CN207571034U - For the molecular vehicle of Molecular Detection - Google Patents

For the molecular vehicle of Molecular Detection Download PDF

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Publication number
CN207571034U
CN207571034U CN201721155927.8U CN201721155927U CN207571034U CN 207571034 U CN207571034 U CN 207571034U CN 201721155927 U CN201721155927 U CN 201721155927U CN 207571034 U CN207571034 U CN 207571034U
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nanometers
substrate
carbon nano
nano tube
molecular
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王营城
金元浩
李群庆
范守善
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Abstract

The utility model is related to a kind of molecular vehicle for Molecular Detection, including:One substrate;One middle layer is set to the surface of the substrate;One metal layer is set to surface of the middle layer far from substrate;Wherein, the substrate is a flexible substrates;The middle layer includes the patterning protrusion of a substrate and multiple settings over the substrate;The metal layer is set to the surface of the patterning protrusion.

Description

For the molecular vehicle of Molecular Detection
Technical field
The utility model is related to a kind of molecular vehicle for Molecular Detection, preparation method and using the carrier sense The method of molecule.
Background technology
Single Molecule Detection (Single Molecule Detection, SMD) technology is a kind of overdelicate detection technique, Individual molecule can be detected, in chemical analysis, DNA sequencing, nano material analysis, medical diagnosis, molecular dynamics machine The fields such as reason, food security are widely used.Compared with traditional analysis method, Single Molecule Detection method research system is in non-equilibrium The fluctuation behavior under individual behavior or equilibrium state under state, thus be particularly suitable for research chemistry and biochemical reaction kinetics, Interaction, structure and the functional information of biomolecule, major disease early diagnosis, pathological study and high-flux medicaments sifting Deng.
At present in molecule detection, molecular vehicle is placed on after usually the detectable substance of detected sample is extracted On be detected, and the molecular vehicle that uses uses hard substrate mostly when detecting.Meanwhile the process for extracting sample may be made Into the destruction of sample structure, the process of sample is extracted but also detection method becomes cumbersome.
Utility model content
In view of this, it is necessory to provide a kind of molecular vehicle that will not destroy sample to be tested.
A kind of molecular vehicle for Molecular Detection, including:One substrate;One middle layer is set to the table of the substrate Face;One metal layer is set to surface of the middle layer far from substrate;Wherein, the substrate is a flexible substrates;The centre Layer includes the patterning protrusion of a substrate and multiple settings over the substrate;The metal layer is set to the patterning protrusion Surface.
The material of the substrate is polyethylene terephthalate, polyimides, polymethyl methacrylate, poly- diformazan One kind in radical siloxane and polyethylene naphthalate.
The thickness range of the substrate is 100 nanometers -200 nanometers.
The patterning protrusion includes multiple raised lines formation network structure arranged in a crossed manner, described so as to define multiple holes Multiple raised lines include multiple the first raised lines extended in a first direction and multiple the second raised lines extended in a second direction, and described the The angle of one direction and second direction is more than or equal to 30 degree and is less than or equal to 90 degree, and the width of each raised line is received for 20 nanometer -150 Rice, is highly 20 nanometers -500 nanometers, and the spacing between adjacent two parallel raised lines is 10 nanometers -300 nanometers.
The width of each raised line is 50 nanometers -100 nanometers, is highly 200 nanometers -400 nanometers, and adjacent two is parallel convex Spacing between item is 10 nanometers -50 nanometers.
The metal layer be continuous layer structure, the metal layer be arranged on the multiple raised line surface and raised line it Between hole in.
The metal layer is discrete layer structure, which is only arranged at the side wall of multiple raised lines and adjacent raised line Between hole in.
The thickness range of the metal layer is 2 nanometers -200 nanometers.
Further comprise a retaining element, which is used to the metal layer being fixed on the surface of determinand, should Retaining element is one kind in fixed band, bent metal framework.
The molecular vehicle generally flexible structure.
Compared to the prior art, the molecular vehicle of the utility model has the advantages that:Due to the molecular vehicle In substrate using flexible substrates, flexible substrates can be very well fitted on irregular surface, and therefore, which can be Molecular Detection is carried out on irregular surface, and can realize in situ detection on determinand surface;Metal layer is arranged on multiple raised line shapes Into reticular structure on, under the excitation of incident light, RESONANCE ABSORPTION occurs for metal surface plasma body, and the raised line of network structure rises To the effect of Surface enhanced Raman scattering, can improve SERS (Surface enhanced Raman scattering) enhancings because Son enhances Raman scattering.
Description of the drawings
Fig. 1 is the structure diagram of molecular vehicle that the utility model first embodiment provides.
Fig. 2 is sectional view of the molecular vehicle that provides of the utility model first embodiment along II-II directions.
Fig. 3 is the preparation method flow chart of molecular vehicle that the utility model first embodiment provides.
Fig. 4 is the sectional view of the IV-IV along the line of the composite structure of carbon nano tube of Fig. 3.
Fig. 5 is the flow chart of monomolecular detection method that the utility model first embodiment provides.
Fig. 6 is the spectrogram that detector measures different testing concentrations from the obverse and reverse of molecular vehicle respectively.
Fig. 7 is the spectral detection result of the 4-ATP molecules on Raman spectrometer in situ detection tomato surface.
Fig. 8 is the Raman spectrum detection knot of 4-ATP molecules on molecular vehicle after wiping apple surface using molecular vehicle Fruit.
Fig. 9 is the structure diagram of molecular vehicle that the utility model second embodiment provides.
Figure 10 is the preparation method flow chart of molecular vehicle that the utility model second embodiment provides.
Figure 11 is the structure diagram of molecular vehicle that the utility model 3rd embodiment provides.
Figure 12 is the preparation method flow chart of multiple molecular vehicles that the utility model 3rd embodiment provides.
Figure 13 is the structure diagram of molecular detector arrangement that the utility model fourth embodiment provides.
Figure 14 is the structure diagram using metal framework fixed member carrier.
Figure 15 is the structure diagram of multiple molecular vehicles that the utility model fourth embodiment provides.
Main element symbol description
Molecular vehicle 10,20
Substrate 11
Middle layer 12
Substrate 121
Patterning protrusion 122
Hole 124
Metal layer 13
Composite structure of carbon nano tube 110
Carbon nano tube structure 112
Preformed layer 114
Micropore 116
Sample to be tested 14
Determinand molecule 15
Retaining element 16
Detector 17
Control computer 18
Specific examples below will further illustrate the utility model with reference to above-mentioned attached drawing.
