CN113138176A - Terahertz metamaterial sensor and application thereof - Google Patents
Terahertz metamaterial sensor and application thereof Download PDFInfo
- Publication number
- CN113138176A CN113138176A CN202010058685.0A CN202010058685A CN113138176A CN 113138176 A CN113138176 A CN 113138176A CN 202010058685 A CN202010058685 A CN 202010058685A CN 113138176 A CN113138176 A CN 113138176A
- Authority
- CN
- China
- Prior art keywords
- terahertz
- ring structure
- resonance
- flexible substrate
- asymmetric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 238000001514 detection method Methods 0.000 claims abstract description 20
- 230000003115 biocidal effect Effects 0.000 claims description 27
- 229920001721 polyimide Polymers 0.000 claims description 21
- 239000004642 Polyimide Substances 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003242 anti bacterial agent Substances 0.000 abstract description 16
- 229940088710 antibiotic agent Drugs 0.000 abstract description 16
- 230000035945 sensitivity Effects 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 230000001808 coupling effect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 18
- 239000010703 silicon Substances 0.000 description 18
- 239000008267 milk Substances 0.000 description 16
- 235000013336 milk Nutrition 0.000 description 16
- 210000004080 milk Anatomy 0.000 description 16
- 239000000843 powder Substances 0.000 description 11
- 235000013365 dairy product Nutrition 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 239000010931 gold Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229960001139 cefazolin Drugs 0.000 description 4
- NNULBSISHYWZJU-LLKWHZGFSA-N ceftizoxime Chemical compound N([C@@H]1C(N2C(=CCS[C@@H]21)C(O)=O)=O)C(=O)\C(=N/OC)C1=CSC(N)=N1 NNULBSISHYWZJU-LLKWHZGFSA-N 0.000 description 4
- 229960001991 ceftizoxime Drugs 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MLYYVTUWGNIJIB-BXKDBHETSA-N cefazolin Chemical compound S1C(C)=NN=C1SCC1=C(C(O)=O)N2C(=O)[C@@H](NC(=O)CN3N=NN=C3)[C@H]2SC1 MLYYVTUWGNIJIB-BXKDBHETSA-N 0.000 description 3
- OKBVVJOGVLARMR-QSWIMTSFSA-N cefixime Chemical compound S1C(N)=NC(C(=N\OCC(O)=O)\C(=O)N[C@@H]2C(N3C(=C(C=C)CS[C@@H]32)C(O)=O)=O)=C1 OKBVVJOGVLARMR-QSWIMTSFSA-N 0.000 description 3
- 229960002129 cefixime Drugs 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 241000283690 Bos taurus Species 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- -1 aminoglycosides Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000001328 terahertz time-domain spectroscopy Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 1
- 208000036649 Dysbacteriosis Diseases 0.000 description 1
- 208000027244 Dysbiosis Diseases 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010023845 Laryngeal oedema Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229940126575 aminoglycoside Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000012984 antibiotic solution Substances 0.000 description 1
- 239000012237 artificial material Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 230000007140 dysbiosis Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001900 immune effect Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003120 macrolide antibiotic agent Substances 0.000 description 1
- 229940041033 macrolides Drugs 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3581—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation
- G01N21/3586—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation by Terahertz time domain spectroscopy [THz-TDS]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N2021/0106—General arrangement of respective parts
- G01N2021/0112—Apparatus in one mechanical, optical or electronic block
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Toxicology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention provides a terahertz metamaterial sensor which comprises a unit structure; the unit structure comprises a flexible substrate and an asymmetric open ring structure arranged on the flexible substrate. Compared with the prior art, the terahertz metamaterial sensor provided by the invention is a flexible substrate, so that the loss can be reduced, and the detection of a sample is facilitated; the asymmetric open-loop structure is arranged on the flexible substrate, Fano resonance and electric dipole resonance can be generated simultaneously, so that the sensor has dual-band resonance frequency in a terahertz band, wherein the Fano resonance is a resonance mode with a high Q value, and the two resonance peaks correspond to the absorption peak positions of antibiotics in the terahertz band, so that the sensing sensitivity of the sensor can be effectively improved through a coupling effect.
Description
Technical Field
The invention belongs to the technical field of terahertz spectrum application, and particularly relates to a terahertz metamaterial sensor and application thereof.
