CN111812059A - Metamaterial terahertz biosensor and preparation method thereof - Google Patents
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Abstract
The invention discloses a metamaterial terahertz biosensor and a preparation method thereof. The metamaterial terahertz biosensor comprises a substrate layer and a dielectric layer, wherein a metal reflecting layer is arranged on the substrate layer, a metal micro-structure layer is arranged on the dielectric layer, a micro-flow channel for the circulation of a liquid to be measured is formed between the metal reflecting layer and the metal micro-structure layer, a liquid inlet and a liquid outlet of the micro-flow channel are formed in the substrate layer, the metal micro-structure layer is a periodic structure unit attached to the dielectric layer, and the metal micro-structure layer is composed of a square metal ring and a double H-shaped crossed metal structure which is arranged in the metal ring and is concentric with the metal ring, wherein the double H-shaped crossed metal structure is composed of two H-shaped metal rings which are completely identical in structure and are vertically crossed. The sensor has the characteristics of extremely high absorption peak, high sensitivity and polarization insensitivity.
Description
Technical Field
The invention relates to a sensor, in particular to a metamaterial terahertz biosensor and a preparation method thereof.
Background
Terahertz (Terahertz, abbreviated as THz, 1THz ═ 1012Hz) wave is an electromagnetic wave with the frequency within the range of 0.1-10 THz (the wavelength is 30-3000 mu m), is in a wave band transiting from macroscopic electronics to microscopic photonics, has unique physical characteristics such as fingerprint spectrum, safety, penetrability and the like in biomolecules, cells and tissues, and has good nondestructive detection characteristics, so the terahertz spectrum technology is particularly suitable for detecting the biomolecules, the cells and the like. Because the terahertz wave has fingerprint spectrum property, and the rotation and vibration energy levels of most of biological molecules are in the terahertz waveband, a specific fingerprint absorption peak can be formed in the terahertz waveband, and the characteristic spectrum of the biological molecules can be analyzed by utilizing the characteristic, so that qualitative and quantitative analysis of the biological molecules can be realized. However, most of biomolecules are weakly absorbed in the terahertz waveband range, the vibration of the biomolecules is greatly influenced by the external environment, and the problems of low sensitivity, high detection difficulty and the like exist in the direct identification by utilizing the terahertz spectrum.
Metamaterial (Metamaterial) is a novel artificial electromagnetic material consisting of periodically arranged sub-wavelength structural units, and has the extraordinary electromagnetic properties which are not possessed by natural materials, such as negative refraction, diffraction limit imaging breakthrough, stealth and the like. The metamaterial can realize local field enhancement and high-quality factor resonance through the mutual coupling effect with the terahertz waves. When a biological sample to be detected is attached to the surface of the metamaterial to cause the change of the environment of the surrounding medium, the resonance frequency can be shifted, and the detection of the biological sample can be realized through the shift degree of the resonance frequency. Therefore, the terahertz biosensor based on the metamaterial draws high attention of researchers at home and abroad.
Researchers have proposed that metamaterials based on Split Ring Resonators (SRRs) are designed as terahertz biosensors and enable detection of microorganisms, DNA, cancer cells, proteins, and the like. In 2015, a terahertz biosensor consisting of a single-opening resonance ring is proposed in the journal of Scientific Reports, volume 4, 4988, so that microorganisms such as fungi and bacteria can be rapidly detected. 2018, on page 31589 of 26 th volume of Optics Express journal, a terahertz metamaterial biosensor consisting of single-opening and double-opening resonance rings is reported, and different types of DNA are identified. However, the SRRs are designed as a transmission-type sensor, the sensor and the terahertz wave generate a single interaction to form low resonance strength, and cannot generate strong local field enhancement, and the interaction between the object to be measured and the local field is weak, so that the SRRs have low Q value and low sensitivity.
A Metamaterial Perfect absorber (PMAs) is composed of a metal periodic structure layer, a dielectric layer and a metal reflecting layer. Due to the existence of the metal reflecting layer and the metal periodic structure layer, incident terahertz waves can form multiple reflections in the dielectric layer. The terahertz wave interacts with the absorber for multiple times to form a Fabry-Perot (F-P) resonant cavity, and the absorber interacts with the terahertz wave strongly to obtain a high quality factor Q and local electric field enhancement. 2019, the Optik journal, volume 194, page 163071, describes a terahertz perfect absorber based on a super surface with a high Q value. The absorber can be used as a terahertz sensor applied to the field of sensing, and the maximum sensitivity of the absorber is 190.4 GHz/RIU. When the existing PMAs-based terahertz sensor is used for detecting substances, the substances to be detected are attached to the surface of the metal periodic structure layer, are positioned outside an F-P resonant cavity and cannot be overlapped with a local enhanced electric field space, and only weak interaction is generated between the substances and the local enhanced electric field space, so that the sensitivity of the sensor is not high.
