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Surfaces, Interfaces, and Applications

Metamaterial-free Flexible Graphene-enabled Terahertz
Sensor for Pesticide Detection at Bio-interface
Wendao Xu, Yuxin Huang, Ruiyun Zhou, Qi Wang, Jifan Yin,
Junichiro Kono, Jianfeng Ping, Lijuan Xie, and Yibin Ying
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.0c11461 • Publication Date (Web): 07 Sep 2020
Downloaded from pubs.acs.org on September 8, 2020

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7 Metamaterial-free Flexible Graphene-enabled Terahertz Sensor for
8 Pesticide Detection at Bio-interface
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10 Wendao Xu, Yuxin Huang, Ruiyun Zhou, Qi Wang, Jifan Yin, Junichiro Kono, Jianfeng Ping, Lijuan
11 Xie,* and Yibin Ying
12 College of Biosystems Engineering and Food Science, Zhejiang University, 866 Yuhangtang Rd., Hangzhou, Zhejiang
13 310058, China
14
Key Laboratory of on Site Processing Equipment for Agricultural Products, Ministry of Agriculture and Rural Affairs, China
15
16 Department of Electrical and Computer Engineering, Department of Physics and Astronomy, and Department of Materials
17 Science and NanoEngineering, Rice University, Houston, Texas 77005, United States
18 Faculty of Agricultural and Food Science, Zhejiang A&F University, Hangzhou, Zhejiang 311300, China
19
20 KEYWORDS: graphene, sensor, flexible, terahertz, pesticide
21
22 ABSTRACT: There is an increasing recognition that terahertz (THz) spectroscopy can be used for high-sensitivity molecular sens-
23 ing. Therefore, in recent years, much work has been devoted to developing flexible, compact, and high-sensitivity THz sensors.
24 However, most designs employ metamaterials, which require complicated, and often expensive, fabrication procedures. Also, the
25 metamaterial structures create a gap between the sensor surface and the target surface, which decreases the effective contact area
26 between them, resulting in reduced sensing performance. Here, we fabricated a metamaterial-free graphene-based THz sensor with
27 user-designed patterns for sensing at bio-interfaces. External molecules can strongly interact with ! electrons in graphene, which
28 moves the Fermi level and changes the amount of THz absorption. We used this sensor to successfully detect chlorpyrifos methyl
29 with a limit of detection at 0.13 mg/L. We also detected pesticide molecules of a concentration of 0.60 mg/L on the surface of an
apple, revealing the flexibility of this sensor. The flexible graphene THz sensor showed high sensing stability and robustness over
30
1000 cycles of bending. These results show that our graphene-based thin-film sensors are easy-to-fabricate, flexible, and versatile,
31
suited for a wide range of sensing applications.
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33
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35 INTRODUCTION metamaterials has been realized. However, existing flexible met-
36 Terahertz (THz) spectroscopy provides a nondestructive and la- amaterials are not widely used because of two issues.20 First,
37 bel-free technique for chemical sensing as abundant information complicated, and often expensive, processes are needed to fabri-
cate metamaterials. Second, the attachment between the met-
38 on intramolecular and intermolecular vibrations exists in the THz
amaterial and the bio-interfaces creates a gap at the joint surface,
39 frequency range,1 including the fingerprints of pesticide2 and sac-
charides.3 However, because of the mismatch between the wave- which significantly deteriorates the sensing performance. There-
40 lengths of THz radiation and the dimensions of the molecules to fore, sensitive, metamaterial-free, and flexible sensors with con-
41 be detected, the sensitivity of free-space THz waves is limited venient fabrication methods are being sought for the THz band.
42 when a trace amount of analytes need to be detected. Thus, signal In the THz and mid-infrared ranges, graphene exhibits a Drude-
43 enhancement methods using photonic crystals4 and like response that changes with controlled free carrier densities,
5,6
44 metamaterials have been developed to increase the interaction which is suitable for dynamical tenability.21,22 In addition, there
45 between the THz wave and analyte. Compared to photonic crys- are various designs to enhance THz absorption in graphene such
tals, metamaterials are easier to operate in both transmission and as a total internal reflection geometry.23 One promising design is
46 reflection modes and thus have attracted much attention in diverse coherent absorption based trilayer structure, consisting of a uni-
47 fields including modulators,7,8 sensors,9,10 and biosensors.11,12 form layer of graphene, a dielectric film, and a metallic plate.
48 Metamaterials are made of periodic artificial structures with a When the impinging wave and the wave reflected by the metallic
49 scale smaller than the wavelength of the external stimuli. Added back plate come in phase at the graphene sheet, enhanced, or even
50 molecules then strongly interact with the electric fields excited in perfect, absorption can be observed. The reported graphene THz
51 the metamaterial, resulting in a shift of the resonant peak.13 THz absorbers have tunability through an external optical pump,21
metamaterials have served as biosensors in transgenic genome electric bias,24 and structural parameters of the device.25 However,
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identification14 and cancer cell detection.12,15 a flexible graphene-based THz absorber for sensing purposes has
53 not been reported.
Flexible devices are strongly desired because, in practical applica-
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tions, the sensing devices should be attached onto bio-interfaces. Here, we fabricated metamaterial-free, flexible graphene-based
55 In the THz regime, metamaterials have been successfully fabricat- THz sensors with user-designed patterns for sensing at bio-
56 ed on flexible substrates made of, e.g., paper,16 silk,17 and polyi- interfaces. The graphene and metal layers were spaced by a poly-
57 mide.18 Detection of glucose16 and cells19 attached to flexible imide film. A near-unity absorption curve was observed as the
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impedance matching requirement was met. External molecules
1 strongly interacted with ! electrons, moving the Fermi level and
2 changing the intensity of the resonance peak,26Ð28 a distinctly dif-
3 ferent mechanism from those commonly used in metamaterial
4 sensors where the resonance frequency shifts. We showed that, by
utilizing a laser engraving method, these graphene sensors can be
5 processed into different lateral shapes. We detected chlorpyrifos
6 methyl with a limit of detection (LOD) at 0.13 mg/L using this
7 sensor. We also fabricated flexible sensors by using conductive
8 tape or a gold film as the bottom mirror, demonstrating the detec-
9 tion of pesticide on the surface of an apple.
10
EXPERIMENTAL SECTION
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Spectrometers and laser engraving system. A THz time-domain
12
spectrometer system (Z-3, Zomega Corporation, East Greenbush,
13 NY, USA) was used to collect the broadband reflection spectra
14 and image from 0.1 to 3.5 THz. The imaging area of the gra-
15 phene-based THz sensor with circle and rectangle patterns was 10
16 mm by 10 mm; for the eagle pattern, the imaging area was 17 mm
17 by 17 mm. THz spectrometer system was purged with nitrogen to
18 prevent THz absorption from water vapor (the humidity was less
than 1%). The temperature was 23 ± 1 ¡C for all the spectra col-
19 lection with signal-to-noise ratio (SNR) over 45 dB. Raman
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measurements were done by a LabRAM HR Evolution Raman
21
microscope system (Horiba Jobin Yvon, Japan) with a He-Ne
22 laser (633 nm) used for excitation. Laser engraving process was
23 accomplished by a LPKF protolaser etching system (LPKF, Ger-
24 many) with a power set at 1.0 W.
25 Fabrication of graphene sensor. The commercialized polyimide
film/tape (Kapton, DuPont, USA) with different thicknesses (50,
26
60, and 80 µm) were utilized in this work. Conductive tape was
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purchased from Chenxi (Shenzhen, China). Chemical vapor depo-
28 sition (CVD) grown monolayer graphene (Trivial Transfer Gra-
29 phene, TTG) was purchased from ACS Material (Medford, MA,
30 USA). It was released onto water for at least two hours and then
31 transferred onto the surface of polyimide film. By removing the
32 polymethyl methacrylate (PMMA) on the top of graphene with
29
33 acetone, a monolayer graphene-based THz sensor was obtained
for future tests.
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THz measurements. Chlorpyrifos methyl and chlorothalonil
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powder was purchased from Sigma-Aldrich Corporation (Mil-
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waukee, WI, USA). In this work, 10 µL of chlorpyrifos methyl
37 was dropped on the surface of graphene sensor and dried before
38 spectra collection with three duplicates. Chlorothalonil solution
39 with a volume of 100 µL was dropped on the surface of an apple
40 (Fushi, Shanxi, China). A flexible graphene THz sensor was used
41 to attach onto the surface of this apple for collecting the chloro-
42 thalonil solution. All the solution was dried at room temperature
before THz measurements and each spectrum was averaged by
43 four scans.
44
Simulation. Simulation results were conducted by FDTD Solu-
45 tions (Lumerical Solutions, Vancouver, Canada).
46
47 RESULTS AND DISCUSSION
48
Fabrication and characteristics of graphene-based THz
49 sensor. The fabrication procedure of a graphene-based THz
50 molecular sensor operating in reflection mode is schematically
51 shown in Figure 1a. The graphene sensor consisted of a gold
52 back-reflector, a thin dielectric layer, and a graphene mono-
layer. We used polyimide for the dielectric layer because of its
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biocompatibility as well as chemical stability. Due to the sem-
54
imetallic nature of graphene, this graphene-dielectric-metal
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structure satisfied the impedance matching requirement and
56 provided a thin resonant cavity that trapped the incident THz
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wave. This structure acted as a horizontal waveguide and
strongly interacted with the incident THz wave through excita-
tion of a waveguide harmonic mode,30 leading to significant
field enhancement and near-unity absorption at its resonant
frequency.
Figures 1b and 1c show simulated and experimental results of
our sensors with different thicknesses of polyimide tape. The
polyimide tape thicknesses were 80 µm, 60 µm, and 50 µm,
respectively. The Fermi level of graphene in the finite-
difference time-domain (FDTD) simulation was set as 100
meV. The transmission for this device is 0 as the back-
reflector (in this work, gold) prevents all THz wave from pass-
ing through this graphene sensor. The absorbance is defined as
A = (1 " |Esample/Ereference|2) # 100%, where Esample (Ereference) is the
intensity of the THz electric field reflected from the sample
(reference). When the impedance of the free space (Z0) match-
es the impedance of graphene absorber (Z), the absorbance
will reach to 100% as the impedance match requirement is
perfectly matched.31 As shown in Figure 1b and 1c, the absorp-
tion peak shows a redshift with increasing polyimide thickness
since the extended travel length of polyimide changed the
impedance. Figure 1d shows a photograph of a sensor with 50
µm polyimide, and Figure 1e shows a photograph of polyi-
mide tapes with different thicknesses. The graphene monolay-
er was confirmed by Raman spectroscopy; as presented in
Figure 1f, a high-intensity 2D peak (~2680 cm-1) and a low-
intensity G peak (~1580 cm-1) are clearly observed.
THz imaging with the graphene-based THz sensor. Figure
2a shows the THz imaging property of our laser engraved gra-
phene-based THz sensor. We processed the graphene THz
sensor into different lateral shapes - a triangle (Figure 2b), a
circle (Figure 2c), and an eagle (Figure 2d). THz images of
these patterned graphene THz sensors are shown in Figure 2e,
2f, and 2g, respectively. The imaging frequency was chosen at
0.89 THz, which was the resonance frequency of the graphene
sensor. In Figure 2e and 2f, the boundaries can be successfully
recognized. However, the boundary of the eagle pattern (Fig-
ure 2g) did not agree well with the optical image in Figure 2d
due to the insufficient spatial resolution at 0.89 THz. By se-
lecting a higher imaging frequency (2.60 THz), we were able
to successfully recognize the eagle pattern (Figure 2h).
Simulated sensing results of graphene-based THz sensor.
To investigate the sensing mechanisms of the graphene-based
THz sensor, we conducted FDTD simulations with a thin-film
analyte on the sensor, as shown in Figure 3a. We focused on
how the sensing performance depended on the graphene Fermi
level, as well as the thickness, refractive index, and absorption
coefficient of the analyte. Figure 3b shows calculated absorp-
tion spectra for different Fermi levels, from 100 to 10 meV,
where the absorption peak intensity decreases from 92% to
75%. As the external molecules containing ! electrons interact
with graphene through !"! stacking, the Fermi level moves
toward the Dirac point and correspondingly the carrier density
decreases.32,33 The reduced Fermi level of graphene enhanced
the impedance mismatch between the graphene sensor and free
space, inducing a smaller absorption.21
Figure 3c shows absorption spectra obtained for different
thicknesses of analyte, ranging from 1 to 5 µm. With increas-
ing analyte thickness, the absorption peak intensity increases
by 5%, accompanied by a slight redshift. Calculated absorp-
tion spectra for different values of refractive index and absorp-
tion coefficient of analyte are shown in Figure 3d and Figure
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