Specific embodiment
Below in conjunction with specific embodiment and attached drawing, the utility model is described in further detail.
Also referring to Fig. 1 to Fig. 2, the utility model first embodiment provides a kind of molecular vehicle for Molecular Detection 10, which includes a substrate 11, a middle layer 12 and a metal layer 13.Specifically, the middle layer 12 is set On the surface of the substrate 11, the metal layer 13 is arranged on the surface of the middle layer 12.The middle layer 12 includes a lining Bottom 121 and multiple patterning protrusions 122 being arranged on the substrate 121, and the patterning protrusion 122 is arranged on the substrate On 121 surfaces far from substrate 11.The patterning protrusion 122 may include multiple raised lines formation reticular structure arranged in a crossed manner, from And define multiple holes 124.The infall of the multiple raised line is structure as a whole.The patterning protrusion 122 may also comprise more A convex block is arranged in array, and the groove between multiple convex block intersects in net distribution.
The substrate 11 can be dielectric base or semiconductor base.The substrate 11 is a flexible substrates, can be positioned over On curved surface, and it is bonded with curved surface.Specifically, the material of the substrate 11 can be polyethylene terephthalate (PET), polyimides (PI), polymethyl methacrylate (PMMA), dimethyl silicone polymer (PDMS), poly- naphthalenedicarboxylic acid second Diol ester (PEN) etc..In the present embodiment, the material of the substrate 11 is polyethylene terephthalate.The substrate 11 Shape, size and thickness are unlimited, can need to select according to the detection of actual molecules.In the present embodiment, the shape of the substrate is One tabular.
The substrate 121 is arranged on the surface of the substrate 11.The shape of the substrate 121 is unlimited, need to only have two A surface being oppositely arranged.The size of the substrate 121 is unlimited, and thickness is 50 nanometers -300 nanometers.Preferably, the lining The thickness at bottom 121 is 100 nanometers -200 nanometers.When the thickness of the substrate 121 is too thin, such as less than 100 nanometers, the substrate 11 Spectrogram during follow-up trace molecules Raman detection can be interfered or be influenced;When the thickness of the substrate 121 is too thick, Such as larger than 200 nanometers, the 10 overall flexibility degree of molecular vehicle can be caused to reduce.The substrate 121 and the patterning protrusion 122 can be the integral structure of material identical or the different multilayered structure of material.The substrate can be silica, The insulating materials such as silicon nitride, the semi-conducting materials such as gallium nitride, GaAs.In the present embodiment, the substrate 121 and the patterning Protrusion 122 is the integral structure formed by silica.The patterning protrusion 122 is arranged on the substrate 121 far from substrate On 11 surface.The utility model is by taking the patterning protrusion 122 includes multiple raised lines as an example, and a definition part is along first party It is the first raised line to the raised line of extension, another part is the second raised line along the raised line that second direction extends.The first direction It is more than 0 degree with the angle of second direction and is less than or equal to 90 degree, it is preferable that more than or equal to 30 degree.The multiple first raised line is basic It is parallel, and the multiple second raised line is substantially parallel.The raised line of the utility model is substantially parallel to be characterized in due to its preparation side What the feature that the extending direction of carbon nanotube is substantially parallel in the carbon nanotube mask used in method determined.The length of each raised line It is unlimited, width be 20 nanometers -150 nanometers, be highly 100 nanometers -500 nanometers, parallel and adjacent to raised line between spacing be 10 nanometers -300 nanometers.Therefore, the opening size of described hole 124 is 10 nanometers -300 nanometers, and depth is 100 nanometer -500 Nanometer.Preferably, the width of each raised line is 50 nanometers -100 nanometers, is highly 200 nanometers -400 nanometers, and spacing is received for 10 - 50 nanometers of rice.In the present embodiment, the multiple first raised line is perpendicular to multiple second raised lines.The raised line is from the substrate 121 One side extend to another side.The height of the raised line is 300 nanometers.
The metal layer 13 is set to the surface of the patterning protrusion 122.Specifically, the metal layer 13 can be to connect Continuous layer structure, or discrete layer structure.The metal layer 13 be set to the multiple raised line surface and In hole 124 between raised line.The metal layer 13 can also be only arranged at multiple raised lines side wall and adjacent raised line between hole In hole 124.The metal layer 13 can be individual layer layer structure or multilayer laminar structure.The 13 substantially uniform deposition of metal layer The surface of substrate 121 between raised line surface and raised line.A gap (Gap) is formed at described hole 124, herein metal layer 13 surface can generate surface plasma body resonant vibration, so as to generate Raman scattering enhancing.The thickness of the metal layer 13 is received for 2 - 200 nanometers of rice, it is preferable that the thickness of the metal layer 13 is uniform.The material of the metal layer 13 is unlimited, can be gold, silver, platinum, The metals such as copper.It is appreciated that the material of the metal layer 13 be not limited to more than it is several, be solid metal material under any room temperature Material can.In the present embodiment, the metal layer 13 is the gold that thickness is 10 nanometers.
Molecular vehicle provided by the utility model has the following advantages:Since the substrate 11 in the molecular vehicle 10 uses Flexible substrates, flexible substrates can be very well fitted on irregular surface, and therefore, which can be in irregular surface Upper carry out Molecular Detection, and can realize in situ detection on determinand surface;Metal layer 13 is arranged on the netted of multiple raised lines formation In structure, under the excitation of incident light, RESONANCE ABSORPTION occurs for metal surface plasma body, and the raised line of network structure plays surface increasing The effect of strong Raman scattering, can improve SERS (Surface enhanced Raman scattering) enhancement factor, and enhancing is drawn Graceful scattering.
Also referring to Fig. 3 and Fig. 4, the utility model first embodiment provides a kind of side for preparing above-mentioned molecular vehicle 10 Method includes the following steps:
Step S11 sets a middle layer 12 in a substrate 11;
Step S12, providing one has the composite structure of carbon nano tube 110 of multiple micropores 116, the composite structure of carbon nano tube 110 include a carbon nano tube structure 112 and one is coated on the preformed layer 114 on 112 surface of carbon nano tube structure, and the carbon Nano tube structure 112 includes multiple carbon nanotubes arranged in a crossed manner;
The composite structure of carbon nano tube 110 is set on a surface 123 of the middle layer 12 by step S13, from And expose 123 part of surface of the middle layer 12;
Step S14 etches the middle layer 12, so as to obtain one with the composite structure of carbon nano tube 110 for mask dry Middle layer 12 with patterning protrusion 122, and patterning protrusion 122 includes multiple raised lines arranged in a crossed manner;
Step S15 removes the composite structure of carbon nano tube 110;
Step S16 deposits a metal layer 13 on the surface of the patterning protrusion 122.
