CN109540847B - graphene/gold/D type plastic optical fiber SPR sensor and preparation method thereof - Google Patents

graphene/gold/D type plastic optical fiber SPR sensor and preparation method thereof Download PDF

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CN109540847B
CN109540847B CN201811526210.9A CN201811526210A CN109540847B CN 109540847 B CN109540847 B CN 109540847B CN 201811526210 A CN201811526210 A CN 201811526210A CN 109540847 B CN109540847 B CN 109540847B
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CN109540847A (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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    • GPHYSICS
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    • 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
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Abstract

The invention belongs to the technical field of SPR sensors, and particularly relates to a graphene/gold/D type plastic optical fiber SPR sensor and a preparation method thereof. The method comprises the following steps: (1) a groove-shaped sensing area is arranged on the fiber to prepare a D-shaped fiber; (2) growing graphene on a copper foil by using a chemical vapor deposition method, and directly evaporating a gold film on the graphene by using a thermal evaporation method to obtain a gold/graphene/copper foil composite layer; (3) and corroding the copper foil in the gold/graphene/copper foil composite layer, and transferring the obtained graphene/gold film to the D-type optical fiber to obtain the graphene/gold film. According to the invention, gold is directly evaporated on graphene by using a thermal evaporation method, so that the graphene and a gold film are perfectly attached, and then the graphene/gold with the copper foil corroded off is transferred to the D-type plastic optical fiber, so that a gold and graphene structure is realized on the plastic optical fiber. The graphene/gold/D type plastic optical fiber SPR sensor prepared by the invention has the characteristic of high identification sensitivity on complementary and non-complementary DNA chains.

Description

graphene/gold/D type plastic optical fiber SPR sensor and preparation method thereof
Technical Field
The invention belongs to the technical field of Surface Plasmon Resonance (SPR) sensors, and particularly relates to a graphene/gold/D type plastic optical fiber SPR sensor and a preparation method thereof.
Background
Since the fiber SPR sensor was proposed in 1993, this technique has attracted increasing research interest. The optical fiber surface plasma sensor can track and research the slight change of the medium surface, realize the ultra-sensitive and unmarked chemical and biological analysis, and has important application in the aspects of food detection, disease diagnosis and the like.
To date, researchers have made many efforts to improve the performance of fiber SPR sensors. For example, various fiber structures are proposed: conical, D-shaped, U-shaped, etc. While the cylindrical fiber geometry is not suitable for transfer of large area material layer films. Meanwhile, the film is not easily stabilized on the cylindrical fibers during the inspection, so that the film may be cracked or peeled off. While the polished face of the D-fiber can better maintain integrity and prevent wrinkling of the material layer film and can also provide a flat detection plane for the probe during detection. In addition, the D-type fiber core is exposed, so that the evanescent wave transmission-type fiber with a large proportion can easily enter a large evanescent field, and high-efficiency sensing application is realized.
In addition, many researchers have improved the performance of fiber optic sensors by optimizing the materials on the sensors, and in metal (usually gold, silver) plus two-dimensional material structures, it is common to first deposit a gold film and then transfer Chemical Vapor Deposition (CVD) -grown graphene onto the gold film by wet transfer. However, the gold film and the graphene are in physical contact, delamination is easily generated at the contact interface of the two, and some inevitable Cu ions are trapped in the graphene layer after corrosion, which further results in imperfect adhesion of the graphene and the gold film, in which case, carriers generate an additional potential barrier, increase the contact resistance at the contact interface, and thus reduce the sensitivity. Furthermore, the process of removing PMMA is unwieldy and time consuming, and several studies have shown that: the wet transfer may leave a large amount of PMMA remaining on the surface of the graphene, thereby affecting the function of the graphene.
