CN110361362A - One kind being based on medium nano-antenna biosensor, preparation method and application - Google Patents

One kind being based on medium nano-antenna biosensor, preparation method and application Download PDF

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Publication number
CN110361362A
CN110361362A CN201910573742.6A CN201910573742A CN110361362A CN 110361362 A CN110361362 A CN 110361362A CN 201910573742 A CN201910573742 A CN 201910573742A CN 110361362 A CN110361362 A CN 110361362A
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antenna
biosensor
medium nano
substrate
nano
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CN110361362B (en
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李强
周焕
刘楚明
吕俊
仇旻
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Zhejiang University ZJU
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55Specular reflectivity
    • G01N21/552Attenuated total reflection
    • G01N21/553Attenuated total reflection and using surface plasmons
    • G01N21/554Attenuated total reflection and using surface plasmons detecting the surface plasmon resonance of nanostructured metals, e.g. localised surface plasmon resonance
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N2021/3595Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nanotechnology (AREA)
  • Engineering & Computer Science (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

The invention discloses one kind to be based on medium nano-antenna biosensor, including substrate and periodic array are arranged in the dielectric substance on the substrate, which is selected from one of silicon, germanium, tellurium and four or six race's lead-containing compounds or a variety of.The present invention has lower intrinsic loss, shows a wide range of angle change for certain structures such as cubic array and responds invariance, good compatibility, loss is low, high-quality-factor resonance may be implemented, to improve sensing sensitivity.Low loss characteristic can avoid generating destruction of the stronger photo-thermal effect to testing molecule while enhancing local fields.And it can realize the control to radiation direction by regulating and controlling designed structure electric resonance and magnetic resonance coupling, be conducive to improve collection efficiency and then improve sensing sensitivity.Dielectric nanometer optical wave antenna has become the main tool that light is manipulated on nanoscale, and the regulation to far-field radiation may be implemented.

Description

One kind being based on medium nano-antenna biosensor, preparation method and application
Technical field
The invention belongs to sensor design technical fields, specifically design a kind of based on medium nano-antenna bio-sensing Device, preparation method and application.
Background technique
In micro-nano technology field, with the nanoprocessing skill of electron beam lithography and focused-ion-beam lithography etc. " downward to pushing up " Art graduallys mature, and the experiment production of nanometer optical wave antenna is increasingly becoming possibility, has attracted the interest of numerous researchers.
Infrared spectrum technology, which can be vibrated in large-scale molecular species and compound by Measurement atom, carries out material Identification, plays increasingly important role in bio-sensing field.In terms of the identification of biomaterial, Fourier transform infrared Spectrometer (Fourier transform infrared spectroscopy, FTIR) is non-damaging by feat of quick, highly sensitive The advantages of be widely used in terms of molecular fingerprint spectrum.But typical molecular size only has 10nm, and the wave of mid-infrared light A length of 4-25 μm, the order of magnitude is three times of molecular size, and the section of light and molecular action is very small.Seriously reduce infrared light spy The sensitivity of molecule is surveyed, the especially trace level chemical substance in food security and bio-sensing field detects.Surface enhanced is infrared Absorption spectroscopy techniques (Surface-enhanced infrared absorption, SEIRA) rely on surface plasma body resonant vibration (surface-plasmon polaritons, SPPs) can improve several quantity in infrared band light-matter interaction The enhancing of grade.1980, surface-enhanced infrared spectroscopy was proved for the first time in gold and silverskin surface.Next more than ten Year, many researchs all concentrate on the film that there are nanoparticle in coarse metal surface and surface.The advantages of this method is to be not required to Advanced nanofabrication technique is wanted, but does not obtain significant progress in terms of Infrared Plasma enhancing.With nearest The development of nanofabrication technique, the preparation of metal Nano structure are not problems, and experimental observation to Infrared Plasma enhances It is more excellent than membrane structure.Then, a large amount of surface-enhanced infrared spectroscopy structure is suggested and experiments have shown that can significantly mention The resonance of high testing molecule has vast application.Recently, novel Infrared Plasma material (such as: graphene Graphene, silicon Si, indium arsenide InAs, indium antimonide InSb, indium arsenic antimony InAsSb, oxide oxides, carbon nanotube carbon Nanotubes (CNTs) etc.) surface-reinforced infrared spectrum absorption can be effectively improved.
In conclusion currently without it is a kind of by high refractive index, low extinction coefficient dielectric substance (such as: germanium, silicon, tellurium with And four or six materials such as race's lead-containing compounds) production highly sensitive middle infrared nanometer light wave antenna sensor.
Summary of the invention
The present invention provides one kind in its operation wavelength model for shortcoming and defect existing for existing nanometer optical wave antenna Internal reflection light is enclosed with humidification based on medium nano-antenna biosensor.
The present invention also provides a kind of above-mentioned preparation methods based on medium nano-antenna biosensor.
Invention also provides a kind of above-mentioned application methods based on medium nano-antenna biosensor.
One kind being based on medium nano-antenna biosensor, including substrate and periodic array are arranged on the substrate Dielectric substance, which is selected from one of silicon, germanium, tellurium and four or six race's lead-containing compounds or a variety of.
The invention discloses one kind to be based on medium nano-antenna biosensor design, and existing sense about nano-antenna is used It is more be using metal nano antenna, but there are the problems of intrinsic loss for metal nano antenna, based on high refractive index The theoretical basis of dielectric nanometer optical wave antenna, light wave antenna have become the main tool in nanoscale manipulation light.Firstly, Dielectric substance has extremely low loss in optical band;Secondly, the dielectric structures of high dielectric constant can both support electricity humorous Vibration mode can support magnetic resonance mode again.Suitable low-loss, the medium of high refractive index are found in visible light to infrared band Material is significant to realization all-dielectric optically wave antenna;The invention is small to the damage of molecule and protein active, greatly improves In the sensitivity that biomolecule and micro substance sense.
Technical solution of the present invention foundation, firstly, dielectric substance has extremely low loss in optical band;Secondly, Gao Jie The dielectric structures of electric constant can not only support electric resonance mode but also can support magnetic resonance mode.In visible light to infrared waves Section finds suitable low-loss, and the dielectric material of high refractive index is most important to realization all-dielectric optically wave antenna.Only two classes are situated between Material shows the positive refracting power greater than 3 in optical band: one kind is Highly crystalline polaritonic Materials, it is another kind of, it is the material (being less than 1.5eV) of narrow band gap.In fact, the first material be it is unsatisfactory, because Great loss is had in the wave band of phonon resonance for them, in addition, the flexibility of its frequency domain response is also extremely limited.And narrowband Gap material shows high refractive index in very wide bandwidth, only when shortwave direction is close to band-gap energy and in long wave direction Loss can be generated when upper free-carrier Absorption.These typical low bandgap materials include: that silicon, germanium, tellurium and four or six races are leaded Compound.
Preferably, the dielectric substance is arranged in a circular formation.Multiple circular dielectric substance periodic arrays are described On substrate.Dispatch from foreign news agency field excitation dielectric substance (such as germanium) disk forms electric resonance, the electromagnetic field and enter radio that electric resonance issues Magnetic field interference, transmission interference cancellation form backscattering, therefore can detect reflection peak, increase surface covering using reflection peak Matter signal realizes sensing.
Nano-sensor element of the invention is made of two-part structure, a substrate, is dielectric substance above two substrates Such as germanium, silicon, the materials such as tellurium and four or six race's lead-containing compounds;Detecting substance is biomolecule, as long as the resonance peak of biomolecule In infrared band, the sensor structure may be by theoretically to realize detection, such as PMMA is coated in element surface.
In the present invention, the working sensor wavelength is middle infrared band, and range is 2 microns -10 microns.Wherein reflection peak Between 4.5 to 6.5 microns, nanostructured surface is radiated at using infrared spectrometric analyzer (FTIR) measurement reflectance spectrum and absorption Spectrum needs first to obtain bias light, can use gold plaque usually to measure reflectance spectrum as bias light, then again when measuring sample Diectric antenna is placed in measure spectrum under analyzer.
Preferably, array period is 3000~5000nm, 1500~3500nm of diameter, with a thickness of 150~400nm.Into One step is preferably to make the germanium disk of period 4500nm, diameter 2650nm, thickness 280nm.The array period includes X-direction and Y Direction can use identical array period, also can choose different array periods.
Preferably, the substrate is calcirm-fluoride.
The present invention provides the systems based on medium nano-antenna biosensor described in a kind of any of the above-described technical solution Preparation Method, using making the dielectric substance on electronic beam photetching process again substrate.
Preferably, emulating by FDTD, the optimized parameter of sensor is determined.When optimum structural parameter, it can make The optimization function of being carried with FDTD software, can obtain optimal parameter with one-off scanning, in addition can be with parallel computing, runing time Reduce very much.It is emulated by FDTD, the parameter after available structure optimization.By selection material appropriate, adjust all dielectric The dimensional parameters of structure can regulate and control spectral characteristic and obtain optimal effect.
The present invention can use dielectric substance such as nanometer germanium for shortcoming and defect existing for existing nanometer optical wave antenna Material is based on micro-nano technology technique, and designing and making array period on calcium fluoride substrate is 3000~5000nm, diameter 1500 ~3500nm, the sensor with disc structure dielectric material coating with a thickness of 150~400nm.
It is a kind of that substance inspection being carried out based on medium nano-antenna biosensor using described in any of the above-described technical solution The application of survey.
Infrared (such as germanium) medium nanometer optical wave antenna is mainly applied in this experiment production: nanometer optical wave antenna is specific Frequency has the phenomenon that high efficiency, resonance wave strong point can show appearance enhancing, and the interaction of light and substance can be enhanced, Light is improved to the susceptibility of external parameter, so that nanometer optical wave antenna is in bio-sensing, all various aspects such as micro substance detection are all Possess huge development potentiality.Destructible bioactive molecule is not allowed in terms of biosensor.On the other hand, low fuel factor is deposited Also off-energy can be being reduced, detectivity is caused to greatly enhance.
Preferably, the characteristic infrared absorption peak of the substance is at 2 microns -10 microns.
Preferably, sample to be tested to be coated on to the dielectric material surface of the sensor when detection.As into one Preferably, the substance to be detected is poly dimethyl silicon oxygen to step, and coating thickness is 20~100nm.
The invention has the advantages that lower intrinsic loss, shows a wide range of angle for certain structures such as cubic array Degree variation response invariance, and it is compatible with CMOS manufacture craft, and high refractive index medium nano-antenna has electricity to incident field Resonance and magnetic resonance response, dielectric substance loss is very low, and high-quality-factor resonance may be implemented, so that it is sensitive to improve sensing Degree.Low loss characteristic can avoid generating destruction of the stronger photo-thermal effect to testing molecule while enhancing local fields.And And the control to radiation direction can be realized by regulating and controlling electric resonance and the magnetic resonance coupling of designed structure, be conducive to improve Collection efficiency improves sensing sensitivity in turn.Dielectric nanometer optical wave antenna has become manipulates the main of light on nanoscale The regulation to far-field radiation may be implemented in tool.
Detailed description of the invention
Fig. 1 is medium nano-antenna biosensor structure schematic diagram;
Fig. 2 is practical germanium disk aerial structure under a scanning electron microscope
Fig. 3 is that the three-dimensional AFM of germanium disk aerial schemes;
Reflectance spectrum situation when Fig. 4 is diectric antenna detection poly dimethyl silicon oxygen under FTIR spectrum analyzer.
Specific embodiment
Specific embodiments of the present invention will be described in detail with reference to the accompanying drawing: present embodiment case is mentioned with the present invention Out based on micro-nano technique processing technology premised on, but protection scope of the present invention is not limited to following embodiments and case; E-beam lithography, the dielectric material that other photoetching techniques etc. can also be used, while being used in present case are used in case Material is not limited only to use germanium, and silicon, germanium, tellurium and four or six race's lead-containing compounds etc. also can be used.
Electron beam lithography (Electron beam lithography, EBL) technique is used in present case.Etched sample obtains To the fabrication cycle 4500nm on calcium fluoride substrate, the horizontal and vertical period is identical, the germanium of diameter 2650nm, thickness 280nm circle Disk.Respectively it can be observed that the structure actually done, as shown in Figures 2 and 3 respectively under electron microscope and atomic force microscope.
Since dispatch from foreign news agency field excitation germanium disk forms electric resonance, the electromagnetic field and incident electromagnetic field that electric resonance issues are interfered, thoroughly Blackberry lily relates to cancellation, forms backscattering, therefore can detect reflection peak.When the biomolecular structure resonance for needing to sense is located at reflection When near peak, so that it may realize the amplification of signal, realize the detection to specific biological molecules.
In the surface spin coating PMMA of design structure doped germanium nanotube antenna array, sample is then placed on Fourier infrared Planar survey reflectance spectrum on spectroanalysis instrument (FTIR), the principle of Fourier Transform Infrared Spectrometer are that light source is issued first Light forms interference light by using Michelson's interferometer, then the interference light of generation is gone irradiating sample, is done with detector Figure is related to, recycles computer that interference pattern is carried out Fourier transformation and calculates to obtain transmitted spectrum and reflectance spectrum.FTIR's Cavity is made of six parts, is respectively: electronics cavity, detector cavity, interferometer cavity, light source cavity, optical path direction control Cavity and sample chamber.The reflectance spectrum situation of gold plaque is first measured as reference background, the sample of production is then measured again, first measures Only substrate when the case where, then be put into PMMA on substrate and measure, be finally coated with PMMA on the diectric antenna of design again Structure on measure, the reflectance spectrum measured in the case of obtaining three kinds next using the reflectance spectrum for most starting gold plaque background, such as Fig. 4 institute Show, when PMMA is with a thickness of 50nm, from the reflectance spectrum measured, spectrum reinforcing effect is 11.02 times, when not having germanium disk just Detection whether there is less than PMMA, and have when germanium disk since the local to light field acts on, and enhance phase interaction of the light with substance With, therefore the presence of PMMA can be detected.