In step s 11, the middle layer 12 can be the insulating materials such as silica, silicon nitride, silicon, gallium nitride, arsenic The semi-conducting materials such as gallium.The middle layer 12 is directly arranged on the surface of the substrate 11.In the present embodiment, the middle layer 12 are formed in the surface of the substrate 11 by Plasma Enhanced Chemical Vapor Deposition (PECVD).It is appreciated that it is formed in the substrate 11 The method of the middle layer 12 is without being limited thereto, and any method that the middle layer 12 can be set to the substrate 11 can.
In step s 12, the carbon nano tube structure 112 include multiple ordered arrangements and carbon nanotube arranged in a crossed manner from And multiple micropores are formed, the preformed layer 114 is coated on the surface of multiple carbon nanotube.Preferably, the preformed layer 114 wraps It is overlying on the whole surface of each carbon nanotube.The multiple carbon nanotube closely connects to make the carbon nanometer by Van der Waals force Pipe structure 112 and composite structure of carbon nano tube 110 form a self supporting structure.So-called self supporting structure refers to that the structure can nothing It needs a supporter and keeps a specific membrane structure.Thus, the composite structure of carbon nano tube 110 can with self-supporting The hanging setting in part.The carbon nanotube includes one kind in single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube It is or a variety of.The carbon nanotube is parallel to the surface of the carbon nano tube structure 112.The single-walled carbon nanotube it is a diameter of 0.5 nanometer~10 nanometers, a diameter of 1.0 nanometers~15 nanometers of double-walled carbon nano-tube, a diameter of the 1.5 of multi-walled carbon nanotube Nanometer~50 nanometers.The length of the carbon nanotube is more than 50 microns.Preferably, the length of the carbon nanotube for 200 microns~ 900 microns.
The carbon nano tube structure 112 includes an at least carbon nano-tube film, at least a carbon nano tube line or combination.It is described Carbon nano-tube film includes multiple equally distributed carbon nanotubes.Multiple carbon nanotubes in the carbon nano-tube film are prolonged in one direction It stretches, multiple carbon nanotube forms multiple carbon nano-tube bundles, and the extending direction of the carbon nanotube is parallel to the carbon nanotube The surface of film.Specifically, which may include a carbon nanotube membrane.The carbon nano tube line can be one non-twisted Carbon nano tube line or the carbon nano tube line of torsion.It is multiple when the carbon nano tube structure 112 includes multiple carbon nano tube lines Carbon nano tube line is mutually parallel interval and cross arrangement at an angle and forms the carbon nano tube structure of a stratiform.The stratiform Carbon nano tube structure includes multiple micropores, the through-hole of the thickness direction for the carbon nano tube structure which runs through the stratiform for one. The size of the micropore is 1 nanometer~0.5 micron.
Specifically, which includes carbon nano-tube bundle that is multiple continuous and aligning.Multiple carbon nanometer Tube bank is joined end to end by Van der Waals force.Each carbon nano-tube bundle includes multiple carbon nanotubes being mutually parallel, multiple mutual Parallel carbon nanotube is combined closely by Van der Waals force.A diameter of 10 nanometers~200 nanometers of the carbon nano-tube bundle, preferably , 10 nanometers~100 nanometers.Carbon nanotube in the carbon nanotube membrane is arranged of preferred orient in the same direction.The carbon is received Mitron membrane includes multiple micropores.The through-hole of the thickness direction for the carbon nano tube structure that the micropore runs through the stratiform for one.This is micro- Kong Kewei holes and/or gap.When the carbon nano tube structure 112 only includes single-layer carbon nano-tube membrane, the carbon nanotube There is gap in membrane between adjacent carbon nanotube segment, wherein, the size in the gap is 1 nanometer~0.5 micron.It can manage Solution, in the carbon nano tube structure 112 being made of multilayer carbon nanotube membrane, the carbon nanometer in two neighboring carbon nanotube membrane The orientation of pipe has an angle α, and 0 ° of < α≤90 °, so as to make the carbon nanotube in adjacent two layers carbon nanotube membrane mutual Intersect one reticular structure of composition, which includes multiple holes, and multiple hole is uniform and is regularly distributed on carbon nanotube In structure 112, wherein, which is 1 nanometer~0.5 micron.The thickness of the carbon nanotube membrane for 0.01 micron~ 100 microns.The carbon nanotube membrane can be directly obtained by pulling a carbon nano pipe array.The carbon nanotube membrane Structure and preparation method thereof refers to model and keeps filed in kind et al. on 2 9th, 2007, on May 26th, 2010 bulletin the No. CN101239712B Chinese issued patents " carbon nano-tube thin-film structure and preparation method thereof ", applicant:Tsinghua University, letter Accurate industrial (Shenzhen) Co., Ltd in Fujin.To save space, this is only incorporated in, but all technology exposure of above-mentioned application should also regard The part disclosed for present utility model application technology.
The non-twisted carbon nano tube line includes multiple carbon arranged along the non-twisted carbon nano tube line length direction and receives Mitron.Specifically, which includes multiple carbon nanotube segments, and multiple carbon nanotube segment passes through model De Huali joins end to end, and each carbon nanotube segment includes multiple carbon nanometers being mutually parallel and combine closely by Van der Waals force Pipe.The carbon nanotube segment has arbitrary length, thickness, uniformity and shape.The non-twisted carbon nanotube line length is not Limit, a diameter of 0.5 nanometer~100 microns.Carbon nanotube membrane is is handled by non-twisted carbon nano tube line by organic solvent It obtains.Specifically, organic solvent is infiltrated to the whole surface of the carbon nanotube membrane, is produced when volatile organic solvent volatilizees Under the action of raw surface tension, the multiple carbon nanotubes being mutually parallel in carbon nanotube membrane are closely tied by Van der Waals force It closes, so as to which carbon nanotube membrane be made to be punctured into a non-twisted carbon nano tube line.The organic solvent is volatile organic solvent, such as Ethyl alcohol, methanol, acetone, dichloroethanes or chloroform use ethyl alcohol in the present embodiment.The non-twisted carbon handled by organic solvent Compared with the carbon nano-tube film handled without organic solvent, specific surface area reduces nanometer pipeline, and viscosity reduces.