The invention patent with publication number CN103499534A discloses a high-sensitivity terahertz microfluidic channel sensor, which comprises a substrate and a cover layer, wherein a metal plane reflector and a metal microstructure layer are respectively arranged on the substrate and the cover layer, a microfluidic channel is formed between the metal plane reflector and the metal microstructure layer, and when a liquid to be detected is stored in the microfluidic channel, a composite structure formed by the metal microstructure layer, the liquid to be detected and the metal plane reflector has a strong absorption characteristic caused by resonance in a terahertz waveband. The micro-flow channel is integrated between the metal plane reflecting mirror and the metal microstructure layer, and a composite structure with resonance absorption characteristics is formed together (the absorption at the resonance frequency can exceed 95%), an electromagnetic field is spatially localized in the micro-flow channel due to the resonance effect and is completely overlapped with the liquid to be detected, the micro-flow channel is very sensitive to the refractive index of the liquid to be detected in the micro-flow channel, and the detection limit of the refractive index of the liquid to be detected reaches 0.0014RIU (calculated according to the spectral resolution of a terahertz spectrometer being 5 GHz). Specifically, in the fifth embodiment of the present invention, two absorption peaks can be obtained by using a sensor designed by combining two simple units. According to the change graph of the absorption spectrum of the sensor designed by the example along with the refractive index, when the refractive index of liquid in the fluid channel is changed within the range of 1-1.5, the absorption rate of the absorption peak of the sensor is about 80% at most and about 40% at least. In the sixth embodiment, a plurality of different metal microstructure layers and microfluidic channels are cascaded in the plane direction of the microfluidic channel, and a double-absorption-peak terahertz sensor is designed. According to the graph of the change of the absorption spectrum of the sensor along with the refractive index, the fluctuation of the absorption rate of the absorption peak of the sensor in liquid with different refractive indexes is large, when the refractive index of the liquid in the fluid channel changes within the range of 1-1.5, the maximum value of the absorption rate exceeds 90%, and the minimum value is lower than 40%. From the above analysis, it can be seen that the sensor of the invention achieves a high detection limit of the refractive index, but the absorption peak amplitude is low and the fluctuation is large. Due to the strong absorption characteristic of water to terahertz, the energy of incident terahertz waves can be weakened by adding liquid into the fluid channel, so that the resonance strength formed by interaction between the sensor and the terahertz waves is weakened, and the absorption rate of an absorption peak is reduced. The absorption peak formed by the sensor of the invention has lower absorptivity, and the absorption peak with lower absorptivity can be obtained when the sensor is used for liquid sensing, so that the detection effect is directly influenced.
Disclosure of Invention
The invention aims to provide a metamaterial terahertz biosensor with high absorption peak, high sensitivity and polarization insensitivity and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a metamaterial terahertz biosensor comprises a substrate layer and a dielectric layer, wherein a metal reflecting layer is arranged on the substrate layer, a metal micro-structure layer is arranged on the dielectric layer, a micro-flow channel for flowing of a measured liquid is formed between the metal reflecting layer and the metal micro-structure layer, a liquid inlet and a liquid outlet of the micro-flow channel are formed in the substrate layer, the metal micro-structure layer is a periodic structure unit attached to the dielectric layer, the metal micro-structure layer is composed of a square metal ring and a double H-shaped crossed metal structure which is arranged in the metal micro-structure layer and concentric with the metal micro-structure, and the double H-shaped crossed metal structure is composed of two H-shaped metal rings which are completely identical in structure and are vertically crossed.
The metal microstructure layer in the sensor is of a quadruple rotational symmetric structure, so that the sensor has the polarization insensitivity. And the polarization insensitivity of the sensor is beneficial to reducing experimental errors and shortening experimental data processing time, and the rapid and high-sensitivity detection of the object to be detected is realized.
In the above technical solution, the metal microstructure layer is at least 4 periodic structure units attached to the dielectric layer. The period of the metal microstructure layer in the X-axis direction is 110-130 mu m, and the period in the Y-axis direction is 110-130 mu m. Under the periodic condition, the length of the outer edge of a square metal ring in the metal microstructure layer structure is 100-110 microns, and the ring width is 5-10 microns; the arm length of the H-shaped metal ring in the double H-shaped crossed metal structure is 25-30 micrometers, the arm width is 5-10 micrometers, the leaf length is 35-45 micrometers, and the leaf width is 4-8 micrometers.
Preferably, the period of the metal microstructure layer in the X-axis direction is 120 μm, and the period in the Y-axis direction is 120 μm. At the moment, in the metal microstructure layer structure, the outer side length of the square metal ring is 108 microns, and the ring width is 8 microns; the arm length of the H-shaped metal ring in the double H-shaped crossed metal structure is 26 micrometers, the arm width is 8 micrometers, the leaf length is 40 micrometers, and the leaf width is 6 micrometers.