Claims (10)

1. one kind is based on medium nano-antenna biosensor, which is characterized in that be arranged in institute including substrate and periodic array The dielectric substance on substrate is stated, which is selected from one of silicon, germanium, tellurium and four or six race's lead-containing compounds or more Kind.
2. according to claim 1 be based on medium nano-antenna biosensor, which is characterized in that the dielectric substance It is arranged in a circular formation.
3. according to claim 1 be based on medium nano-antenna biosensor, which is characterized in that the operating wave of sensor A length of middle infrared band, range are 2 microns -10 microns.
4. according to claim 2 be based on medium nano-antenna biosensor, which is characterized in that array period 3000 ~5000nm, 1500~3500nm of diameter, with a thickness of 150~400nm.
5. according to claim 1 be based on medium nano-antenna biosensor, which is characterized in that the substrate is fluorination Calcium.
6. a kind of described in any item preparation methods based on medium nano-antenna biosensor of Claims 1 to 5, feature It is, using making the dielectric substance on electronic beam photetching process again substrate.
7. preparation method according to claim 6, which is characterized in that emulated by FDTD, determine the optimal ginseng of sensor Number.
8. a kind of carry out substance detection based on medium nano-antenna biosensor using described in 5 any one of Claims 1 to 5 Using.
9. application according to claim 8, which is characterized in that the characteristic infrared absorption peak of the substance is micro- at 2 micron -10 Rice.
10. application according to claim 8, which is characterized in that when detection, sample to be tested is coated on the sensor Dielectric material surface.
CN201910573742.6A 2019-06-28 2019-06-28 Biosensor based on dielectric nano antenna, preparation method and application Expired - Fee Related CN110361362B (en)

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CN110836860A (en) * 2019-11-07 2020-02-25 厦门大学 Surface enhanced infrared substrate based on metamaterial and molecular detection method thereof
CN111000566A (en) * 2019-12-13 2020-04-14 江南大学 Wearable flexible sensor with photothermal effect and antibacterial function

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CN110836860A (en) * 2019-11-07 2020-02-25 厦门大学 Surface enhanced infrared substrate based on metamaterial and molecular detection method thereof
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CN111000566A (en) * 2019-12-13 2020-04-14 江南大学 Wearable flexible sensor with photothermal effect and antibacterial function

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