, which possess high sensitivity,

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fastresponse and recovery, low hysteresis and good long-term stability. SEM microscopy, Raman

and FTIR spectroscopy, frequency-dependent impedance measurement, as well as equivalent

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Polyethyleneimine (PEI); Tannic acid (TA); Direct laser writing carbonization (DLWc); Porous carbon interdigitated
electrode (PC-IDE);.

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 circuit modeling have been performed to gain an in-depth understanding of the humidity sensing

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behavior and the underlying mechanism for the newly developed PC-IDE enabled TA-x-PEI

based humidity sensors.

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Keywords

Polyethyleneimine; tannic acid; crosslinking; humidity sensor;porous interdigitated electrode;

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direct laser writing carbonization

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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4436274
 Crosslinked tannic acid/polyethyleneimine for high-

ed
performance flexible humidity sensors enabled with porous
interdigitated electrode created by direct laser writing

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carbonization
Hongyan He, Yanbo Yao, Tao Liu

College of Chemistry, Chemical Engineering and Materials Science, Soochow

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University, Soochow 215123, PR China

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Email: tliu@suda.edu.cn; ybyao@suda.edu.cn

1. Introduction er
Humidity sensorsplay important roles inour daily life as well as indifferent areas of
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modern industries [1-4]. They can be found from the routine applications for weather

forecasting androom air conditioning to theindispensable tools for process quality

control in textile, petroleum, automotive, semiconductor and biotech industries.The

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read-out schemes adopted by ahumidity sensor typically include

optical/photonic/spectroscopic [5], quartz microbalance [6], and capacitive and

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resistive/impedance type [7], among which the resistive/impedance ones gain the

most popularity for their simplicity, convenience and cost effectiveness. Regardless
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the read-out schemes, the sensing mechanisms and the material composition of the

sensing elements, the conventional humidity sensors are typically built on a rigid
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substrate, which lacks the desired flexibility as demanded by the newly emerged trend
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Tannic acid (TA); Polyethyleneimine (PEI); Direct laser writing carbonization (DLWc); Interdigitated
porous carbon electrode (PC-IDE); Polyimide (PI); Scanning electron microscopy (SEM); Fourier
transform infrared spectroscopy (FTIR); Polyaniline and graphene oxide (PANI/GO).
1

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 inwearable and flexible electronics. In recent years, more and more research worksare

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focusing on developing flexible and wearable humidity sensors with the

characteristics of lightweight, thin-film structured, multi-functional, low cost, and

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ease of fabrication, in addition to the commonly required high sensitivity, fast

response, wide detection range and good stability [8-13]. Up-to-date, a variety of

humidity sensing materials[14] including conductive carbon materials [15,16], semi-

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conductive 2D materials [17], insulating ceramics [18], metal oxides [19,20] and

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metal-organic-frameworks [21], polymer and polymer composites [22-24], etc. have

been developed, among which the polymer and polymer composite, for their
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compliant nature and additional advantages like low cost, ease of processing and
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synthesis, and good compatibility with different fabrication techniques, are considered

to be the most suitable candidates as the humidity sensing materials in fabricating the

wearable and flexible humidity sensors. The typical polymers used for humidity
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sensing, such as polyaniline, polyimide, polyvinyl alcohol, PEDOT:PSS, and

polyethylene oxide [14], are hydrophilic in nature and also possess a linear chain
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structure. Due to a lack of three-dimensional crosslinked molecular network structure,

such polymers may be subjected to significant chain/segmental

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dissolution/migration/relaxation at a high level of humidity, which can lead to a long-

term stability issue. The constant mechanical deformation experienced by a wearable

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and flexible humidity sensor would make such a problem even worse. Therefore, in

order to enhance the long-term stability of a wearable and flexible humidity sensor, it
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is necessary to select an appropriate hydrophilic polymer or polymer system that can

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 be easily processed and crosslinked, such that the long-term stability issue caused by

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polymer chain/segmental dissolution/migration/relaxation can be mitigated [25].