The carbon nanotube membrane both ends is are turned round using a mechanical force by the carbon nano tube line of the torsion in opposite direction Turn to obtain.The carbon nano tube line of the torsion includes the carbon nanotube that multiple carbon nano tube line axial screws around the torsion arrange. Specifically, the carbon nano tube line of the torsion includes multiple carbon nanotube segments, and multiple carbon nanotube segment passes through Van der Waals force It joins end to end, each carbon nanotube segment includes multiple carbon nanotubes being mutually parallel and combine closely by Van der Waals force.It should Carbon nanotube segment has arbitrary length, thickness, uniformity and shape.The carbon nanotube line length of the torsion is unlimited, diameter It is 0.5 nanometer~100 microns.Further, the carbon nano tube line that a volatile organic solvent handles the torsion can be used.It is waving Under the action of the surface tension generated during the organic solvent volatilization of hair property, adjacent carbon is received in the carbon nano tube line for torsion that treated Mitron is combined closely by Van der Waals force, reduces the specific surface area of the carbon nano tube line of torsion, density and intensity increase.
Described liner structure of carbon nano tube and preparation method thereof refers to model and keeps kind et al. to be applied on the 16th in September in 2002 , in No. CN100411979C Chinese issued patents " a kind of Nanotubes and its manufacturer of the bulletin on the 20th of August in 2008 Method ", applicant:Filed in Tsinghua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd. and 16 days December in 2005, In No. CN100500556C Chinese issued patents application " carbon nano-tube filament and its making side of bulletin on June 17th, 2009 Method ", applicant:Tsinghua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..To save space, this is only incorporated in, but above-mentioned Apply for that all technology exposure also should be regarded as a part for present utility model application technology exposure.
In the present embodiment, carbon nanotube membrane of the carbon nano tube structure 112 for two layers of square crossing setting, the carbon Nanotube membrane directly pulls to obtain from the carbon nano pipe array grown, multiple carbon nanometers in the carbon nano tube structure 112 Pipe is joined end to end by Van der Waals force and arranged in the same direction.
The material of the preformed layer 114 can be the metals such as gold, nickel, titanium, iron, aluminium, chromium, aluminium oxide, magnesia, zinc oxide, At least one of the metal oxides such as hafnium oxide or metal sulfide etc..It is appreciated that the material of the preformed layer 114 Be not limited to it is above-mentioned enumerate material, can also be non-metallic carbides or the nitridations such as nonmetal oxides, the silicon carbide such as silica Non-metal nitrides such as silicon etc., if the surface for being deposited on the carbon nano tube structure 112 that can be physical, and subsequent It is not etched during etching middle layer 12.The physical deposition refers to that the preformed layer 114 is not received with the carbon Nanotube structures 112 chemically react, but are combined closely, and invest by Van der Waals force and the carbon nano tube structure 112 The surface of carbon nanotube in the carbon nano tube structure 112.The thickness of the preformed layer 114 is unlimited, can be received for 3 nanometers~50 Rice.The nano-wire array of nano-grade size and the quilt for avoiding the micropore in the carbon nano tube structure 112 excessive in order to obtain The preformed layer 114 covers, and the thickness of the preformed layer 114 is preferably 3 nanometers~20 nanometers.The composite structure of carbon nano tube 110 116 aperture of micropore is less than the micropore size in the carbon nano tube structure 112.
The composite structure of carbon nano tube 110 can be prepared by the following method:First, by the carbon nano tube structure 112 at least partly hanging settings;Then, preformed layer 114 is deposited on 112 surface of carbon nano tube structure.
The carbon nano tube structure 112 has two opposite surfaces, and the carbon nano tube structure 112 can pass through a frame It is fixed, it is vacantly set positioned at the part of lower portion, so that the fully exposure of carbon nano tube structure 112, in favor of subsequent The preformed layer 114 is formed simultaneously on two opposite surfaces of carbon nano tube structure 112.The frame is a hollow structure, With a through-hole.The edge of the carbon nano tube structure 112 is securable in the frame, is passed through positioned at intermediate part described Through-hole is exposed and vacantly sets.Pass through the frame so that the edge of the carbon nano tube structure 112 can firmly be consolidated It is fixed, and remain in the fully exposure of the carbon nano tube structure 112 at lead to the hole site.In the present embodiment, the frame is one " mouth " The frame of font, the edge of the carbon nano tube structure 112 are fixed by the frame.It is appreciated that the carbon nanotube knot The mode that structure 112 is vacantly set may be other means, such as metallic mesh, the ring bodies etc. with hollow structure, as long as Realization makes the carbon nano tube structure 112 hanging.Can the preformed layer 114 be deposited on by the carbon by e-beam evaporation The surface of nano tube structure 112.It is appreciated that the method for the deposition is not limited to the above-mentioned method enumerated, can also be magnetic control The vapour deposition processes such as sputtering method, atomic layer deposition method, as long as ensureing that the preformed layer 114 does not destroy institute during deposition State the form and structure of carbon nano tube structure 112.
Since the carbon nano tube structure 112 is vacantly set, thus two surfaces quilt of the carbon nano tube structure 112 The preformed layer 114 covers.Specifically, the preformed layer 114 coats in the carbon nano tube structure 112 multiple carbon nanotubes extremely Small part surface.The carbon nano tube structure 112 includes multiple microcellular structures, it will be understood that can also divide in the microcellular structure It is furnished with the preformed layer 114.Carbon nanotube in the carbon nano tube structure 112 is combined closely with the preformed layer 114, is formed One whole composite structure of carbon nano tube 110.Wherein, the carbon nano tube structure 112 plays the preformed layer 114 support and makees With.The composite structure of carbon nano tube 110 includes multiple micropores 116.The micropore 116 is through the carbon nanotube composite structures The dented space of the thickness direction of structure 110, the dented space can be gap or micropore.
In the present embodiment, preformed layer 114 is set to obtain on the surface of the carbon nano tube structure 112 by e-beam evaporation To the composite structure of carbon nano tube 110, the material of the preformed layer 114 is aluminium oxide, and the thickness of the preformed layer 114 is 5 Nanometer.Each carbon nanotube in the carbon nano tube structure 112 is coated completely by the preformed layer 114.