In recent years, Plastic Optical Fibers (POF) have attracted much attention, and usually made of polymethyl methacrylate (PMMA) as a core material, have a large hole diameter and a light receiving angle of 60 ° compared to expensive and fragile silica optical fibers, and have a coupling efficiency of only 16 °; good flexibility, easy processing and use, light weight and low price. Patent document 201210067372.7 discloses a D-type optical fiber SPR sensor based on graphene thin film sensitization, which includes a D-type optical fiber having a silver film layer on a polished surface of the D-type optical fiber and a graphene thin film layer on a surface of the silver film layer. The preparation method comprises the following steps: (1) preparing a D-type optical fiber; preparing a silver film layer on the polished surface of the D-type optical fiber; (2) and preparing a graphene film layer on the surface of the silver film. However, when the method is used for preparing the plastic optical fiber with the PMMA core layer, the method is not suitable for adding the graphene layer by a method for removing PMMA in wet transfer, and is not suitable for a method for directly growing graphene by covering a layer of metal in a tubular furnace with overhigh temperature; in addition, according to the method, graphene is directly grown on gold or silver, but in the CVD growth of graphene, the quality of graphene can be ensured only by growing on copper foil, large-area single crystal graphene can be grown, and ideal graphene structures are difficult to grow on gold and silver.
In summary, it is necessary to research a method capable of preparing a graphene/gold structure on a plastic optical fiber without physical contact so as to obtain an SPR sensor with good performance and low cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a graphene/gold/D type plastic optical fiber SPR sensor and a preparation method thereof. The invention utilizes a thermal evaporation method to directly evaporate gold on the graphene grown on the copper foil, so that the graphene and the gold are perfectly attached, and then the graphene/gold with the copper foil corroded off is transferred to the D-type plastic optical fiber together, so that the graphene/gold/D-type plastic optical fiber SPR sensor for detecting biomolecules can be obtained.
The first object of the present invention: provided is a graphene/gold film/D type plastic optical fiber SPR sensor.
Second object of the invention: a preparation method of a graphene/gold/D type plastic optical fiber is provided.
The third object of the present invention: the application of the graphene/gold/D type plastic optical fiber SPR sensor and the preparation method are provided.
In order to solve the above object, the present invention provides the following technical solutions:
the invention discloses a graphene/gold/D type plastic optical fiber SPR sensor, which consists of a D type plastic optical fiber, graphene and gold, wherein a groove-shaped sensing area is formed in the D type plastic optical fiber, a gold film is arranged in the sensing area, and the graphene is arranged on the surface of the gold film.
Furthermore, the plastic optical fiber is made of PMMA, the diameter of a plurality of holes of the plastic optical fiber is large, the light receiving angle can reach 60 degrees, the quartz optical fiber is only 16 degrees, and the coupling efficiency is high; good flexibility, easy processing and use, light weight and low price.
Furthermore, the sensing area of the D-type plastic optical fiber is 1-2cm, the depth is 20-50% of the diameter of the fiber, insufficient sensing energy cannot be achieved in an excessively narrow sensing area, and energy loss can be caused in an excessively wide sensing area.
Further, the thickness of the gold film is 40-60nm, the charge energy excited by the excessively thin metal is insufficient, and the energy cannot reach the sensing interface in time due to the excessively thick metal.
Further, the number of graphene layers is 1-3, and an excessive number of graphene layers can cause energy loss, thereby affecting sensitivity.
Secondly, the invention discloses a preparation method of a graphene/gold/D type plastic optical fiber SPR sensor, which comprises the following steps:
(1) a groove-shaped sensing area is arranged on the plastic optical fiber to prepare a D-shaped optical fiber;
(2) growing graphene on a copper foil by using a Chemical Vapor Deposition (CVD) method, and directly evaporating gold on the graphene by using a thermal evaporation method to obtain a gold/graphene/copper foil composite layer;
(3) and removing the copper foil in the gold/graphene/copper foil composite layer, transferring the gold/graphene/copper foil composite layer into deionized water for cleaning to obtain graphene/gold, and then transferring the graphene/gold onto a D-type optical fiber to obtain the gold/graphene/D-type optical fiber.
In the step (1), the length of the sensing area is 1-2cm, and the depth is 20-50% of the diameter of the fiber.
In the step (2), the method for growing the graphene on the high-purity copper foil comprises the following steps: and (3) putting the polished copper foil into a tubular furnace, introducing mixed gas of hydrogen and methane in different proportions into the tubular furnace, and keeping the mixed gas at 1000 ℃ for 30min to obtain high-quality graphene.
In the step (2), the method for directly evaporating gold onto graphene comprises the following steps: putting high-purity gold wire into a molybdenum boat, placing graphene grown on copper foil on the top of the molybdenum boat, and vacuumizing to 10 DEG-3Pa, temperature modulation 110 degrees, gold wire evenly evaporated to graphene, obtaining gold/graphene/copper foil.
