CN109540847A - A kind of graphene/gold/D plastic optical fiber SPR sensor and preparation method - Google Patents

A kind of graphene/gold/D plastic optical fiber SPR sensor and preparation method Download PDF

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CN109540847A
CN109540847A CN201811526210.9A CN201811526210A CN109540847A CN 109540847 A CN109540847 A CN 109540847A CN 201811526210 A CN201811526210 A CN 201811526210A CN 109540847 A CN109540847 A CN 109540847A
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graphene
optical fiber
gold
plastic optical
copper foil
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CN109540847B (en
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张超
姜守振
徐纪华
修显武
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Shandong Normal University
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    • 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
    • G01N21/55Specular reflectivity
    • G01N21/552Attenuated total reflection
    • G01N21/553Attenuated total reflection and using surface plasmons
    • 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
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation

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Abstract

The invention belongs to spr sensor technical field more particularly to a kind of graphene/gold/D plastic optical fiber SPR sensor and preparation methods.Described method includes following steps: (1) offering the sensing unit of groove-like on fiber, be prepared into D-shaped fiber;(2) graphene is grown on copper foil with chemical vapour deposition technique, golden film is directly deposited onto graphene using the method for hot evaporation, obtains gold/graphene/copper foil composite layer;(3) erode the copper foil in gold/graphene/copper foil composite layer, by obtained graphene/golden film be transferred in D-type optical fiber to get.The present invention, by gold directly vapor deposition to graphene, is bonded graphene and golden film perfectly, the graphene/gold for eroding copper foil is transferred on D plastic optical fiber later, the structure of gold plus graphene is realized on plastic optical fiber using the method for hot evaporation.Graphene/gold prepared by the present invention/D plastic optical fiber SPR sensor has the characteristics that the identification high sensitivity to complementary and incomplementarity DNA chain.

Description

A kind of graphene/gold/D plastic optical fiber SPR sensor and preparation method
Technical field
The invention belongs to surface plasma body resonant vibration (SPR) sensor technical field more particularly to a kind of graphene/gold/D Plastic optical fiber SPR sensor and preparation method.
Background technique
After optical fiber SPR sensor in 1993 is suggested, this technology attracts always more and more research interests.Light Fine surface plasmon sensor, it can carry out follow-up study to the slight change of media surface, realize hypersensitive and without mark The chemistry of note and bioanalysis, food inspection, in terms of have important application.
Up to the present, researcher has carried out many effort to improve the performance of optical fiber SPR sensor.For example it proposes Various optical fiber structures: tapered, D type, U-shaped etc..And cylindrical fibre geometry is not suitable for the transfer of large area material tunic. Meanwhile in the detection process, film is not easy to stablize on cylindrical fibre, so that film may be ruptured or be peeled off.And D-type optical fiber Burnishing surface can be better maintained integrality and prevent the wrinkle of material tunic, can also be provided during the test for probe flat Smooth detection plane.In addition, D type fibre core is exposed, therefore the transmission of the evanescent wave with large scale shape optical fiber can easily enter greatly Evanescent field, realize efficient Application in Sensing.
In addition, many researchers improve the performance of sensor by the material on optimization fibre optical sensor, in metal In (usually gold, silver) plus two-dimensional material structure, usually by first depositing one layer of golden film, then in such a way that wet process shifts Chemical vapour deposition technique (CVD) graphene grown is transferred in golden film.However golden film and graphene are physical contacts, two The contact interface of person is easy to generate layering, and some inevitable Cu ions are trapped in graphene layer after corrosion Interior, this will further result in the imperfect fitting of graphene and golden film, and in this case, carrier can generate additional potential barrier, Contact resistance is increased in contact interface, to reduce sensitivity.In addition, the process of removal PMMA should not operate and time-consuming, It is some research shows that: wet process transfer a large amount of PMMA can be made to remain on the surface of graphene, to influence the function of graphene.