Background
The terahertz spectrum is an electromagnetic wave between microwave and infrared, the frequency range of the terahertz spectrum is 0.1-10 THz, the wavelength range of the terahertz spectrum is 30 mu m-3 mm, and the terahertz spectrum is in a transition stage from macroscopic electronics to microscopic photonics. This segment of electromagnetic waves has not been studied intensively due to the lack of effective radiation sources and sensitive detection techniques in the past, and is therefore also referred to as a "terahertz gap". With the development of ultrafast photoelectric technology and micro semiconductor devices, more effective radiation source and detection technology are provided for terahertz research, so that the terahertz technology is widely and deeply researched. The terahertz wave band contains physical, chemical and structural information of related substances, so that the terahertz wave band is widely applied to the fields of material science, biomedical science, food chemistry, communication radar and the like.
The terahertz metamaterial is a novel artificial material acting on a terahertz waveband, and can be used for adjusting the amplitude and the phase of terahertz waves. A metal open-loop resonator (SRR) is one of the most common types of meta-material structures, and can be regarded as a circuit including a capacitance and an inductance, wherein the inductance is mainly determined by the geometrical parameters of the designed meta-material, and the capacitance is closely related to the effective dielectric constant of a capacitor. When the surface of the metamaterial is covered by other substances, the change of the local effective dielectric constant of the metamaterial can cause the change of capacitance, thereby causing the shift of the resonant frequency of the metamaterial. Therefore, the trace residue can be detected through the shift of the resonance frequency of the terahertz metamaterial.
In daily life, food safety problems are more and more emphasized by consumers, and especially the problem of antibiotic residues in food matrixes is a focus of attention, wherein the antibiotic residues in dairy products are one of more serious problems. The milk is one of the foods which are often taken by people of all ages due to the characteristic of rich nutrition. At present, in the dairy processing industry, in order to increase the yield of animal husbandry, an excessive amount of antibiotics is often used, including antibiotics such as lactams, aminoglycosides, tetracyclines, macrolides, and the like. Generally, the reasons for antibiotic residues in dairy products mainly include: 1) because antibiotics can be used for preventing and treating various diseases of cows, the antibiotics are generally injected or fed into the body of the cows and then enter the breasts through blood circulation to remain in the milk; 2) in order to prevent spoilage of dairy products during storage and transportation, some illegal vendors add too many antibiotics to inhibit bacterial growth. The abuse of antibiotics inevitably causes the residual of the antibiotics in the milk, and the long-term drinking of the milk containing the residual antibiotics has great harm to human bodies, can cause certain pathogenic bacteria in the human bodies to generate drug resistance, dysbacteriosis and immunity reduction, can cause hypersensitivity reaction of susceptible people, can cause symptoms such as larynx edema, dyspnea, blood pressure reduction and the like in a short time, and even can cause serious shock.
The following methods are generally used for detecting antibiotic residues in dairy products: 1) the method comprises the following steps of (1) qualitatively measuring the residue of the antimicrobial in a sample to be measured according to the inhibition effect of the antibiotic on the physiological function and metabolism of the microorganism; 2) a physicochemical detection method, which is a method for separating and detecting by using a test instrument based on the properties of antibiotic molecules, and commonly used test technologies comprise infrared, ultraviolet, fluorescence, chromatography, mass spectrum and the like; 3) the immunoassay method and the enzyme-linked immunosorbent assay have the characteristics of high sensitivity, strong specificity, large treatment capacity and the like; 4) in other detection methods, the surface plasmon resonance biosensor detects a sample by using an immunological principle; the protein chip technology is to fix known protein molecule product on solid phase carrier after special chemical treatment and capture the protein to be detected based on the biological molecule characteristic for confirmation and analysis. However, these conventional detection methods are generally time-consuming, complicated to operate, and generate harmful waste.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a terahertz metamaterial sensor and an application thereof, where the terahertz metamaterial sensor has a dual-wavelength and high-Q resonance response in a terahertz waveband, and can be used for detecting antibiotic residues in dairy products.
The invention provides a terahertz metamaterial sensor which comprises a unit structure; the unit structure comprises a flexible substrate and an asymmetric open ring structure arranged on the flexible substrate.
Preferably, the flexible substrate is a polyimide substrate, and the asymmetric open-ring structure is an asymmetric open-gold ring structure.
Preferably, the thickness of the flexible substrate is 25 μm.
Preferably, the thickness of the asymmetric open ring structure is 200 nm.
Preferably, the period of the in-cell structure is 75 μm.
Preferably, the asymmetric open ring structure has an outer radius of 30 μm and an inner radius of 25 μm.