In the step (3), the method for transferring the graphene/gold onto the optical fiber comprises the following steps: and (3) downwards turning the sensing area of the D-type plastic optical fiber, aiming at the gold film exposed outside (because the gold is exposed on the air side of the composite film in the ionized water), fishing out the composite film in the opposite direction, sticking the gold film on the optical fiber, and arranging the graphene film on the optical fiber to obtain the gold/graphene/D-type optical fiber.
Finally, the invention discloses the application of the graphene/gold film/D type optical fiber SPR sensor and the preparation method thereof in the field of biological detection.
Compared with the prior art, the invention has the advantages that,
(1) the structure of gold and graphene is realized on the plastic optical fiber, and compared with the conventional sensor with only a metal layer, the sensitivity and the chemical stability of the sensor are greatly improved due to the addition of the graphene. And the use of the plastic optical fiber greatly reduces the cost of the sensor. The method replaces the traditional PMMA effect with the gold film, and not only can fully utilize Au as a supporting layer for graphene transfer, but also is considered as the most appropriate metal layer due to perfect oxidation stability and corrosion resistance; meanwhile, the Au film is tightly and firmly contacted with the graphene, so that the contact resistance is effectively reduced, and the model is closer to an ideal sensing layer model. In addition, the method can avoid the residual PMMA on the surface of the graphene, thereby influencing the function of the graphene. Meanwhile, the graphene grown on the copper foil has better quality, and the high-quality graphene is more beneficial to detection of the sensor.
(2) When graphene is in contact with the Au film, it can cause significant electric field enhancement at the substrate interface due to the change in electronic properties. The original graphene is a zero-bandgap semiconductor, and the valence band and the conduction band of the original graphene are contacted at a conical point. Since the work function of Au (5.54eV) is higher than graphene (4.5eV), charge transfer from the graphene layer to the metal layer will occur under optical excitation. In this case, the graphene will become a p-type dopant as electrons transfer to balance the fermi level, and the charge transfer will enhance the oscillation of the resonance electrons of the Au surface, thereby promoting the field of the SPP and further resulting in higher sensitivity to the target analyte.
(3) The cylindrical optical fiber is not suitable for transferring a large-area single-layer graphene film, and meanwhile, the film is not easy to be stable on the cylindrical optical fiber in the detection process, so that the film can be cracked or peeled off. The polishing surface of the D-shaped optical fiber used by the invention can better maintain the integrity and prevent the graphene/Au film from being folded, so that evanescent waves can be better released, high-efficiency sensing is realized, a flat detection plane is provided for the probe during detection, and the sensitivity of the sensor is obviously improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic flow chart of the graphene/gold/D type plastic optical fiber SPR sensor prepared in example 1.
Fig. 2(a) is a raman spectrum of graphene prepared in example 1, and fig. 2(b) is a picture of graphene/gold prepared in example 1 in deionized water according to the present invention
Fig. 3(a) is a scanning electron microscope image of a sensing region of a D-type optical fiber in example 1, and fig. 3(b) is a scanning electron microscope image of a graphene/gold/D-type plastic optical fiber prepared in example 1.
FIG. 4 is a transmission spectrum of glucose solutions with different concentrations obtained by preparing a graphene/gold/D type plastic fiber SPR sensor in example 1.
