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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- graphene
- optical fiber
- gold
- plastic optical
- copper foil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/55—Specular reflectivity
- G01N21/552—Attenuated total reflection
- G01N21/553—Attenuated total reflection and using surface plasmons
- G01N21/554—Attenuated total reflection and using surface plasmons detecting the surface plasmon resonance of nanostructured metals, e.g. localised surface plasmon resonance
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/55—Specular reflectivity
- G01N21/552—Attenuated total reflection
- G01N21/553—Attenuated total reflection and using surface plasmons
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
Landscapes
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811526210.9A CN109540847B (en) | 2018-12-13 | 2018-12-13 | graphene/gold/D type plastic optical fiber SPR sensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811526210.9A CN109540847B (en) | 2018-12-13 | 2018-12-13 | graphene/gold/D type plastic optical fiber SPR sensor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109540847A true CN109540847A (en) | 2019-03-29 |
| CN109540847B CN109540847B (en) | 2021-10-19 |
Family
ID=65854984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811526210.9A Active CN109540847B (en) | 2018-12-13 | 2018-12-13 | graphene/gold/D type plastic optical fiber SPR sensor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109540847B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110132328A (en) * | 2019-04-08 | 2019-08-16 | 东莞理工学院 | Fibre optical sensor and preparation method thereof based on thermal coupling enhancement effect |
| CN110132322A (en) * | 2019-04-08 | 2019-08-16 | 东莞理工学院 | A kind of ultraviolet irradiation enhanced fiber sensor and preparation method thereof |
| CN110408907A (en) * | 2019-08-05 | 2019-11-05 | 安徽大学 | Detect the super surface sensing platform of all dielectric and design method of tumor biomarker |
| CN110987227A (en) * | 2019-12-12 | 2020-04-10 | 燕山大学 | Temperature sensor based on graphene micro-nano optical fiber and preparation method thereof |
| CN111189787A (en) * | 2020-01-15 | 2020-05-22 | 电子科技大学 | Hypersensitive gas sensor based on graphene D-shaped optical fiber |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1606494A (en) * | 2001-11-19 | 2005-04-13 | 尼克桑斯公司 | Method for making a plastic optical fiber, and resulting plastic optical fiber |
| CN1687760A (en) * | 2005-05-01 | 2005-10-26 | 福州大学 | Method for preparing fiber optic probe made from porous plastics for measuring oxygen |
| EP1892518A2 (en) * | 2000-10-30 | 2008-02-27 | SRU Biosystems, Inc. | A label-free high throughput optical technique for detecting bio-molecular interactions |
| CN102592973A (en) * | 2012-03-02 | 2012-07-18 | 山东师范大学 | Transfer method of large area graphene |
| CN102621104A (en) * | 2012-03-15 | 2012-08-01 | 电子科技大学 | Graphene film sensitized D-shaped optical fiber surface plasmon resonance (SPR) sensor and preparation method thereof |
| CN102645420A (en) * | 2012-04-17 | 2012-08-22 | 王利兵 | Method for detecting multiple harmful substance residual components in food based on surface plasma resonance technique |
| CN105651738A (en) * | 2016-03-10 | 2016-06-08 | 哈尔滨工程大学 | Helical-core optical fiber SPR sensor |
| CN108458994A (en) * | 2018-03-27 | 2018-08-28 | 南京信息工程大学 | Double D-type optical fiber sensors based on graphene composite film and preparation method thereof |
-
2018
- 2018-12-13 CN CN201811526210.9A patent/CN109540847B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1892518A2 (en) * | 2000-10-30 | 2008-02-27 | SRU Biosystems, Inc. | A label-free high throughput optical technique for detecting bio-molecular interactions |
| CN1606494A (en) * | 2001-11-19 | 2005-04-13 | 尼克桑斯公司 | Method for making a plastic optical fiber, and resulting plastic optical fiber |
| CN1687760A (en) * | 2005-05-01 | 2005-10-26 | 福州大学 | Method for preparing fiber optic probe made from porous plastics for measuring oxygen |
| CN102592973A (en) * | 2012-03-02 | 2012-07-18 | 山东师范大学 | Transfer method of large area graphene |
| CN102621104A (en) * | 2012-03-15 | 2012-08-01 | 电子科技大学 | Graphene film sensitized D-shaped optical fiber surface plasmon resonance (SPR) sensor and preparation method thereof |
| CN102645420A (en) * | 2012-04-17 | 2012-08-22 | 王利兵 | Method for detecting multiple harmful substance residual components in food based on surface plasma resonance technique |
| CN105651738A (en) * | 2016-03-10 | 2016-06-08 | 哈尔滨工程大学 | Helical-core optical fiber SPR sensor |
| CN108458994A (en) * | 2018-03-27 | 2018-08-28 | 南京信息工程大学 | Double D-type optical fiber sensors based on graphene composite film and preparation method thereof |
Non-Patent Citations (7)
| Title |
|---|
| DEJUN FENG 等: "D-shaped fiber optic SPR biosensors based on a metal-graphene structure", 《CHINESE OPTICS LETTERS》 * |
