CN102288583A - Transmission-type metal grating coupling SPR (Surface Plasmon Resonance) detection chip and detection instrument - Google Patents

Transmission-type metal grating coupling SPR (Surface Plasmon Resonance) detection chip and detection instrument Download PDF

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Publication number
CN102288583A
CN102288583A CN2011101982403A CN201110198240A CN102288583A CN 102288583 A CN102288583 A CN 102288583A CN 2011101982403 A CN2011101982403 A CN 2011101982403A CN 201110198240 A CN201110198240 A CN 201110198240A CN 102288583 A CN102288583 A CN 102288583A
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detection chip
metal grating
grating coupling
transmissive metal
detection
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张宝顺
刘帆
李海军
付凯
刘冬
杨乐臣
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Abstract

The invention discloses a transmission-type metal grating coupling SPR (Surface Plasmon Resonance) detection chip and a detection instrument, which are used for detecting a target analyte in a micro fluid. The detection chip comprises a non-light tight substrate, a metal film layer and a micro fluid layer, wherein the metal film layer is formed on the substrate, and has a grating structures; the micro fluid layer is covered on the surface of the metal film layer; and a micro fluid channel is formed in the micro fluid layer, and is contacted with a metal film surface. The detection instrument comprises a light source, a spectrometer and the detection chip. By using the local characteristic of a surface plasma excimer and the frequency selection characteristic of a grating, enhancement and filtration of signals are realized; and moreover, the change of a transmittance peak value is measured by performing grating coupling on incident light, so that the biological information or concentration change of a detected object is detected. During detection, an incident angle does not need to be changed. The detection chip and the detection instrument have the advantages of real-time monitoring, high sensitivity, stability, quickness, small instrument size, convenience for carrying and operating, and the like.