In the technical scheme, the thicknesses of the substrate layer, the dielectric layer, the metal reflecting layer and the metal microstructure layer and the height of the microfluidic channel are the same as those of the prior art, preferably, the thickness of the substrate layer is 100-120 μm, and further preferably 110 μm; the thickness of the dielectric layer is 2-8 μm, and the preferred thickness is 4 μm; the thickness of the metal microstructure layer is 0.1-0.5 μm, and the preferable thickness is 0.2 μm; the thickness of the metal reflecting layer is 0.1-0.5 μm, and more preferably 0.2 μm; the height of the microfluidic channel is 4-8 μm, and more preferably 6 μm.
In the above technical solution, the materials of the substrate layer, the dielectric layer, the metal reflective layer and the metal microstructure layer are the same as those of the prior art, specifically, the materials of the dielectric layer and the substrate layer may be any one of high-resistivity silicon, polyimide, quartz crystal, cyclic olefin polymer, Polytetrafluoroethylene (PTFE), and the like, and the materials of the metal reflective layer and the metal microstructure layer may be any one of gold, silver, copper, aluminum, and the like. In the present application, the material of the dielectric layer is preferably polytetrafluoroethylene, the material of the substrate layer is preferably high-resistance silicon, the material of the metal reflective layer is preferably silver, and the material of the metal microstructure layer is preferably silver.
The preparation method of the metamaterial terahertz biosensor provided by the invention comprises the following steps:
1) preparing a top module: forming a metal microstructure layer on the dielectric layer through the processes of gluing, exposing, developing, coating and stripping on the dielectric layer to obtain a top layer module;
2) preparing a bottom layer module: etching a groove with the size matched with that of the top module on the substrate layer, then laminating a metal film on the bottom surface of the groove to form a metal reflecting layer, and finally forming a liquid inlet and a liquid outlet which are communicated with the groove on the substrate layer to obtain a bottom module;
3) and bonding the top layer module and the bottom layer module, and forming a microfluidic channel between the metal microstructure layer of the top layer module and the metal reflecting layer of the bottom layer module to obtain the metamaterial terahertz biosensor.
In step 1) of the above method, when the material of the dielectric layer is polytetrafluoroethylene, plasma enhanced chemical deposition may be used to obtain polytetrafluoroethylene with a corresponding thickness as the dielectric layer. The procedures of gluing, exposure, development, coating and peeling are operated according to the prior conventional technology. The film coating is preferably a metal film formed on the dielectric layer by an electron beam evaporation deposition method, the metal type of the metal film is the same as the material of the metal microstructure layer, and the thickness of the metal film is determined according to the thickness of the metal microstructure layer.
In step 2) of the method, the length and width of the groove are respectively matched with the length and width of the top module, and the depth of the groove is the sum of the thickness of the metal reflecting layer and the height of the microfluidic channel. Etching a groove on the substrate layer by utilizing an ICP (inductively coupled plasma) etching technology, and laminating a metal film on the bottom surface of the groove by adopting an electron beam evaporation deposition method, wherein the metal type of the metal film is the same as the material selection of the metal reflecting layer, and the thickness of the metal film is determined according to the thickness of the metal reflecting layer.
In the step 3) of the method, the top layer module and the bottom layer module are bonded by adopting a sealant, at the moment, a micro-flow channel is formed between the metal micro-structure layer of the top layer module and the metal reflection layer of the bottom layer module, and the liquid inlet and the liquid outlet which are formed in the step 2) and are communicated with the groove form a liquid inlet and a liquid outlet of the micro-flow channel.
Compared with the prior art, the invention is characterized in that:
1. the metal microstructure layer is of a quadruple rotational symmetric structure, so that the sensor has the polarization insensitivity. And the polarization insensitivity of the sensor is beneficial to reducing experimental errors and shortening experimental data processing time, and the rapid and high-sensitivity detection of the object to be detected is realized.
2. The sensor disclosed by the invention adopts a special metal microstructure layer structure design and combines a microfluidic channel, so that the sensing sensitivity of the sensor is greatly improved, the maximum sensitivity can reach 620GHz/RIU, and the problem of low sensitivity of the conventional metamaterial terahertz sensor is effectively solved.
3. The sensor provided by the invention adopts a special metal microstructure layer structure design and combines a microfluidic channel, so that the obtained sensor has two high-absorptivity resonance peaks within the frequency range of 0.4-1.4 THz, the absorptivity is higher than 98%, and the maximum Q value reaches 30.8.
Drawings
FIG. 1 is a schematic longitudinal cross-sectional view of one embodiment of a sensor according to the present invention.