Preferably, the opening gap of the asymmetric opening ring structure is 2.
Preferably, the opening gaps of the asymmetric open-ring structure are all 5 μm.
Preferably, the angle between the midline of the opening gap of the asymmetric opening ring structure and the vertical diameter is 20 degrees, and the two opening gaps are positioned on one side of the vertical diameter of the non-opening ring structure.
The invention also provides application of the terahertz metamaterial sensor in antibiotic residue detection.
The invention provides a terahertz metamaterial sensor which comprises a unit structure; the unit structure comprises a flexible substrate and an asymmetric open ring structure arranged on the flexible substrate. Compared with the prior art, the terahertz metamaterial sensor provided by the invention is a flexible substrate, so that the loss can be reduced, and the detection of a sample is facilitated; the asymmetric open-loop structure is arranged on the flexible substrate, Fano resonance and electric dipole resonance can be generated simultaneously, so that the sensor has dual-band resonance frequency in a terahertz band, wherein the Fano resonance is a resonance mode with a high Q value, and the two resonance peaks correspond to the absorption peak positions of antibiotics in the terahertz band, so that the sensing sensitivity of the sensor can be effectively improved through a coupling effect.
Drawings
FIG. 1 is a schematic structural diagram of a terahertz metamaterial sensor provided by the invention;
FIG. 2 is a three-dimensional perspective view of a terahertz metamaterial sensor provided by the invention;
FIG. 3 is a structural simulation diagram of a terahertz metamaterial sensor prepared in embodiment 1 of the present invention;
FIG. 4 is a simulation diagram of a conventional single-split resonant ring structure according to the present invention;
FIG. 5 is an absorption spectrum of the antibiotic in the terahertz wave band in example 1 of the present invention;
fig. 6 is a schematic structural diagram of a metamaterial sensor in the transmission-type terahertz time-domain spectroscopy detection in embodiment 1 of the present invention;
FIG. 7 is a diagram of simulation results of antibiotic residue detection at different concentrations in milk powder.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a terahertz metamaterial sensor which comprises a unit structure; the unit structure comprises a flexible substrate and an asymmetric open ring structure arranged on the flexible substrate.
Referring to fig. 1 and fig. 2, fig. 1 is a schematic structural diagram of a terahertz metamaterial sensor provided by the present invention, where P is a period, r1 is an outer radius, r2 is an inner radius, g is an opening gap, w is a width of an asymmetric split ring, and α is an included angle between the opening gap of the asymmetric split ring and a vertical diameter; fig. 2 is a three-dimensional perspective view of the terahertz metamaterial sensor provided by the invention.
The terahertz metamaterial sensor provided by the invention comprises unit structures, wherein the unit structures are arranged according to a period; in the present invention, the period of the unit structure is preferably 75 μm.
In order to obtain the metamaterial sensor with high Q-value resonance response, loss can be reduced through two aspects, on one hand, a low-loss dielectric material is used as a substrate of the metamaterial, on the other hand, low-loss resonance is realized through designing a special metamaterial structure, and therefore the purposes of the metamaterial sensor with high Q-value and high sensitivity are achieved.
In the present invention, the unit structure includes a flexible substrate; the flexible substrate is preferably a polyimide substrate; the thickness of the flexible substrate is preferably 25 μm; the polyimide has low-loss dielectric property, and can be used as an ultrathin flexible substrate, so that the loss can be reduced, and the detection of a sample to be detected is facilitated.
An asymmetric open ring structure is arranged on the flexible substrate; the asymmetric split-ring structure means that the split of the split ring is in an asymmetric position; when the electric field direction of the incident light is vertically incident along the vertical direction, the open ring structure is in an asymmetric position. The asymmetric open ring structure is an asymmetric open gold ring structure, namely the asymmetric open ring structure is made of gold; the thickness of the asymmetric open ring structure is preferably 200 nm; the outer radius of the asymmetric open ring structure is preferably 30 μm; the inner radius is preferably 25 μm; the width of the film is 5 mu m; the number of the opening gaps of the asymmetric opening ring structure is preferably 2, and the two opening gaps are in asymmetric positions; in the invention, the included angles between the opening gap central line of the asymmetric opening ring structure and the vertical diameter are preferably 20 degrees; the vertical diameter is the diameter parallel to the unit structure period; the two open gaps are preferably located on one side of the vertical diameter of the non-split ring structure; the opening gaps of the asymmetric opening ring structures are preferably 5 μm.