Description

Transmissive metal grating coupling SPR detection chip and detector
Technical field
The present invention be more particularly directed to a kind of transmissive metal grating coupling SPR detection chip and the detector in surface plasma body resonant vibration (SPR) biology, chemical detection technique field.
Background technology
Nineteen eighty-three, Nylander and Liedberg are used for gas detection and biology sensor with the SPR technology, after this this technology has been subjected to numerous researchists' concern and growing up continuously and healthily, the polytype New type of S PR sensing arrangement and the device of physics, chemistry, biomass occurred detecting.That the SPR technology has is highly sensitive, need not mark, stablize quick, convenient characteristics such as in real time, is particularly suitable for studying bio-molecular interaction.
The SPR technology is based on light wave and the interactional physical phenomenon of metal electron.Free electron when incident light and metal surface interacts, incident light wave will excite charge density wave under certain conditions, thereby cause the transmission light intensity to strengthen greatly, this phenomenon is called as the surface plasma body resonant vibration transmission and strengthens, and the incident angle of this moment is called as resonant angle.Resonant angle is relevant with the variations in refractive index of metal surface material, and change of refractive is relevant with the material that absorption or specificity are combined in the metal surface, so the variation on metallic sensing film surface can cause moving of resonance peak.By detect inhaling the variation of resonance, can detect the dynamic process of biochemical reaction, and by relatively obtaining the concentration of detected sample with typical curve.
According to the difference of excitation resonance mode, the type of surface plasma resonance sensor mainly is divided into prism-type, waveguide type and grating type, i.e. three kinds of coupling scheme.Wherein, most of SPR devices adopt the prism-coupled incident light, because its making is simple relatively, but also there is limitation, for example: on the prism directly metal-coated films have certain difficulty, and during the detection of biological sample, the angle that needs to regulate incident light, increase the volume of instrument, be unfavorable for the development of miniaturization.The waveguide-coupled mode adopts optical fiber to do waveguide usually, peels off optical fiber section covering, plates metal again, but that this mode is tested difficulty is bigger.And the coupling of traditional grating only utilizes the selecting frequency characteristic of grating to select the incident light wavelength, remains the test reflectance spectrum, and promptly the intensity of resonance peak is with the curve of the angle variation of incident light.This coupling scheme only reduce than the volume of prism-coupled mode chips, but still need to regulate the angle of incident light, increase the volume of detector.
Utilize transmission-type grating coupling incident light, only need fixedly incident angle, by detecting transmissivity with wavelength change, the variation of promptly measuring the SPR peak position comes detection of biological information.Utilize grating manifold type SPR Measurement for Biotechnique, can be so that detecting instrument mechanism be simpler, detect more stable and detection chip and more miniaturization of detecting instrument.
Summary of the invention
The object of the present invention is to provide a kind of transmissive metal grating coupling SPR detection chip and detector, it can be by being fixed into the real-time test sample of shooting angle, thereby overcome deficiency of the prior art.
A kind of transmissive metal grating coupling SPR detection chip is characterized in that it comprises:
The light transmission substrate;
Be formed at suprabasil, as to have optical grating construction metallic diaphragm;
And, cover microfluid layer in the metallic diaphragm surface, be distributed with microfluidic channel in the described microfluid layer, and described microfluidic channel contacts with metallic film surface.
As preferred scheme, described metallic diaphragm surface also can be modified with the material that can combine with the target component in the detected material.
Described microfluid layer and metallic diaphragm bonding.
Preferably, the thickness of described metallic diaphragm is no more than 200nm.
Preferably, the cycle of described optical grating construction is no more than 3000nm
As a kind of more preferred scheme, described optical grating construction is made up of the rectangular strip array, and the scope of dutycycle is 10%-25%.
Described metallic diaphragm is formed by Au.
Described microfluid layer is formed by organic material, and described organic material comprises dimethyl silicone polymer.
A kind of transmissive metal grating coupling SPR detector, comprise light source and spectrometer, it is characterized in that, described detector also comprises the aforesaid transmissive metal grating coupling SPR detection chip of being located on the light path that forms between light source and the spectrometer, and one side, light transmission substrate place of this detection chip is to light source.
Also be respectively equipped with the focus prism unit between described transmissive metal grating coupling SPR detection chip and light source and the spectrometer.
By aforementioned chip structure design, the present invention utilizes the free electron of grating coupling incident light and metal surface to resonate, the electronics dilatational wave that formation is propagated along the metal surface is a surface plasma excimer, and the peak position that detects transmitted spectrum changes the peak position change-detection biomolecule of the response peak that is SPR, strength of fluid etc.
Particularly, incident light is directly incident on the metal surface can't produce surface plasmon resonance, and this is by the decision of the dispersion relation of material.The dispersion curve of surface plasma wave is in the right side of incident light wave dispersion curve, under the same frequency, the wave vector Ko of surface plasma is bigger than plane Ksp, both do not have intersection point, the communication mode that is to say surface plasma wave communication mode and incident light can't realize coupling, therefore must adopt the suitable horizontal wave vector of method introducing to change the relative position of surface plasma wave dispersion curve and incident light wave dispersion curve, make the two have identical frequency and wave number, just to satisfy the law of conservation of momentum, thereby excite the generation surface plasma body resonant vibration.The grating coupling scheme are to introduce an extra wave vector to get increment realization wave vector coupling, to satisfy the shooting conditions of surface plasma excimer.For this reason, the present invention's optical grating construction that the metal film cycle of making is changed promptly forms metal grating and realizes the coupling of incident light is strengthened.
Simultaneously, the specific inductive capacity of the cycle of metal grating, the specific inductive capacity of metal and grating upper and lower medium has determined the position of surface plasma peak value of response, promptly determined the wavelength location that plasma resonance strengthens, when the detected sample and the metal surface albumino reaction that are adsorbed on the nanometer metallic film material, when perhaps detected sample concentration changes, the capital changes the specific inductive capacity of medium on the metal surface, thereby the peak position with the response peak of wavelength variations is subjected to displacement, and then can reflects the variation of the biological information of sample.
Compare with prior art such as conventional prism coupling SPR biosensors, good effect of the present invention is: this transmissive metal grating coupling SPR detection chip and detector can be that the peak position variation of the response peak of SPR is analyzed detected sample by the peak position variation that detects transmitted spectrum, need not to change the angle of incident angle, and then instrument volume and cost have been significantly reduced, detect accurately stable more, have can monitor in real time, highly sensitive, stable fast, volume is little, carry and advantage such as easy to operate.
Description of drawings
Fig. 1 is the structural representation of transmissive metal grating coupling SPR detector in the embodiment of the invention 1;
Fig. 2 is the cross-sectional view of transmissive metal grating coupling SPR detection chip in the embodiment of the invention 1;
Fig. 3 a is the stereographic map of metal grating coupling layer shown in Fig. 2;
Fig. 3 b is the cross-sectional view of metal grating coupling layer shown in Fig. 2;
Fig. 4 is the curve map when using transmissive metal grating coupling SPR detection chip detection concentration of alcohol in the embodiment of the invention 2.
Embodiment
Below engaging accompanying drawing and some preferred embodiments is further described technical scheme of the present invention.
Embodiment 1 consults Fig. 1, this transmissive metal grating coupling SPR detector comprises light source 1, spectrometer 2 and the chipset of being made up of the above transmissive metal grating coupling of a slice SPR detection chip 3, this chipset places on the light path that forms between light source 1 and the spectrometer 2, and also is respectively equipped with focus prism 4,5 between chipset and light source 1 and the spectrometer 2.
Aforementioned light source preferably adopts near infrared laser, and its wavelength of transmitted light scope is decided according to optical grating construction in the detection chip 3.
The aforementioned lights spectrometer preferably adopts the spectrometer of band Optical Fiber Transmission, and it is corresponding with the wavelength of transmitted light of laser instrument that it receives optical wavelength range, such as, can be at 350-1200nm.
Aforementioned detection chip 3 comprises light transmissive substrate 31, metal grating coupling layer 32 and microfluid layer 33, and distribution microfluidic channel 34 in this microfluid layer, microfluidic channel are intersected with the metal grating coupling layer and contacted.
Aforementioned light transmissive substrate preferably adopts common glass substrate, also can adopt other transparent inorganic or organic substrates certainly;
Aforementioned metal grating coupling layer is to be made of the metallic film that is formed at substrate surface, and this metallic film has optical grating construction.The array that this optical grating construction can be made up of rectangular bars, its cycle is no more than 3000nm, is preferably 1 μ m~3 μ m, especially is preferably 1 μ m.The duty cycle range of this optical grating construction can be 10%-25%, preferably in the array between two rectangular body centers distance be 1 μ m, the wide 500nm of each rectangular bars.
This thickness of metal film is no more than 200nm, is preferably 100nm~200nm, the especially preferred Au film that adopts thick 100nm.
Aforementioned microfluid layer is formed by the material with better light transmission, and for example, (Polydimethylsiloxane is PDMS) as material of main part can to select dimethyl silicone polymer for use.
The methods for making and using same of aforementioned detection chip 3 is as follows:
1) on substrate with technology growing metal films such as magnetron sputterings;
2) adopt the step-by-step movement litho machine, prepare the figure mask of metal grating, with IBE etching machine engraving erosion metallic film, remove the photoresist that mask is used thereafter again, form metal grating structure;
3) chipset for preparing is modified with bioprotein, even the bioprotein bonding, stick to metal grating coupling layer surface, when containing certain viral sample by the metal surface, just can stick on the albumen key of corresponding this virus, make the specific inductive capacity of metal surface medium change;
4) making of microfluid layer: (Polydimethylsiloxane PDMS) is material of main part, by the mask of photoresist, prepares the figure of microfluidic channel, etching figure then with the uv-exposure machine with dimethyl silicone polymer;
5) with the metal grating coupling layer and the microfluid layer bonding that make;
6) build detection platform (being aforementioned transmissive metal grating coupling SPR detector), incide in the chip 3 the chip 3 positive spectrometer received signals of using from the substrate of chip 3 by the light of light emitted;
7) in microfluidic channel, splash into detected sample, begin test.
Structure, methods for making and using same and the embodiment of embodiment 2 present embodiment transmissive metal gratings coupling SPR detection chip are basic identical, but modify on metal grating coupling layer surface.It can be after building test platform when using, and by directly splashing into sample in the microfluidic channel in chip, and then tests the variation of certain sample concentration.
For example detect the dielectric layer specific inductive capacity that alcohol volatilization causes and change the displacement of drawing resonance peak.At first certain density ethanol is dropped in the metal coupling layer surface of optical grating construction,, obtain a resonance peak according to its transmitted spectrum.The concentration of alcohol on growth gold film surface in time reduces gradually, and the specific inductive capacity of contact bed can change, and causes moving of resonance peak, as shown in Figure 4.This detector can also apply to the detection of other samples except that alcohol etc.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims (10)