Beyond the issue aforementioned for the sensing material selection, the electrode

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patterning and fabrication [26-28] and its robust integration/assembly with the

substrate and the sensing material also play a critical role in making the humidity

sensors of capacitive or resistive/impedance type. A variety of techniques, such

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asinkjet printing, screen-printing, 3D printing, andphysical and chemical vapor

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deposition [29], are now available that can be used for making the patterned

electrodes. Nevertheless, these methods, either due to the complicated process for ink
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formulation preparation or requiring high-vacuum processing environment, are not
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optimal in making the wearable and flexible humidity sensors in terms of cost

effectiveness and the capability for robust integration with the flexible substrate and

the sensing materials.

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With regard to the above-mentioned critical issues in sensing material selection as

well as electrode preparation, we are herein proposing a solution, which relies on TA-
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x-PEI, namelythe tannic acid (TA) crosslinked polyethyleneimine (PEI) as the

humidity sensing material in combination with anewly emerged direct laser writing
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carbonization (DLWc) technology for preparingthe interdigitated porous carbon

electrode (PC-IDE). Such an approach enables the facile fabrication of high-

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performance wearable and flexible humidity sensors. PEI (Scheme 1a) is a

biocompatible and hydrophilic polymer, which possesses rich amino functional

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groups to allow for protonation and ionic conduction when absorbing moisture. Such

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 a characteristic makes PEI a good candidate as the sensing material [30-32]for

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humidity sensor of resistive/impedance type. Nevertheless, the pristine PEI polymers

without crosslinking treatment can be readily swollen and dissolved in water.This

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makes the PEI-based humidity sensor subject to long-term stability issue in particular

when working at high moist environment. In the present work, we adopt the naturally

abundant, non-toxic and low-cost chemical of TA [33] (Scheme 1b) to crosslink PEI

v
through Michaeladdition reaction [34](Scheme 1c) to form a TA-x-PEI humidity

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sensing layer. Similar to polydopamine, the multiple phenolic hydroxyl groups of the

TA impart the TA-x-PEIa strong binding affinity to different substrates, which is

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advantageous for enhancing the durability of the TA-x-PEI based sensor or sensing
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system, as evidenced by thelong-term stability of the flexible humidity sensors

fabricatedin our present work through spray coating of a mixture of TA and PEI onto

the PC-IDE created by DLWc on a compliant polyimide (PI) film. The DLWc is a
ot

methodutilizing the photothermal action between a CO2 laser beam and a

carbonizable polymer substrate for readily generating electrically conductive carbon

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patterns at ambient conditions [35-39]. This process has been applied in the past for

making the humidity sensors by generating graphene oxide [40,41] or used for
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creating piezoresistive elements in fabricating bi-metal-like humidity sensor[42].

Nevertheless, the advantage of DLWc for rapid patterning interdigitated porous

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carbon electrodes for making performance enhanced humidity sensor has not been

demonstrated previously. With interdigitated gold electrode as a comparison, in the

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present work, we demonstrated that the use of DLWc generated PC-IDE can

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 significantly improve the sensitivity of the TA-x-PEI based humid sensors. Beyond

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the sensitivity, the PC-IDE enabled TA-x-PEI based flexible humid sensor also

manifest fast-response, low-hysteresis and good durability, which along with its

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simple and low-cost fabrication procedures would make it useful for a variety of

humidity sensing applications.

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Scheme 1. Chemical structures of (a) TA and (b) PEI and (c) Mechanism of
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crosslinking reaction between TA and PEI through Michael Addition. The symbol

highlights the multiple sites of TA crosslinkingwith PEI.

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2. Experimental

2.1 Fabrication of the PC-IDE enabled TA-x-PEI humidity sensor

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Fig. 1a shows the geometric design of the PC-IDE. Its fabrication was carried out by

using a CO2 Laser cutting machine (QL-CO2L30, Xunlei Laser Technology Co.,
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Ltd.)with the similar procedure in our previous work[37,39]and summarized in S1

(See Supporting Information). Fig. 1b schematically summarizes the procedures for

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making the PC-IDE enabled TA-x-PEI humidity sensor (A photograph shown in Fig.

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 1a for demonstration). To fabricate the TA-x-PEI sensing layer, a 10 wt% PEI

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(Sigma-Aldrich, Mw ~ 25,000 g/mol and Mn ~ 10,000 g/mol) and a 10 wt% TA

(Shanghai Yuanye Biotechnology Co., Ltd., AR) aqueous solution were prepared first.

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Tris buffer was used to adjust the pH value of the TA solution at 8.5. Subsequently,

the PEI solution and the TA solution were thoroughly mixed at room temperature

according to a pre-determined volume ratio and then stored in a biochemical chamber

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(BPC-70F, Shanghai Yiheng Scientific Instrument Co., Ltd.) at 25℃ for overnight.

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The aged PEI/TA mixing solution was sprayed with a spray gun (HP-BS, Anest Iwata

(Shanghai) Corp.) onto the previously prepared PI supported PC-IDE electrodes at a

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distance of 50 mm for 5 min for the formation of TA-x-PEI sensing layer. For
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comparison, the same procedure was also applied to make the TA-x-PEI based

humidity sensor on a gold IDE supported by a PI film that was prepared with vacuum

sputtering (GVC-2000, Shanghai Hezao Electronic Technology Co., Ltd.).

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2.2 Material characterization and sensor performanceevaluation

The morphology of the PC-IDE before and after coating the TA-x-PEI sensing layer
tn

was observed by scanning electron microscopy (SEM, Hitachi SU8010)at 5 kV. The

microstructure of the PC-IDE was also characterized bya confocal Raman microscope
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with a 514 nm excited laser (LabRam HR800, 50×objective). The Fourier transform

infrared spectroscopy (FTIR, Bruker Invenio R) was applied to examine the reaction
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between TA and PEI. The evaluation of the humidity sensing performance for the PC-

DLWc enabled TA-x-PEI humidity sensor was carried out in a programmable

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temperature and humidity chamber (2K-150GB, Qinzhuo Environmental Testing

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 Equipment Co., Ltd. See S1 for its operation principle and specifications).Unless

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otherwise specified, the temperature was maintained at 30 ℃ for all humidity tests

and the test environment is in air. An electrochemical workstation impedance analyzer

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(RST5260F, Suzhou Risetest Electronic Co., Ltd.) was used to measure the

impedance of the sensor in a frequency range from 0.01 Hz to 1 MHz. For all

measurements, the amplitude of the exciting voltage was set at 20 mV.

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3. Results and Discussion

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3.1 Characterization of PC-IDE electrode and TA-x-PEI sensing layer

By following the procedures as summarized in Fig. 1 and detailed in the experimental

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section, we prepared a PC-IDE electrode, onto which the mixed solution of TA/PEI
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with volume ratio of TA:PEI =0.20 was sprayed. The Raman spectrum of the as-

prepared PC-IDE as shown in Fig. 2a reveals its amorphous carbon structure [36,37]

as evidenced by the signature features of the D band (1350 cm-1) and the G band
ot

(1576 cm-1), respectively related to the disorder/defect structure and the vibration of

the sp2 carbon network. The morphologies of the PC-IDE electrode before and after
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spray coating of the TA/PEI solution are show in Fig. 2b-2d and 2e-2g, respectively.

Similar to the previous studies [36,37,39], the DLWc generated PC-IDEpatterns

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protrude above the surface of the PI film (Fig. 2b) and manifest a rich porous structure

(Fig. 2c and 2d). After spray coating and formation of the TA-x-PEI sensing layer, the
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structure of the PC-IDE maintains intact (Fig. 2e) and the pores of the PC-IDE has not

been filled/blocked by the deposited polymers (Fig. 2g). Instead, the carbon/graphitic
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platelets of the PC-IDE are coated by a layer of TA-x-PEI (Fig 2e vs. Fig. 2b). Due to

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 the large surface-to-volume ratio of such an open structure, the water molecules can

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easily get access to a large amounts of sensing sites of the TA-x-PEI sensing materials,

which is responsible for the high sensitivity of the PC-IDE enabled TA-x-PEI based

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humidity sensor as shown later.

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a

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)

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Fig. 1. (a) Geometric design of the PC-IDE fabricated by DLWc technique and a

photograph of aPC-IDE enabled TA-x-PEI flexible sensor; (b) Summary of the

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procedures used for fabricating the PC-IDE enabled TA-x-PEI humidity sensor.
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Fig. 2. (a)Raman spectrum of the as-prepared PC-IDE and(b-g) SEM images of the
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PC-IDEbefore (b – overall view, c – magnified surface view, d – magnified cross-

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 section view) and after (e – overall view, f – magnified surface view, g – magnified

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cross-section view) spray coating and formation of the TA-x-PEI sensing layer.

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In order to follow the crosslinking reaction between TA and PEI to identify the

formation of TA-x-PEI, the FITR spectra of the neat PEI and TA as well as the TA-x-

PEI formed at various volume ratios of PEI to TA were collected (Fig. 3a). We

v
consulted the previous studies for PEI [43,44] and TA [45,46] to assign the major IR

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bands appeared in the spectra, as detailed in S2 (See Supporting Information).

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Fig. 3. (a) FTIR spectra of PEI and TA as well as the TA-x-PEI formed by
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crosslinking reaction between PEI (10 wt%) and TA (10 wt%) at varied volume ratio.

The spectrum of PEI+TA is formed by a simple mathematical addition of the spectra

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of PEI and TA. (b) Dissolution/swellingbehavior upon water immersionfor the dried

films of PEI and TA-x-PEI with varied volume ratio of TA:PEI.

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In a previous study by Li et al [34], thebroadening of the IR feature in the region

from 3000 to 3700 cm-1for the TA-x-PEI as compared to the neat PEI was used as an
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indication for the successful crosslinking reaction between TA and PEI. Nevertheless,

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 the intrinsic broadness of the IR feature in this region for both PEI (N-H) and TA (OH)

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makes it difficult to draw such a conclusion solely based on the broadening of the N-

H stretching. As such, additional spectroscopic evidence should be pursued to verify

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the formation of TA-x-PEI. In order to do so, we first synthesized the IR spectrum of

PEI+TA by a simple mathematical addition of the spectra of PEI and TA (Fig. 3a),

which is used as a reference for identifying the possible spectroscopic changes caused

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by the chemical reaction between TA and PEI. With the spectrum of PEI+TA as a

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reference, we can see in Fig. 3a that the bands at1715 cm-1 and 1531 cm-1 originally

existing in TA is reduced significantly in TA-x-PEI. Such an observation is in accord

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with the crosslinking reaction mechanism shown in Scheme 1, since the reaction
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converts C=O to C-OH to cause the reduction of the band at 1715 cm-1. Similarly, due

to the crowding and intramolecular hydrogen bonding between the neighboring OH

groups, the in-plane bending motion of the aromatic C–OH is greatly suppressedto
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lead to an inactivation of the band at 1531 cm-1 in TA-x-PEI. Moreover, as shown in

Fig. 3a, we can also observe that the band at 1200 cm-1 due to asymmetric stretching
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of aromatic C-O in TA becomes broadened and shifted in TA-x-PEI, which is also an

indication of the occurrence of crosslinking between TA and PEI. Lastly, the sharp
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stretching of aromatic ring at 1448cm-1 in TA becomes disappeared in TA-x-PEI,

which is presumed a result of the covalently bonding formation between PEI and TA
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through as well as the intramolecular hydrogen bonding among neighboring

OH and NH groups. To further verify the formation of crosslinked TA-x-PEI, we

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deposited a drop of the selected aqueous solution on a glass substrate, including PEI,

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 TA:PEI = 0.40, TA:PEI = 0.20 and TA:PEI = 0.10. After drying, the residual polymer

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films were then immersed in water at room temperature for monitoring their

dissolution and swelling behavior with time. As shown in Fig 3b, we observed that the

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water resistant ability for the selected samples follow the order of PEI <TA:PEI =

0.10 <TA:PEI = 0.20 <TA:PEI = 0.40. Upon 12hrs of soaking in water, the films of

neat PEI andTA-x-PEI formed by TA:PEI = 0.10 were completely dissolved. In

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contrast, the TA-x-PEI samples formed by TA:PEI = 0.20 and TA:PEI = 0.40 only

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showed minor swellingand no sign of dissolution even upon 24 hrs of soaking in

water. The cursory dissolution/swelling experiment along with the detailed IR

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spectroscopic characterization suggest that PEI indeed can be crosslinked by TA to
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form TA-x-PEI as suggested in [34]; and the crosslinking density can be readily

tailored by adjusting the ratio of TA to PEI.