In recent years, plastic optical fiber (POF) obtains the concern of Many researchers, usually by polymethyl methacrylate (PMMA) As core material, compared with those expensive and frangible silica fibres, plastic optical fiber number bore dia is big, acceptance angle up to 60 °, And silica fibre only has 16 °, coupling efficiency is high;Flexibility is good, easy to process and use, light-weight and cheap.Patent text It offers 201210067372.7 and discloses a kind of D-type optical fiber spr sensor based on graphene film enhanced sensitivity, including D-type optical fiber, The burnishing surface of D-type optical fiber has silver film, has graphene film layer in silverskin layer surface.Preparation method are as follows: (1) prepare D Type optical fiber;And silver film is prepared in the burnishing surface of D-type optical fiber;(2) graphene film layer is prepared on silverskin surface.However, the party When method prepares the plastic optical fiber that sandwich layer is PMMA, graphene is added in the method for being not appropriate for removing PMMA in shifting by wet process Layer, in the more unsuitable tube furnace excessively high in temperature, the method for graphene is directly grown by covering one layer of metal;In addition, should Method is by directly growing graphene on gold or silver, but in CVD growth graphene, grow on copper foil to protect enough The quality of graphene is demonstrate,proved, and the single crystal graphene of large area can be grown, is difficult to grow ideal graphene on gold and silver Structure.
To sum up, it is necessary to study a kind of graphene/gold structure that non-physical contact can be prepared on plastic optical fiber Method, to obtain the spr sensor that performance is good, at low cost.
Summary of the invention
For above-mentioned problems of the prior art, the present invention is intended to provide a kind of graphene/gold/D plastic optical fiber Spr sensor and preparation method.The graphite that the present invention will be grown out using the method for hot evaporation on golden directly vapor deposition to copper foil On alkene, makes graphene and the perfect fitting of gold, the graphene/Jin Yiqi for eroding copper foil is transferred to D plastic optical fiber later On can be obtained detection graphene/gold/D plastic optical fiber SPR sensor for biomolecule, SPR prepared by the present invention is passed Sensor has the characteristics that the identification high sensitivity to complementary and incomplementarity DNA chain.
The first object of the present invention: a kind of graphene/golden film/D plastic optical fiber SPR sensor is provided.
The second object of the present invention: a kind of preparation method of graphene/gold/D plastic optical fiber is provided.
The third object of the present invention: answering for above-mentioned graphene/gold/D plastic optical fiber SPR sensor and preparation method is provided With.
In order to solve above-mentioned purpose, the invention provides the following technical scheme:
Firstly, the present invention discloses a kind of graphene/gold/D plastic optical fiber SPR sensor, the sensor is by D-shaped plastics Optical fiber, graphene and Jin Zucheng, the sensing unit of groove-like is offered on the D plastic optical fiber, and golden film is arranged in the sensing unit In, the graphene is arranged on golden film surface.
Further, the material of the plastic optical fiber is PMMA, and this plastic optical fiber number bore dia is big, and acceptance angle is reachable 60 °, and silica fibre only has 16 °, coupling efficiency is high;Flexibility is good, easy to process and use, light-weight and cheap.
Further, the D plastic Fibre Optical Sensor region is 1-2cm, and depth is the 20-50% of fibre diameter, narrow Sensitive zones inductive energy deficiency is not achieved, wide sensitive zones will lead to energy loss.
Further, the golden film is with a thickness of 40-60nm, the gold that the energy of a charge of excessively thin metal excitation is insufficient, blocked up Category causes energy that cannot reach sensing interface in time.
Further, the graphene number of plies is 1-3 layers, and the excessive number of plies, which obtains graphene, will lead to the loss of energy, in turn Influence sensitivity.
Secondly, the present invention discloses a kind of preparation method of graphene/gold/D plastic optical fiber SPR sensor, including as follows Step:
(1) sensing unit that groove-like is offered on plastic optical fiber is prepared into D-shaped optical fiber;
(2) graphene is grown on copper foil with chemical vapour deposition technique (CVD), directly steamed gold using the method for hot evaporation It is plated on graphene, obtains gold/graphene/copper foil composite layer;
(3) copper foil in gold/graphene/copper foil composite layer is removed, is transferred in deionized water and cleans, obtained graphite Alkene/gold is then transferred into D-type optical fiber to get gold/graphene/D-type optical fiber.
In step (1), the sensing section length is 1-2cm, and depth is the 20-50% of fibre diameter.
In step (2), the method that graphene is grown on high-purity copper foil are as follows: the copper foil after polishing is put into tubular type In furnace, by being passed through the hydrogen of different proportion and the mixed gas of methane into tube furnace, 30min is kept under 1000 ° Obtain the graphene of high quality.
It is described by gold directly vapor deposition to the method on graphene in step (2) are as follows: high-purity spun gold is put into molybdenum boat, and And the graphene grown on copper foil is placed on to the top of molybdenum boat, it is evacuated down to 10-3Pa, 110 ° of temperature modulation, spun gold is uniform It is evaporated on graphene, obtains gold/graphene/copper foil.