1. transmissive metal grating coupling SPR detection chip is characterized in that it comprises:
The light transmission substrate;
Be formed at suprabasil, as to have optical grating construction metallic diaphragm;
And, cover microfluid layer in the metallic diaphragm surface, be distributed with microfluidic channel in the described microfluid layer, and described microfluidic channel contacts with metallic film surface.
2. transmissive metal grating coupling SPR detection chip according to claim 1, it is characterized in that: described metallic diaphragm surface also is modified with the material that can combine with the target component in the detected material.
3. transmissive metal grating coupling SPR detection chip according to claim 1 is characterized in that: described microfluid layer and metallic diaphragm bonding.
4. according to each described transmissive metal grating coupling SPR detection chip among the claim 1-3, it is characterized in that: the thickness≤200nm of described metallic diaphragm.
5. transmissive metal grating coupling SPR detection chip according to claim 1 is characterized in that: the cycle≤3000nm of described optical grating construction.
6. transmissive metal grating coupling SPR detection chip according to claim 1 or 5, it is characterized in that: described optical grating construction is made up of the rectangular strip array, and the scope of dutycycle is 10%-25%.
7. transmissive metal grating coupling SPR detection chip according to claim 4, it is characterized in that: described metallic diaphragm is formed by Au.
8. transmissive metal grating coupling SPR detection chip according to claim 1, it is characterized in that: described microfluid layer is formed by organic material, and described organic material comprises dimethyl silicone polymer.
9. transmissive metal grating coupling SPR detector, comprise light source and spectrometer, it is characterized in that, described detector also comprises the transmissive metal grating coupling SPR detection chip of being located on the light path that forms between light source and the spectrometer as claimed in claim 1, and one side, light transmission substrate place of this detection chip is to light source.
10. transmissive metal grating coupling SPR detector as claimed in claim 9 is characterized in that: also be respectively equipped with the focus prism unit between described transmissive metal grating coupling SPR detection chip and light source and the spectrometer.
CN2011101982403A 2011-07-15 2011-07-15 Transmission-type metal grating coupling SPR (Surface Plasmon Resonance) detection chip and detection instrument Pending CN102288583A (en)

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CN103217739A (en) * 2013-04-22 2013-07-24 上海理工大学 Three-channel terahertz metal grating waveguide with compound period and application method
CN103499534A (en) * 2013-07-25 2014-01-08 中国科学院苏州纳米技术与纳米仿生研究所 High-sensitivity terahertz microfluidic channel sensor and preparation method thereof
CN104458660A (en) * 2014-11-15 2015-03-25 新疆大学 Biomolecule detection method based on porous transmission-type silicon photonic crystal microcavity angular detection device
CN104730038A (en) * 2014-12-25 2015-06-24 中北大学 Handheld high-flux biological sensor
CN105548179A (en) * 2015-12-04 2016-05-04 深圳市赛尔生物技术有限公司 Method and system for determination of biochip based on transmitted light or self luminescence
CN105675536A (en) * 2016-01-19 2016-06-15 首都师范大学 Metal grating surface plasma effect biological-detection chip for THz-TDS system
CN108548807A (en) * 2018-03-15 2018-09-18 国家纳米科学中心 Graphene phasmon device and preparation method thereof for enhanced highpass filtering signal
CN108593585A (en) * 2018-06-21 2018-09-28 国家纳米科学中心 A kind of graphene phasmon gas sensor
CN108593590A (en) * 2018-06-21 2018-09-28 国家纳米科学中心 A kind of graphene phasmon liquid sensor
CN108917927A (en) * 2018-07-27 2018-11-30 京东方科技集团股份有限公司 Dispersion means and spectrometer
CN108982424A (en) * 2018-07-23 2018-12-11 量准(上海)医疗器械有限公司 It is a kind of based on equal CRP concentration detection apparatus and detection method from photon harmonic technology
CN112934281A (en) * 2021-03-20 2021-06-11 山东大学 Artificial surface plasmon micro-fluidic detection chip structure based on periodic structure and preparation and detection methods thereof
US11256012B2 (en) 2019-02-27 2022-02-22 Boe Technology Group Co., Ltd. Color dispersion apparatus and spectrometer