3.2 Humidity sensing behavior for the PC-IDE enabled TA-x-PEI humidity sensor
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There are multiple factors, e.g., the porous structure, the surface chemistry and the

geometric design of the IDE electrode, as well as the thickness of the TA-x-PEI
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sensing layer, etc., that can influence the humidity sensing behavior for the newly

developed PC-IDE enabled TA-x-PEI humidity sensor. In the present study, we

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mainlyfocus on thecrosslinking density of TA-x-PEI to understand its impact on the

humidity sensing behavior of the PC-IDE enabled TA-x-PEI humidity sensor. In order
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to perform this task, we first carried out a screening experiment to determine the

appropriate thickness or amount of TA-x-PEI that is used for making the sensor.
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According to the impedance response at 60% RH and 30 ℃for the sensor prepared

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 with the selected solution of TA:PEI = 0.20 at varied spraying time (S3 and Fig. S1,

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Supporting Information), we fixedthe spraying time at 5 min and prepared a series of

sensors to investigate the effect of crosslinking density on the humidity sensing

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behavior of the PC-IDE enabled TA-x-PEI humidity sensor. Fig. 4a shows the graph

of the controlled humidity at 30℃ used for sensor performance evaluation.As a

representative example, Fig. 4b shows the Bode plots for the sensor prepared

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withTA:PEI = 0.20and tested at relative humidity varied from 35% to 90%. As

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expected, at all frequencies, the impedance of the sensor shows a decreasing trend

with increasing the humidity level. This is because, with increasing the humidity,
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more water molecules are adsorbed into the TA-x-PEI sensing layer to result in the
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protonation of PEI and create more free ionic charges to lead to a smaller value of the

impedance. As noted in Fig. 4b, the frequency response of the sensor impedance at

low humidity level (< 60% RH) is drastically different from that at high humidity
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level (> 60% RH). In the former case, the impedance decreases with increasing the

frequency, which indicatesthat the protonation of PEI is not sufficient at low humidity
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to create high concentration of free ionic charges. Therefore, the impedance response

of the sensor is mainly capacitance dominant. The higher is the frequency, the smaller
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is the impedance. In the latter case, a relatively high concentration of free ionic

charges is created by protonation of PEI, which dominate the impedance behavior of

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the senor and results in an increase of the impedance with frequency, due to the

motion of the large sized ionic species cannot response timely to the rapid changing of
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the electric field. With increasing the ratio of TA to PEI, the mobility of the ionic

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 charges originating from the protonation of PEI decreases due to the enhanced viscous

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drag upon the increase of the crosslinking density of TA-x-PEI, which consequently

causes an increase of the impedance of the sensor.

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Fig. 4. (a) Graph of the controlled humidity at 30℃ used for sensor performance

evaluation; and the correspondingly determined (b) Bode plots of the PC-IDE enabled
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TA-x-PEI humidity sensor with TA:PEI = 0.20 and tested at varied relative humidity;

(c) Effects of the ratio of the TA:PEI and the relative humidity on the averaged
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impedance response (0.01 Hz – 10 Hz) of the sensors; (d) Evaluation of the humidity

sensing behavior for the PC-IDE enabled TA-x-PEI humidity sensor with varied ratio
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of TA:PEI. |Znorm| is the averaged impedance in a range from 0.01 Hz to 10 Hz and

normalized by the value at 35% RH.

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To further examine this point, in Fig. 4c, we summarize the averaged impedance
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response from 0.01 Hz to 10 Hz tested at 35% and 90% RH for the sensors prepared

with different ratios of TA to PEI.As can be seen, at high humidity level (90% RH),
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 the sensor impedance indeed increases with the ratio of TA to PEI when the value of

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TA:PEI is relatively low (< 0.10). Such an increase of the impedance with the ratio of

TA:PEI at low concentration of TA is due tothe reduction of the mobility of the ionic

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charge carriers upon increasing the crosslinking density. However, when further

increasing the ratio of TA:PEI (> 0.10), the sensor impedance begins to decrease and

then shows an up-turn transition at TA:PEI ~ 0.20 – 0.25. Such a peculiar behavior is

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due to the competing effect caused by TA when its concentration is high. On the one

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hand, the dissociation of the polyphenol groups in TA contributes additional ionic

charges, which tends to decrease the impedance; but on the other hand, the high
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crosslinking density associated with the high concentration of TA would reduce the
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mobility of the ionic charge carriers, which tends to increase the impedance. As a

consequence of such a competing effect, one observes the decrease and then increase

behavior of the impedance for the conditions of TA:PEI > 0.10. In contrast to high
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humidity condition, the protonation of the PEI and the dissociation of the polyphenol

groups in TA are suppressed at low humidity (35% RH), which makes the impedance
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response of the sensor being mainly dominated by capacitance effect that showslittle

dependence on the ratio of TA:PEI, as evidenced in Fig. 4c. By taking the averaged
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impedance in a rangefrom0.01 Hz to 10 Hz and normalizing it with the value at 35%

RH, which is termed as |Znorm| for convenience, we evaluated the humidity sensing
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behavior for all sensors. As shown in Fig. 4d, the values of |Znorm| for all

sensorsmonotonical decreaseswith increasing the humidity. Qualitatively, one can tell

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that the loweris the ratio of TA:PEI, the higher is the sensitivity of the sensor to

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 humidity change. The sensors prepared with the neat PEI andthe TA-x-PEI with low

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crosslinking density have the highest sensitivity. Nevertheless, when considering the

possible long-term stability issue induced by swelling/dissolution of the neat PEI or

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slightly crosslinked TA-x-PEI (Fig. 3b), we chose the TA-x-PEI sensing layer

prepared with TA/PEI = 0.20 as the candidate for further evaluating the sensing

performance of the PC-IDE enabled TA-x-PEI humidity sensor. The approximate

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linear relation between |Znorm| and the relative humidity shown in Fig. 4d (in particular

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for intermediate and high humidity) is commonly observed in different types of

polymer-based humidity sensors [47-54]. This suggests that we can use the analytical
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relation:
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|Z| = 𝑎𝑒𝑥𝑝( ― 𝑏 × 𝑅𝐻) (1)

to fit the experimentally measured relation between impedance and humidity, from

which the absolute and the relative sensitivity at a given humidity can be respectively
ot

evaluated as:

d|Z|
tn

dRH
= ―𝑎𝑏e𝑥p ( ― 𝑏 × RH) (2a)
d|Z|/a
dRH
= ―𝑏e𝑥p ( ― 𝑏 × RH) (2b)

With this approach, we evaluated the relatively sensitivity at 60% RH for the PC-IDE
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enabled TA-x-PEI humidity sensor prepared with TA:PEI = 0.20 and compared it

with the literature reported results [47-54]. As shown in Table S1 (Supporting

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Information), the sensitivity of our sensor is comparable to the highly sensitive

humidity sensor made of the composite of polyaniline and graphene oxide (PANI/GO)
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[54]. We attribute the high sensitivity of the PC-IDE enabled TA-x-PEI humidity

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 sensor to the porous structure of the IDE electrode. The porous structure of the IDE in

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combination with anappropriate amount of TA-x-PEI being deposited would be able

to create a large amount of readily accessible sensing sites for water moleculesto lead

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to a high sensitivity, which otherwise cannot be achieved by a uniform IDE. In order

to verify this point, we prepared a TA-x-PEI (TA:PEI = 0.20) based humidity sensor

by using a uniform gold IDE electrode, which isdeposited on a PI film through

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vacuum sputtering. The geometric dimension of the gold IDE is similar to that of the

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PC-IDE; and in the sensor preparation, the spraying time of the aqueous solution of

TA/PEI was maintained at 5 min. Fig. 5a shows the Bode plots for theTA-x-PEI on
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gold IDE tested at varied humidity levels. Even at high humidity level, its frequency
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response is capacitance dominated, which is in drastic contrast to the PC-IDE enabled

sensors (Fig. 4b). With |Znorm| as a measure, we compare in Fig. 5b the humidity

sensing behavior of the gold IDE based sensor with the PC-IDE enabled TA-x-PEI
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humidity sensor (TA:PEI = 0.20). Apparently, the sensitivity of the gold IDE based

sensor is significantly inferior to that of the PC-IDE enabled sensor.The comparison

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study on the sensitivity of the sensor made from the same TA-x-PEI sensing layer but

on different IDE electrodes (uniform gold vs. porous DLWc carbon) indicate the
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benefit of using porous IDE electrodes for greatly enhancing the number of sensing

sites and therefore the sensitivity of the sensor.

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 ed
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er
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Fig. 5. (a) Bode plots for the humidity sensor prepared by spraying the aqueous

solution of TA:PEI = 0.20 on a uniform gold IDE electrode; (b) Comparison of the

humidity sensing behavior for the sensors made from TA:PEI = 0.20 deposited onto
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the uniform gold IDE and the PC-IDE; Comparison of the experimentally measured

and the equivalent circuit model fitted results for the complex impedance diagram (c)
tn

and Bode plot (d) of the PC-IDE enabled TA-x-PEI humidity sensor (TA:PEI = 0.20).