| KAMRUN NAHAR SHUSHAMA 等: "Graphene coated fiber optic surface Plasmon resonance biosensor for the DNA hybridization detection: Simulationanalysis", 《OPTICS COMMUNICATIONS》 * |
| MING-HUNG CHIU 等: "D-type fiber biosensor based on surface-plasmon resonance technology and heterodyne interferometry", 《OPTICS LETTERS》 * |
| RAMONA GALATUS 等: "Sensitivity enhancement of a D-shape SPR-POF low-cost sensor using graphene", 《INTERNATIONAL JOURNAL OF EDUCATION AND RESEARCH》 * |
| WEIXIONG LI 等: "Fabrication and application of a graphene polarizer with strong saturable absorption", 《PHOTON. RES.》 * |
| 吴冬芹: "石墨烯化学气相沉积法制备与DNA传感器应用研究", 《万方》 * |
| 郑燃: "石墨烯锁模光纤器件设计制备及应用研究", 《中国优秀硕士学位论文全文数据库 信息科技辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110132328A (en) * | 2019-04-08 | 2019-08-16 | 东莞理工学院 | Fibre optical sensor and preparation method thereof based on thermal coupling enhancement effect |
| CN110132322A (en) * | 2019-04-08 | 2019-08-16 | 东莞理工学院 | A kind of ultraviolet irradiation enhanced fiber sensor and preparation method thereof |
| CN110408907A (en) * | 2019-08-05 | 2019-11-05 | 安徽大学 | Detect the super surface sensing platform of all dielectric and design method of tumor biomarker |
| CN110408907B (en) * | 2019-08-05 | 2021-03-12 | 安徽大学 | All-dielectric super-surface sensing platform for detecting tumor biomarkers and design method |
| CN110987227A (en) * | 2019-12-12 | 2020-04-10 | 燕山大学 | Temperature sensor based on graphene micro-nano optical fiber and preparation method thereof |
| CN111189787A (en) * | 2020-01-15 | 2020-05-22 | 电子科技大学 | Hypersensitive gas sensor based on graphene D-shaped optical fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109540847B (en) | 2021-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109540847A (en) | A kind of graphene/gold/D plastic optical fiber SPR sensor and preparation method | |
| Sakib et al. | High performance dual core D-shape PCF-SPR sensor modeling employing gold coat | |
| Rifat et al. | Highly sensitive D-shaped photonic crystal fiber-based plasmonic biosensor in visible to near-IR | |
| Wei et al. | Flexible nanowire cluster as a wearable colorimetric humidity sensor | |
| Hsu et al. | Generally applicable self-masked dry etching technique for nanotip array fabrication | |
| CN108226137B (en) | Preparation method and application of flexible and transparent molybdenum disulfide @ silver particle/three-dimensional pyramid structure PMMA SERS substrate | |
| KR101090430B1 (en) | Optical Fiber Containing Carbon Nanostructure Layer, Optical Fiber Chemical Sensor and Method of Forming Carbon Nanostructure Layer on Optical Fiber Core | |
| Osváth et al. | The structure and properties of graphene on gold nanoparticles | |
| Li et al. | LSPR optical fiber biosensor based on a 3D composite structure of gold nanoparticles and multilayer graphene films | |
| CN107014799A (en) | A kind of graphene/silver nano flower-like/PMMA " sandwich " structural flexibility SERS substrates and preparation method thereof | |
| Rea et al. | Fabrication and characterization of a porous silicon based microarray for label-free optical monitoring of biomolecular interactions | |
| Khalaf et al. | Modified plastic optical fiber with CNT and graphene oxide nanostructured coatings for ethanol liquid sensing | |
| Feng et al. | LSPR optical fiber sensor based on 3D gold nanoparticles with monolayer graphene as a spacer | |
| Zheng et al. | Graphene plasmon-enhanced IR biosensing for in situ detection of aqueous-phase molecules with an attenuated total reflection mode | |
| CN102798615A (en) | Periodic nanostructure-based biosensor and preparation method thereof | |
| Liu et al. | Suspended 3D AgNPs/CNT nanohybrids for the SERS application | |
| Xu et al. | Adsorbable and self-supported 3D AgNPs/G@ Ni foam as cut-and-paste highly-sensitive SERS substrates for rapid in situ detection of residuum | |
| Yang et al. | Silica nanocone array as a template for fabricating a plasmon induced hot electron photodetector | |
| CN101190829B (en) | Method for preparing optical fiber SPR sensor gold film by microwave radiation assisted chemical plating | |
| Kuznetsov et al. | Lossy mode resonance fiber-optic sensors based on niobium pentoxide thin film | |
| Liu et al. | 3D flexible compositing resonant cavity system for high-performance SERS sensing | |
| CN107331717A (en) | A kind of organic-inorganic nano line and preparation method thereof and organic-inorganic photo-detector and preparation method thereof | |
| Fallah et al. | Excitation of core modes through side coupling to multimode optical fiber by hydrothermal growth of ZnO nanorods for wide angle optical reception | |
| Wang et al. | Tip-enhanced Raman spectroscopy with silver-coated optical fiber probe in reflection mode for investigating multiwall carbon nanotubes | |
| Zhao et al. | Graphene oxide modified surface plasmon resonance sensor based on side-polished fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |