Humidity Sensor

Subscriber access provided by University of Kansas Libraries
Interfaces: Adsorption, Reactions, Films, Forces, Measurement Techniques, Charge

Transfer, Electrochemistry, Electrocatalysis, Energy Production and Storage
Highly Responsive PEG/Gold Nanoparticle Thin
Film Humidity Sensor via Inkjet Printing Technology
Chun-Hao Su, Hsien-Lung Chiu, Yen-Chi Chen, Mazlum Yesilmen,
Florian Schulz, Bendix Ketelsen, Tobias Vossmeyer, and Ying-Chih Liao
Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.8b03433 • Publication Date (Web): 04 Jan 2019
Downloaded from http://pubs.acs.org on January 4, 2019
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.
Page 1 of 33 Langmuir
1
2
3
4
5 Highly Responsive PEG/Gold Nanoparticle Thin Film
6
7
8 Humidity Sensor via Inkjet Printing Technology
9
10 Chun-Hao Su,1 Hsien-Lung Chiu,1 Yen-Chi Chen,1Mazlum Yesilmen,2 Florian Schulz,2 Bendix
11
12
13 Ketelsen,2 Tobias Vossmeyer,2 and Ying-Chih Liao1*
14
15
16 1 Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan
17
18
19 2 Institute of Physical Chemistry, University of Hamburg, Grindelallee 117, 20146 Hamburg,
20
21
22 Germany
23
24
25 ABSTRACT
26
27
28 In this study, a highly responsive humidity sensor is developed by printing gold nanoparticles
29
30
31 (GNP) grafted with a hygroscopic polymer. These GNPs are inkjet printed to form a uniform thin film
32
33
34 over an interdigitated electrode with controllable thickness by adjusting the printing parameters. The
35
36
37 resistance of the printed GNP thin film decreases significantly upon exposure to water vapor and
38
39
40 exhibits a semi-log relationship with relative humidity (RH). The sensor can detect RH variations
41
42
43 from 1.8% to 95% with large resistance changes up to 4 order of magnitude with no hysteresis and
44
45
46 small temperature dependence. In addition, with a thin thickness, the sensor can reach absorption
47
48
49 equilibrium quickly with response and recovery times of ≤ 1.2 and ≤ 3 seconds, respectively. The
50
51
52 fast response to humidity changes also allows the GNP thin film sensor to distinguish signals from
53
54
55 intermittent humidification/dehumidification cycles with a frequency up to 2.5 Hz. The printed
56
57
58 * Author to whom the correspondence should be addressed. Telephone: 886-2-3366-9688, e-mail: liaoy@ntu.edu.tw.
59
60 ACS Paragon Plus Environment
Langmuir Page 2 of 33
1
2
3
4 sensors on flexible substrates show little sensitivity to bending deformation and can be embedded in
5
6
7 a mask for human respiratory detection. In summary, this study demonstrates the feasibility of
8
9
10 applying printing technology for the fabrication of thin film humidity sensors, and the developed
11
12
13 methodology can be further applied to fabricate many other types of nanoparticle based sensor devices.
14
15
16
17
18
19 Keywords Humidity sensor, gold nanoparticle, inkjet printing, poly(ethylene glycol), respiratory
20
21
22 monitoring
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
1
2
3
4 Introduction
5
6
7 Humidity measurement is important to various applications such as goods storage, cellular
8
9
10 biology, environmental monitoring, agriculture, and biomedical analysis1. To detect humidity changes
11
12
13 and to convert the humidity measurements into electric or optical signals, a variety of humidity sensing
14
15
16 technologies have been developed2, such as resistive and capacitive sensors3, gravimetric sensors4,
17
18
19 optics5, and surface acoustic wave technology6. In addition, many sensing materials have also been
20
21
22 discovered or synthesized for humidity detection, such as carbon7-10, metal oxides11-17, 2D materials
23
24
25 18-20, and polymers21-26. Among these methods and materials, polymer based resistive humidity sensors
26
27
28 possess the advantages of simple structure, easy preparation, low cost, high sensitivity, rapid response,
29
30
31 and compatibility with modern integrated circuit technology, and therefore have been used widely.
32
33
34 Despite the aforementioned advantages of resistive humidity sensors, several challenges still
35
36
37 remain regarding polymeric humidity sensors. First, detection at low relative humidity is still a
38
39
40 problem for polymer based resistive humidity sensors. Due to the extremely low electrical
41
42
43 conductivity of polymers in dry atmosphere, it is technically difficult to detect the resistance change
44
45
46 at very low humidity, and therefore the range of detection is limited. Next, in order to cope with the
47
48
49 low conductivity of the humidity sensing materials, thick polymer films are needed for resistance
50
51
52 measurements. The large thickness leads to long water vapor absorption and desorption times when
53
54
55 the humidity changes, and thus these humistors usually have long response and recovery times. To
56
57
58
59
1
2
3
4 increase the conductivity of these sensing materials and to reduce the thickness of resistive humidity
5
6
7 sensors, conductive materials have been added to the sensing films. Li et al. added carbon black to
8
9
10 poly(4-vinylpyridine) to reduce the resistance at low humidity27. However, although the sensing range
11
12
13 is extended (0 to 97 RH%), the sensitivity for humidity also decreases after the addition of carbon
14
15
16 black. Khan et al. prepared metal nanoparticle loaded poly(ethylene glycol) (PEG) thin films for
17
18
19 humidity sensing over a wide range from 0 to 100 RH%28. Their results show that the inclusion of
20
21
22 gold or silver nanoparticles into a hygroscopic polymer matrix can greatly improve the conductivity
23
24
25 of nanometer thin films and provide good sensitivity for humidity measurements. On the other hand,
26
27
28 Zhang et al. used a layer-by-layer self assembly method to prepare polyaniline (PANI)/graphene oxide
29
30
31 (GO) films for humidity sensing, and the results show high sensitivity, fast response/recovery
32
33
34 characteristics, and good repeatability 29. More recently, Kano et al. utilized inorganic colloidal silicon
35
36
37 nanocrystals as a humidity-sensitive thin ﬁlm 30. The nanocrystal thin film with nanometer thickness
38
39
40 shows great sensitivity and a dynamic response time down to 40 ms. These frontier studies show that
41
42
43 the reduced thickness of humidity sensors can significantly reduce the response times. Thus, sensitive
44
45
46 thin films with controllable conductivity and thickness are necessary for resistive humidity sensors
47
48
49 with improved response characteristics.
50
51
52 Despite the advances in sensing material synthesis, challenges still remain in the manufacturing
53
54
55 process for humidity sensing thin films. In general, the sensing layers of polymeric resistive humidity
56
57
58
59
1
2
3
4 sensors are usually fabricated by spin coating to produce thin films with nanometer thickness23, 30. The
5
6
7 polymer film cannot be deposited directly onto the desired area and leads to vast material waste during
8
9
10 the manufacturing process. To resolve these issues, inkjet printing technology, a direct writing method,
11
12
13 provides accurate liquid deposition, and has been widely used to fabricate thin film patterns with
14
15
16 negligible loss of materials31-32. With the advantages of pattern formation and flexible processability,
17
18
19 inkjet printing technology have been widely used to print thin film sensors on miniaturized circuits33-
20
21
22 37. However, inkjet printing with nanoparticles requires stable nanoparticle inks with long term
23
24
25 stability. Thus, polymer grafting methods38-39 are widely adopted to avoid nanoparticle aggregation
26
27
28 or enhance nanoparticle ink stability. Recently, Schulz et al.39 utilized a two-layer strategy to greatly
29
30
31 stabilize GNPs in aqueous solutions. The inner layer composed of mercaptoundecanoic acid (MUA)
32
33
34 can create a high-density protection layer on GNPs, while the outer PEG layer provides sufficient
35
36
37 steric stabilization for GNPs in aqueous solutions. Because the great ink stability and the hygroscopic
38
39
40 nature of exposed PEG layers, this two-layer approach will be adopted here to prepare GNP inks for
41
42
43 printed humidity sensing thin films.
44
45
46 In this study, GNPs grafted with hygroscopic polymers are used as sensing material for resistive
47
48
49 humidity sensor. The GNPs, which were synthesized using established protocols, 39-40 offer
50
51
52 advantages of stable dispersity, a well-defined and tunable surface chemistry, and very high chemical
53
54
55 stability. By utilizing inkjet printing technology, uniform thin films with controllable thickness down
56
57
58
59
1
2
3
4 to the sub-micrometer scale will be deposited in a confined area on flexible substrates. The contained
5
6
7 gold nanoparticles facilitate electron transfer and thus result in a measurable resistance for these
8
9
10 printed films with submicron thickness. The conductivity of the hygroscopic polymers will increase
11
12
13 when exposed to water vapor, and thus one can detect humidity change by measuring the electrical
14
15
16 resistance of printed thin films. Moreover, because of the reduced film thickness, fast water
17
18
19 absorption/desorption is achieved and is observed as fast dynamic electric signal responses. The
20
21
22 sensitivity, repeatability, response and recovery time with potential applications of the printed sensors
23
24
25 will be carefully examined to demonstrate the feasibility of printed sensors for quick and accurate
26
27
28 humidity detection.
29
30
31
32 Experiments
33
34
35 Materials
36
37
38
39 Tetrachloroauric(III) acid (≥99.9% trace metal basis), trisodium citrate dihydrate (≥99.0%), and 11-
40
41
42 mercaptoundecanoic acid (95%) (MUA) were ordered from Sigma-Aldrich; ethanol absolute (≥99.9%)
43
44
45 was obtained from VWR Chemicals. Ethylenediaminetetraacetic acid tetrasodium salt hydrate (EDTA)
46
47
48 and citric acid monohydrate (≥99.5%) were obtained from Merck. α-Methoxypoly(ethylene glycol)-
49
50
51 ω-(11-mercaptoundecanoate) (PEGMUA, 2 kDa) was synthesized as described previously.41
52
53
54
55
56
57
58
59
1
2
3
4 Deionized (DI) water with a resistivity of 18.2 MΩ cm was used. Regenerated cellulose (RC) filters
5
6
7 (pore size: 0.2 µm) were obtained from Carl Roth GmbH.
8
9
10
11 Synthesis of functionalized PEGMUA/MUA-GNP ink
12
13
14
15 An aqueous citrate-stabilized GNP suspension was prepared following our previously published
16
17
18 procedure40, scaled up to a total volume of 2 L. The GNPs were then functionalized with
19
20
21 PEGMUA/MUA via ligand displacement39. The PEGMUA/MUA mixture used for the displacement
22
23
24 reaction was prepared by mixing 6 mL of an aqueous solution containing 161 mg (80.5 µmol)
25
26
27 PEGMUA with 3 mL of an ethanolic solution containing 17.4 mg (79,8 µmol) MUA. The resulting
28
29
30 mixture corresponded to a 1:1 molar ratio of PEGMUA/MUA. The total volume of 9 mL ligand
31
32
33 mixture was added rapidly to the stirred solution of citrate stabilized GNPs (volume: ~2 L). After
34
35
36 stirring overnight at room temperature the solution was filled into centrifugation flasks and
37
38
39 centrifuged at 10 °C and 17700 g for 2 h. The supernatant containing excess ligands and reaction
40
41
42 byproducts was discarded and the obtained pellets of PEGMUA/MUA functionalized GNPs were
43
44
45 dispersed in purified water and pooled. The centrifugation procedure was repeated at least two times.
46
47
48 Finally, the GNP dispersion was passed through a syringe filter (0.2 µm, RC) and a total volume of 5
49
50
51 mL purified GNP dispersion was obtained. The GNP particle concentration was 0.53 µM, as
52
53
54 determined via the method of Haiss et al. 42, corresponding to a gold mass concentration of 5.8 mg/mL.
55
56
57
58
59
1
2
3
4 The inkjet GNP ink was prepared by adding DI water into the GNP solution and the final GNP
5
6
7 concentration was 1.93 mg/mL.
8
9
10
11 Fabrication of printed thin film sensors
12
13
14
15 Interdigitated carbon electrodes were printed using a robotic dispensing system (DT-200F; Dispenser
16
17
18 Tech Co., Ltd.). A stainless steel nozzle with an inner diameter of 0.06 mm (34G) was used to print
19
20
21 the conductive carbon paste (Nissin EM Co. Ltd., Japan) over a polyethylene terephthalate (PET) thin
22
23
24 film (Universal Films, Japan). The PEGMUA/MUA-GNP ink was deposited over the interdigitated
25
26
27 electrodes on the PET thin film, which was placed on a heating stage at an operating temperature of 45
28
29
30 °C, by using an inkjet printing system (JetLab 4, MicroFab Technologies Inc.). Droplets of 55 μm
31
32
33 diameter were ejected from a 50 μm piezoelectric nozzle at a frequency of 800 Hz at a speed of 6 m/s. A
34
35
36 dot spacing of 35 μm was used for all the printed GNP thin film patterns.
37
38
39
40 Instrumentation
41
42
43
44 Transmission electron microscopy (TEM) measurements were performed using a JEOL JEM-1011
45
46
47 instrument operated at 100kV. The morphologies of PEGMUA/MUA-AuNPs thin films were
48
49
50 observed with a scanning electron microscope (SEM, Nova NanoSEM 230). The UV-vis absorbance
51
52
53 measurements were carried out with a spectrophotometer (Jasco V-670). GNP sizes in aqueous
54
55
56 suspension were measured by dynamic light scattering (DLS, Nano ZS, Malvern Instruments, UK).
57
58
59
1
2
3
4 Measurements
5
6
7
8 The printed sensors were placed in an environmental chamber (Terchy Tech. Ltd., HRM-80FA,
9
10
11 Nantou, Taiwan) for humidity detection tests. The operating ranges of the chamber were between 10-
12
13
14 45°C and 35- 95 RH%. The resistance of the printed sensors was measured by electric meter (DM2630,
15
16
17 HOLA). The repeatability test was performed by using an electrochemical workstation (CHI 6271E,
18
19
20 CHI, USA). Due to slow humidity elevation rate and control difficulties at low humidity (<35 RH%)
21
22
23 in the operation of the commercial environmental chamber, a small sensor test chamber (∼24 mL in
24
25
26 volume) with gas flow control was used for response/recovery time measurements. For this purpose,
27
28
29 transients of humidified nitrogen were supplied using a commercial programmable calibration system
30
31
32 (Kalibriersystem Model CGM 2000, Umwelttechnik MCZ). In order to maintain a sufficiently high
33
34
35 flow through test chamber (400 mL/min), and to avoid condensation of water within the system, the
36
37
38 accessible relative humidity range was limited between 0 to ~40%. The sensor signals were acquired
39
40
41 by supplying a constant DC voltage of 5 V (Keithley Sourcemeter 2601A) and measuring the change
42
43
44 in current (Keithley Multimeter 2002).
45
46
47
48 Results and discussion
49
50
51
52 Material characterization and sensor appearance
53
54
55
56
57
58
59
1
2
3
4 The synthesized PEGMUA/MUA-GNPs have a gold core diameter of 12 nm with a polymer shell
5
6
7 thickness of around 6 nm. As shown in the TEM image (Figure 1(a)), the GNP cores have a very
8
9
10 narrow size distribution with an average diameter (12.2 ± 0.6 nm). The UV-vis absorption spectrum
11
12
13 (Figure 1(b)) shows a surface plasmon resonance peak of the GNPs at the wavelength of 521 nm,
14
15
16 which is consistent with the characteristic absorption peak for 12 nm GNPs reported in the literature
17
18
19 previously 43. Although both TEM and UV-vis results reveal that the synthesized particles have a GNP
20
21
22 core of ~12 nm, dynamic light scattering results (Figure 1(c)) show a particle diameter of 24.5 nm,
23
24
25 much larger than the GNP core size determined by TEM. This indicates that in aqueous solution the
26
27
28 grafted ligand layer (see Figure S1 for the schematic diagram) has a thickness of ~ 6 nm. These results
29
30
31 are consistent with those reported in the literature 44. The PEGMUA/MUA-GNPs could be easily
32
33
34 suspend in water without aggregation and the suspension exhibits a deep purple color (Figure 1(b)) 39.
35
36
37 This PEGMUA/MUA-GNP suspension could be printed by inkjet printing technology to form any
38
39
40 pattern (Figure1(d)), and is used to prepare the sensing layer of the humidity sensor. As shown in
41
42
43 Figure 1(e), the PEGMUA/MUA-GNP thin film is printed over an interdigitated carbon paste
44
45
46 electrode, which has 4 pairs of fingers with 280 μm width and 150 μm gap. The assembled humidity
47
48
49 sensor (Figure 1(e)) has a sensing area of 4×3.5 mm2, and the film thickness is controlled by using a
50
51
52 layer-by-layer approach. The incremental thicknesses, determined by AFM measurements, of printed
53
54
55 thin films are summarized in Figure 2(a). The thickness increases almost linearly with the number of
56
57
58
59
1
2
3
4 printed layers, showing the liquid deposition accuracy of the inkjet printing technology. The AFM
5
6
7 results show that the GNP thin film is fairly smooth with a roughness of 20 nm, which is close to the
8
9
10 diameter of GNP, with uniformly distributed particles (Figure 2(b)). In the optical microscopy images,
11
12
13 the printed PEGMUA/MUA-GNP thin films show a shiny gold color on the carbon paste fingers and
14
15
16 a smooth surface between the fingers when the number of layers is lower than 8 (Figure S2). However,
17
18
19 small cracks or drying patterns appear when 8 or more layers of GNPs are printed (Figure S2),
20
21
22 probably because the thickness exceeds the critical crack thickness45 of this material. This non-
23
24
25 uniformity may affect the resistance behaviour in humidity detection.
26
27
28
29 Resistance responses to humidity
30
31
32
33 The printed GNP-based humidity sensor shows large resistive response to environmental humidity
34
35
36 changes. Due to the grafted PEGMUA/MUA layer, the printed GNP thin films have a large resistance
37
38
39 (M) despite the large volume fraction of conductive gold particles. As expected, when the number
40
41
42 of printed layers or thickness increases (Figure S3), the resistance of the printed sensor is reduced.
43
44
45 Moreover, the grafted hygroscopic polymer can absorb water vapor resulting in a much higher
46
47
48 conductivity46-47. Thus, when the relative humidity increases, the sensor resistance decreases
49
50
51 exponentially (Figure 3(a)). The equilibrium film resistance R as a function of relative humidity can
52
53
54 be expressed as 28, 36, 48:
55
56
57
58
59
1
2
3
4 R  R0 e  aRH (1)
5
6
7
8 where R0 is the resistance of the thin film at dry condition and a is an empirical constant. Figure 3(b)
9
10
11 shows the values of an extracted by fitting the resistance/humidity data to Eq. (1) for printed sensors
12
13
14 with different thickness. The resistance at dry condition R0 decreases as GNP film thickness increases;
15
16
17 however, when more than 8 layers are printed, the sensitivity parameter a decreases as well. The lower
18
19
20 sensitivity in thicker films is probably due to the formation of cracks or film nonuniformity mentioned
21
22
23 above. For the sake of sensitivity, printed sensors with 8 layers are used in the following sections.
24
25
26
27 Hysteresis test and temperature effects
28
29
30
31 The printed GNP-based humidity sensor shows consistent resistive responses to humidity
32
33
34 changes and the equilibrium resistances show nearly no hysteresis. As shown in Figure 4, as the
35
36
37 relative humidity gradually increases from 35% to 95%, the resistance decreases exponentially as
38
39
40 shown in Figure 3. As the relative humidity decreases again from 95% to 35%, the resistance increases
41
42
43 again and is nearly the same as those in the humidity increasing step. The overlapping resistance
44
45
46 curves in the humidification and dehumidification processes indicate that the sensing mechanism is
47
48
49 based on physical water absorption and desorption process.
50
51
52
53
54
55
56
57
58
59
1
2
3
4 The resistance of the GNP-based humidity sensor also shows temperature dependence as other
5
6
7 polymeric humidity sensors 36. Because the absolute water content in air at a given RH level, as well
8
9
10 as the partition coefficient for sorption of water in the GNP/polymer film, are both affected by
11
12
13 temperature variations, the sensor response is expected to vary with temperature. As shown in Figure
14
15
16 5(a), at a higher temperature, the GNP thin film absorbs more water and thus the resistance is lower.
17
18
19 Nevertheless, as the temperature changes, the resistance curve follows the prediction of Eq. (1) and
20
21
22 shifts almost in parallel, i.e. the slope of the resistance to humidity remains constant. The consistent
23
24
25 coefficient a for the resistance/humidity correlation at different temperatures indicates that the
26
27
28 resistance change is mostly associated with amount of the absorbed water. The temperature
29
30
31 dependence is also examined in Figure 5(b). At a fixed relative humidity of 65%, the resistance
32
33
34 decreases around 5 times when the temperature rises from 10 oC to 45 oC. This resistance variation
35
36
37 with temperature is comparably smaller than that caused by humidity changes, which can be as large
38
39
40 as 105 times. To include the temperature effect, the resistance of the sensor can be described as
41
42
43
44 R  R0 e  aRH bT (2)
45
46
47
48
49 where b is an empirical coefficient and T is the absolute temperature. The values extracted from fits
50
51
52 to the data are a=0.13 (Figure 5(a)) and b=0.052 (Figure 5(b)). Therefore, although this printed GNP
53
54
55
56
57
58
59
1
2
3
4 sensor still needs temperature adjustment, the temperature dependence is much less than the humidity
5
6
7 influence.
8
9
10
11
Response and recovery times
12
13
14
15
16 The printed GNP-based sensor has a fast resistive response to sudden environmental humidity changes.
17
18
19 To characterize the response times, the sensor is put into a smaller flow-through chamber at room
20
21
22 temperature (~25 °C). A flow of dry nitrogen is purged first, and suddenly switched to humidified
23
24
25 nitrogen at various RH levels. The temporal resistance responses are summarized in Figure 6(a). As
26
27
28 the humidified gas enters the chamber, the sensor resistance drops quickly, and reaches a plateau.
29
30
31 After that, the chamber is purged again with dry nitrogen and the sensor resistance returns to the
32
33
34 original value. The minimum detection limit of this sensor is 1.8 RH%. At the high constant flow rate
35
36
37 though the test chamber, which is required to measure short response/recovery times, the accessible
38
39
40 relative humidity levels are limited and data can only be provided up to 35 RH%. The equilibrium
41
42
43 resistance at low humidity is plotted in Figure 6(b). The resistance/humidity curve also follows a semi-
44
45
46 log relationship as described by Eq. (1). The response and recovery times are examined (Figure 6(c-
47
48
49 d)) to test the sensor’s response dynamics. The measured response and recovery times are around 1.2
50
51
52 and 3 seconds, respectively. In this context it is noteworthy that complete exchange of dry nitrogen
53
54
55 by humidified nitrogen and vice versa (i.e. purging with 5 cell volumes) takes ~18 s. Thus, the
56
57
58
59
1
2
3
4 measured response and recovery times can only be considered as upper limits of the true
5
6
7 response/recovery times. Compared to previously reported resistive humidity sensors (Table S1) 24, 30,
8
9
10 35, 49-54, the sensor investigated here exhibit excellent response and recovery characteristics.
11
12
13
14
In addition to the response dynamics, repeatability and reliability of the printed humidity sensor
15
16
17
are examined. As shown in Figure 7(a), dry air is purged through water to generate water saturated air
18
19
20
at a fixed flow rate of 100 mL/min. A circular card board with an opened segment (~90o of a circle)
21
22
23
is mounted on a rotor to pass the saturated gas at a fixed frequency onto the sensor intermittently. The
24
25
26
GNP sensor absorbs water quickly upon the exposure to humidified gas and thus gives sharp cyclic
27
28
29
current peaks. At a low frequency of 0.5 Hz (Figure 7(b)), the rotating shutter provides the sensor with
30
31
32
humidified air every 2 s. The water absorption, starting at ~0.5 s in the first cycle, enhances the film’s
33
34
35
conductivity and thus the current increases sharply from 2 nA to 45 nA. When the disk moves to the
36
37
38
solid section, ~ 1 s in the first cycle, environmental air moves in and the absorbed water evaporates,
39
40
41
leading to a current reduction from 45 nA back to 2 nA. Same current patterns can repeat for many
42
43
44
cycles with nearly no change in the peak height. As the frequency is increased to 2.5 Hz, the sensor
45
46
47
shows nearly the same cyclic responses (Figure 7(c)); however, the peak height decreases to ~ 9 nA
48
49
50
due to less water absorption amount in the faster humidification/dehumidification cycles. Further
51
52
53
increase in rotating speed to 5 Hz leads to insufficient water absorption, and thus no obvious current
54
55
56
57
58
59
1
2
3
4 peak signals are observed (Figure 7(d)). Nonetheless, the printed sensor gives a quite consistent cyclic
5
6
7 current response to the humidity stimulation up to 2.5 Hz and is sufficient for respiratory rate
8
9
10 measurements.
11
12
13
14
Breath monitoring
15
16
17
18
19 The printed humidity sensor on flexible PET sheet has a great mechanical stability, and can be
20
21
22 integrated easily into masks for breath monitoring. Bending tests show that the resistance remains
23
24
25 nearly the same even when the sensor is bent with a radius of 1.8 cm (Figure 8). With the fast response
26
27
28 time, low sensitivity to bending deformation, and mechanical stability, the humidity sensor can be
29
30
31 used for breath monitoring. As shown in Figure 9 (a), the printed GNP sensor is mounted inside a
32
33
34 mask to detect respiratory behavior (Figure 9(b)). As one breathes, air with nearly saturated humidity
35
36
37 is exhaled and dry air from the environment is inhaled. This large humidity change can thus be used
38
39 30, 55-56.
40 to detect respiratory frequency Normal people breathe about 20 times per minute, but when
41
42
43 they are sick or have an asthma attack, the breathing frequency can increase to 40 times per minute.
44
45
46 As shown in Figure 9 (c), the printed GNP sensor embedded in the mask can clearly identify the
47
48
49 breathing frequency of a person before and after exercise (20- 40 breath/minute). Moreover, when a
50
51
52 person is exhaling more heavily, for example after exercise, the faster or stronger exhaled gas flow
53
54
55 leads to faster and more water absorption in the sensing GNP thin film, and thus larger amperometric
56
57
58
59
1
2
3
4 amplitudes are detected. The printed GNP-based sensor not only detects inhalation/exhalation
5
6
7 behavior but also detects breath holding (Figure 9(d)). After exhalation, the humidity in the mask
8
9
10 increases to a peak value and then decreases to a certain level, until the next inhaling process, which
11
12
13 takes in air from the environment and causes a valley in the humidity level or current response. After
14
15
16 inhaling, the moisture in the mask replenishes and gradually recovers until the next exhalation. These
17
18
19 inhaling/holding/exhaling cycles can be well characterized by the printed sensor consistently, and thus
20
21
22 might be useful for health monitoring applications.
23
24
25
26
27
Conclusions
28
29
30
31 A highly responsive humidity sensor is fabricated by using inkjet printing technology. Gold
32
33
34 nanoparticles with a well-defined ligand layer composed of α-methoxypoly(ethylene glycol)-ω-(11-
35
36
37 mercaptoundecanoate) and 11-mercaptoundecanoic acid are first synthesized and suspended well in
38
39
40 water. This GNP ink is printed over an interdigitated carbon electrode on a flexible PET foil to form
41
42
43 a uniform sensing thin film. With the evenly distributed GNPs separated with hygroscopic polymers,
44
45
46 the conductivity of the printed GNP thin film is quite sensitive to environmental humidity changes.
47
48
49 The printed sensor resistance shows a semi-log relationship with relative humidity, and can decrease
50
51
52 105 times as the humidity increases from 1.8 RH% to 95 RH%. The GNP sensor shows no hysteresis
53
54
55 and only small sensitivity to temperature variations around room temperature. The sensor also shows
56
57
58
59
1
2
3
4 fast responses to humidity changes with response and recovery times of ≤ 1.2 and ≤ 3 seconds,
5
6
7 respectively. Based on the fast absorption/desorption of water molecules in the printed GNP thin films,
8
9
10 the sensor can distinguish signals from intermittent humidification/dehumidification cycles with a
11
12
13 frequency up to 2.5 Hz. The printed sensors on PET also show good flexibility and can be embedded
14
15
16 in a mask for human respiratory detection. The results show the versatility and feasibility of the printed
17
18
19 GNP humidity sensor for breath monitoring. In summary, this study demonstrates the feasibility of
20
21
22 applying printing technology to sensor fabrication and the developed strategy can be further extended
23
24
25 to fabricate many other types of electrochemical sensing devices.
26
27
28
29
30
Acknowledgment
31
32
33
34 The authors are grateful to the Ministry of Science and Technology (MOST 106-2628-E-002 -008
35
36
37 -MY3) of Taiwan for supporting this research. F.S. acknowledges support by the DFG via the project
38
39
40 SCHU 3019/2-1.
41
42
43
44
45
Supporting information
46
47
48
Schematic diagram of the polymer layer on a gold nanoparticle, optical and SEM images of inkjet
49
50
51
printed PEGMUA/MUA-GNP thin films, resistance of humidity sensor with number of printed layer,
52
53
54
55
56
57
58
59
1
2
3
4 and comparison of response times for various resistive humidity sensors. This information is available
5
6
7 free of charge via the Internet at http://pubs.acs.org/.
8
9
10
11
12
13
14
15
16 References
17
18
19 (1) Lee, C.-Y.; Lee, G.-B., Humidity sensors: a review. Sensor Letters 2005, 3 (1-2), 1-15.
20 (2) Tripathy, A.; Pramanik, S.; Cho, J.; Santhosh, J.; Abu Osman, N. A., Role of Morphological
21
22 Structure, Doping, and Coating of Different Materials in the Sensing Characteristics of Humidity
23 Sensors. Sensors-Basel 2014, 14 (9), 16343-16422.
24
25 (3) Wang, Y.; Park, S.; Yeow, J. T. W.; Langner, A.; Muller, F., A capacitive humidity sensor based
26 on ordered macroporous silicon with thin film surface coating. Sensor Actuat B-Chem 2010, 149 (1),
27
28 136-142.
29 (4) Pascal-Delannoy, F.; Sorli, B.; Boyer, A., Quartz Crystal Microbalance (QCM) used as humidity
30
31 sensor. Sensor Actuat a-Phys 2000, 84 (3), 285-291.
32 (5) Blank, T. A.; Eksperiandova, L. P.; Belikov, K. N., Recent trends of ceramic humidity sensors
33
34 development: A review. Sensor Actuat B-Chem 2016, 228, 416-442.
35 (6) Hong, H. S.; Phan, D. T.; Chung, G. S., High-sensitivity humidity sensors with ZnO nanorods
36
37 based two-port surface acoustic wave delay line. Sensor Actuat B-Chem 2012, 171, 1283-1287.
38 (7) Yoo, K. P.; Lim, L. T.; Min, N. K.; Lee, M. J.; Lee, C. J.; Park, C. W., Novel resistive-type
39
40 humidity sensor based on multiwall carbon nanotube/polyimide composite films. Sensor Actuat B-
41 Chem 2010, 145 (1), 120-125.
42
43 (8) Ali, S.; Hassan, A.; Hassan, G.; Bae, J.; Lee, C. H., All-printed humidity sensor based on
44 graphene/methyl-red composite with high sensitivity. Carbon 2016, 105, 23-32.
45
46 (9) Itoh, E.; Yuan, Z., Comparative study of all-printed polyimide humidity sensors with single-and
47 multiwalled carbon nanotube gas-permeable top electrodes. Japanese Journal of Applied Physics
48
49 2017, 56 (5S2), 05EC03.
50 (10) Zhang, D.; Chang, H.; Li, P.; Liu, R.; Xue, Q., Fabrication and characterization of an
51
52 ultrasensitive humidity sensor based on metal oxide/graphene hybrid nanocomposite. Sensors and
53 Actuators B: Chemical 2016, 225, 233-240.
54
55
56
57
58
59
1
2
3
4
(11) Yin, H. H.; Ni, J.; Jiang, W. T.; Zhang, Z. L.; Yu, K., Synthesis, field emission and humidity
5 sensing characteristics of monoclinic VO2 nanostructures. Physica E 2011, 43 (9), 1720-1725.
6
7
(12) Wang, H. Y.; Wang, Y. Q.; Hu, Q. F.; Li, X. J., Capacitive humidity sensing properties of SiC
8 nanowires grown on silicon nanoporous pillar array. Sensor Actuat B-Chem 2012, 166, 451-456.
9
10
(13) Wang, C. T.; Willey, R. J., Mechanistic aspects of methanol partial oxidation over supported iron
11 oxide aerogels. J Catal 2001, 202 (2), 211-219.
12
13
(14) Aneesh, R.; Khijwania, S. K., Titanium dioxide nanoparticle based optical fiber humidity sensor
14 with linear response and enhanced sensitivity. Appl Optics 2012, 51 (12), 2164-2171.
15
16
(15) Shukla, S. K.; Tiwari, A.; Parashar, G. K.; Mishra, A. P.; Dubey, G. C., Exploring fiber optic
17 approach to sense humid environment over nano-crystalline zinc oxide film. Talanta 2009, 80 (2),
18
19
565-571.
20 (16) Wang, J.; Su, M. Y.; Qi, J. Q.; Chang, L. Q., Sensitivity and complex impedance of nanometer
21
22
zirconia thick film humidity sensors. Sensor Actuat B-Chem 2009, 139 (2), 418-424.
23 (17) Sun, A.; Huang, L.; Li, Y., Study on humidity sensing property based on TiO2 porous film and
24
25
polystyrene sulfonic sodium. Sensors and Actuators B: Chemical 2009, 139 (2), 543-547.
26 (18) Miao, J.; Cai, L.; Zhang, S.; Nah, J.; Yeom, J.; Wang, C., Air-Stable Humidity Sensor Using
27
28
Few-Layer Black Phosphorus. ACS Appl. Mater. Interfaces 2017, 9, 10019-10026.
29 (19) Smith, A. D.; Elgammal, K.; Niklaus, F.; Delin, A.; Fischer, A. C.; Vaziri, S.; Forsberg, F.;
30
31
Råsander, M.; Hugosson, H.; Bergqvist, L.; Schröder, S.; Kataria, S.; Östling, M.; Lemme, M. C.,
32 Resistive graphene humidity sensors with rapid and direct electrical readout. Nanoscale 2015, 7 (45),
33
34
19099-19109.
35 (20) Zhao, X.; Long, Y.; Yang, T.; Li, J.; Zhu, H., Simultaneous High Sensitivity Sensing of
36
37
Temperature and Humidity with Graphene Woven Fabrics. ACS applied materials & interfaces 2017,
38 9 (35), 30171-30176.
39
40
(21) Yao, Z. W.; Yang, M. J., A fast response resistance-type humidity sensor based on organic silicon
41 containing cross-linked copolymer. Sensor Actuat B-Chem 2006, 117 (1), 93-98.
42
43
(22) Okazaki, M.; Maruyama, K.; Tsuchida, M.; Tsubokawa, N., A novel gas sensor from
44 poly(ethylene glycol)-grafted carbon black. Responsibility of electric resistance of poly(ethylene
45
46
glycol)-grafted carbon black against humidity and solvent vapor. Polym J 1999, 31 (8), 672-676.
47 (23) Muthukumaran, P.; Ion, S.; Xing, L.; Gino, R., A polyimide based resistive humidity sensor.
48
49
Sensor Review 2005, 25 (4), 271-276.
50 (24) Nohria, R.; Khillan, R. K.; Su, Y.; Dikshit, R.; Lvov, Y.; Varahramyan, K., Humidity sensor
51
52
based on ultrathin polyaniline film deposited using layer-by-layer nano-assembly. Sensor Actuat B-
53 Chem 2006, 114 (1), 218-222.
54
55
56
57
58
59
1
2
3
4
(25) Kim, Y.-H.; Lee, J.-Y.; Kim, Y.-J.; Kim, J.-H., A highly sensitive humidity sensor using a
5 modified polyimide film. JSTS: Journal of Semiconductor Technology and Science 2004, 4 (2), 128-
6
7
132.
8 (26) Miyoshi, Y.; Miyajima, K.; Saito, H.; Kudo, H.; Takeuchi, T.; Karube, I.; Mitsubayashi, K.,
9
10
Flexible humidity sensor in a sandwich configuration with a hydrophilic porous membrane. Sensors
11 and Actuators B: Chemical 2009, 142 (1), 28-32.
12
13
(27) Li, Y.; Hong, L. J.; Chen, Y. S.; Wang, H. C.; Lu, X.; Yang, M. J., Poly (4-vinylpyridine)/carbon
14 black composite as a humidity sensor. Sensor Actuat B-Chem 2007, 123 (1), 554-559.
15
16
(28) Khan, M.; Schuster, S.; Zharnikov, M., Effect of Humidity on Electrical Conductivity of Pristine
17 and Nanoparticle-Loaded Hydrogel Nanomembranes. J Phys Chem C 2015, 119 (25), 14427-14433.
18
19
(29) Zhang, D. Z.; Wang, D. Y.; Li, P.; Zhou, X. Y.; Zong, X. Q.; Dong, G. K., Facile fabrication of
20 high-performance QCM humidity sensor based on layer-by-layer self-assembled
21
22
polyaniline/graphene oxide nanocomposite film. Sensor Actuat B-Chem 2018, 255, 1869-1877.
23 (30) Kano, S.; Kim, K.; Fujii, M., Fast-Response and Flexible Nanocrystal-Based Humidity Sensor
24
25
for Monitoring Human Respiration and Water Evaporation on Skin. ACS Sensors 2017, 2, 828-833.
26 (31) Su, C. H.; Kung, C. W.; Chang, T. H.; Lu, H. C.; Ho, K. C.; Liao, Y. C., Inkjet-printed
27
28
porphyrinic metal-organic framework thin films for electrocatalysis. J Mater Chem A 2016, 4 (28),
29 11094-11102.
30
31
(32) Chen, S. P.; Chiu, H. L.; Wang, P. H.; Liao, Y. C., Inkjet Printed Conductive Tracks for Printed
32 Electronics. Ecs J Solid State Sc 2015, 4 (4), P3026-P3033.
33
34
(33) Cho, N. B.; Lim, T. H.; Jeon, Y. M.; Gong, M. S., Inkjet printing of polymeric resistance
35 humidity sensor using UV-curable electrolyte inks. Macromol Res 2008, 16 (2), 149-154.
36
37
(34) Clifford, B.; Beynon, D.; Phillips, C.; Deganello, D., Printed-Sensor-on-Chip devices - Aerosol
38 jet deposition of thin film relative humidity sensors onto packaged integrated circuits. Sensor Actuat
39
40
B-Chem 2018, 255, 1031-1038.
41 (35) Santra, S.; Hu, G.; Howe, R. C. T.; De Luca, A.; Ali, S. Z.; Udrea, F.; Gardner, J. W.; Ray, S.
42
43
K.; Guha, P. K.; Hasan, T., CMOS integration of inkjet-printed graphene for humidity sensing. Sci
44 Rep-Uk 2015, 5, 17374.
45
46
(36) Hsiao, F. R.; Liao, Y. C., Printed Micro-Sensors for Simultaneous Temperature and Humidity
47 Detection. IEEE Sensors Journal 2018, 18 (16), 6788-6793.
48
49
(37) Huang, C. C.; Kao, Z. K.; Liao, Y. C., Flexible Miniaturized Nickel Oxide Thermistor Arrays
50 via Inkjet Printing Technology. ACS Appl. Mater. Interfaces 2013, 5, 12954-12959.
51
52
(38) Toshima, N.; Yonezawa, T., Bimetallic nanoparticles—novel materials for chemical and
53 physical applications. New Journal of Chemistry 1998, 22 (11), 1179-1201.
54
55
56
57
58
59
1
2
3
4
(39) Schulz, F.; Dahl, G. T.; Besztejan, S.; Schroer, M. A.; Lehmkühler, F.; Grübel, G.; Vossmeyer,
5 T.; Lange, H., Ligand layer engineering to control stability and interfacial properties of nanoparticles.
6
7
Langmuir 2016, 32 (31), 7897-7907.
8 (40) Schulz, F.; Homolka, T.; Bastús, N. G.; Puntes, V.; Weller, H.; Vossmeyer, T., Little adjustments
9
10
significantly improve the Turkevich synthesis of gold nanoparticles. Langmuir 2014, 30 (35), 10779-
11 10784.
12
13
(41) Schulz, F.; Vossmeyer, T.; Bastús, N. G.; Weller, H., Effect of the spacer structure on the stability
14 of gold nanoparticles functionalized with monodentate thiolated poly (ethylene glycol) ligands.
15
16
Langmuir 2013, 29 (31), 9897-9908.
17 (42) Haiss, W.; Thanh, N. T.; Aveyard, J.; Fernig, D. G., Determination of size and concentration of
18
19
gold nanoparticles from UV− Vis spectra. Analytical chemistry 2007, 79 (11), 4215-4221.
20 (43) Seol, S. K.; Kim, D.; Jung, S.; Hwu, Y., Microwave synthesis of gold nanoparticles: Effect of
21
22
applied microwave power and solution pH. Mater Chem Phys 2011, 131 (1-2), 331-335.
23 (44) Schulz, F.; Moller, J.; Lehmkuhler, F.; Smith, A. J.; Vossmeyer, T.; Lange, H.; Grubel, G.;
24
25
Schroer, M. A., Structure and Stability of PEG- and Mixed PEG-Layer-Coated Nanoparticles at High
26 Particle Concentrations Studied In Situ by Small-Angle X-Ray Scattering. Part Part Syst Char 2018,
27
28
35 (2), 1700319.
29 (45) Singh, K. B.; Tirumkudulu, M. S., Cracking in drying colloidal films. Phys Rev Lett 2007, 98
30
31
(21), 218302.
32 (46) Thijs, H. M. L.; Becer, C. R.; Guerrero-Sanchez, C.; Fournier, D.; Hoogenboom, R.; Schubert,
33
34
U. S., Water uptake of hydrophilic polymers determined by a thermal gravimetric analyzer with a
35 controlled humidity chamber. Journal of Materials Chemistry 2007, 17 (46), 4864-4871.