The equivalent circuit model is given in the inset of (c). In (c) and (d), the scattered
rin

data are the experimentally measured values; and the smooth curves are the

theoretical calculation results based on equivalent circuit fitting.

ep

In order to further understand the humidity sensing behavior of the PC-IDE

Pr

enabled TA-x-PEI humidity sensor, we fitted the frequency dependent impedance of

17

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4436274
 the sensor (TA:PEI = 0.20) tested at varied humidity levels by using equivalent circuit

ed
modeling [55,56]. The equivalent circuit model is given in the inset of Fig 5c. In the

circuit, the Warburg element – W1 [57] represents the impedance induced by the

iew
diffusion of the ionic species of H3O+ and OH- in the TA-x-PEI sensing layer, which

are respectively generated through the dissociation of the polyphenol groups of TA

and the protonation of the amino groups of PEI upon the adsorption and diffusion of

v
water molecules in TA-x-PEI. The capacitance element C1 is for describing the

re
geometric capacitance of the sensor due to the dielectric response of the PI substrate

film and the polymeric network of the TA-x-PEI. In parallel with C1 is a constant
er
phase element – CPE1, which is for modeling the distributed capacitance contributed
pe
by the electrical double layer (EDL) built up in the porous structure of the PC-IDE.

The modification of EDL by the diffusion and sub-diffusion of the ionic species in the

pores leads to the CPE impedance behavior [58]. The ionic transport resistance
ot

associated with CPE1 in the pores is reflected by the serially connected resistor

element - R1. The interesting inducive loop observed in the complex impedance
tn

diagram as shown in Fig. 5c, which is more evident for high humidity condition, is

modeled in the circuit by an inductor element – L1. According to the previous studies
rin

[56,59], we attribute the appearance of the inductive behavior in our PC-IDE enabled

TA-x-PEI humidity sensor to the kinetics associated with the dissociation of the
ep

polyphenol groups of TA and the protonation of the amino groups of PEI. We

hypothesize that the multiple-step kinetics formed by dissociation of the hydrogen

Pr

ions from TA, their transportation by water molecules, and then consumption in

18

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4436274
 protonation of the neighboring amino groups of PEI, and/or the cyclic

ed
adsorption/desorption of the ionic species to the PC-IDE is able to create a current

loop, which results in the experimentally observed inductive behavior. The serial

iew
resistor element - R2 connected with L1 is due tothe transportation resistance of the

ionic species involved in the multi-step kinetics mentioned above. The equivalent

circuit such established allows us to fit the experimentally measured frequency-

v
dependent impedance results obtained at all humidity levels. With the results of 35%

re
RH and 90% RH as the representative examples, the experimental and the fitted

complex impedance diagram and the Bode plot are shown in Fig. 5c and 5d,
er
respectively, both of which show good agreement between the experimental
pe
measurements and the modeling fitting results. On the basis of the equivalent circuit

modeling study, we found that, in addition to L1, it is necessary to include the element

of W1 and CPE1 to be able to fit the experimentally measured impedance results,

ot

which again suggests the critical role played by the PC-IDE in dictating the humidity

sensing behavior of our sensors.

tn

In addition to sensitivity, the response time and the recovery time, the hysteresis

and the long-term stability are also important metrics in evaluating the performance of
rin

a humidity sensor. By repeatedly transferringthe tested humidity sensor between

twohome-assembled chambersat room temperature (~25 ℃) with constant humidity,

ep

respectively controlled at 33% RH by the saturated MgCl2 solution and at 85% RH by

the saturated KCl solution,we estimated the response time and the recovery time for
Pr

ourPC-IDE enabled TA-x-PEI humidity sensor (TA:PEI = 0.20). Fig. 6a shows the

19

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4436274
 cyclic impedance response measured at 10 Hz, from which the response time and the

ed
recovery time were estimated to be 10 s and 12 s, respectively. The comparison of the

response/recovery time of our sensor with the literature reported results [47-54] can

iew
be found in Table S1. The consistent and rapid time response of our sensor is

attributedto the large surface area of the TA-x-PEI sensing material exposed through

porous structures of the PC-IDE electrode, which allows for the moisture to be

v
quickly absorbed and evaporated and thus leads to a short response/recovery

re
time.With a similar humidity ramping procedurefor the hysteresis evaluation as in

[60], we measured the impedance response of the PC-IDE enabled TA-x-PEI

er
humidity sensor (TA:PEI = 0.20) at 10 Hz to evaluate its hysteresis performance. Fig.
pe
6b shows the impedance results recorded during humidity ramping-up (humification)

and ramping-down (desiccation) in the range of 35% RH - 90% RH. The well-

overlapped curves for humification and desiccation qualitatively manifest the good
ot

hysteresis performance of our sensor. The quantitative hysteresis value of ~ 2% was

calculated according to [60]:

tn

∆𝐻𝑚𝑎𝑥
𝛾𝐻 =± 2𝐹𝐹𝑆 (3)

where ∆𝐻𝑚𝑎𝑥 is the maximum impedance difference between the humification and the
rin

desiccation curves, and𝐹𝐹𝑆 is the full-scale impedance output in the testing range of 35%-

90% RH. This value is comparable to the literature reported results [47-54]as
ep

summarized in Table S1. To evaluate the long-term stability of our PC-IDE enabled

TA-x-PEI humidity sensor, we performed a 30-day humidity measurement test. In

Pr

such a test, a freshly prepared sensor (TA:PEI = 0.20) was exposed in ambient

20

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4436274
 environment for 30 days without any special protection and care. Every 6 days during

ed
this period, we set the sensor in thecontrolled humidity environment at a few selected

humidity levels to record its impedance. Fig. 6c shows the results of impedance

iew
change over time during this 30-day testing period. According to the test, the

impedance change at each humidity level is less than 2%, which indicate the good

stability possessed by our PC-IDE enabled TA-x-PEI humidity sensor.

v
re
er
pe
ot
tn

Fig. 6. Evaluation of the humidity sensing performance for the PC-IDE enabled TA-

x-PEI humidity sensor (TA:PEI = 0.20). (a) Response and recovery time measurement;
rin

(b) Hysteresis evaluation; (c) Long-term stability test. In all tests, theaverage

impedance value from 0.01 Hz to 10 Hz was used as the measure for the related
ep

performance evaluation.
Pr

21

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4436274
 4. Conclusion

ed
On the basis of the robust crosslinking reaction between polyethyleneimine (PEI) and

tannic acid (TA) in aqueous solution, as well as the direct laser writing carbonization

iew
(DLWc) for creation of porous carbon interdigitated electrode (PC-IDE), we

developed a facile approach for fabricating PC-IDE enabled chemically crosslinked

TA-x-PEI based humidity sensors, which have the advantages of high sensitivity, fast

v
responseand recovery time, low hysteresis and good long-term stability. The

re
comprehensive studies upon SEM microscopy, Raman and FTIR spectroscopy,

frequency-dependent impedance measurement, and equivalent circuit modeling

er
indicate that the crosslinking density of TA-x-PEI and the porous structure of the PC-
pe
IDE are critical for the good humidity sensing performance of the PC-IDE enabled

TA-x-PEI based humidity sensors. The simple and low-cost fabrication procedures for

the sensor developed in this work and its inherent compliant nature and good sensing
ot

performance would make it useful for a variety of humidity sensing applications.

tn

Credit authorship contribution statement

rin

Hongyan He: Conceptualization, Methodology, Investigation, Writing – Original

Draft. Yanbo Yao: Conceptualization, Investigation, Writing – review &editing.Tao

ep

Liu: Conceptualization, Methodology, Writing – review & editing, Supervision,

Project administration, Funding acquisition.

Pr

22

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4436274
 Declaration of Competing Interest

ed
The authors declare that they have no known competing financial interests or personal

relationships that could have appeared to influence the work reported in this paper.

iew
Acknowledgments

This work was supported by the National Natural Science Foundation of China

(NSFC 22105141); Startup funds provided by Soochow University (Q410900116);

v
State and Local Joint Engineering Laboratory for Novel Functional Polymeric

re
Materials; Priority Academic Program Development (PAPD) of Jiangsu Higher

Education Institutions; and Jiangsu Engineering Laboratory of Novel Functional

er
Polymeric Materials.
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Data Availability

Data will be made available on request.

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ot

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