In step (3), the method that graphene/gold is transferred on optical fiber are as follows: the sensitive zones with D plastic optical fiber are downward Overturning, alignment are exposed to the golden film (because of the composite membrane in ionized water, gold is an exposure to air side) in outside, reversely will Composite membrane is fished for, and golden film is allowed to be attached on optical fiber, and graphene film obtains gold/graphene/D-type optical fiber upper.
It is led finally, the present invention discloses above-mentioned graphene/golden film/D-type optical fiber spr sensor and preparation method in biological detection Application in domain.
Compared with prior art, the invention has the advantages that
(1) structure that gold plus graphene are realized on plastic optical fiber, compared with the sensor for there was only metal layer in the past, stone The addition of black alkene substantially increases sensitivity, also improves chemical stability.And the use of plastic optical fiber, greatly reduce sensing The cost of device.For present invention golden film instead of the effect of traditional PMMA, this method can not only make full use of Au as graphene The supporting layer of transfer, and it is considered as most suitable metal layer due to its perfect oxidation stability and corrosion resistance;Together When contact close and firm of the Au film with graphene, contact resistance is effectively reduced, closer to ideal sensing layer model.In addition, this Invention can be to avoid the remaining residual of PMMA on graphene surface, to influence the function of graphene.Meanwhile the present invention uses The graphene to grow out on copper foil possesses better quality, and the graphene of high quality is more advantageous to the detection of sensor.
(2) when graphene and Au film contact, due to the change of electronic property, it can cause significantly at substrate interface Electric-field enhancing.Original graphite alkene is a kind of zero gap semiconductor, and valence band and conduction band contact at conical point.Due to Au The work function of (5.54eV) is higher than graphene (4.5eV), therefore the electricity under light excitation by generation from graphene layer to metal layer Lotus transfer.In this case, with electronics transfer to balance fermi level, graphene will become p-type dopant, electric charge transfer The oscillation that the resonating electron on the surface Au will be enhanced, to promote the field of SPP and further result in the more Gao Ling to target analytes Sensitivity.
(3) optical fiber of cylindrical type is not suitable for the transfer of large area single-layer graphene film, meanwhile, it is in the detection process, thin Film is not easy to stablize on cylindrical fibre, so that film may be ruptured or be peeled off.The D-shaped optical fiber that the present invention uses, burnishing surface It can be better maintained integrality and prevent graphene/Au film fold, can preferably discharge evanescent wave in this way, realize efficient Sensing, while flat detection plane is provided for probe during the test, significantly improves the susceptibility of sensor.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is graphene/gold/D plastic optical fiber SPR sensor flow diagram prepared by embodiment 1.
Fig. 2 (a) be embodiment 1 prepare graphene Raman spectrogram, Fig. 2 (b) be implementation of the present invention in embodiment 1 The picture of graphene/gold of example preparation in deionized water
Fig. 3 (a) is the scanning electron microscope image of D-type optical fiber sensitive zones in embodiment 1, and Fig. 3 (b) is embodiment 1 Prepare graphene/gold/D plastic optical fiber scanning electron microscope image.
Fig. 4 is that embodiment 1 prepares graphene/gold/D plastic optical fiber SPR sensor acquisition different glucose solution Transmitted light spectrogram.