In step s 13, the composite structure of carbon nano tube 110 can be directly arranged at the surface of the middle layer 12 123.Specifically, the frame and the composite structure of carbon nano tube 110 can be first transferred to the table of the middle layer 12 together Face 123, then remove the frame.Since the composite structure of carbon nano tube 110 has multiple micropores 116, thus the centre 123 part of surface of layer 12 is exposed by multiple micropore 116.The composite structure of carbon nano tube 110 and the centre It is in close contact between the surface 123 of layer 12 and non-fully, the composite structure of carbon nano tube 110 of part and the middle layer 12 There may be air between surface 123.
The composite structure of carbon nano tube 110 is set to after the surface 123 of the middle layer 12, it further can be with The composite structure of carbon nano tube 110 is handled by solvent including one, attaches the composite structure of carbon nano tube 110 The surface on the surface 123 of the middle layer 12 the step of.It is molten when being added dropwise to the surface of the composite structure of carbon nano tube 110 Agent, the solvent can infiltrate the composite structure of carbon nano tube 110, soften the composite structure of carbon nano tube 110, and by described in Air discharge between composite structure of carbon nano tube 110 and the surface 123 of the middle layer 12.After the solvent is removed, The composite structure of carbon nano tube 110 is formed with the surface on the surface 123 of the middle layer 12 and is closely contacted.The solvent can For water, organic solvent etc..The organic solvent is volatile organic solvent, such as ethyl alcohol, methanol, acetone, dichloroethanes and chloroform. In the present embodiment, the solvent is ethyl alcohol, by being added dropwise the ethyl alcohol in the surface of the composite structure of carbon nano tube 110, Then natural air drying so that the composite structure of carbon nano tube 110 adhere well to the surface 123 of the middle layer 12.
In step S14, the dry etching refers to that be passed through a gas obtains a plasma under electric field action, such Gas ions can react with the substance that is etched and obtain volatile materials, such as:Reactive ion etching (RIE), inductance coupling Close plasma etching (ICPE).In the present embodiment, pass through the middle layer 12 being exposed described in reactive ion etching method etching Surface 123.Specifically, by being passed through a gas to a plasma system, the gas can be oxygen, chlorine, hydrogen, Chlorine, argon gas, carbon tetrafluoride etc..The gas be not limited to it is above-mentioned enumerate gas, as long as the gas can occur instead with middle layer 12 It should.Preferably, the substrate 12 is etched using the reactive ion etching method of chlorine and argon gas, wherein, the plasma The power of system system is 20 watts~70 watts, and chlorine plasma is passed through rate as 10 mark condition milliliter (standard- per minute State cubic centimeter per minute, sccm), argon plasma is passed through rate as 40sccm, formation Air pressure is 2 pas, and etch period is 10 seconds~400 seconds.The portion of middle layer 12 being exposed by reactive ion etching method etching Divide surface, since plasma is fully reacted with middle layer 12, therefore, the process reaction time is short, and efficiency is higher.
During the middle layer 12 is etched, the etching gas and the part of middle layer 12 being exposed Learn reaction, and with the preformed layer 114 of the composite structure of carbon nano tube 110 occur chemical reaction or with preformed layer 114 The speed and degree chemically reacted is far smaller than the chemical reaction that etching gas occurs with middle layer 12.That is, the carbon is received Mitron composite construction 110 plays the role of mask.The etching gas and the material of middle layer 12 and the material of preformed layer 114 It can be found in the following table 1.
1 etching gas of table and the material of middle layer, the corresponding table of the material of preformed layer
Number The material of substrate The material of preformed layer Etching gas
1 SiO2 One kind in Al, Cr, Fe, Ti, Ni or Au CF4
2 SiNx One kind in Al, Cr, Fe, Ti, Ni or Au CF4
3 GaN Al2O3 Cl2And Ar2
During etching, since etching gas and the preformed layer 114 of selection do not chemically react, but with centre Layer 12 chemically reacts, thus the surface of middle layer 12 being exposed can gradually be etched, and the middle layer 12 is by the carbon The surface that nanotube composite construction 110 covers will not change.Also, due to the composite structure of carbon nano tube 110 with it is described The surface of middle layer 12 is combined closely, thus the surface institute shape that the middle layer 12 is covered by the composite structure of carbon nano tube 110 Into figure, the figure formed when hanging to the forward projection of the middle layer 12 with the composite structure of carbon nano tube 110 Unanimously.The global pattern base of the global pattern and the composite structure of carbon nano tube 110 of patterning protrusion 122 finally obtained This is consistent.
In the present embodiment, when the carbon nano tube structure 112 uses the carbon nanotube membrane that multilayer is intersected, by changing phase The intersecting angle of adjacent carbon nanotube membrane can obtain the patterning protrusion 122 with different pattern.Intersect when using positive Carbon nanotube membrane as carbon nano tube structure when, obtain the patterning protrusion 122 include it is multiple along two Vertical Squares To the raised line of cross arrangement.
The raised line of the patterning protrusion 122 is class strip or strip structure.The width of the raised line for 20 nanometers~ 150 nanometers.Spacing on the extending direction perpendicular to carbon nanotube between two adjacent width is received for 10 nanometers~300 Rice.The raised line of the patterning protrusion 122 is defined as raised line in the size on the direction on the surface of the middle layer 12 Height.The height of the raised line is unlimited, can be 50 nanometers~1000 nanometers depending on the time specifically etched.It is described Multiple raised lines are mutually perpendicular to cross-distribution in a reticular structure.In the present embodiment, the width of the raised line is received for 50 nanometers~100 Rice, spacing are 10 nanometers~50 nanometers, are highly 100 nanometers~500 nanometers.
It is appreciated that due to multiple after the carbon nanotube cladding preformed layer 114 in the composite structure of carbon nano tube 110 The diameter of structure, spacing are closed in nano-scale range, therefore, the raised line width and spacing of the patterning protrusion 122 being prepared Also in nano-scale range.Therefore, the patterning protrusion 122 on 12 surface of middle layer and multiple holes 124 are nanostructured. The spacing of adjacent raised line and the spacing of adjacent holes 124 are tens nanometers on 12 surface of middle layer, therefore, are greatly improved The density of the nanostructured on 12 surface of middle layer so as to improve SERS enhancement factors, enhances Raman scattering.For example, When the spacing of adjacent raised line and the spacing of adjacent holes 124 are 20 nanometers, in 1 micron of width range, the raised line and The quantity of hole 124 is 50.And in the prior art, the preparation generally use photoetching technique of micro-structure, due to by resolution ratio The nanostructured scale of limitation, protrusion and recess is difficult to all control in tens nanometer ranges.
