A Thz-Tds Based Metamaterial Sensor For The Sensitive Distinguishment of Food Additives
A Thz-Tds Based Metamaterial Sensor For The Sensitive Distinguishment of Food Additives
A Thz-Tds Based Metamaterial Sensor For The Sensitive Distinguishment of Food Additives
3
2022 年 6 月 J. Infrared Millim. Waves June,2022
MA Jia-Lu, TANG Jing-Chao, WANG Kai-Cheng, GUO Liang-Hao, WANG Shao-Meng, GONG Yu-Bin*
(School of Electronic Science and Engineering,University of Electronic Science and Technology of China,Chengdu
610054,China)
Abstract:A sensitive terahertz(THz)metamaterial sensor for the distinguishment of common additives in the
food industry is proposed. The metamaterial sensor consists of an array of split ring resonator(SRR)with double
tip ends. By checking resonate frequency shift of the sensor,the concentration and the type of the solution sample
can be distinguished. The metamaterial sensor is fabricated on a quartz substrate,which is transparent for THz
wave. The solutions with the concentration of 0. 2,0. 4,1. 5,2,3 and 4 mg/ml have been measured by using a
terahertz time domain spectroscopy(THz-TDS). The results illustrate that the proposed metamaterial sensor can
detect the concentration of the solution sample,as low as 0. 2 mg/ml. Meanwhile,different solutions with same
concentration can also be clearly distinguished. Our study provides new insights for the application of terahertz
metamaterial sensor based on SRR structure in the field of food safety.
Key words:terahertz sensor,metamaterial,TDS technology,highly sensitive,food safety
摘要:论文提出了一种用于食品工业中常用添加剂(肌醇、亮氨酸、牛磺酸)高灵敏度区分的太赫兹超材料传
感器。该传感器由带有双尖端的开口谐振环(Split Ring Resonator, SRR)阵列组成。液体样品的不同浓度和
种类对应于传感器不同的频率偏移,可以被用于液体样品浓度和种类的区分和辨别。该超材料传感器使用
微纳工艺制作在对太赫兹波透明的石英基板上。利用太赫兹时域光谱仪(THz-TDS)系统分别测量了浓度为
0.2、0.4、1.5、2、3 和 4 mg/ml 的液体样品。结果表明,所提出的超材料传感器能检测的最低样品浓度为 0.2 mg/
ml。同时,该传感器也可以实现相同浓度,不同种类液体样品的辨别。该研究为基于开口谐振环结构的太赫
兹超材料传感器在食品安全领域的应用提供了新的参考。
关 键 词:太赫兹传感器;超材料;时域光谱技术;高灵敏度;食品安全
中图分类号:TN16 文献标识码:A
Received date:2021‐ 07‐ 07,revised date:2022‐ 03‐ 05 收稿日期:2021‐ 07‐ 07,修回日期:2022‐ 03‐ 05
Foundation items:Supported by the National Natural Science Foundation of China(61921002,61988102)
Biography:MA Jialu(1992-),male,Xuchang,Ph. D. Research area involves Microwave and Terahertz sensors. E-mail:littlehorses0592@gmail. com
*
Corresponding author:E-mail:ybgong@uestc. edu. cn
582 红外与毫米波学报 41 卷
cal or chemical materials which have strong THz respons‐ ellipse is 136 μm,while the minor axis is 124 μm,the
es. Furthermore,the inter-molecular signatures in vast edge of the rectangle going across the center of the circle
biological and chemical molecules are within the broad has a height of 12 μm. The incident THz wave was pro‐
THz spectral bands[10-12]. jected vertically onto the structure,with the E-field polar‐
With the rapid development of the food industry and ization perpendicular to the major axis of the proposed
the progress of chemical synthesis technology,food addi‐ metamaterial structure. The inset of Fig. 1 shows the de‐
tives are widely used in the worldwide[13-15]. Inositol(IS) tails of a single unit of the metamaterial sensor. The oth‐
plays a specific role as the signaling molecule involves er optimized dimensional parameters of the single unit of
the regulation of vesicular trafficking as well as several the sensor are listed in Table 1.
other nuclear events[16-17]. Leucine (LC) and Taurine
(TR)are also important amino acids that play important
roles in human life activities[18-19]. IS,LC and TR have
been widely added as food additive in the infant formula,
health food and drink beverage because of the essential
supplements for the human body[20-21]. The traditional de‐
tection methods for these food activities mainly include
chemical methods,microbiological methods,spectrosco‐
py methods,chromatography methods including gas chro‐
matography,gas chromatography mass spectrometry,ion
chromatography and liquid chromatography [22-26]. Tera‐
hertz detection technology provides the possibility to
achieve high sensitivity,low cost and simple operation in
the field of food activities. Especially,terahertz waves
show great potential in bio-sensing applications because
of the absorption of terahertz waves in these bio-molecu‐ Fig. 1 The geometric diagram of the proposed metamaterial
lar systems are pretty impressive. sensor based on SRR structure
In this paper,a terahertz sensor based on metamate‐
图 1 提出的基于开口谐振环结构的超材料传感器结构示意图
rial which is composed of an array of double-gap SRR
structure with tip ends has been proposed. The proper‐ Table 1 Parameter values of the proposed metamaterial
sensor
ties of the sensor are studied both numerically and experi‐
表1 超材料传感器结构参数
mentally. Meanwhile,the electric field distribution of
Parameters Description Values(μm)
the sensor with tip end has been studied. The sensing ca‐
pability of the metamaterial sensor for the distinguish‐ a The length of single unit 72
ment of IS,LC and TR has been investigated by using r The radius of outer circle 70
the THz-TDS technology. The rapid and real-time moni‐ l The half of major axis 68
toring of IS,LC and TR have been demonstrated based m The half of minor axis 60
on the proposed metamaterial sensor. This method has w The height of rectangle 12
the advantage of simple operation and low cost,which
provide an effective reference for realizing the application
of metamaterial in the field of food safety. The simulation results of surface current and E-field
distribution have been studied and shown in Fig. 2. The
1 Materials and methods E-field polarization direction is parallel to the y-axis,as
1. 1 Design and fabrication of the terahertz meta⁃ indicated by the red arrow in the figure. It can be ob‐
material sensor served that the electric field of SRR structure with tip
The split ring resonator(SRR)with tip ends is se‐ ends becomes much stronger compared with ones without
lected as the metamaterial resonator element. Simula‐ tip ends. Stronger E-field will lead more intense surface
tions were carried out by using Computer Software Tech‐ current accumulate at the tip ends,which means a higher
nology (CST) Microwave Studio to study the high fre‐ sensitivity of the metamaterial sensor.
quency properties of the metamaterial sensor. The sche‐ Then,the proposed metamaterial sensor based on
matic of the proposed metamaterial sensor is shown in SRR structure was fabricated by using semiconductor pro‐
Fig. 1,in which a 400 μm thick quartz wafer with the di‐ cessing technology. Fig. 3 presents a typical optical mi‐
electric constant of 3. 75 and loss tangent of 0. 000 1 is croscopy image of the fabricated structure and the en‐
used as the substrate. On the upper surface of the quartz larged demonstration of unit cell.
substrate,a 200 nm thick gold with an electrical conduc‐ 1. 2 Samples preparation and experiment setup
tivity of 4. 56 x 107 S/m is deposited to construct the reso‐ IS,LC and TR powder with a purity of 99. 6% was
nators. The tip ends are created by cutting an ellipse off purchased from Shanghai Macklin Biochemical Co. ,
a circle that has the same center and cutting a rectangle Ltd. The Deionized water was purchased form Chengdu
with a long side of 140 μm parallel to the x direction. Kelong Chemical Co. ,Ltd. Then,solutions to concen‐
The radius of the circle is 70 μm,the major axis of the trations of 0. 2 mg/ml,0. 4 mg/ml,1. 5 mg/ml,2 mg/ml,
3期 MA Jia-Lu et al:A THz-TDS based metamaterial sensor for the sensitive distinguishment of food additives
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(a)
(b)
Fig. 2 The surface current and electric field profiles of SRR structure (a) with and (b) without tip ends, the red colored y-axis signifies
the polarization direction of the incident electric field
图 2 (a)有尖端和(b)没有尖端的开口谐振环结构表面电流和电场分布,红色 y 轴表示入射电场的极化方向
3 mg/ml and 4 mg/ml were obtained by mixing the IS,LC surement area by using the 4-methyl-1-pentene (TPX)
and TR powder and deionized water,respectively. We lens. The proposed metamaterial sensor was placed in
focused on these six solutions to concentrations ranging the measurement area. Then,the transmitted THz signal
from 0. 2 to 4 mg/ml because it was found that the solu‐ through the sensor was measured by electro-optic sam‐
tion was beginning to crystallize when the concentration pling technique based on ZnTe crystal using time delay
is greater than 4 mg/ml,leading to an uneven sample between the probe beam and the generated THz pulse.
film when the water is evaporated. When the concentra‐ The measurement system is shown in Fig. 4(a-b),sen‐
tion of solution was lower than 0. 2 mg/ml,the sample sor assembled with fixture was placed into the holder to
thin film could not be detected due to the limited sensitiv‐ ensure the consistency of sensing position. During the ex‐
ity of the proposed sensor and the limited frequency reso‐ periment,THz time-domain spectra of samples were col‐
lution of the TH-TDS. lected in transmission mode. All collections were carried
The transmission spectra from 0. 01~6 THz were ob‐ out at room temperature and humidity less than 2%. The
tained by using the TH-TDS provided by Neaspace Com‐ specific measurement process was as follows:firstly,the
pany,which supplies 0. 01 THz resolution and 80dB dy‐ fabricated metamaterial sensor was cleaned with deion‐
namic range. The Ti:sapphire femtosecond laser was ized water and dried with drying oven;then,the sensor
used to drive the THz-TDS system. The femtosecond la‐ was putted into a sample cell,and 10 μl sample solu‐
ser beam was dived into pump and probe beam. The tions were dropped on the surface of the sensor by using
pump beam was incident on the photoconductive antenna Sartorius Mechanical Pipette;after that,the metamateri‐
to generate THz pulse. The generated THz pulse was col‐ al sensor was placed into the drying oven for 20 minutes
limated by parabolic mirrors and focused onto the mea‐ with the temperature at 60 °C to avoid any additional ab‐
584 红外与毫米波学报 41 卷
(a)
(a)
(b) (b)
Fig. 3 The optical microscopy images of the fabricated metama‐ Fig. 4 (a) Sensor assembled with fixture, (b) measurement plat‐
terial sensor (a) array structure of SRR, (b) single structure of form of the THz-TDS system
SRR 图 4 (a) 与夹具组装的传感器, (b) THz-TDS 系统测试平台
图 3 加工的超材料传感器的光学显微图像(a)SRR 的阵列结
构,(b)SRR 的单个结构
2 Results and discussions
sorption by the water;finally,the sensor was mounted at 2. 1 Sensing characteristics of the metamaterial sen⁃
normal incidence to the THz beam for spectrum collec‐ sor
tion. After the measurement,the metamaterial sensor The whole SRR resonant unit can be regarded as an
coated with samples was rinsed thoroughly with deionized LC resonant circuit,the resonance frequency of which is
water and dried in drying oven again. The measurement
for the clean and dry metamaterial sensor was taken be‐ defined as f = 1/2 LC where C and L are the capaci‐
fore next deposition of the sample in order to ensure that tance and inductance of the SRR metamaterial sensor,re‐
the metamaterial was completely clean and there was no spectively. Our previous work[27] has shown that the reso‐
change in its optical properties. In addition,special at‐ nance frequency of the LC circuit model is strongly de‐
tention was taken to ensure that each transmission spec‐ pendent on the capacitance of the dielectric over-layer
trum was measured from the fixed location with the meta‐ coated on the sensor surface. Therefore,the resonance
material sensor before and after depositing sample in or‐ frequency changes when the refractive index of the sam‐
der to avoid the measurement error. Three times of whole ple changes. The resonance frequency shifts induced by
3期 MA Jia-Lu et al:A THz-TDS based metamaterial sensor for the sensitive distinguishment of food additives
585
(a)
(a)
(b)
(b)
(a)
3 Conclusion
In short,we have proved the feasibility of detecting
food additives based on a metamaterial sensor in the tera‐
hertz range both theoretically and experimentally. The
(b) common additives such as inositol(IS),LC and TR have
been sensed as examples. The results show that the pro‐
Fig. 8 (a) and (b) represent the relationship between frequency posed metamaterial sensor can effectively detect concen‐
shift and concentration of inositol (IS) and leucine (LC) solution tration of LC as low as 0. 2 mg/ml. The proposed detec‐
changing from 0.2 to 4 mg/ml, respectively tion method is based on the principle that samples of dif‐
图 8 (a)和(b)分别表示肌醇(IS)和亮氨酸(LC)溶液浓度在 ferent thicknesses cause different frequency shifts,and it
0.2~4 mg/ml 时对应的频率偏移关系图 has its positive side and negative one. The positive side
was that this approach could be universally applied to
indicate that the concentration of solution samples could other food additives or even biological materials;while
be predicted based on the different frequency shift, the negative one was that the precision and accuracy of
which means the quantitative analysis of sample could be the measured results were quite sensitive to the deposi‐
achieved. tion of any non-target samples. Therefore,we must pre‐
In addition,selective detection of proposed metama‐ vent the metamaterials from being contaminated by the
terial sensor for different samples with the same concen‐ non-target samples during the sample preparation and
tration has been studied,and the results were shown in measurement. The detection method with the advantage
of simple operation and low cost,which provides an ef‐
Fig. 9. The black line represents a sensor without any
fective reference for realizing the application of metama‐
samples. The samples with concentration of 4 mg/ml
terial in the field of food safety in the future.
were successively coated on the sensor surface,and the
transmittance spectra were obtained. The green,blue References
and red lines represent the transmission spectra of IS,
LC and TR,respectively. There was a significant differ‐ [1]Tao H,Strikwerda A C,Liu M,et al. Performance enhancement of
terahertz metamaterials on ultrathin substrates for sensing applica‐
ence in the transmittance spectra,because the character‐ tions[J]. Applied Physics Letters,2010,97(26):261909.
istic frequency of IS is closer to the resonant frequency of [2]O’Hara J F,Singh R,Brener I,et al. Thin-film sensing with planar
the SRR sensor than the characteristic frequency of LC terahertz metamaterials:sensitivity and limitations[J]. Optics Ex⁃
press,2008,16(3):1786-1795.
and TR,which means higher resonant coupling strength. [3]George P A,Hui W,Rana F,et al. Microfluidic devices for tera‐
Furthermore,the SRR sensor can be specifically de‐ hertz spectroscopy of biomolecules[J]. Optics Express,2008,16
588 红外与毫米波学报 41 卷