Fig. 5 (a) is the detection for preparing graphene/golden film/D plastic fibre optical sensor and identifying DNA chain prepared by embodiment 2 Transmitted spectrum;Wherein Fig. 5 (a) is the transmission spectrum of modification;Fig. 5 (b) is the transmission spectrum for identifying the complementary DNA of various concentration; Fig. 5 (c) is the transmission spectrum for identifying incomplementarity chain.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As described in background, when prior art preparation spr sensor, golden film and graphene are physical contacts, two The contact interface of person is easy to generate layering, and some inevitable Cu ions are trapped in graphene layer after corrosion Interior, this further results in the imperfect fitting of graphene and golden film, and in this case, carrier can generate additional potential barrier, Contact interface increases contact resistance, has a negative impact to sensitivity.The characteristic of plastic optical fiber is considered simultaneously, for this purpose, this Invention proposes a kind of graphene/gold/D plastic optical fiber SPR sensor and preparation method, now in conjunction with attached drawing and specific embodiment party Formula is further illustrated the present invention
Embodiment 1
A kind of preparation method of graphene/gold/D plastic optical fiber SPR sensor, including following preparation step:
(1) D-type optical fiber: one section of 15cm is made, diameter is long 1 micron of plastic optical fiber (material PMMA), passes through side Polishing method removes the fibre cladding and segment core in sensitive zones, and opening up length is 1cm, and depth is fibre diameter 30% groove-like sensing unit.Then D type sensitive zones are rinsed to remove impurity with deionized water;
(2) it grows graphene: the copper foil after polishing being put into tube furnace, by the hydrogen for being passed through 50sccm into tube furnace The mixed gas of gas and 50sccm methane keeps 30min under 1000 °, and graphene number of plies is single layer, then by graphene/copper Foil is cut into small rectangle striped (1.2cm × 0.5cm);
(3) in the direct thermal evaporation to graphene of golden film: by high-purity spun gold of 7.5cm be put into molybdenum boat (length: 100mm, it is wide Degree: 10mm, thickness: 0.3mm) in.Graphene/the copper foil for the small rectangle shape of stripes that step (2) obtains is placed on molybdenum boat Top (distance is 9cm), when pressure is pumped to 5 × 10-3When Pa, temperature is heated to 110 °, and spun gold is uniformly evaporated to graphite On alkene, the thickness of the golden film is about 50nm, obtains gold/graphene/copper foil;
(4) erode copper foil: gold/graphene/copper foil that step (3) is obtained is placed in FeCl3It is complete to copper foil in solution It is corroded, obtains gold/graphene, rinsed gold/graphene 5 times with deionized water, residual etching liquid is washed, with D plastic The sensitive zones of optical fiber downwardly turn over, and the golden film that alignment is exposed to outside reversely fishes for composite membrane, and golden film is allowed to be attached on optical fiber, Graphene film obtains graphene/gold/D-type optical fiber upper.
Embodiment 2
A kind of preparation method of graphene/gold/D plastic optical fiber SPR sensor, including following preparation step:
(1) D-type optical fiber: one section of 15cm is made, diameter is long 1 micron of plastic optical fiber (material PMMA), passes through side Polishing method removes the fibre cladding and segment core in sensitive zones, and opening up length is 2cm, and depth is fibre diameter 45% groove-like sensing unit.Then D type sensitive zones are rinsed to remove impurity with deionized water;
(2) it grows graphene: the copper foil after polishing being put into tube furnace, by the hydrogen for being passed through 60sccm into tube furnace The mixed gas of gas and 40sccm methane keeps 30min under 1000 °, and graphene number of plies is 3 layers, then by graphene/copper foil It is cut into small rectangle striped (2cm × 0.5cm);
(3) in the direct thermal evaporation to graphene of golden film: high-purity spun gold of 8.5cm is put into molybdenum boat (length 100mm, width 10mm, thickness 0.3mm) in, the graphene/copper foil for the small rectangle shape of stripes that step (2) obtains is placed on to the top of molybdenum boat (distance is 9cm), when pressure is pumped to 5 × 10-3When Pa, spun gold is uniformly evaporated on graphene, the thickness of the golden film About 60nm is to get gold/graphene/copper foil;
(4) erode copper foil: gold/graphene/copper foil that step (3) is obtained is placed in FeCl3It is complete to copper foil in solution It is corroded, obtains gold/graphene, rinsed gold/graphene 5 times with deionized water, residual etching liquid is washed, with D plastic The sensitive zones of optical fiber downwardly turn over, and the golden film that alignment is exposed to outside reversely fishes for composite membrane, and golden film is allowed to be attached on optical fiber, Graphene film obtains graphene/gold/D-type optical fiber upper.
Embodiment 3
A kind of preparation method of graphene/gold/D plastic optical fiber SPR sensor, including following preparation step:
(1) D-type optical fiber: one section of 15cm is made, diameter is long 1 micron of plastic optical fiber (material PMMA), passes through side Polishing method removes the fibre cladding and segment core in sensitive zones, and opening up length is 1.2cm, and depth is fibre diameter 20% groove-like sensing unit.Then D type sensitive zones are rinsed to remove impurity with deionized water;
(2) it grows graphene: the copper foil after polishing being put into tube furnace, by the hydrogen for being passed through 50sccm into tube furnace The mixed gas of gas and 50sccm methane keeps 30min under 1000 °, and graphene number of plies is single layer, then by graphene/copper Foil is cut into small rectangle striped (1.2cm × 0.5cm);
(3) in the direct thermal evaporation to graphene of golden film: high-purity spun gold of 6.5cm is put into molybdenum boat (length 100mm, width 10mm, thickness 0.3mm) in, the graphene/copper foil for the small rectangle shape of stripes that step (2) obtains is placed on to the top of molybdenum boat (distance is 9cm), when pressure is pumped to 5 × 10-3When Pa, spun gold is uniformly evaporated on graphene, the thickness of the golden film About 40nm is to get gold/graphene/copper foil;
(4) erode copper foil: gold/graphene/copper foil that step (3) is obtained is placed in FeCl3It is complete to copper foil in solution It is corroded, obtains gold/graphene, rinsed gold/graphene 5 times with deionized water, residual etching liquid is washed, with D plastic The sensitive zones of optical fiber downwardly turn over, and the golden film that alignment is exposed to outside reversely fishes for composite membrane, and golden film is allowed to be attached on optical fiber, Graphene film obtains graphene/gold/D-type optical fiber upper.
Embodiment 4
A kind of preparation method of graphene/gold/D plastic optical fiber SPR sensor, including following preparation step:
(1) D-type optical fiber: one section of 15cm is made, diameter is long 1 micron of plastic optical fiber (material PMMA), passes through side Polishing method removes the fibre cladding and segment core in sensitive zones, and opening up length is 1.5cm, and depth is fibre diameter 50% groove-like sensing unit.Then D type sensitive zones are rinsed to remove impurity with deionized water;
(2) it grows graphene: the copper foil after polishing being put into tube furnace, by the hydrogen for being passed through 50sccm into tube furnace The mixed gas of gas and 50sccm methane keeps 30min under 1000 °, and graphene number of plies is single layer, then by graphene/copper Foil is cut into small rectangle striped (1.6cm × 0.5cm);
(3) in the direct thermal evaporation to graphene of golden film: high-purity spun gold of 7cm is put into molybdenum boat (length 100mm, width 10mm, thickness 0.3mm) in, the graphene/copper foil for the small rectangle shape of stripes that step (2) obtains is placed on to the top of molybdenum boat (distance is 9cm), when pressure is pumped to 5 × 10-3When Pa, spun gold is uniformly evaporated on graphene, the thickness of the golden film About 45nm is to get gold/graphene/copper foil;
(4) erode copper foil: gold/graphene/copper foil that step (3) is obtained is placed in FeCl3It is complete to copper foil in solution It is corroded, obtains gold/graphene, rinsed gold/graphene 5 times with deionized water, residual etching liquid is washed, with D plastic The sensitive zones of optical fiber downwardly turn over, and the golden film that alignment is exposed to outside reversely fishes for composite membrane, and golden film is allowed to be attached on optical fiber, Graphene film obtains graphene/gold/D-type optical fiber upper.
Performance test
(1) graphene/gold/D plastic optical fiber SPR sensor microstructure prepared by observation embodiment 1, as a result such as Under:
Fig. 2 (a) is the Raman spectrogram of graphene prepared by embodiment 1, as can be seen from this figure: (1) making on copper foil It is single layer for the graphene of high quality, the number of plies has been gone out, this is above directly to grow a counsel of perfection structure in gold or silver;(b) For graphene/gold picture in deionized water of preparation of the embodiment of the present invention, as can be seen from this figure: golden film is in deionized water In can be very good self-supporting, successfully maintain the integrality of graphene, successfully replace tradition PMMA in transfer graphene Effect.
Fig. 3 (a) is the scanning electron microscope image of D-type optical fiber sensitive zones in embodiment 1, and Fig. 3 (b) is embodiment 1 Prepare graphene/gold/D plastic optical fiber scanning electron microscope image.As can be seen from the figure graphene/golden film is flat It is covered on optical fiber surface.
(2) graphene/gold/D plastic optical fiber SPR sensor performance prepared to embodiment 1 is tested, specifically Are as follows: by the glucose solution of configured various concentration, it is added dropwise with dropper draw solution and is detected on sensitive zones;As a result As shown in figure 4, as can be seen from the figure: the transmitted spectrum of high sensitivity is obtained using the sensor of preparation, by meter The mobile ratio with variations in refractive index of wavelength is calculated, up to 1227nm/RIU.