In step S15, the method for removing composite structure of carbon nano tube 110 is unlimited, can be ultrasonic method, remove method, oxidation Method etc..In the present embodiment, the composite structure of carbon nano tube 110 is removed using ultrasonic method.Specifically, the carbon nanometer will be carried The centre of pipe composite construction 110 is placed on several minutes of ultrasound in the solution of a N-Methyl pyrrolidone, due to N- crassitudes The polarity of ketone is larger, thus can be easily by the composite structure of carbon nano tube 110 and intermediate layer separation.
In step s 16, it is unlimited in the method for the surface deposited metal layer 13 of the patterning protrusion 122, electricity can be used The modes such as beamlet evaporation, ion beam sputtering, atomic layer deposition, magnetron sputtering, vapor deposition, chemical vapor deposition.The metal layer 13 Be deposited on each raised line surface and adjacent raised line between middle layer 12 surface.The thickness of the metal layer 13 is received for 2 - 200 nanometers of rice, the material of the metal layer 13 is unlimited, can be the metals such as gold, silver, copper, iron or aluminium.In the present embodiment, in institute The golden metallic film that 10 nano thickness are vertically deposited in 12 surface of middle layer is stated, so as to will be patterned into all coverings of protrusion 122.
The preparation method of molecular vehicle provided by the utility model has the following advantages:It is prepared using flexible substrates Molecular vehicle 10 can carry out Molecular Detection on irregular surfaces, and can realize in situ detection on determinand surface;By metal layer 13 are deposited on the reticular structure that multiple raised lines are formed, so as to which under the excitation of incident light, metal surface plasma body can occur RESONANCE ABSORPTION, the raised line of network structure can play the role of Surface enhanced Raman scattering, can improve SERS (Surface Enhanced Raman scattering) enhancement factor, enhance Raman scattering.Moreover, using carbon nano tube structure as bone Frame, carbon nano tube structure have multiple micropores, and mask layer also has multiple micropores accordingly because obtained from, and this method can be easily The patterned mask layer of realization.The preparation method is simple, efficient, and is easy to industrialization.
Referring to Fig. 5, the utility model first embodiment further provides for a kind of molecule using the molecular vehicle 10 Detection method, the detection method mainly include the following steps that:
Step S21, provides a sample to be tested 14, and determinand molecule 15 is distributed in the surface of the sample to be tested 14;
Step S22 provides a molecular vehicle 10, which includes a substrate 11, a middle layer 12 and a gold medal Belong to layer 13, the middle layer 12 is sandwiched between the substrate 11 and the metal layer 13;The middle layer 12 includes a substrate 121 and multiple patterning protrusions 122 being arranged on the substrate 121;
Surface of the metal layer 13 far from the substrate 11 is fitted in the surface of the sample to be tested 14 by step S23, So that the determinand molecule 15 is formed in the surface of the metal layer 13;
Step S24 is detected the determinand molecule 15 on 13 surface of metal layer using detector.
In the step s 21, the surface of the sample to be tested 14 can be arbitrary surfaces, specifically, the surface of the sample to be tested 14 Can be plane, curved surface or other irregular surfaces, such as the surface of apple, tomato.The type of the determinand molecule 15 is unlimited, And can be with Arbitrary distribution in the surface of sample to be tested 14, such as remain in the pesticide on tomato surface.In the present embodiment, this is to be measured Object molecule is crystal violet (CV).
In step S23, since the substrate 11 is a flexible substrates, which can be attached directly to treat test sample The surface of product 14, and can be consistent with the curvature on 14 surface of sample to be tested.Specifically, the metal layer 13 is directly with treating test sample The surface of product 14 is in direct contact, and then, the determinand molecule 15 positioned at 14 surface of sample to be tested can accordingly be adhered to the metal On layer 13.It further, can also be in the sample to be tested 14 before the metal layer 13 is attached at the surface of the sample to be tested 14 Drip appropriate solvent in surface so that determinand molecule 15 is dissolved in solvent, then the metal layer 13 is pasted to drop has treating for solvent The surface of sample 14.Since determinand molecule 15 is dissolved in solvent, mobility improves, and can be easier to be attached to the metal layer 13 surface.Meanwhile the solvent for dropping in 14 surface of sample to be tested can be also discharged between sample to be tested 14 and metal layer 13 Air so that the molecular vehicle 10 is tightly adsorbed on the surface of the sample to be tested 14, is fixed without applying external force.Its In, the solvent can be water, ethyl alcohol, propyl alcohol etc., and the solvent can be used that needle tubing drop is several to drop to 14 surface of sample to be tested, specifically Ground, solvent are equal or slightly larger than the area of the metal layer 13 in the area of 14 surface spreading of sample to be tested.
It in step s 24, can be directly to the determinand molecule on 13 surface of metal layer using detector such as Raman spectrometer 15 carry out in situ detection, without the molecular vehicle 10 is removed from the surface of sample to be tested 14.It is remote to set the metal layer 13 Surface from substrate 11 is the front of the molecular vehicle 10, and the surface of the substrate 11 far from metal layer 13 is carried for the molecule The reverse side of body 10.The detector can be from the incident detection in the front of molecular vehicle 10, also can be from the reverse side incidence of molecular vehicle 10 Detection, and it is used equally for detection determinand molecule 15.Referring to Fig. 6, detector is surveyed respectively from the obverse and reverse of molecular vehicle The collection of illustrative plates of different testing concentrations is measured, it can be seen from the figure that the collection of illustrative plates that detector is measured from obverse and reverse is basically identical.
In detection process, since metal layer 13 is attached directly to the surface of the sample to be tested 14, what detector was sent out Laser can be directly transmitted to the surface of the substrate 11 far from metal layer 13 and be detected, that is to say, that detector can be from described The reverse side incidence of molecular vehicle 10 is detected.Referring to Fig. 7, Fig. 7 is Raman spectrometer in situ detection tomato Surface testing Different CV molecular concentrations profiling results.Wherein, optical maser wavelength 633nm, laser power 0.1mW, time for exposure 5s.
When detector directly detection incident from the front of the molecular vehicle 10, first metal layer 13 is attached at and treats test sample Behind 14 surface of product, the surface of sample to be tested 14 is wiped using the molecular vehicle 10 so that treat on 14 surface of sample to be tested The surface that 15 part of object molecule is transferred to the metal layer 13 is surveyed, then again removes the molecular vehicle 10.At this moment, the detection The surface that device can be directly transmitted to the metal layer 13 is detected.Referring to Fig. 8, it is that apple is wiped using molecular vehicle in Fig. 8 Behind fruit surface, the inspection of the test map (III) of p-aminophenyl thiophenol (4-ATP) molecule and in situ detection on the molecular vehicle is detected The comparison diagram of mapping spectrum (I, II).Wherein, optical maser wavelength 633nm, laser power 0.1mW, time for exposure 5s.It can from figure The collection of illustrative plates for going out the collection of illustrative plates detected after wiping and in situ detection is basically identical.