Fig. 2 is a three-dimensional expanded view of the embodiment shown in fig. 1.
Fig. 3 is a top view of a metallic microstructure layer in the embodiment shown in fig. 1.
Fig. 4 is a schematic structural diagram of a top module prepared in example 1 of the present invention.
Fig. 5 is a schematic structural diagram of a bottom module prepared in embodiment 1 of the present invention.
Fig. 6 is a schematic structural view of the bonding of the top module and the bottom module in example 1 of the present invention.
Fig. 7 is a schematic structural diagram of a basic sensor structural unit for performing absorption characteristic analysis, resonance mechanism analysis, polarization insensitivity characteristic analysis and sensing performance analysis on the sensor of the present invention.
Fig. 8 is a reflection and absorption spectrum of the sensor, wherein the dashed line represents the reflection spectrum and the solid line represents the absorption spectrum.
FIG. 9 shows the sensor at resonant frequency point f1And f2Electric field profile of (a); wherein (a) is the sensor at the resonance frequency point f1(b) is the sensor at the resonant frequency point f2The electric field profile of (a).
FIG. 10 shows the metal microstructure layer at the resonant frequency f1And f2Surface current distribution pattern and metal reflection layer at resonance frequency point f1And f2Surface current profile of (a); wherein (a) is the metal microstructure layer at the resonance frequency point f1The surface current distribution diagram of (c) is the resonance frequency point f of the metal microstructure layer2The surface current distribution pattern of (b) is the resonance frequency point f of the metal reflection layer1The surface current distribution pattern of (d) is the resonance frequency point f of the metal reflection layer2Surface current distribution map of (1).
FIG. 11 is an absorption spectrum of a sensor under TE and TM mode terahertz waves, wherein
In the form of the TM mode, the optical fiber is,
is in TE mode.
Fig. 12 shows absorption spectra of the sensor at different polarization angles and incidence angles, wherein (a) shows the absorption spectra at different polarization angles, and (b) shows the absorption spectra at different incidence angles.
FIG. 13 shows absorption spectra of sensors under different dielectric constants of the analyte.
FIG. 14 shows the low resonant frequency f of the DUT with different dielectric constants1And a high-frequency resonance frequency f2。
FIG. 15 is an absorption spectrum of a sensor at different analyte loss tangent values.
FIG. 16 shows the low resonant frequency f1And a high resonance frequency f2Absorption rates at different dielectric constants of the analyte, wherein,
denotes f1，
Denotes f2。
The reference numbers in the figures are:
1 a dielectric layer, 2 a metal microstructure layer, 3 a micro-flow channel, 4a metal reflecting layer, 5 a basal layer, 6 a liquid outlet and 7 a liquid inlet; a represents the outer side length of the square metal ring, b represents the ring width of the square metal ring, c represents the arm length of the H-shaped metal ring in the double H-shaped crossed metal structure, d represents the arm width of the H-shaped metal ring in the double H-shaped crossed metal structure, e represents the leaf length of the H-shaped metal ring in the double H-shaped crossed metal structure, and f represents the leaf width of the H-shaped metal ring in the double H-shaped crossed metal structure.
Detailed Description
The invention relates to a metamaterial terahertz biosensor, which comprises a substrate layer 5 and a dielectric layer 1, wherein a metal reflecting layer 4 is arranged on the substrate layer 5, a metal micro-structure layer 2 is arranged on the dielectric layer 1, a micro-flow channel 3 for flowing of a measured liquid is formed between the metal reflecting layer 4 and the metal micro-structure layer 2, and a liquid inlet 7 and a liquid outlet 6 of the micro-flow channel 3 are formed on the substrate layer 5. When the liquid to be detected is stored in the microfluidic channel 3, a composite structure formed by combining the metal microstructure layer 2, the liquid to be detected and the metal reflecting layer 4 has strong absorption characteristics caused by resonance in a terahertz waveband.
The metal microstructure layer 2 is formed by M gamma N units which are periodically arranged on the dielectric layer 1, the metal microstructure layer 2 is of a quadruple rotational symmetry structure, and M and N are integers larger than or equal to 4. The period of the metal microstructure layer 2 in the X-axis direction is 110 to 130 μm, and the period in the Y-axis direction is 110 to 130 μm. Under the periodic condition, the length a of the outer edge of a square metal ring in the metal microstructure layer 2 structure is 100-110 microns, and the width b of the metal ring is 5-10 microns; in the double H-shaped crossed metal structure, the arm length c of the H-shaped metal ring is 25-30 mu m, the arm width d is 5-10 mu m, the leaf length e is 35-45 mu m, and the leaf width f is 4-8 mu m.
The thickness of the substrate layer 5 is 100-120 μm, and the substrate layer can be made of any one of high-resistance silicon, polyimide, quartz crystal, cyclic olefin polymer, polytetrafluoroethylene and the like; the thickness of the dielectric layer 1 is 2-8 μm, and the material can be any one of high-resistance silicon, polyimide, quartz crystal, cyclic olefin polymer, polytetrafluoroethylene and the like; the thickness of the metal microstructure layer 2 is 0.1-0.5 μm, and the material can be any one of gold, silver, copper, aluminum and the like; the thickness of the metal reflecting layer 4 is 0.1-0.5 μm, and the material thereof may be any one of gold, silver, copper, aluminum, and the like.
The preparation method of the metamaterial terahertz biosensor comprises the following steps:
1) preparing a top module: forming a metal microstructure layer 2 on the dielectric layer 1 through the processes of gluing, exposing, developing, coating and stripping on the dielectric layer 1 to obtain a top layer module;
2) preparing a bottom layer module: etching a groove matched with the size of the top module on the substrate layer 5, then laminating a metal film on the bottom surface of the groove to form a metal reflecting layer 4, and finally forming a liquid inlet 7 and a liquid outlet 6 which are communicated with the groove on the substrate layer 5 to obtain a bottom module;
3) and (3) bonding the top layer module and the bottom layer module, and forming a microfluidic channel 3 between the metal microstructure layer 2 of the top layer module and the metal reflecting layer 4 of the bottom layer module to obtain the metamaterial terahertz biosensor.
In step 1) of the above method, when the material of the dielectric layer 1 is polytetrafluoroethylene, plasma enhanced chemical deposition may be used to obtain polytetrafluoroethylene with a corresponding thickness as the dielectric layer 1. The procedures of gluing, exposure, development, coating and peeling are operated according to the prior conventional technology. The metal film is formed on the dielectric layer 1 by adopting an electron beam evaporation deposition method, the metal type of the metal film is the same as the material of the metal microstructure layer 2, and the thickness of the metal film is determined according to the thickness of the metal microstructure layer 2.
In step 2) of the method, the length and width of the groove are respectively matched with the length and width of the top module, and the depth of the groove is the sum of the thickness of the metal reflecting layer 4 and the height of the microfluidic channel 3. Etching a groove on the substrate layer 5 by utilizing an ICP (inductively coupled plasma) etching technology, and laminating a metal film on the bottom surface of the groove by adopting an electron beam evaporation deposition method, wherein the metal type of the metal film is the same as the material selection of the metal reflecting layer 4, and the thickness of the metal film is determined according to the thickness of the metal reflecting layer 4.
In the step 3) of the method, the top layer module and the bottom layer module are bonded by adopting a sealant, at the moment, a micro-flow channel 3 is formed between the metal micro-structure layer 2 of the top layer module and the metal reflection layer 4 of the bottom layer module, and the liquid inlet 7 and the liquid outlet 6 which are formed in the step 2) and are communicated with the groove form the liquid inlet 7 and the liquid outlet 6 of the micro-flow channel 3.
The present invention will be better understood from the following detailed description of preferred embodiments thereof, taken in conjunction with the accompanying drawings.
Example 1
The structure and preparation of the sensor according to the present invention will be described with reference to the structural diagrams shown in fig. 1 to 3.
Referring to fig. 1 to 3, the metal microstructure layer 2 is 4X 4 units periodically arranged on the dielectric layer 1, and both the period of the metal microstructure layer 2 in the X-axis direction and the period of the metal microstructure layer 2 in the Y-axis direction are 120 μm. In the structure of the metal microstructure layer 2, the length a of the outer edge of the square metal ring is 108 μm, and the width b of the metal ring is 8 μm; in the double H-shaped crossed metal structure, the arm length c of the H-shaped metal ring is 26 μm, the arm width d is 8 μm, the leaf length e is 40 μm, and the leaf width f is 6 μm.
The thickness of the substrate layer 5 is 110 μm, and the substrate layer is made of high-resistance silicon; the thickness of the medium layer 1 is 6 μm, and the material is polytetrafluoroethylene; the thickness of the metal microstructure layer 2 is 0.2 μm, and the material is silver; the thickness of the metal reflecting layer 4 is 0.2 μm, and the material is silver; the height of the microfluidic channel 3 was 6 μm.
The sensor designed by the application needs to be tested in a THz time-domain spectroscopy system, and the diameter of a THz light beam on a focusing plane in the THz time-domain spectroscopy system is about 5mm, so that the effective size of the sensor is larger than 5mm x 5mm, specifically 10mm x 10mm in the embodiment.