(3) graphene/gold/D plastic optical fiber SPR sensor performance prepared to embodiment 2 is tested, specifically Are as follows: the PBASE of the 10mM of preparation is added on graphene surface 2 hours at room temperature, is then washed with DMSO and deionized water Remove unmodified PBASE.Secondly, the DNA sample of freeze-drying is dissolved and is regenerated in PBS solution.By the fiber that PBASE is fixed It immerses in DNA probe solution 4 hours at room temperature, to ensure the abundant reaction between DNA probe and PBASE.It is molten with PBS respectively Liquid and deionized water remove unreacted DNA probe.Incomplementarity DNA is added to induction region to detect;It then will be different dense The complementary DNA solution of degree is added to sensitive zones, as a result as shown in Figure 5, wherein Fig. 5 (a) is the transmission spectrum of modification, from this As can be seen that successfully adsorbing DNA probe chain using the graphene layer of the sensor of preparation to obtain high saturating of homogeneity in figure Penetrate spectrum;Fig. 5 (b) is the transmission spectrum for identifying the complementary DNA of various concentration, it will be apparent from this figure that utilizing the sensor of preparation Successfully identify that complementary DNA obtains the transmission spectrum of high sensitivity;Fig. 5 (c) is the transmission spectrum for identifying incomplementarity chain, from the figure As can be seen that successfully identifying that incomplementarity DNA obtains transmission spectrum using the sensor of preparation.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention The limitation enclosed, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not Need to make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.

Claims (10)

1. a kind of graphene/gold/D plastic optical fiber SPR sensor, it is characterised in that: the sensor by D-shaped plastic optical fibre, Graphene and golden film form, and the sensing unit of groove-like is offered on the D-shaped plastic optical fibre, and golden film is arranged in the sensing unit, The graphene is arranged on golden film surface.
2. graphene/gold as described in claim 1/D plastic optical fiber SPR sensor, it is characterised in that: the plastic optical fiber Material is PMMA, it is preferable that the plastic optical fiber sensing section length is 1-2cm, and depth is the 20-50% of fibre diameter.
3. graphene/gold as described in claim 1/D plastic optical fiber SPR sensor, it is characterised in that: the golden film with a thickness of 40-60nm。
4. graphene/gold/D plastic optical fiber SPR sensor as described in claim any one of 1-3, it is characterised in that: the stone The number of plies of black alkene is 1-3 layers.
5. a kind of graphene/gold/D plastic optical fiber SPR sensor preparation method, characterized by the following steps:
((1) offers the sensing unit of groove-like on plastic optical fiber, is prepared into D-shaped optical fiber;
(2) graphene is grown on copper foil with chemical vapour deposition technique, gold directly vapor deposition is arrived into graphite using the method for hot evaporation On alkene, gold/graphene/copper foil composite layer is obtained;
(3) copper foil in gold/graphene/copper foil composite layer is removed, is transferred in deionized water and cleans, obtained graphene/gold, It is then transferred into D-type optical fiber to get graphene/gold/D-type optical fiber.
6. graphene/golden film as claimed in claim 5/D plastic optical fiber SPR sensor preparation method, it is characterised in that: step Suddenly in (1), the sensing section length is 1-3cm, and depth is the 20-50% of fibre diameter.
7. graphene/golden film as claimed in claim 5/D plastic optical fiber SPR sensor preparation method, it is characterised in that: step Suddenly in (2), the graphene is grown on copper foil by chemical vapour deposition technique.
8. graphene/golden film as claimed in claim 5/D plastic optical fiber SPR sensor preparation method, it is characterised in that: step Suddenly described by gold directly vapor deposition to the method on graphene are as follows: high-purity spun gold to be put into molybdenum boat, and will be on copper foil in (2) The graphene of growth is placed on the top of molybdenum boat, and vacuum is extracted into 10-3Pa is heated to 110 °, and spun gold is uniformly evaporated on graphene, Obtain gold/graphene/copper foil.
9. graphene/golden film as claimed in claim 5/D plastic optical fiber SPR sensor preparation method, it is characterised in that: step Suddenly in (2), the method that graphene/gold is transferred on optical fiber are as follows: downwardly turned over, be aligned with the sensitive zones of D plastic optical fiber Be exposed to outside golden film, reversely composite membrane is fished for, allow graphene film it is upper to get.
10. graphene/golden film/D plastic optical fiber SPR sensor and/or such as claim as described in claim any one of 1-4 Any one of 5-9 graphene/golden film/D plastic optical fiber SPR sensor preparation method answering in field of biological detection With.
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