Monomolecular detection method provided by the utility model, has the following advantages:Since metal layer 13 is arranged on patterning The surface of protrusion 122, and pattern protrusion 122 and include multiple raised lines arranged in a crossed manner or the projection cube structure of multiple arrays, because This, under the excitation of extraneous incident light, metal surface plasma body generation RESONANCE ABSORPTION, and raised line arranged in a crossed manner or array Convex block play the role of Surface enhanced Raman scattering, can improve SERS enhancement factors, enhance Raman scattering.Due to the molecule Carrier 10 uses flexible substrates, and the overall structure of the molecular vehicle 10 can arbitrarily be bent with flexible substrates, so that the molecule 10 overall performance of carrier is flexible structure, and therefore, which can carry out Molecular Detection on irregular surfaces, and can be In situ detection is realized on determinand surface, and method is simple, quick.
Referring to Fig. 9, the utility model second embodiment provides a kind of molecular vehicle 20 for Molecular Detection, this point Subcarrier 20 includes a substrate 11, a middle layer 12, a composite structure of carbon nano tube 110 and a metal layer 13.Specifically, The middle layer 12 is arranged on the surface of the substrate 11, and the composite structure of carbon nano tube 110 is arranged on the middle layer 12 Surface far from the substrate, the metal layer 13 are arranged on the surface of the composite structure of carbon nano tube 110.The middle layer 12 include a substrate 121 and multiple patterning protrusions 122 being arranged on the substrate 121, and the patterning protrusion 122 is set It puts on the surface of the substrate 121 far from substrate 11.The patterning protrusion 122 includes multiple raised lines formation net arranged in a crossed manner Shape structure, so as to define multiple holes 124.The infall of the multiple raised line is structure as a whole.
The knot for the molecular vehicle 10 that the molecular vehicle 20 that the utility model second embodiment provides is provided with first embodiment Structure is essentially identical, and difference lies in further comprise that a composite structure of carbon nano tube 110 is set to the patterning protrusion 122 Top surface and the metal layer 13 between.The metal layer 13 is whole by patterning protrusion 122 and composite structure of carbon nano tube 110 Covering.
Referring to Fig. 10, the utility model second embodiment provides a kind of method for preparing above-mentioned molecular vehicle 20, packet Include following steps:
Step S31 provides a middle layer 12 and is set in a substrate 11;
One composite structure of carbon nano tube 110 is set on a surface 123 of the middle layer 12 by step S32, so as to Expose 123 part of surface of the middle layer 12;
Step S33 etches the middle layer 12, so as to obtain one with the composite structure of carbon nano tube 110 for mask dry Middle layer 12 with patterning protrusion 122, and patterning protrusion 122 includes multiple raised lines arranged in a crossed manner;
Step S34 deposits a metal layer 13 on the surface of the composite structure of carbon nano tube 110, and the metal layer 13 will The composite structure of carbon nano tube 110 and all coverings of middle layer 12.
The molecule that the preparation method for the molecular vehicle 20 that the utility model second embodiment provides is provided with first embodiment The preparation method of carrier 10 is essentially identical, and difference lies in need not remove the composite structure of carbon nano tube in the present embodiment 110, but the Direct precipitation metal layer 13 directly on the composite structure of carbon nano tube 110, the metal layer 13 is by the carbon nanometer Pipe composite construction 110 and all coverings of middle layer 12.In the preparation method, the both conducts of composite structure of carbon nano tube 110 The mask of middle layer 12 is etched, and as the mask of deposited metal layer 13, has not only saved manufacturing cost, but also improve preparation Efficiency.
The utility model second embodiment further provides for a kind of molecular detecting method using the molecular vehicle 20.It should It is basic that method with the utility model first embodiment further provides for a kind of molecular detecting method using the molecular vehicle 10 Identical, difference lies in the molecular vehicle of use is different.
1 is please referred to Fig.1, the utility model 3rd embodiment provides a kind of molecular vehicle 30 for Molecular Detection, this point Subcarrier 30 includes a substrate 11, a middle layer 12 and a metal layer 13.Specifically, the middle layer 12 is arranged on the base The surface at bottom 11, the metal layer 13 are arranged on the surface of the middle layer 12.The middle layer 12 includes a substrate 121 and more A patterning protrusion 122 being arranged on the substrate 121, and the patterning protrusion 122 is arranged on the substrate 121 far from base On the surface at bottom 11.The patterning protrusion 122 includes multiple raised lines formation reticular structure arranged in a crossed manner, multiple so as to define Hole 124.The infall of the multiple raised line is structure as a whole.
The knot for the molecular vehicle 10 that the molecular vehicle 30 that the utility model 3rd embodiment provides is provided with first embodiment Structure is essentially identical, and difference lies in the metal layer 13 is discontinuous structure.Specifically, the metal layer 13 is only arranged at 121 surface of substrate between the side wall of the raised line and adjacent raised line.That is, the metal layer 13 is only arranged at described hole 124 Side wall and bottom surface on.
2 are please referred to Fig.1, the utility model 3rd embodiment provides a kind of method for preparing above-mentioned molecular vehicle 30, packet Include following steps:
Step S41 provides a middle layer 12 and is set in a substrate 11;
One composite structure of carbon nano tube 110 is set on a surface 123 of the middle layer 12 by step S42, so as to Expose 123 part of surface of the middle layer 12;
Step S43 etches the middle layer 12, so as to obtain one with the composite structure of carbon nano tube 110 for mask dry Middle layer 12 with patterning protrusion 122, and patterning protrusion 122 includes multiple raised lines arranged in a crossed manner;
Step S44 deposits a metal layer 13 on the surface of the composite structure of carbon nano tube 110, and the metal layer 13 will The composite structure of carbon nano tube 110 and all coverings of middle layer 12.
Step S45 removes the composite structure of carbon nano tube 110.
The molecule that the preparation method for the molecular vehicle 30 that the utility model 3rd embodiment provides is provided with second embodiment The preparation method of carrier 20 is essentially identical, and difference lies in deposit a metal layer 13 on the surface of the patterning protrusion 122 Afterwards, then the composite structure of carbon nano tube 110 is removed.In step S44, it is compound which is partially depositing in carbon nanotube 110 surface of structure, another part are deposited between raised line side and adjacent raised line.In step S45, it is deposited on carbon nanotube and answers The partial metal layers 13 on 110 surface of structure are closed as the composite structure of carbon nano tube 110 removes together, in 12 surface shape of middle layer Into discontinuous metal layer 13.Meanwhile in actual fabrication process, after composite structure of carbon nano tube removal, in the top surface of raised line Some metal layer corners can be remained with the position of the boundary of side, these metal corner particles or small―gap suture are to improving SERS enhancings Effect.In the method for the utility model 3rd embodiment, the composite structure of carbon nano tube 110 is both as etching middle layer 12 Mask, and as the mask of deposited metal layer 13, manufacturing cost has not only been saved, but also improve preparation efficiency.
The utility model 3rd embodiment further provides for a kind of monomolecular detection method using the molecular vehicle 30. This method further provides for a kind of molecular detecting method base using the molecular vehicle 20 with the utility model second embodiment This is identical, and difference lies in the molecular vehicle of use is different.
3 are please referred to Fig.1, the utility model fourth embodiment provides a kind of molecule inspection of above-mentioned molecular vehicle 10,20,30 Survey device 1.The present embodiment only illustrates by taking molecular vehicle 10 as an example.The molecular detector arrangement 1 includes a molecular vehicle 10, and one is solid Element 16 is determined for the molecular vehicle 10 to be fixed on to the surface of sample to be tested, and a detector 17 is used for 10 table of molecular vehicle The determinand molecule in face is detected and a control computer 18 being connect with the detector 17.
The retaining element 16 is the fixing device that the molecular vehicle 10 can be arbitrarily fixed on to detected sample surface. Specifically, the retaining element 16 can be a fixation band, and the molecular vehicle 10 is tied to detected sample using fixed band Surface, and the fixation band is caused not block whole patterning protrusions 122 of the molecular vehicle 10.Please refer to Fig.1 4, it is described solid It can be also a bent metal framework to determine element 16, the edge of the substrate 11 is fixed on the metal framework, the metal Frame can simultaneously be bent with molecular vehicle, so as to which molecular vehicle can be fixed on the surface of sample to be tested 14 by the metal framework. It is appreciated that when the molecular vehicle 10 can be separately attached to 14 surface of sample to be tested, the retaining element 16 can for one Selection element.The detector 17 can be Raman spectrometer or other detectors that can realize Molecular Detection.
Further, 5 are please referred to Fig.1, the molecular detector arrangement 1 may include multiple molecular vehicles 10, the multiple molecule Carrier 10 is interconnected to form a molecular vehicle band, and specifically, multiple molecular vehicle 10 can share same substrate, described more The patterning protrusion of a molecular vehicle is located at the same surface of the substrate.It is described since the molecular vehicle is a flexible structure Molecular vehicle band is rollable into tubular, to save space, while can intercept as required when in use, easy to use.
The molecular detector arrangement 1 is in use, the molecular vehicle 10 is fixed on by the retaining element 16 described The surface of sample to be tested, then the determinand molecule on 10 surface of molecular vehicle is detected using the detector 17, the detection Testing result is sent to the control computer 18 by device 17.The control computer 18 analyzes testing result, so as to fulfill Real-time dynamic monitoring is carried out to determinand molecule.
In addition, those skilled in the art can also make other variations within the spirit of the present invention, these are according to this reality certainly The variation made with novel spirit, all is included in the scope of protection of the present invention.

Claims (10)

1. a kind of molecular vehicle for Molecular Detection, including:
One substrate;
One middle layer is set to the surface of the substrate;
One metal layer is set to surface of the middle layer far from substrate;
It is characterized in that, the substrate is a flexible substrates;The middle layer includes a substrate and multiple settings over the substrate Patterning protrusion;The metal layer is set to the surface of the patterning protrusion.
2. molecular vehicle as described in claim 1, which is characterized in that the material of the substrate is polyethylene terephthalate One kind in ester, polyimides, polymethyl methacrylate, dimethyl silicone polymer and polyethylene naphthalate.
3. molecular vehicle as described in claim 1, which is characterized in that the thickness range of the substrate is received for 100 nanometer -200 Rice.
4. molecular vehicle as described in claim 1, which is characterized in that it is arranged in a crossed manner that the patterning protrusion includes multiple raised lines Form network structure, so as to define multiple holes, the multiple raised line include multiple the first raised lines extended in a first direction and The angle of multiple the second raised lines extended in a second direction, the first direction and second direction is less than or equal to more than or equal to 30 degree 90 degree, the width of each raised line is 20 nanometers -150 nanometers, is highly 20 nanometers -500 nanometers, and adjacent two parallel raised lines it Between spacing be 10 nanometers -300 nanometers.
5. molecular vehicle as claimed in claim 4, which is characterized in that the width of each raised line is 50 nanometers -100 nanometers, high It is 200 nanometers -400 nanometers to spend, and the spacing between adjacent two parallel raised lines is 10 nanometers -50 nanometers.
6. molecular vehicle as described in claim 1, which is characterized in that the metal layer be continuous layer structure, the metal Layer be arranged on the multiple raised line surface and raised line between hole in.
7. molecular vehicle as described in claim 1, which is characterized in that the metal layer be discrete layer structure, the gold Belong to layer be only arranged at multiple raised lines side wall and adjacent raised line between hole in.
8. molecular vehicle as described in claim 1, which is characterized in that the thickness range of the metal layer is received for 2 nanometer -200 Rice.
9. molecular vehicle as described in claim 1, which is characterized in that further comprise a retaining element, which uses In the surface that the metal layer is fixed on to determinand, which is one kind in fixed band, bent metal framework.
10. molecular vehicle as described in claim 1, which is characterized in that the molecular vehicle generally flexible structure.
CN201721155927.8U 2017-09-08 2017-09-08 For the molecular vehicle of Molecular Detection Active CN207571034U (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109470682A (en) * 2017-09-08 2019-03-15 清华大学 Molecular vehicle for Molecular Detection
CN111489897A (en) * 2019-01-25 2020-08-04 清华大学 Photocatalytic structure and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109470682A (en) * 2017-09-08 2019-03-15 清华大学 Molecular vehicle for Molecular Detection
CN111489897A (en) * 2019-01-25 2020-08-04 清华大学 Photocatalytic structure and preparation method thereof

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