36
37
(47) Ying, L. Y.; Shyang, C. W., Kinetics of water absorption and thermal properties of poly(lactic
38 acid)/organomontmorillonite/poly(ethylene glycol) nanocomposites. Journal of Vinyl and Additive
39
40
Technology 2011, 17 (1), 40-47.
41 (48) Murugendrappa, M. V.; Khasim, S.; Prasad, M. V. N., Conductivity and DSC studies of
42
43
poly(ethylene glycol) and its salt complexes. Indian J. Eng. Mater. Sci. 2000, 7, 456-458.
44 (49) Burman, D.; Ghosh, R.; Santra, S.; Guha, P. K., Highly proton conducting MoS2/graphene oxide
45
46
nanocomposite based chemoresistive humidity sensor. Rsc Adv 2016, 6 (62), S7424-S7433.
47 (50) Burman, D.; Santra, S.; Pramanik, P.; Guha, P. K., Pt decorated MoS2 nanoflakes for
48
49
ultrasensitive resistive humidity sensor. Nanotechnology 2018, 29 (11), 115504.
50 (51) Kuang, Q.; Lao, C. S.; Wang, Z. L.; Xie, Z. X.; Zheng, L. S., High-sensitivity humidity sensor
51
52
based on a single SnO2 nanowire. J Am Chem Soc 2007, 129 (19), 6070-6071.
53 (52) Lv, X. J.; Yao, M. S.; Wang, G. E.; Li, Y. Z.; Xu, G., A new 3D cupric coordination polymer as
54
55
chemiresistor humidity sensor: narrow hysteresis, high sensitivity, fast response and recovery. Sci
56 China Chem 2017, 60 (9), 1197-1204.
57
58
59
1
2
3
4
(53) Yao, Y.; Chen, X. D.; Guo, H. H.; Wu, Z. Q.; Li, X. Y., Humidity sensing behaviors of graphene
5 oxide-silicon bi-layer flexible structure. Sensor Actuat B-Chem 2012, 161 (1), 1053-1058.
6
7
(54) Yu, Y. L.; Chen, H.; Liu, Y.; Li, L. H.; Chen, Y., Humidity sensing properties of single Au-
8 decorated boron nitride nanotubes. Electrochem Commun 2013, 30, 29-33.
9
10
(55) Yan, S.; Liu, X.; Skeete, Z.; He, N.; Xie, Z.-H.; Zhao, W.; Lombardi, J. P.; Liu, K.; Kang, N.;
11 Luo, J.; Hsiao, B. S.; Poliks, M.; Gitsov, I.; Zhong, C.-J., Decoration of Nanofibrous Paper
12
13
Chemiresistors with Dendronized Nanoparticles toward Structurally Tunable Negative-Going
14 Response Characteristics to Human Breathing and Sweating. Advanced Materials Interfaces 2017, 4
15
16
(22), 1700380.
17 (56) Ali, I.; Chen, L.; Huang, Y.; Song, L.; Lu, X.; Liu, B.; Zhang, L.; Zhang, J.; Hou, L.; Chen, T.,
18
19
Humidity-Responsive Gold Aerogel for Real-Time Monitoring of Human Breath. Langmuir 2018, 34
20 (16), 4908-4913.
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
1
2
3
4
Figure 1
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
Figure 1 (a) TEM image and (b) UV-vis spectrum of PEGMUA/MUA-GNPs. (c) particle size
29
30
31
distribution of the GNP solution from DLS measurements. (d) Inkjet printed pattern using
32
33
34
GNP solution on PET thin films. (e) Schematic illustration and (e) optical image of the
35
36
37
printed humidity sensor on PET thin films under an optical microscope.
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
1
2
3
4
5 Figure 2
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
Figure 2 (a) Variation of thickness with number of printed layers measured by AFM. (b) AFM image
50
51
52
of the printed GNP thin film with two printed layers.
53
54
55
56
57
58
59
1
2
3
4
Figure 3
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46 Figure 3 (a) Resistance variation of printed sensors with humidity at 30oC. The dashed lines are the
47
48
49 best fits according to Eq. (1) to the experimental data. (b) The parameters a and R0
50
51
52 extracted from fitting the resistance/humidity data measured at 30oC.
53
54
55
56
57
58
59
1
2
3
4
Figure 4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34 Figure 4 Humidity hysteresis test. The humidity sensor is printed with 8 GNP layers.
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
1
2
3
4
Figure 5
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49 Figure 5 Resistance of the printed GNP humidity sensor: (a) variation with relative humidity at
50
51
52 different temperatures, and (b) variation with temperature at a fixed relative humidity. The
53
54
55 humidity sensor is printed with 8 GNP layers.
56
57
58
59
1
2
3
4
Figure 6
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33 Figure 6 (a) Resistance responses of the printed sensor to low relative humidities. (b) Resistance
34
35
36 variation with relative humidity. (c) Response time and (d) recovery time of the printed
37
38
39 sensor.
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
1
2
3
4
Figure 7
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
Figure 7. (a) Schematic illustration of repeatability test. The resistance of sensor at different revolving
38
39
40
frequencies of (b) 0.5 Hz, (c) 2.5 Hz, and (d) 5 Hz.
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
1
2
3
4
Figure 8
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
Figure 8 The resistance variation of the printed humidity sensor under different bending radii.
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
1
2
3
4
Figure 9
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
Figure 9 (a-b) Picture of the printed GNP sensor embedded in a mask for breath detection. (c)
38
39
40
Amperometric curve of the breath sensor with normal breathing and rapid breathing after
41
42
43
exercise. (d) Amperometric responses of the sensor with exhalation, inhalation and hold
44
45
46
breath at a constant applied voltage of 5 V. The exhaling and inhaling process cost around
47
48
49
1 and 2 seconds, respectively.
50
51
52
53
54
55
56
57
58
59
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25 TOC
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59

Humidity Sensor

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Humidity Sensor

Uploaded by

Copyright:

Available Formats

Subscriber access provided by University of Kansas Libraries

Interfaces: Adsorption, Reactions, Films, Forces, Measurement Techniques, Charge

is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

You might also like