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Cited By (18)

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CN103217739B (en) * 2013-04-22 2015-07-22 上海理工大学 Three-channel terahertz metal grating waveguide with compound period and application method
CN103217739A (en) * 2013-04-22 2013-07-24 上海理工大学 Three-channel terahertz metal grating waveguide with compound period and application method
CN103499534A (en) * 2013-07-25 2014-01-08 中国科学院苏州纳米技术与纳米仿生研究所 High-sensitivity terahertz microfluidic channel sensor and preparation method thereof
CN103499534B (en) * 2013-07-25 2015-09-09 中国科学院苏州纳米技术与纳米仿生研究所 Highly sensitive Terahertz microfluidic channel sensor and preparation method thereof
CN104458660B (en) * 2014-11-15 2017-07-18 新疆大学 Biomolecule detecting method based on transmission-type Porous silicon photonic Crystal structures microcavity angle detection device
CN104458660A (en) * 2014-11-15 2015-03-25 新疆大学 Biomolecule detection method based on porous transmission-type silicon photonic crystal microcavity angular detection device
CN104730038A (en) * 2014-12-25 2015-06-24 中北大学 Handheld high-flux biological sensor
CN105548179A (en) * 2015-12-04 2016-05-04 深圳市赛尔生物技术有限公司 Method and system for determination of biochip based on transmitted light or self luminescence
CN105675536A (en) * 2016-01-19 2016-06-15 首都师范大学 Metal grating surface plasma effect biological-detection chip for THz-TDS system
CN105675536B (en) * 2016-01-19 2018-05-04 首都师范大学 Metal grating surface plasma bulk effect biological detection chip for THz-TDS systems
CN108548807A (en) * 2018-03-15 2018-09-18 国家纳米科学中心 Graphene phasmon device and preparation method thereof for enhanced highpass filtering signal
CN108593585A (en) * 2018-06-21 2018-09-28 国家纳米科学中心 A kind of graphene phasmon gas sensor
CN108593590A (en) * 2018-06-21 2018-09-28 国家纳米科学中心 A kind of graphene phasmon liquid sensor
CN108982424A (en) * 2018-07-23 2018-12-11 量准(上海)医疗器械有限公司 It is a kind of based on equal CRP concentration detection apparatus and detection method from photon harmonic technology
CN108917927A (en) * 2018-07-27 2018-11-30 京东方科技集团股份有限公司 Dispersion means and spectrometer
CN108917927B (en) * 2018-07-27 2020-08-25 京东方科技集团股份有限公司 Dispersion device and spectrometer
US11256012B2 (en) 2019-02-27 2022-02-22 Boe Technology Group Co., Ltd. Color dispersion apparatus and spectrometer
CN112934281A (en) * 2021-03-20 2021-06-11 山东大学 Artificial surface plasmon micro-fluidic detection chip structure based on periodic structure and preparation and detection methods thereof

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