The preparation method of the sensor comprises the following steps:
1) preparing a top module:
1.1) depositing a dielectric layer 1: polytetrafluoroethylene with the thickness of 4 mu m is obtained by adopting a plasma enhanced chemical phase deposition method and is used as a dielectric layer 1;
1.2) gluing: coating AZ 5214 positive photoresist on the dielectric layer 1, and baking for 90s in an oven at 100 ℃;
1.3) exposure: masking the substrate coated with the photoresist by using a mask plate, and then exposing the substrate under ultraviolet rays for 60 s;
1.4) developing: placing the substrate after the exposure in AZ300MIF developing solution for developing for 100s to obtain a pattern on the mask;
1.5) coating: forming a metal silver film with the thickness of 0.2 mu m on the polytetrafluoroethylene layer by utilizing an electron beam evaporation deposition technology;
1.6) stripping: after the coating is finished, the sample wafer is placed in an acetone solution for 10min, the photoresist is stripped, and then the sample wafer is washed by deionized water to obtain a top layer module (as shown in fig. 4).
2) Preparing a bottom layer module:
2.1) etching grooves on the base layer 5: etching a groove with the height of 6.2 mu m on the high-resistance silicon surface with the thickness of 100 mu m by utilizing an ICP (inductively coupled plasma) etching technology;
2.2) depositing a metal film on the bottom surface of the groove: depositing a metal silver film with the thickness of 0.2 mu m on the bottom surface of the groove by using an electron beam evaporation deposition technology to serve as a metal reflecting layer 4;
2.3) arranging a liquid inlet 7 and a liquid outlet 6 which are communicated with the grooves on the substrate layer 5 to obtain a bottom layer module (as shown in figure 5).
3) And (3) bonding the top layer module and the bottom layer module (as shown in fig. 6), forming a micro-flow channel 3 with the height of 6 microns between the metal micro-structure layer 2 of the top layer module and the metal reflection layer 4 of the bottom layer module, wherein the liquid inlet 7 and the liquid outlet 6 which are formed in the step 2) and are communicated with the groove form a liquid inlet 7 and a liquid outlet 6 of the micro-flow channel 3, and thus the metamaterial terahertz biosensor is obtained.
Example 2
The absorption characteristics of the sensor were analyzed with the sensor structure unit having the structure shown in fig. 7.
In the sensor structural unit shown in fig. 7, the period (Dx) in the X-axis direction and the period (Dy) in the Y-axis direction of the metal micro-structural layer 2 are both 120 μm. In the structure of the metal microstructure layer 2, the length a of the outer edge of the square metal ring is 108 μm, and the width b of the metal ring is 8 μm; in the double H-shaped crossed metal structure, the arm length c of the H-shaped metal ring is 26 μm, the arm width d is 8 μm, the leaf length e is 40 μm, and the leaf width f is 6 μm. The thickness of the substrate layer 5 is 110 μm, and the substrate layer is made of high-resistance silicon; the thickness of the medium layer 1 is 6 μm, and the material is polytetrafluoroethylene; the thickness of the metal microstructure layer 2 is 0.2 μm, and the material is silver; the thickness of the metal reflecting layer 4 is 0.2 μm, and the material is silver; the height of the microfluidic channel 3 was 6 μm.
In order to research the absorption characteristics of the sensor, full-wave simulation is carried out on the structure of the sensor unit by using CSTCmicrowave Studio based on a finite element algorithm. And the solver adopts a frequency domain solver, and the self-adaptive grid is used for structural grid division. Periodic boundary conditions are set along both the x-axis and y-axis directions, and open boundary conditions are set along the z-axis direction. The absorption rate of the sensor can be obtained by calculating an S parameter, and the calculation formula is as follows:
A＝1-|S11|2-|S21|2(1)
wherein A represents the absorption rate of the sensor and S11And S21Respectively the reflection coefficient and the transmission coefficient of the sensor. The thickness of the metal reflecting layer 4 is 0.2 μm and is larger than the skin depth of the metal silver in the terahertz wave band, the terahertz wave does not penetrate through the metal reflecting layer 4, and S in the formula 210. Therefore, the above-mentioned absorption rate calculation formula of the sensor can be simplified as follows:
A＝1-|S11|2(2)
when there is no analyte in the microfluidic channel 3 (n ═ 1, where n denotes the refractive index under vacuum), the absorption and reflection spectra of the sensor are shown in fig. 8. As can be seen from the figure, the sensor forms two high-absorptivity resonance peaks with absorptivity higher than 98% in a 0.4-1.4 THz frequency band under the vertical incidence of the terahertz waves in the TE mode. Wherein the resonant frequency f of the low-frequency absorption peak10.65THz, absorption A199.5%; resonant frequency f of high-frequency absorption peak21.15THz, absorption A2＝98.5％。
Example 3
The resonance mechanism of the sensor was analyzed with the sensor structural unit having the structure shown in fig. 7.
In order to explore the resonance mechanism of the sensor, the electric field distribution and the surface current distribution of the sensor at the resonance frequency point are solved by using CST Microwave Studio simulation. The simulation result shows that the structural unit is at the resonant frequency point f under the action of the TE mode terahertz wave of the sensor1And f2As shown in fig. 9. As can be seen from FIG. 9(a), at the resonance frequency point f1The upper and lower sides of the square metal ring form a remarkable local enhanced electric field at a resonant frequency point f2The longitudinal "H" shaped metal structure forms a significant local enhanced electric field. From this, f is1Has an absorption peak ofFormed by coupling a square metal ring and a terahertz wave to each other, and f2The absorption peak is obtained from a double 'H' -type crossed metal structure. Further, the resonance type of the sensor can be judged by analyzing the distribution condition of the surface current excited by the sensor. FIGS. 10(a) and (c) show the metal microstructure at the resonant frequency point f under the action of TE mode terahertz waves of the sensor1And f2The surface current distribution of (a), (b) and (d) show the resonant frequency f of the metal reflective layer 4, respectively1And f2Surface current distribution. As can be seen from fig. 10, at the resonant frequency point, the directions of the surface currents excited by the metal microstructures and the metal reflective layer 4 are opposite, a current loop is formed between the two layers, magnetic dipole resonance is generated, and terahertz wave absorption at a specific frequency point is realized.
Example 4
The polarization insensitive properties of the sensor were analyzed for the sensor structure unit in the configuration shown in fig. 7.
Due to the linear polarization of the terahertz measurement system, the polarization angle and the incident angle of terahertz waves generated by the system fluctuate. If the designed sensor is a polarization sensitive structure, errors will be generated in measured data, and the sensor cannot realize rapid and high-sensitivity detection. In practical application, a terahertz sensor with excellent performance needs not only high absorption peak, high quality factor and high sensitivity, but also polarization insensitivity. Therefore, the structural unit of the sensor designed by the invention is a quadruple rotational symmetry structure (the structures are still overlapped after the structural center point is rotated by 90 degrees, 180 degrees, 270 degrees and 360 degrees), and the sensor has good polarization insensitivity. The invention performs polarization insensitive property verification on the proposed sensor. Firstly, the polarization characteristics of the sensor under the action of the TE mode terahertz waves and the TM mode terahertz waves are verified, and as shown in FIG. 11, the absorption spectra of the sensor almost completely coincide under the action of the TE mode terahertz waves and the TM mode terahertz waves; second, the polarization characteristics of the sensor under the action of TE mode terahertz waves of different polarization angles and incidence angles (0 °, 10 °, 20 °, 30 °, 40 °, and 50 °). As shown in FIG. 12, the terahertz of the sensor at different polarization angles and incidence anglesResonance frequency point f under the action of wave1And f2There was no significant shift and the absorption amplitude was unchanged. The results show that the sensor provided by the invention has good polarization insensitivity.
Example 5
The sensor structure unit having the structure shown in fig. 7 was used to analyze the sensing performance of the sensor.
When the traditional metamaterial perfect absorber detects an object to be detected, the object to be detected is attached to the surface of the metal periodic structure layer, so that the object to be detected cannot be fully overlapped with the local field enhancement space, the interaction between the object to be detected and the local field enhancement space is weak, and the detection sensitivity of a sensor is relatively low. According to the invention, through the integrated microfluidic channel 3, the analyte is fully superposed with the local enhanced electric field space in the F-P resonant cavity, so that the interaction between the analyte and the local enhancement is greatly enhanced, and the sensitivity of the sensor can be effectively improved.
The sensitivity and the quality factor are important indexes for measuring the sensing performance of the sensor. The sensitivity S represents the frequency deviation degree of the object to be measured under the unit refractive index change, and the calculation formula is as follows:
wherein, Δ f is the resonance frequency offset, and Δ n is the refractive index variation of the object. And according to the relation between the dielectric constant and the refractive index:
in the formula, n represents the refractive index of the object to be measured; representing the dielectric constant of the object to be measured; mu.s0Permeability, value 1. The sensing sensitivity of the sensor when objects to be measured with different dielectric constants are added can be calculated.
The quality factor Q represents the degree of loss of the coupling effect of the terahertz wave and the sensor. The larger the Q value is, the smaller the resonance loss is, and the sharper the resonance peak is. The formula for the quality factor Q is:
wherein f is0At the resonance frequency, FWHM is the full width at half maximum.
Fig. 13 is an absorption spectrum of the sensor under different dielectric constants of the object to be measured, and fig. 14 is a variation of the resonant frequency with the dielectric constant of the object to be measured. As can be seen from fig. 13 and 14, the resonant frequency of the sensor is red-shifted as the dielectric constant of the object increases. Linear fitting, low resonant frequency f1Has a sensitivity of S1Quality factor Q of 330GHz/RIU128; high resonance frequency f2Has a sensitivity of S2Quality factor Q620 GHz/RIU230.8. In addition, the integrated microfluidic channel 3 may enable solution analyte detection, and the angle of depletion of solution analyte is also a factor affecting sensor performance. FIG. 15 shows the absorption spectra of the sensor at different analyte loss tangent values when the dielectric constant of the analyte is fixed at 1. As can be seen from fig. 15, when the loss tangent of the analyte is increased from 0.02 to 0.1, the resonant frequency of the sensor remains unchanged, and the absorption rate of the absorption peak is significantly reduced due to the impedance matching failure and the electromagnetic loss, as shown in fig. 16, but when the loss tangent reaches 0.1, the absorption peak of the sensor still maintains a high absorption rate, which is greater than 60%. In addition, the sensor can also distinguish the loss of the object to be measured with different loss angles according to the change of the absorption rate of the resonance frequency point.
Claims (10)
1. A metamaterial terahertz biosensor comprises a substrate layer (5) and a dielectric layer (1), a metal reflecting layer (4) is arranged on the substrate layer (5), a metal microstructure layer (2) is arranged on the dielectric layer (1), a micro-flow channel (3) for the circulation of the liquid to be detected is formed between the metal reflecting layer (4) and the metal micro-structure layer (2), a liquid inlet (7) and a liquid outlet (6) of the micro-flow channel (3) are arranged on the basal layer (5), it is characterized in that the metal microstructure layer (2) is a periodic structure unit attached on the dielectric layer (1), the metal microstructure layer (2) consists of a square metal ring and a double H-shaped crossed metal structure which is arranged in the metal ring and is concentric with the metal ring, wherein the double H-shaped crossed metal structure is composed of two H-shaped metal rings with the same structure which are vertically crossed.
2. The metamaterial terahertz biosensor as claimed in claim 1, wherein the period of the metal microstructure layer (2) in the X-axis direction is 110-130 μm, and the period in the Y-axis direction is 110-130 μm.
3. The metamaterial terahertz biosensor as claimed in claim 2, wherein in the structure of the metal microstructure layer (2), the outer side length (a) of the square metal ring is 100-110 μm, and the ring width (b) is 5-10 μm; in the double H-shaped crossed metal structure, the arm length (c) of the H-shaped metal ring is 25-30 μm, the arm width (d) is 5-10 μm, the leaf length (e) is 35-45 μm, and the leaf width (f) is 4-8 μm.
4. The metamaterial terahertz biosensor as claimed in any one of claims 1 to 3, wherein the period of the metal microstructure layer (2) in the X-axis direction is 120 μm, and the period in the Y-axis direction is 120 μm.
5. The metamaterial terahertz biosensor as claimed in claim 4, wherein in the structure of the metal microstructure layer (2), the outer side length (a) of a square metal ring is 108 μm, and the ring width (b) is 8 μm; in the double H-shaped crossed metal structure, the arm length (c) of the H-shaped metal ring is 26 μm, the arm width (d) is 8 μm, the leaf length (e) is 40 μm, and the leaf width (f) is 6 μm.
6. The metamaterial terahertz biosensor as claimed in any one of claims 1 to 3, wherein the thickness of the base layer (5) is 100 to 120 μm, and the thickness of the dielectric layer (1) is 2 to 8 μm.
7. The metamaterial terahertz biosensor as claimed in any one of claims 1 to 3, wherein the thickness of the metal microstructure layer (2) is 0.1 to 0.5 μm.
8. The metamaterial terahertz biosensor as claimed in any one of claims 1 to 3, wherein the thickness of the metal reflective layer (4) is 0.1 to 0.5 μm.
9. The metamaterial terahertz biosensor as claimed in any one of claims 1 to 3, wherein the height of the microfluidic channel (3) is 4 to 8 μm.
10. The preparation method of the metamaterial terahertz biosensor as claimed in claim 1, comprising the following steps:
1) preparing a top module: forming a metal microstructure layer (2) on the dielectric layer (1) through the processes of gluing, exposing, developing, coating and stripping on the dielectric layer (1) to obtain a top layer module;
2) preparing a bottom layer module: etching a substrate layer (5) to form a groove with the size matched with that of the top module, then laminating a metal film on the bottom surface of the groove to form a metal reflecting layer (4), and finally forming a liquid inlet (7) and a liquid outlet (6) which are communicated with the groove on the substrate layer (5) to obtain a bottom module;
3) and (3) bonding the top layer module and the bottom layer module, and forming a microfluidic channel (3) between the metal microstructure layer (2) of the top layer module and the metal reflecting layer (4) of the bottom layer module to obtain the metamaterial terahertz biosensor.
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