FIG. 5(a) is a detection transmission spectrum of a prepared graphene/gold film/D-type plastic optical fiber sensor prepared in example 2 for identifying a DNA strand; wherein FIG. 5(a) is a transmission spectrum of a modification process; FIG. 5(b) is a transmission spectrum identifying different concentrations of complementary DNA; FIG. 5(c) is a transmission spectrum identifying a non-complementary strand.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background art, when the SPR sensor is manufactured in the prior art, the gold film and the graphene are in physical contact, delamination is easily generated at the contact interface between the two, and some inevitable Cu ions are captured in the graphene layer after corrosion, which further results in imperfect adhesion of the graphene and the gold film, in which case, carriers may generate an additional potential barrier, and contact resistance is increased at the contact interface, which adversely affects the sensitivity. Meanwhile, in consideration of the characteristics of the plastic optical fiber, the invention provides a graphene/gold/D type plastic optical fiber SPR sensor and a preparation method thereof, and the invention is further described with reference to the accompanying drawings and the specific implementation mode
Example 1
A preparation method of a graphene/gold/D type plastic optical fiber SPR sensor comprises the following preparation steps:
(1) manufacturing a D-type optical fiber: a15 cm plastic optical fiber (PMMA) with the diameter of 1 micron is removed from the optical fiber cladding and part of the fiber core in the sensing area by a side polishing method, and a groove-shaped sensing area with the length of 1cm and the depth of 30 percent of the fiber diameter is formed. Then washing the D-type sensing area by deionized water to remove impurities;
(2) growing graphene: placing the polished copper foil into a tubular furnace, introducing a mixed gas of 50sccm hydrogen and 50sccm methane into the tubular furnace, keeping the temperature at 1000 ℃ for 30min, wherein the number of graphene layers is a single layer, and then cutting the graphene/copper foil into small rectangular stripes (1.2cm multiplied by 0.5 cm);
(3) the gold film is directly thermally evaporated onto graphene: a7.5 cm high purity gold wire was placed in a molybdenum boat (length: 100mm, width: 10mm, thickness: 0.3 mm). Placing the small rectangular stripe-shaped graphene/copper foil obtained in the step (2) on the top of a molybdenum boat (the distance is 9cm), and pumping to 5 multiplied by 10 when the pressure is pumped-3When Pa is needed, heating to 110 degrees, uniformly evaporating gold wires onto graphene, wherein the thickness of the gold film is about 50nm, and obtaining gold/graphene/copper foil;
(4) etching off the copper foil: placing the gold/graphene/copper foil obtained in the step (3) in FeCl3And in the solution, after the copper foil is completely corroded to obtain gold/graphene, washing the gold/graphene for 5 times by using deionized water, washing away residual etching liquid, downwards overturning a sensing area of the D-type plastic optical fiber, reversely fishing out the composite film aiming at the gold film exposed outside, attaching the gold film to the optical fiber, and arranging the graphene film on the optical fiber to obtain the graphene/gold/D-type optical fiber.
Example 2
A preparation method of a graphene/gold/D type plastic optical fiber SPR sensor comprises the following preparation steps:
(1) manufacturing a D-type optical fiber: a15 cm plastic optical fiber (PMMA) with the diameter of 1 micron is removed from the optical fiber cladding and part of the fiber core in the sensing area by a side polishing method, and a groove-shaped sensing area with the length of 2cm and the depth of 45 percent of the fiber diameter is formed. Then washing the D-type sensing area by deionized water to remove impurities;
(2) growing graphene: placing the polished copper foil into a tubular furnace, introducing a mixed gas of 60sccm hydrogen and 40sccm methane into the tubular furnace, keeping the temperature at 1000 ℃ for 30min, wherein the number of graphene layers is 3, and then cutting the graphene/copper foil into small rectangular stripes (2cm multiplied by 0.5 cm);
(3) the gold film is directly thermally evaporated onto graphene: putting 8.5cm of high-purity gold wire into a molybdenum boat (length 100mm, width 10mm, thickness 0.3mm), placing the small rectangular stripe-shaped graphene/copper foil obtained in step (2) on the top of the molybdenum boat (distance 9cm), and pumping to 5 × 10 when pressure is applied-3When Pa is needed, the gold wire is uniformly evaporated on the graphene, and the thickness of the gold film is about 60nm, so that gold/graphene/copper foil is obtained;
(4) etching off the copper foil: placing the gold/graphene/copper foil obtained in the step (3) in FeCl3And in the solution, after the copper foil is completely corroded to obtain gold/graphene, washing the gold/graphene for 5 times by using deionized water, washing away residual etching liquid, downwards overturning a sensing area of the D-type plastic optical fiber, reversely fishing out the composite film aiming at the gold film exposed outside, attaching the gold film to the optical fiber, and arranging the graphene film on the optical fiber to obtain the graphene/gold/D-type optical fiber.
Example 3
A preparation method of a graphene/gold/D type plastic optical fiber SPR sensor comprises the following preparation steps:
(1) manufacturing a D-type optical fiber: a15 cm plastic optical fiber (PMMA) with the diameter of 1 micron is removed from the cladding and part of the fiber core in the sensing area by a side polishing method, and a groove-shaped sensing area with the length of 1.2cm and the depth of 20 percent of the fiber diameter is formed. Then washing the D-type sensing area by deionized water to remove impurities;
(2) growing graphene: placing the polished copper foil into a tubular furnace, introducing a mixed gas of 50sccm hydrogen and 50sccm methane into the tubular furnace, keeping the temperature at 1000 ℃ for 30min, wherein the number of graphene layers is a single layer, and then cutting the graphene/copper foil into small rectangular stripes (1.2cm multiplied by 0.5 cm);
(3) the gold film is directly thermally evaporated onto graphene: putting 6.5cm of high-purity gold wire into a molybdenum boat (with the length of 100mm, the width of 10mm and the thickness of 0.3mm), and placing the small rectangular stripe-shaped graphene/copper foil obtained in the step (2) on the top of the molybdenum boat (away from the molybdenum boat by a distance of 0.3mm)9cm) apart) when pressure is pumped to 5 x 10-3When Pa is needed, the gold wire is uniformly evaporated on the graphene, and the thickness of the gold film is about 40nm, so that gold/graphene/copper foil is obtained;
(4) etching off the copper foil: placing the gold/graphene/copper foil obtained in the step (3) in FeCl3And in the solution, after the copper foil is completely corroded to obtain gold/graphene, washing the gold/graphene for 5 times by using deionized water, washing away residual etching liquid, downwards overturning a sensing area of the D-type plastic optical fiber, reversely fishing out the composite film aiming at the gold film exposed outside, attaching the gold film to the optical fiber, and arranging the graphene film on the optical fiber to obtain the graphene/gold/D-type optical fiber.
Example 4
A preparation method of a graphene/gold/D type plastic optical fiber SPR sensor comprises the following preparation steps:
(1) manufacturing a D-type optical fiber: a15 cm plastic optical fiber (PMMA) with the diameter of 1 micron is removed from the cladding and part of the fiber core in the sensing area by a side polishing method, and a groove-shaped sensing area with the length of 1.5cm and the depth of 50 percent of the fiber diameter is formed. Then washing the D-type sensing area by deionized water to remove impurities;
(2) growing graphene: placing the polished copper foil into a tubular furnace, introducing a mixed gas of 50sccm hydrogen and 50sccm methane into the tubular furnace, keeping the temperature at 1000 ℃ for 30min, wherein the number of graphene layers is a single layer, and then cutting the graphene/copper foil into small rectangular stripes (1.6cm multiplied by 0.5 cm);
(3) the gold film is directly thermally evaporated onto graphene: placing 7cm of high-purity gold wire into a molybdenum boat (length 100mm, width 10mm, thickness 0.3mm), placing the small rectangular stripe-shaped graphene/copper foil obtained in step (2) on the top of the molybdenum boat (distance 9cm), and pumping to 5 × 10 when pressure is reached-3When Pa is needed, the gold wire is uniformly evaporated on the graphene, and the thickness of the gold film is about 45nm, so that gold/graphene/copper foil is obtained;
(4) etching off the copper foil: placing the gold/graphene/copper foil obtained in the step (3) in FeCl3In the solution, when the copper foil is completely corroded, obtaining gold/graphene, washing the gold/graphene for 5 times by deionized water,and (3) cleaning residual etching liquid, downwards overturning a sensing area of the D-type plastic optical fiber, reversely fishing the composite membrane by aiming at the gold membrane exposed outside, and attaching the gold membrane to the optical fiber with the graphene membrane on the top to obtain the graphene/gold/D-type optical fiber.
Performance testing
(1) The microstructure of the graphene/gold/D type plastic optical fiber SPR sensor prepared in example 1 was observed, and the results were as follows:
fig. 2(a) is a raman spectrum of graphene prepared in example 1, from which it can be seen that: (1) high-quality graphene is prepared on a copper foil, the number of layers is a single layer, and the graphene is an ideal structure which cannot be directly grown on gold or silver; (b) for the picture of the graphene/gold prepared in the embodiment of the present invention in deionized water, it can be seen from the figure that: the gold film can be well self-supported in deionized water, the integrity of graphene is successfully maintained, and the effect of traditional PMMA in transfer graphene is successfully replaced.
Fig. 3(a) is a scanning electron microscope image of a sensing region of a D-type optical fiber in example 1, and fig. 3(b) is a scanning electron microscope image of a graphene/gold/D-type plastic optical fiber prepared in example 1. It can be seen from the figure that the graphene/gold film is evenly coated on the surface of the optical fiber.
(2) The performance of the graphene/gold/D type plastic optical fiber SPR sensor prepared in example 1 was tested, specifically: the prepared glucose solutions with different concentrations are absorbed by a dropper and are dripped on a sensing area for detection; the results are shown in FIG. 4, from which it can be seen that: the prepared sensor is utilized to obtain a transmission spectrum with high sensitivity, and the ratio of wavelength shift to refractive index change is calculated to reach 1227 nm/RIU.
(3) The performance of the graphene/gold/D type plastic optical fiber SPR sensor prepared in example 2 was tested, specifically: the prepared 10mM PBASE was added to the graphene surface at room temperature for 2 hours, and then the unmodified PBASE was removed by washing with DMSO and deionized water. Second, the lyophilized DNA sample was dissolved and reconstituted in PBS solution. The PBASE-immobilized fiber was immersed in the probe DNA solution at room temperature for 4 hours to ensure sufficient reaction between the probe DNA and PBASE. Unreacted probe DNA was removed with PBS solution and deionized water, respectively. Adding non-complementary DNA to the sensing region for detection; then, complementary DNA solutions of different concentrations were added to the sensing region, and the result is shown in fig. 5, where fig. 5(a) is a transmission spectrum of the modification process, from which it can be seen that a transmission spectrum with high uniformity was obtained by successfully adsorbing probe DNA strands using the graphene layer of the prepared sensor; FIG. 5(b) is a transmission spectrum for identifying complementary DNA at different concentrations, from which it can be seen that a highly sensitive transmission spectrum is obtained with the successful identification of complementary DNA using the prepared sensor; FIG. 5(c) is a transmission spectrum for identifying a non-complementary strand, and from this figure, it can be seen that a transmission spectrum was obtained using a sensor prepared to successfully identify non-complementary DNA.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.

Claims (1)

1. A graphene/gold/D type plastic optical fiber SPR sensor for identifying complementary and non-complementary DNA strands, characterized in that: the sensor consists of D-shaped plastic fibers, graphene and a gold film, wherein groove-shaped sensing areas are formed in the D-shaped plastic fibers, the gold film is arranged in the sensing areas, and the graphene is arranged on the surface of the gold film;
the preparation method of the graphene/gold/D type plastic optical fiber SPR sensor comprises the following steps:
(1) manufacturing a D-type optical fiber: a section of 15cm plastic optical fiber with the diameter of 1 micron is made of PMMA, the optical fiber cladding and part of the fiber core in the sensing area are removed by a side polishing method, a groove-shaped sensing area with the length of 1cm and the depth of 30 percent of the fiber diameter is formed, and then the D-type sensing area is washed by deionized water to remove impurities;
(2) growing graphene: placing the polished copper foil into a tubular furnace, introducing a mixed gas of 50sccm hydrogen and 50sccm methane into the tubular furnace, keeping the temperature at 1000 ℃ for 30min, wherein the number of graphene layers is a single layer, and then cutting the graphene/copper foil into small rectangular stripes of 1.2cm multiplied by 0.5 cm;
(3) the gold film is directly thermally evaporated onto graphene: placing 7.5cm of high-purity gold wire into a molybdenum boat, wherein the length: 100mm, width: 10mm, thickness: 0.3mm, placing the small rectangular stripe-shaped graphene/copper foil obtained in step (2) on top of a molybdenum boat at a distance of 9cm when the pressure is pumped to 5X 10-3When Pa is needed, heating to 110 degrees, uniformly evaporating gold wires onto graphene, wherein the thickness of the gold film is about 50nm, and obtaining gold/graphene/copper foil;
(4) etching off the copper foil: placing the gold/graphene/copper foil obtained in the step (3) in FeCl3And in the solution, after the copper foil is completely corroded to obtain gold/graphene, washing the gold/graphene for 5 times by using deionized water, washing away residual etching liquid, downwards overturning a sensing area of the D-type plastic optical fiber, reversely fishing out the composite film aiming at the gold film exposed outside, attaching the gold film to the optical fiber, and arranging the graphene film on the optical fiber to obtain the graphene/gold/D-type optical fiber.
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