The terahertz metamaterial sensor provided by the invention is a flexible substrate, so that the loss can be reduced, and the detection of a sample is facilitated; the asymmetric open-loop structure is arranged on the flexible substrate, Fano resonance and electric dipole resonance can be generated simultaneously, so that the sensor has dual-band resonance frequency in a terahertz band, wherein the Fano resonance is a resonance mode with a high Q value, and the two resonance peaks correspond to the absorption peak positions of antibiotics in the terahertz band, so that the sensing sensitivity of the sensor can be effectively improved through a coupling effect.
The invention also provides a preparation method of the terahertz metamaterial sensor, which comprises the following steps: preparing a flexible substrate; and spin-coating photoresist on the flexible substrate, processing the designed mask pattern by adopting a photoetching process, depositing a metal thin layer, and removing the photoresist to obtain the terahertz metamaterial sensor.
The flexible substrate of the metamaterial sensor provided by the invention preferably adopts a polyimide film, the asymmetric ring structure adopts a gold material, and the preparation process preferably comprises the following steps:
(1) and cleaning the surface of the silicon substrate. In order to ensure that the surface of the silicon substrate is clean and the polyimide solution is firmly attached to the silicon substrate, firstly, the silicon surface is subjected to ultrasonic cleaning by using acetone, alcohol and deionized water.
(2) The polyimide solution was spin coated. A 25 micron thick polyimide film was coated on a silicon wafer using a spin coating process.
(3) And (5) curing. In order to evaporate all the water in the polyimide solution, the solution is solidified and attached to a silicon substrate, and the polyimide solution which is spun and coated is placed in a vacuum drying oven for solidification.
(4) And removing the silicon substrate. The polyimide film is peeled from the silicon substrate by utilizing the corrosiveness of hydrofluoric acid solution to silicon.
(5) A periodic structure is prepared. Firstly, a layer of photoresist is spin-coated on the prepared polyimide film, then the designed mask pattern is used for photoetching processing, finally, gold with the thickness of 200 nanometers is plated on the photoresist, and the photoresist is removed. The metamaterial structure is designed as shown in fig. 1, and is a metal ring structure consisting of two openings, and the special asymmetric opening metal resonant ring structure has a unique resonance response compared with a traditional single opening resonant ring structure, and when the electric field direction of a terahertz wave is vertically incident along the vertical direction, the structure can simultaneously induce two resonant peaks, one is Fano resonance, and the other is electric dipole resonance. The Fano resonance is asymmetric resonance generated by interference of discrete spectral lines and continuous spectral lines with narrow line widths, and the Fano resonance has narrow line widths and higher Q value.
The invention also provides application of the terahertz metamaterial sensor in antibiotic residue detection, preferably application in antibiotic residue detection in dairy products.
The dairy product is preferably milk powder; the antibiotic is preferably one or more of cefixime, cefazolin oxime and cefazolin.
The terahertz metamaterial sensor provided by the invention has dual-waveband resonance frequency in a terahertz waveband, has the sensor characteristics of high Q value and high sensitivity, and can be used for detecting and analyzing antibiotic residues in milk powder by combining a terahertz time-domain spectroscopy technology, so that trace detection can be performed on the antibiotic residues in the milk powder, and the detection line reaches the highest content of national standards for food safety.
In order to further illustrate the invention, the following describes in detail a terahertz metamaterial sensor and applications thereof provided by the invention with reference to embodiments.
The reagents used in the following examples are all commercially available.
Example 1
1. Preparation of metamaterial sensor
The flexible substrate of the metamaterial sensor designed by the invention adopts a polyimide film, the periodic structure adopts a gold material, and the preparation process comprises the following steps: (1) and cleaning the surface of the silicon substrate. In order to ensure that the surface of the silicon substrate is clean and the polyimide solution is firmly attached to the silicon substrate, firstly, the silicon surface is subjected to ultrasonic cleaning by using acetone, alcohol and deionized water. (2) The polyimide solution was spin coated. A 25 micron thick polyimide film was coated on a silicon wafer using a spin coating process. (3) And (5) curing. In order to evaporate all the water in the polyimide solution, the solution is solidified and attached to a silicon substrate, and the polyimide solution which is spun and coated is placed in a vacuum drying oven for solidification. (4) And removing the silicon substrate. The polyimide film is peeled from the silicon substrate by utilizing the corrosiveness of hydrofluoric acid solution to silicon. (5) A periodic structure is prepared. Firstly, a layer of photoresist is spin-coated on the prepared polyimide film, then the designed mask pattern is used for photoetching processing, finally, gold with the thickness of 200 nanometers is plated on the photoresist, and the photoresist is removed. The outer radius of the asymmetric open ring structure is 30 mu m; the inner radius is 25 μm; the width of the film is 5 mu m; the number of the opening gaps is 2; the opening gaps are all 5 mu m; the angle between the centre line of the opening gap and the vertical diameter is 20 deg.
The metamaterial sensor is simulated by a frequency domain solver in CST software, and the simulation result is shown in FIG. 3, which shows that the positions of two obtained resonance peaks are 1.0THz and 1.7THz respectively. The two resonance peak positions of the sensor are basically consistent with the positions of antibiotic absorption peaks, so that the sensitivity of the sensor can be improved.
In addition, the experiment simulates the resonance response of the traditional single-opening resonance ring (that is, other structural parameters are the same as those of embodiment 1, and only one opening gap is included), and as a result, as shown in fig. 4, it can be seen that the resonance response spectral line of the structure is wide, and the requirement of a high-sensitivity sensor cannot be met.
In addition, three common antibiotics of cefixime, ceftizoxime and cefazolin are researched by utilizing a terahertz spectrum to obtain an absorption spectrogram of the antibiotics in a terahertz waveband, as shown in fig. 5. As can be seen from fig. 5, the three common antibiotics (cefixime, ceftizoxime and cefazolin) obtained by experimental measurement have obvious characteristic absorption peaks near 1.0, 1.4 and 1.8 THz. Therefore, the two resonance peaks of the metamaterial structure designed by the invention are closer to the absorption peak position of the antibiotic in the terahertz waveband, and the coupling effect can more effectively improve the sensing sensitivity.
2. Preparing standard solution
Selecting ceftizoxime as a sample to be detected, accurately weighing a proper amount of a standard substance to be detected, using cyclohexane as a solvent to prepare the concentration of a standard solution of the ceftizoxime, and then diluting the solution step by step according to actual needs to prepare an antibiotic solution with the standard concentration of 0.1, 0.3, 0.5, 0.7 and 0.9 mu g/mL. In addition, a proper amount of 10g of milk powder is accurately weighed and dissolved in a cyclohexane solution, and the prepared antibiotics with different concentration ratios are added into the milk powder solution to prepare the milk powder solution with the antibiotic concentrations of 0.1, 0.3, 0.5, 0.7 and 0.9 mug/mL for detection.
3. Detection of antibiotic residues at different concentrations in milk powder
Dropping 10 μ l of the prepared solution onto the metamaterial sensor, attaching the sample solution to be detected on the surface of the metamaterial structure (the polyimide film and the open gold ring are both attached with the sample solution to be detected), as shown in fig. 6, performing spectrum collection by using a transmission-type terahertz time-domain spectrometer, and analyzing the frequency domain signal. The simulation result of the antibiotic residue detection with different concentrations in the milk powder is shown in fig. 7, when the antibiotic is not contained in the sample to be detected, the obtained resonance peak positions are respectively 1.0THz and 1.7THz, when the antibiotic is contained in the sample to be detected, the dielectric constant of the surrounding environment of the sensor surface is changed, so that the two resonance peak positions are subjected to red shift, and as the antibiotic milk powder solutions with different concentrations have different dielectric constants, the dielectric constant of the sample solution to be detected is increased along with the increase of the antibiotic concentration, so that the red shift of the resonance peaks is increased along with the increase of the antibiotic concentration, and the antibiotic residue in the milk is quantitatively detected by the principle. The metamaterial structure sensor designed by the invention has high Q value and high sensitivity, can detect trace concentration antibiotics remained in milk powder, and the detection line can reach the highest content of national standard for food safety.
Claims (10)
1. A terahertz metamaterial sensor is characterized by comprising a unit structure; the unit structure comprises a flexible substrate and an asymmetric open ring structure arranged on the flexible substrate.
2. The terahertz metamaterial sensor according to claim 1, wherein the flexible substrate is a polyimide substrate, and the asymmetric open ring structure is an asymmetric open gold ring structure.
3. The terahertz metamaterial sensor of claim 1, wherein the flexible substrate is 25 μ ι η thick.
4. The terahertz metamaterial sensor according to claim 1, wherein the asymmetric open ring structure has a thickness of 200 nm.
5. The terahertz metamaterial sensor according to claim 1, wherein the period of the intra-cell structure is 75 μ ι η.
6. The terahertz metamaterial sensor according to claim 1, wherein the asymmetric open ring structure has an outer radius of 30 μm and an inner radius of 25 μm.
7. The terahertz metamaterial sensor according to claim 1, wherein the asymmetric open ring structure has 2 opening gaps.
8. The terahertz metamaterial sensor according to claim 7, wherein the opening gaps of the asymmetric open ring structure are each 5 μm.
9. The terahertz metamaterial sensor according to claim 7, wherein the asymmetric split-ring structure has a split gap centerline that is at an angle of 20 ° to the vertical diameter, and the two split gaps are located on one side of the vertical diameter of the non-split ring structure.
10. The terahertz metamaterial sensor as claimed in any one of claims 1 to 9, which is applied to antibiotic residue detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010058685.0A CN113138176A (en) | 2020-01-19 | 2020-01-19 | Terahertz metamaterial sensor and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010058685.0A CN113138176A (en) | 2020-01-19 | 2020-01-19 | Terahertz metamaterial sensor and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113138176A true CN113138176A (en) | 2021-07-20 |
Family
ID=76809916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010058685.0A Pending CN113138176A (en) | 2020-01-19 | 2020-01-19 | Terahertz metamaterial sensor and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113138176A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113670848A (en) * | 2021-08-23 | 2021-11-19 | 中国人民解放军军事科学院国防科技创新研究院 | High-resolution broadband terahertz detector based on pixelized structure and detection method |
-
2020
- 2020-01-19 CN CN202010058685.0A patent/CN113138176A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113670848A (en) * | 2021-08-23 | 2021-11-19 | 中国人民解放军军事科学院国防科技创新研究院 | High-resolution broadband terahertz detector based on pixelized structure and detection method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN212228734U (en) | Terahertz metamaterial sensor | |
| He et al. | Applications of Raman spectroscopic techniques for quality and safety evaluation of milk: A review of recent developments | |
| Qin et al. | A high-sensitivity terahertz spectroscopy technology for tetracycline hydrochloride detection using metamaterials | |
| CN111766221A (en) | Terahertz super-surface biosensor based on Fano resonance and preparation method thereof | |
| Yang et al. | A terahertz metamaterial sensor used for distinguishing glucose concentration | |
| CN110455743B (en) | Method for detecting aflatoxins B1 and B2 by utilizing terahertz waveband metamaterial sensor | |
| Zhang et al. | Rapid field trace detection of pesticide residue in food based on surface-enhanced Raman spectroscopy | |
| CN213041733U (en) | Terahertz metamaterial biosensor | |
| Sun et al. | Raman spectroscopy for food quality assurance and safety monitoring: A review | |
| KR20080100645A (en) | Surface plasmon resonance sensor chip using molecular imprinting technique for detecting the mycotoxins zearalenone and its derivatives, and method of the same, and detecting method of the mycotoxins zearalenone and its derivatives using the same | |
| Yan et al. | Research progress of terahertz wave technology in food inspection | |
| AU2015293757A1 (en) | Sensor and device for detecting an analyte in a liquid | |
| Zhang et al. | High-sensitivity detection of chlorothalonil via terahertz metasensor | |
| Hong et al. | A label-free biosensing platform using a PLL circuit and Biotin-Streptavidin Binding system | |
| CN113138176A (en) | Terahertz metamaterial sensor and application thereof | |
| Bailly et al. | Influence of the design in microwave-based gas sensors: ammonia detection with titania nanoparticles | |
| Liang et al. | [Retracted] A Review of Detection of Antibiotic Residues in Food by Surface‐Enhanced Raman Spectroscopy | |
| Yang et al. | Ultra-fast and high-sensitive tacrolimus solution detection based on microwave biosensor | |
| Yang et al. | The terahertz metamaterial sensor for imidacloprid detection | |
| US20220341846A1 (en) | Sample signal amplification method using terahertz band graphene absorber | |
| CN112803172B (en) | Quantitative detection method for trace IAA in pepper extract of terahertz metamaterial absorber | |
| CN111766218A (en) | Terahertz metamaterial biosensor and preparation method and application thereof | |
| CN114813625A (en) | Multi-parameter sensing evaluation method based on multi-resonance-peak terahertz metamaterial | |
| CN114264627A (en) | Terahertz sensor and using method thereof | |
| Rosman et al. | Correlation between reflection coefficient, dielectric properties and brix level of Malaysian oranges at microwave frequencies |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |