WO2020024466A1 - Method for preparing graphene optical fibre composite material - Google Patents

Method for preparing graphene optical fibre composite material Download PDF

Info

Publication number
WO2020024466A1
WO2020024466A1 PCT/CN2018/112900 CN2018112900W WO2020024466A1 WO 2020024466 A1 WO2020024466 A1 WO 2020024466A1 CN 2018112900 W CN2018112900 W CN 2018112900W WO 2020024466 A1 WO2020024466 A1 WO 2020024466A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
optical fiber
composite material
preparing
composite film
Prior art date
Application number
PCT/CN2018/112900
Other languages
French (fr)
Chinese (zh)
Inventor
黄国家
冯文林
杨波
李茂东
彭志清
尹宗杰
李悦
Original Assignee
广州特种承压设备检测研究院
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 广州特种承压设备检测研究院 filed Critical 广州特种承压设备检测研究院
Publication of WO2020024466A1 publication Critical patent/WO2020024466A1/en

Links

Images

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
    • G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
    • 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
    • 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
    • G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
    • G01N21/4133—Refractometers, e.g. differential
    • 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
    • G01N2021/0106—General arrangement of respective parts
    • G01N2021/0112—Apparatus in one mechanical, optical or electronic block

Definitions

  • the invention relates to the technical field of sensors, in particular to a method for preparing a graphene optical fiber composite material.
  • Graphene as a new two-dimensional nanomaterial, is a carbon allotrope with a single layer of carbon atoms arranged in a hexagonal lattice. It has the characteristics of high strength, almost transparency, large specific surface area, and high stability. It can be used as an adsorbent. material. There are a large number of microstructures in the cross section of photonic crystal fiber, which makes the operation space large, which makes it widely used in various fields such as optical communication, optical devices and optical sensing. It has new anti-electromagnetic interference ability, high insulation, flame-proof and explosion-proof, flexible and flexible deflection, and suitable for long-distance monitoring. It is especially suitable for monitoring under severe and dangerous environmental conditions.
  • Mach-Zehnder interferometer can be widely used to measure strain, temperature and refractive index.
  • the principle of this device is the interference between the core mode and cladding mode of an optical fiber.
  • the sensing substance of the existing optical fiber sensor is a simple optical fiber, and its sensitivity needs to be improved when it is used for the substance concentration detection. So far, the research work of using graphene-coated optical fibers as sensing materials for Mach-Zehnder interference refractive index sensors has not been reported. Such refractive index sensors can be used for concentration detection.
  • an object of the present invention is to provide a method for preparing a graphene optical fiber composite material, which can be used as a sensing material of a refractive index sensor and effectively applied to concentration detection.
  • the object of the present invention is achieved by the following technical scheme: a method for preparing a graphene optical fiber composite material, including the following steps:
  • the present invention combines an optical fiber with graphene and utilizes the special structure of graphene to adsorb molecules in a solution, thereby changing the refractive index of the optical fiber and improving its sensitivity.
  • the graphene optical fiber composite material of the present invention is used as a sensing material of a refractive index sensor. It has high linear response and excellent sensitivity for the concentration detection of liquid and gaseous substances. Used in mass production.
  • step S1 graphene is first grown on a copper foil by a chemical vapor deposition method, and then a polymethylmethacrylate precursor solution is spin-coated on the copper foil having graphene, and the composite film is obtained by drying. .
  • the polymethylmethacrylate precursor when spin-coated, it is first spin-coated at 500 rpm for 3 s, and then spin-coated at 5000 rpm for 40 s.
  • the temperature during the drying process is 115-125 ° C, and the time is 8-12 minutes.
  • step S2 the copper foil coated with the composite film is first placed in an etching solution. After the copper foil is dissolved, the composite film floats in the etching solution; and then the glass substrate or PET sheet is used to float the floating film. The composite film is transferred to deionized water, and the photonic crystal fiber is immersed in the deionized water and placed at the bottom of the composite film. The photonic crystal fiber is lifted up to transfer the composite film to the surface of the photonic crystal fiber.
  • the etching solution is a ferric nitrate solution, and its mass concentration is 15-20 g / ml.
  • the solvent in the ferric nitrate solution is usually water, or deionized water, or hydrochloric acid (36 to 38% by mass), hydrogen peroxide (30% by mass), and deionized water in a ratio of 1: 1: 20. Configured mixture.
  • step S3 the calcination temperature is 280-320 ° C, and the time is 3.5-4.5h.
  • FIG. 1 is a schematic diagram of a composite film preparation and transfer process of Example 1.
  • FIG. 1 is a schematic diagram of a composite film preparation and transfer process of Example 1.
  • FIG. 2 is a surface morphology diagram of the graphene-coated optical fiber of Example 1.
  • FIG. 3 is a Raman spectrum chart of the graphene-coated optical fiber of Example 1.
  • FIG. 4 is a schematic diagram of a graphene optical fiber sensor of Example 1.
  • FIG. 5 is a schematic diagram of a refractive index detection system of Embodiment 1.
  • FIG. 5 is a schematic diagram of a refractive index detection system of Embodiment 1.
  • FIG. 6 is a spectrum diagram of sucrose solutions with different concentrations and a linear relationship between sucrose concentration and troughs.
  • FIG. 7 is a graph showing a relationship between a wavelength shift of a resonance peak and a refractive index of a sucrose solution.
  • FIG. 8 is a spectrum chart of hydrogen sulfide gas with different concentrations.
  • Fig. 9 is a graph showing the linear relationship between the concentration of hydrogen sulfide and the trough.
  • the present invention proposes a graphene-based optical fiber composite material, which combines optical fibers with graphene and uses the special structure of graphene to adsorb molecules in a solution, thereby changing the refractive index of the optical fiber and improving its sensitivity.
  • the graphene optical fiber composite material of the present invention as a sensing material of a refractive index sensor, can be effectively applied to the concentration detection of liquid and gaseous substances.
  • This embodiment provides a method for preparing a graphene optical fiber composite material. Referring to FIG. 1, the method includes the following steps:
  • a composite film (PMMA / Graphene) of graphene (Graphene) and polymethyl methacrylate (PMMA) is prepared on a copper foil. These include:
  • S11 Graphene is grown on a copper foil (Cu) by a chemical vapor deposition method.
  • S12 Place the copper foil with graphene on a clean, smooth surface substrate, and stick the four sides of the copper foil with tape to make the copper foil evenly spread on the substrate. When sticking, pay attention to the copper foil being flat. Reduce the crease, otherwise it is easy to get uneven glue.
  • a few drops of deionized water can be dropped on a round / square silicon wafer, and the graphene-coated copper foil is laid on the silicon wafer, and the periphery of the copper foil is gently pressed with tweezers to ensure the copper foil. It is closely attached to the silicon wafer, and there should be no gap on the edge of the copper foil, otherwise it will easily fly out.
  • the composite film is transferred to the surface of a photonic crystal fiber (PCF) by a copper dissolution method.
  • PCF photonic crystal fiber
  • S22 Put the coated copper foil on the surface of the etching solution, and corrode the etching solution (time is more than 20min). Hold the copper foil with tweezers and drag its back on rubber gloves to remove the graphene on the back, and then The copper foil is placed on the filter paper, and the liquid on the back of the copper foil is absorbed by the filter paper, which is convenient for cutting the copper foil in the next step. In another embodiment, the coated copper foil is placed on the surface of the etching solution for 8 minutes.
  • the copper foil is clamped with tweezers and the back is dragged on a rubber glove to remove the back Graphene, drag repeatedly for several times, and then place the copper foil on the surface of deionized water for 10 minutes. In the process, continue to scrape to ensure that the lower surface of the copper foil is cleaned.
  • the PET When it is picked up, the PET is tilted at a certain angle, which can drive the composite film to the wall of the petri dish to increase the tilt angle of the PET.
  • One side of the film will stick to the PET.
  • the PET can be lifted out of the water surface, and then PET is gently placed in the mixed solution of hydrochloric acid and hydrogen peroxide, and the PET is removed in the direction perpendicular to the membrane. Do not shake it back and forth. Soak the mixture in the mixed solution for 2 hours to remove impurities, and then transfer the membrane to deionized water. The operation should be slow to prevent graphene from being damaged.
  • the two ends of the obtained graphene optical fiber composite material can be respectively coupled with the single-mode optical fiber through an optical fiber fusion splicer, and a thick enlarged optical fiber cone is formed at the two coupling points, respectively, so as to obtain a graphene optical fiber sensor.
  • the parameters of the optical fiber fusion splicer are set as follows: the first discharge start intensity + 100 mA, the first discharge end intensity + 100 mA, the second discharge start intensity + 100 mA, the second discharge end intensity + 100 mA, the pre-fusion time + 260 ms, and the advance distance + 315 ⁇ m.
  • the advancing distance indicates the distance that the two optical fibers are squeezed to the middle during arc fusion to obtain a thick cone (bulb) structure.
  • a larger advancing distance can obtain a larger waist size and a shorter taper transition area. length.
  • the obtained waist size and taper transition zone length are: a waist length of 400 ⁇ m, a waist diameter of 179.25 ⁇ m, and a taper transition zone length of 4 cm.
  • the graphene optical fiber sensor 10 includes a photonic crystal fiber 11 and two single-mode optical fibers 12. Both ends of the photonic crystal fiber 11 are coupled to the single-mode optical fiber 12 respectively, and are coupled between the two.
  • a thick enlarged fiber cone 13 at the waist is formed at each point; the surface of the photonic crystal fiber 12 is covered with a graphene layer.
  • the distance between the two coupling points is 3.9 to 4.1 cm; the waist length of the waist enlarged fiber thick cone is 395 to 405 ⁇ m and the waist diameter is 179 to 180 ⁇ m; the thickness of the graphene layer is 1 to There are 10 layers, and the thickness of the single-layer graphene is 0.33 to 0.35 nm.
  • the two coupling portions can be formed by arc fusion to form a waist enlarged optical fiber thick cone 13 for splicing.
  • the cladding modes can be excited from the fundamental mode and then propagate in the photonic crystal fiber; at the second coupling point, the cladding modes can be recoupled with each other or with the fundamental mode and then form interference.
  • the distance between the two coupling points is regarded as the interference arm length, and the interference arm length, waist length, and waist diameter are represented by L, l, and d, respectively.
  • the interference arm length L, waist length l, and waist diameter d are 4 cm, 400 ⁇ m, and 179.25 ⁇ m, respectively; graphene is a single-layer graphene with a thickness of 0.334 nm.
  • the effective refractive index difference between the excited state and the excited state and the phase difference between the excited state and the fundamental mode cause joint interference.
  • the transmission intensity of the sensor can be defined as:
  • I 1 and I 2 are the intensities of different modes; Is the inter-mode phase difference and can be expressed as:
  • ⁇ is the wavelength of the incident light
  • ⁇ n eff is the difference between the effective refractive indices of the core and the cladding mode
  • L is the distance between the two coupling points, which corresponds to the physical length of the interferometer.
  • the interference's m-th order wavelength ⁇ m can be expressed as:
  • the refractive index of the cladding in the evanescent field of the tapered photonic crystal fiber changes, and the difference between the effective index of the core mode and the cladding mode will also change.
  • the coupling and recombination of the core and cladding modes in the thick cone, the valleys in the corresponding transmission spectrum are shifted. Therefore, refractive index detection can be achieved by measuring the corresponding wavelength shift.
  • This embodiment also provides a system for performing refractive index detection by using the above graphene optical fiber sensor.
  • the system includes a graphene optical fiber sensor 10, a light source 20, a sample chamber 30, and a signal processing system 40.
  • the olefin optical fiber sensor 10 is disposed in the sample chamber 30, and two ends thereof are respectively connected to the light source 20 and the signal processing system 40.
  • the light source 10 uses an amplified spontaneous radiation source (ASE)
  • the signal processing system 40 uses a light source analyzer (OSA, Yokogawa AQ6370D)
  • the sample chamber 30 may be a colorimetric cup or a gas collection bag, respectively Liquid samples and gas samples of different concentrations are used as refractive index measurement samples.
  • the transmission spectrum of the sensor at different refractive indices is detected by an amplified spontaneous radiation source and a spectrum analyzer.
  • the surface morphology and molecular structure of the graphene fiber composite material prepared in the above examples were characterized by using a scanning electron microscope (SEM, TESCAN MIRA3) and Raman spectroscopy (LabRAM HR Evolution, HORIBA Scientific).
  • SEM scanning electron microscope
  • TESCAN MIRA3 Raman spectroscopy
  • LabRAM HR Evolution HORIBA Scientific
  • FIG. 2 (a) the SMF is spliced at the end of the PCF.
  • the PCF pores around the end completely collapse.
  • the welding machine can control the motor to accurately push the middle part between the SMF and the PCF.
  • Form a tapered waist The morphology of the outer surface of the tapered PCF is shown in Fig. 2 (b). It can be seen that the outer surface is uniform, indicating that the graphene film is uniformly distributed on the PCF surface.
  • Sucrose solutions with different concentrations (0 to 233 ppm) were used as refractive index liquid samples for refractive index measurement, and their refractive indices ranged from 1.3338 to 1.3376, which were detected by a sensor at 300K at room temperature.
  • a comparative optical fiber sensor was manufactured, which was basically the same as Example 1, except that the surface of the PCF was not coated with a graphene layer.
  • the experimental results are shown in Figure 6 (a).
  • the wavelength drift between the two concentrations (0 ppm and 230 ppm) is only 0.3 nm.
  • the experimental results are shown in Figure 6 (b).
  • the wavelength drift between the two concentrations (0 ppm and 230 ppm) can reach 1 nm. It can be seen that the graphene film can significantly improve the sensitivity of the refractive index sensor.
  • the graphene fiber optic sensor shows comparable performance. Good linear response.
  • the sensitivity of graphene to sucrose solution is 3.36pm / ppm.
  • the experimental results show that when When the external refractive index changes from 1.3338 to 1.3376, the sensitivity of the sensor can reach 205.26nm / RIU.
  • the graphene optical fiber sensor of Example 1 is not limited to the experiment of sucrose solution.
  • solutions such as glucose and sodium chloride can be tested, and if a layer of other sensitive substances is deposited on the surface of the graphene film, it can be used for detection.
  • nano-copper was deposited on the graphene film surface of the graphene fiber sensor of Example 1 to detect hydrogen sulfide gas.
  • the experimental results show that the graphene optical fiber sensor of Example 1 exhibits a good linear response in the range of a hydrogen sulfide gas concentration of 0 to 80 ppm, as shown in FIG. 9.
  • the sensor is easy to manufacture, has low cost and small size, and can be used for the detection of low-concentration hydrogen sulfide gas.
  • the present invention combines an optical fiber with graphene and utilizes the special structure of graphene to adsorb molecules in a solution, thereby changing the refractive index of the optical fiber and improving its sensitivity.
  • the graphene optical fiber composite material of the present invention is used as a sensing material of a refractive index sensor, and has high linear response and excellent sensitivity for the detection of substance concentrations (such as hydrogen sulfide gas and sucrose), and has low cost, simple manufacturing method, and repeatability. High characteristics, can be used in mass production.

Abstract

Disclosed is a method for preparing a graphene optical fibre composite material. The preparation method comprises: preparing a composite film of graphene and polymethyl methacrylate on a copper foil; transferring the composite film onto a surface of a photonic crystal optical fibre by means of a copper dissolution method; and removing the polymethyl methacrylate in the composite film transferred onto the surface of the photonic crystal optical fibre, and then calcinating same to obtain a graphene optical fibre composite material. The graphene optical fibre composite material, as a sensing material of a refractive index sensor, has a high linear response and excellent sensitivity for a concentration detection of substances such as hydrogen sulfide gas and sucrose, has characteristics of a low cost, a simple manufacturing method and a high repeatability, and can be mass-produced and used.

Description

一种石墨烯光纤复合材料的制备方法Preparation method of graphene optical fiber composite material 技术领域Technical field
本发明涉及传感器技术领域，尤其涉及一种石墨烯光纤复合材料的制备方法。The invention relates to the technical field of sensors, in particular to a method for preparing a graphene optical fiber composite material.
背景技术Background technique
石墨烯作为一种新型的二维纳米材料，是由单层碳原子排列成六方晶格的碳同素异形体，其具有强度高、几乎透明、比表面积大、稳定性高等特点，可作为吸附材料。光子晶体光纤横截面内部存在大量的微结构，使得可操作空间大，使得它在光通信、光器件和光传感等各大领域中获得了极为广泛的应用，在光纤传感领域应用最为突出，具有抗电磁干扰能力强、绝缘性高、可防燃防爆、灵活柔性挠曲、适于远距离监测等的新型传感技术，特别适宜恶劣和危险环境条件下的监测。马赫-曾德尔干涉仪(Mach-Zehnder interferometer，MZI)可以广泛用于测量应变、温度和折射率，该器件的原理是光纤的纤芯模式和包层模式之间的干涉。现有的光纤传感器的传感物质为单纯的光纤，其在用于物质浓度检测时，灵敏度有待提高。迄今为止，利用石墨烯包覆的光纤作为传感材料用于Mach-Zehnder干涉折射率传感器的研究工作还没有报道，这种折射率传感器可应用于浓度检测。Graphene, as a new two-dimensional nanomaterial, is a carbon allotrope with a single layer of carbon atoms arranged in a hexagonal lattice. It has the characteristics of high strength, almost transparency, large specific surface area, and high stability. It can be used as an adsorbent. material. There are a large number of microstructures in the cross section of photonic crystal fiber, which makes the operation space large, which makes it widely used in various fields such as optical communication, optical devices and optical sensing. It has new anti-electromagnetic interference ability, high insulation, flame-proof and explosion-proof, flexible and flexible deflection, and suitable for long-distance monitoring. It is especially suitable for monitoring under severe and dangerous environmental conditions. Mach-Zehnder interferometer (MZI) can be widely used to measure strain, temperature and refractive index. The principle of this device is the interference between the core mode and cladding mode of an optical fiber. The sensing substance of the existing optical fiber sensor is a simple optical fiber, and its sensitivity needs to be improved when it is used for the substance concentration detection. So far, the research work of using graphene-coated optical fibers as sensing materials for Mach-Zehnder interference refractive index sensors has not been reported. Such refractive index sensors can be used for concentration detection.
发明内容Summary of the invention
基于此，本发明的目的在于，提供一种石墨烯光纤复合材料的制备方法，其可以作为折射率传感器的传感材料，并有效地应用于浓度检测。Based on this, an object of the present invention is to provide a method for preparing a graphene optical fiber composite material, which can be used as a sensing material of a refractive index sensor and effectively applied to concentration detection.
本发明的目的是通过以下技术方案实现的：一种石墨烯光纤复合材料的制备方法，包括以下步骤：The object of the present invention is achieved by the following technical scheme: a method for preparing a graphene optical fiber composite material, including the following steps:
S1：在铜箔上制备石墨烯和聚甲基丙烯酸甲酯的复合膜；S1: preparing a composite film of graphene and polymethyl methacrylate on a copper foil;
S2：通过铜溶解法将所述复合膜转移到光子晶体光纤的表面；S2: transferring the composite film to the surface of a photonic crystal fiber by a copper dissolution method;
S3：去除转移到所述光子晶体光纤表面的复合膜中的聚甲基丙烯酸甲酯，再进行煅烧，获得石墨烯光纤复合材料。S3: removing the polymethyl methacrylate transferred to the composite film on the surface of the photonic crystal optical fiber, and then calcining to obtain a graphene optical fiber composite material.
相对于现有技术，本发明将光纤与石墨烯相结合，利用石墨烯的特殊结构对溶液中的分子具有吸附性，由此改变光纤的折射率，提高其灵敏度。本发明的石墨烯光纤复合材料作为折射率传感器的传感材料，对于液体和气体物质浓度检测具有高线性响应和优异的灵敏度，且具有成本低、制作方法简单、可重复性高的特点，可大量生产使用。Compared with the prior art, the present invention combines an optical fiber with graphene and utilizes the special structure of graphene to adsorb molecules in a solution, thereby changing the refractive index of the optical fiber and improving its sensitivity. The graphene optical fiber composite material of the present invention is used as a sensing material of a refractive index sensor. It has high linear response and excellent sensitivity for the concentration detection of liquid and gaseous substances. Used in mass production.
进一步地，步骤S1中，先通过化学气相沉积法在铜箔上生长石墨烯，然后在长有石墨烯 的铜箔上旋涂聚甲基丙烯酸甲酯前驱液，经烘干得到所述复合膜。Further, in step S1, graphene is first grown on a copper foil by a chemical vapor deposition method, and then a polymethylmethacrylate precursor solution is spin-coated on the copper foil having graphene, and the composite film is obtained by drying. .
进一步地，旋涂聚甲基丙烯酸甲酯前驱液时，先在500rpm转速下旋涂3s，再在5000rpm转速下旋涂40s。Further, when the polymethylmethacrylate precursor is spin-coated, it is first spin-coated at 500 rpm for 3 s, and then spin-coated at 5000 rpm for 40 s.
进一步地，所述烘干过程的温度为115～125℃，时间为8～12min。Further, the temperature during the drying process is 115-125 ° C, and the time is 8-12 minutes.
进一步地，步骤S2中，先将涂有复合膜的铜箔置于刻蚀液中，待铜箔溶解后，复合膜漂浮于刻蚀液中；然后用载玻片或PET片将该漂浮的复合膜转移至去离子水中，将光子晶体光纤浸入去离子水中并置于复合膜的底端；再将光子晶体光纤往上提，使复合膜转移到光子晶体光纤表面。Further, in step S2, the copper foil coated with the composite film is first placed in an etching solution. After the copper foil is dissolved, the composite film floats in the etching solution; and then the glass substrate or PET sheet is used to float the floating film. The composite film is transferred to deionized water, and the photonic crystal fiber is immersed in the deionized water and placed at the bottom of the composite film. The photonic crystal fiber is lifted up to transfer the composite film to the surface of the photonic crystal fiber.
进一步地，所述刻蚀液为硝酸铁溶液，其质量浓度为15～20g/ml。所述硝酸铁溶液中的溶剂通常为水，或去离子水，或采用盐酸(质量分数为36～38％)、双氧水(质量分数为30％)与去离子水按1:1:20的比例配置的混合液。Further, the etching solution is a ferric nitrate solution, and its mass concentration is 15-20 g / ml. The solvent in the ferric nitrate solution is usually water, or deionized water, or hydrochloric acid (36 to 38% by mass), hydrogen peroxide (30% by mass), and deionized water in a ratio of 1: 1: 20. Configured mixture.
进一步地，步骤S3中，所述煅烧的温度为280～320℃，时间为3.5～4.5h。Further, in step S3, the calcination temperature is 280-320 ° C, and the time is 3.5-4.5h.
为了更好地理解和实施，下面结合附图详细说明本发明。For better understanding and implementation, the present invention is described in detail below with reference to the accompanying drawings.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1的复合膜制备与转移过程示意图。FIG. 1 is a schematic diagram of a composite film preparation and transfer process of Example 1. FIG.
图2为实施例1的石墨烯包覆光纤的表面形貌图。FIG. 2 is a surface morphology diagram of the graphene-coated optical fiber of Example 1. FIG.
图3为实施例1的石墨烯包覆光纤的拉曼光谱图。FIG. 3 is a Raman spectrum chart of the graphene-coated optical fiber of Example 1. FIG.
图4为实施例1的石墨烯光纤传感器的示意图。FIG. 4 is a schematic diagram of a graphene optical fiber sensor of Example 1. FIG.
图5为实施例1的折射率检测***的示意图。FIG. 5 is a schematic diagram of a refractive index detection system of Embodiment 1. FIG.
图6为不同浓度蔗糖溶液的光谱图以及蔗糖浓度与波谷的线性关系图。FIG. 6 is a spectrum diagram of sucrose solutions with different concentrations and a linear relationship between sucrose concentration and troughs.
图7为共振峰的波长位移与蔗糖溶液的折射率之间的变化关系图。FIG. 7 is a graph showing a relationship between a wavelength shift of a resonance peak and a refractive index of a sucrose solution.
图8为不同浓度硫化氢气体的光谱图。FIG. 8 is a spectrum chart of hydrogen sulfide gas with different concentrations.
图9为硫化氢浓度与波谷的线性关系图。Fig. 9 is a graph showing the linear relationship between the concentration of hydrogen sulfide and the trough.
具体实施方式detailed description
本发明提出一种基于石墨烯光纤复合材料，将光纤与石墨烯相结合，利用石墨烯的特殊结构对溶液中的分子具有吸附性，由此改变光纤的折射率，提高其灵敏度。本发明的石墨烯光纤复合材料作为折射率传感器的传感材料，可以有效地应用于液体和气体物质的浓度检测。The present invention proposes a graphene-based optical fiber composite material, which combines optical fibers with graphene and uses the special structure of graphene to adsorb molecules in a solution, thereby changing the refractive index of the optical fiber and improving its sensitivity. The graphene optical fiber composite material of the present invention, as a sensing material of a refractive index sensor, can be effectively applied to the concentration detection of liquid and gaseous substances.
实施例1Example 1
本实施例提供了一种石墨烯光纤复合材料的制备方法，请参阅图1，包括以下步骤：This embodiment provides a method for preparing a graphene optical fiber composite material. Referring to FIG. 1, the method includes the following steps:
S1：在铜箔上制备石墨烯(Graphene)和聚甲基丙烯酸甲酯(PMMA)的复合膜(PMMA/Graphene)。具体的包括：S1: A composite film (PMMA / Graphene) of graphene (Graphene) and polymethyl methacrylate (PMMA) is prepared on a copper foil. These include:
S11：通过化学气相沉积法在铜箔(Cu)上生长石墨烯。S11: Graphene is grown on a copper foil (Cu) by a chemical vapor deposition method.
S12：将长有石墨烯的铜箔放在干净、表面光滑的基片上，用胶带粘住铜箔的四边，使得铜箔均匀平铺在基片上，粘的时候要注意将铜箔铺平，减小折痕，否则容易涂胶不匀。在另一实施例中，可以在圆形/方形硅片上滴几滴去离子水，将长有石墨烯的铜箔平铺在硅片上，用镊子轻轻按压铜箔四周，保证铜箔与硅片紧密贴合，铜箔边缘不要有缝隙，否则易飞出。S12: Place the copper foil with graphene on a clean, smooth surface substrate, and stick the four sides of the copper foil with tape to make the copper foil evenly spread on the substrate. When sticking, pay attention to the copper foil being flat. Reduce the crease, otherwise it is easy to get uneven glue. In another embodiment, a few drops of deionized water can be dropped on a round / square silicon wafer, and the graphene-coated copper foil is laid on the silicon wafer, and the periphery of the copper foil is gently pressed with tweezers to ensure the copper foil. It is closely attached to the silicon wafer, and there should be no gap on the edge of the copper foil, otherwise it will easily fly out.
S13：采用匀胶机在长有石墨烯的铜箔上旋涂聚甲基丙烯酸甲酯前驱液，将基片放在载物台上，用吸管滴几滴质量分数为2.5％的PMMA溶液在铜箔上，然后先在500rpm转速下旋涂3s，再在5000rpm转速下旋涂40s，旋涂结束后，将铜箔放在恒温平台上120℃烘烤10min，使PMMA胶凝固以保持足够的强度。PMMA的作用是支撑石墨烯膜，旋涂PMMA后可使得石墨烯在后续处理过程中保持足够的强度，不易在溶液中破裂。S13: Use a homogenizer to spin coat a polymethyl methacrylate precursor solution on graphene-coated copper foil, place the substrate on a stage, and use a pipette to drop a few drops of 2.5% PMMA solution in On the copper foil, spin-coat at 500 rpm for 3 s, and then spin-coat at 5000 rpm for 40 s. After the spin coating, place the copper foil on a constant temperature platform and bake at 120 ° C for 10 min to allow the PMMA glue to solidify to maintain sufficient strength. The role of PMMA is to support the graphene film. After spin-coating PMMA, the graphene can maintain sufficient strength during subsequent processing and it is not easy to crack in solution.
S2：通过铜溶解法将所述复合膜转移到光子晶体光纤(PCF)的表面。具体的包括：S2: The composite film is transferred to the surface of a photonic crystal fiber (PCF) by a copper dissolution method. These include:
S21：配置硝酸铁刻蚀液，其中硝酸铁与溶剂的比为15～20g:100ml，溶剂通常取水或去离子水200ml，或采用采用盐酸(质量分数为36～38％)、双氧水(质量分数为30％)与去离子水按1:1:20比例配置的混合液200ml。S21: Equipped with iron nitrate etching solution, where the ratio of iron nitrate to solvent is 15-20g: 100ml, the solvent usually takes water or deionized water 200ml, or uses hydrochloric acid (mass fraction 36-38%), hydrogen peroxide (mass fraction) (30%) and 200 ml of a mixed solution prepared with deionized water at a ratio of 1: 1: 20.
S22：将涂胶后的铜箔放在刻蚀液表面，经刻蚀液腐蚀(时间大于20min)，用镊子夹住铜箔让其背面在橡胶手套上拖动，去除背面石墨烯，然后将铜箔放在滤纸上，利用滤纸吸收铜箔背面的液体，便于下一步剪切铜箔。在另一实施例中，将涂胶后的铜箔放在刻蚀液表面8min，在此过程中，约5min时，用镊子夹取铜箔在让其背面在橡胶手套上拖动，去除背面石墨烯，反复拖动多次，然后将铜箔放在去离子水表面10min，在此过程中，继续刮擦，保证铜箔下表面的石墨烯清除干净。S22: Put the coated copper foil on the surface of the etching solution, and corrode the etching solution (time is more than 20min). Hold the copper foil with tweezers and drag its back on rubber gloves to remove the graphene on the back, and then The copper foil is placed on the filter paper, and the liquid on the back of the copper foil is absorbed by the filter paper, which is convenient for cutting the copper foil in the next step. In another embodiment, the coated copper foil is placed on the surface of the etching solution for 8 minutes. In the process, about 5 minutes, the copper foil is clamped with tweezers and the back is dragged on a rubber glove to remove the back Graphene, drag repeatedly for several times, and then place the copper foil on the surface of deionized water for 10 minutes. In the process, continue to scrape to ensure that the lower surface of the copper foil is cleaned.
S23：将铜箔放置于手上，将边缘胶带粘住未涂石墨烯、有残胶的部分及镊子夹持部分剪去，根据所需尺寸将铜箔剪成合适大小约1*1cm即可，用镊子夹住放在刻蚀液表面至铜箔刻蚀完毕，得到浮于刻蚀液表面的PMMA/石墨烯复合膜。S23: Put the copper foil on the hand, and cut off the edge tape to the uncoated graphene, the adhesive residue and the tweezers, and then cut the copper foil to a suitable size of about 1 * 1cm. With a tweezer, the PMMA / graphene composite film floating on the surface of the etching solution was obtained by holding the surface of the etching solution until the copper foil was etched.
S24：将盐酸(质量分数为36％-38％)、双氧水(质量分数为30％)与去离子水按照1:1:10的比例配置溶液(双氧水比例可略小于1，减小气泡)，将PMMA/石墨烯复合膜捞到该溶液中，以清除硝酸铁溶液带来的杂质。没有气泡附着的膜可用载玻片捞取，有气泡附着的膜可用PET片捞取，利用PET的吸附力去除气泡。PET片用镊子夹持，捞取时，PET倾斜一定角度，可将复合膜赶到培养皿壁，增大PET的倾角，膜的一边会粘在PET上，此时可将PET提出水面，然后将PET轻轻放入盐酸、双氧水混合液中，将PET沿垂直于膜的方向撤走，不 要前后晃动，在混合液中浸泡2h以去除杂质，再将膜转移到去离子水中。操作过程动作要缓慢，防止石墨烯破损。S24: Configure a solution of hydrochloric acid (mass fraction: 36% -38%), hydrogen peroxide (mass fraction: 30%) and deionized water in a ratio of 1: 1: 10 (the ratio of hydrogen peroxide can be slightly less than 1 to reduce air bubbles), The PMMA / graphene composite film was fished into the solution to remove impurities brought by the iron nitrate solution. Films without air bubbles attached can be retrieved from glass slides, and films with air bubbles attached can be retrieved from PET sheets, and bubbles are removed using PET's adsorption force. The PET sheet is held with tweezers. When it is picked up, the PET is tilted at a certain angle, which can drive the composite film to the wall of the petri dish to increase the tilt angle of the PET. One side of the film will stick to the PET. At this time, the PET can be lifted out of the water surface, and then PET is gently placed in the mixed solution of hydrochloric acid and hydrogen peroxide, and the PET is removed in the direction perpendicular to the membrane. Do not shake it back and forth. Soak the mixture in the mixed solution for 2 hours to remove impurities, and then transfer the membrane to deionized water. The operation should be slow to prevent graphene from being damaged.
S25：将光子晶体光纤浸入去离子水中并置于复合膜的底端，再将光子晶体光纤往上提，使复合膜转移到光子晶体光纤表面，之后再用丙酮去除PMMA，即可得到纯粹的石墨烯膜包覆于光子晶体光纤表面。S25: immerse the photonic crystal fiber in deionized water and place it on the bottom of the composite film, and then lift the photonic crystal fiber upward to transfer the composite film to the surface of the photonic crystal fiber, and then remove PMMA with acetone to obtain a pure The graphene film is coated on the surface of the photonic crystal fiber.
S3：将涂有石墨烯膜的光子晶体光纤置于280～320℃的温度下煅烧3.5～4.5h，增强薄膜附着力，获得石墨烯光纤复合材料。S3: The photonic crystal fiber coated with a graphene film is calcined at a temperature of 280-320 ° C for 3.5-4.5 hours to enhance the film adhesion to obtain a graphene fiber composite material.
所得石墨烯光纤复合材料的两端可通过光纤熔接机分别与单模光纤耦合，并在两耦合点处分别形成腰部扩大光纤粗锥，从而制得石墨烯光纤传感器。具体的，光纤熔接机的参数设为：首次放电开始强度+100mA，首次放电结束强度+100mA，再次放电开始强度+100mA，再次放电结束强度+100mA，预熔时间+260ms，推进距离+315μm。其中，推进距离表示将两根光纤在电弧熔接的时候往中间挤压的距离，以得到粗锥(鼓包)的结构，较大的推进距离可以得到较大的腰部尺寸和较短的锥度过渡区长度。在该参数下，得到的腰部尺寸和锥度过渡区长度为：腰长400μm、腰径179.25μm、锥度过渡区长度4cm。The two ends of the obtained graphene optical fiber composite material can be respectively coupled with the single-mode optical fiber through an optical fiber fusion splicer, and a thick enlarged optical fiber cone is formed at the two coupling points, respectively, so as to obtain a graphene optical fiber sensor. Specifically, the parameters of the optical fiber fusion splicer are set as follows: the first discharge start intensity + 100 mA, the first discharge end intensity + 100 mA, the second discharge start intensity + 100 mA, the second discharge end intensity + 100 mA, the pre-fusion time + 260 ms, and the advance distance + 315 μm. Among them, the advancing distance indicates the distance that the two optical fibers are squeezed to the middle during arc fusion to obtain a thick cone (bulb) structure. A larger advancing distance can obtain a larger waist size and a shorter taper transition area. length. Under this parameter, the obtained waist size and taper transition zone length are: a waist length of 400 μm, a waist diameter of 179.25 μm, and a taper transition zone length of 4 cm.
所述石墨烯光纤传感器10如图4所示，包括一光子晶体光纤11和两单模光纤12，所述光子晶体光纤11的两端分别与一所述单模光纤12耦合，并在两耦合点处分别形成一腰部扩大光纤粗锥13；所述光子晶体光纤12表面包覆有石墨烯层。优选的，所述两耦合点之间的距离为3.9～4.1cm；所述腰部扩大光纤粗锥的腰长为395～405μm，腰径为179～180μm；所述石墨烯层的厚度为1～10层，单层石墨烯的厚度为0.33～0.35nm。As shown in FIG. 4, the graphene optical fiber sensor 10 includes a photonic crystal fiber 11 and two single-mode optical fibers 12. Both ends of the photonic crystal fiber 11 are coupled to the single-mode optical fiber 12 respectively, and are coupled between the two. A thick enlarged fiber cone 13 at the waist is formed at each point; the surface of the photonic crystal fiber 12 is covered with a graphene layer. Preferably, the distance between the two coupling points is 3.9 to 4.1 cm; the waist length of the waist enlarged fiber thick cone is 395 to 405 μm and the waist diameter is 179 to 180 μm; the thickness of the graphene layer is 1 to There are 10 layers, and the thickness of the single-layer graphene is 0.33 to 0.35 nm.
具体的，所述光子晶体光纤11的一部分夹在两个单模光纤12中，两个耦合部分可通过电弧熔合构成腰部扩大光纤粗锥13拼接。在第一个耦合点处，包层模式可以从基模激发，然后在光子晶体光纤中传播；在第二个耦合点处，包层模式可以彼此重新耦合或与基模耦合，然后形成干扰。两个耦合点之间的距离被视为干涉臂长度，干涉臂长度、腰长和腰径分别用L、l和d表示。本实施例中，干涉臂长度L、腰长l和腰径d分别为4cm、400μm和179.25μm；石墨烯为单层石墨烯，厚度为0.334nm。Specifically, a part of the photonic crystal optical fiber 11 is sandwiched between two single-mode optical fibers 12, and the two coupling portions can be formed by arc fusion to form a waist enlarged optical fiber thick cone 13 for splicing. At the first coupling point, the cladding modes can be excited from the fundamental mode and then propagate in the photonic crystal fiber; at the second coupling point, the cladding modes can be recoupled with each other or with the fundamental mode and then form interference. The distance between the two coupling points is regarded as the interference arm length, and the interference arm length, waist length, and waist diameter are represented by L, l, and d, respectively. In this embodiment, the interference arm length L, waist length l, and waist diameter d are 4 cm, 400 μm, and 179.25 μm, respectively; graphene is a single-layer graphene with a thickness of 0.334 nm.
激发态与激发态之间的有效折射率差以及激发态与基模之间的相位差引起了联合干涉，所述传感器的传输强度可以定义为：The effective refractive index difference between the excited state and the excited state and the phase difference between the excited state and the fundamental mode cause joint interference. The transmission intensity of the sensor can be defined as:
Figure PCTCN2018112900-appb-000001
Figure PCTCN2018112900-appb-000001
其中，I 1、I 2是不同模式的强度；
Figure PCTCN2018112900-appb-000002
是互模式相位差，可以表示为： Among them, I 1 and I 2 are the intensities of different modes;
Figure PCTCN2018112900-appb-000002
Is the inter-mode phase difference and can be expressed as:
Figure PCTCN2018112900-appb-000003
Figure PCTCN2018112900-appb-000003
其中，λ是入射光的波长；Δn eff是纤芯和包层模的有效折射率之差；L是两个耦合点之间的距离，对应于干涉仪的物理长度。干涉的第m阶波长λ m可以表示为： Among them, λ is the wavelength of the incident light; Δn eff is the difference between the effective refractive indices of the core and the cladding mode; L is the distance between the two coupling points, which corresponds to the physical length of the interferometer. The interference's m-th order wavelength λ m can be expressed as:
Figure PCTCN2018112900-appb-000004
Figure PCTCN2018112900-appb-000004
当包覆的石墨烯浸没目标液体时，锥形光子晶体光纤消逝场中包层的折射率发生变化，纤芯模式和包层模式的有效指数之间的差异也将改变，由于在腰部扩大光纤粗锥中纤芯和包层模的耦合和复合，相应透射光谱中的谷被移动。因此，可以通过测量相应的波长偏移来实现折射率检测。When the coated graphene is immersed in the target liquid, the refractive index of the cladding in the evanescent field of the tapered photonic crystal fiber changes, and the difference between the effective index of the core mode and the cladding mode will also change. The coupling and recombination of the core and cladding modes in the thick cone, the valleys in the corresponding transmission spectrum are shifted. Therefore, refractive index detection can be achieved by measuring the corresponding wavelength shift.
本实施例还提供了一种利用上述石墨烯光纤传感器进行折射率检测的***，如图5所示，其包括石墨烯光纤传感器10、光源20、样品室30和信号处理***40，所述石墨烯光纤传感器10设于所述样品室30内，其两端分别与所述光源20和所述信号处理***40连接。This embodiment also provides a system for performing refractive index detection by using the above graphene optical fiber sensor. As shown in FIG. 5, the system includes a graphene optical fiber sensor 10, a light source 20, a sample chamber 30, and a signal processing system 40. The olefin optical fiber sensor 10 is disposed in the sample chamber 30, and two ends thereof are respectively connected to the light source 20 and the signal processing system 40.
具体的，所述光源10采用放大自发辐射源(ASE)，所述信号处理***40采用光源分析仪(OSA，Yokogawa AQ6370D)，样品室30可以为比色杯或者集气袋，分别用于装不同浓度的液体样品和气体样品，作为折射率测量样品，传感器在不同折射率下的透射谱由放大自发辐射源和光谱分析仪检测。Specifically, the light source 10 uses an amplified spontaneous radiation source (ASE), the signal processing system 40 uses a light source analyzer (OSA, Yokogawa AQ6370D), and the sample chamber 30 may be a colorimetric cup or a gas collection bag, respectively Liquid samples and gas samples of different concentrations are used as refractive index measurement samples. The transmission spectrum of the sensor at different refractive indices is detected by an amplified spontaneous radiation source and a spectrum analyzer.
表面形貌和分子结构表征Surface morphology and molecular structure characterization
利用扫描电子显微镜(SEM，TESCAN MIRA3)和拉曼光谱(LabRAM HR Evolution，HORIBA Scientific)对上述实施例制得的石墨烯光纤复合材料的表面形貌和分子结构进行了表征。如图2(a)所示，SMF拼接在PCF的末端，在熔接过程中，端部周围的PCF气孔完全塌陷，然后，熔接机可以控制电机准确的推动SMF和PCF之间的中间部分，并形成腰部扩大的锥形。锥形PCF的外表面形貌如图2(b)所示，可见外表面均匀，表明石墨烯膜在PCF表面分布均匀。拉曼光谱如图3所示，可见G(～1591cm -1)和2D(～2697cm -1)峰与石墨烯标准拉曼峰一致，证明PCF所包覆的薄膜确实由石墨烯制成，同时，G和2D峰的相对强度比小于1，说明石墨烯膜为单层结构。 The surface morphology and molecular structure of the graphene fiber composite material prepared in the above examples were characterized by using a scanning electron microscope (SEM, TESCAN MIRA3) and Raman spectroscopy (LabRAM HR Evolution, HORIBA Scientific). As shown in Figure 2 (a), the SMF is spliced at the end of the PCF. During the welding process, the PCF pores around the end completely collapse. Then, the welding machine can control the motor to accurately push the middle part between the SMF and the PCF. Form a tapered waist. The morphology of the outer surface of the tapered PCF is shown in Fig. 2 (b). It can be seen that the outer surface is uniform, indicating that the graphene film is uniformly distributed on the PCF surface. The Raman spectrum is shown in Figure 3. It can be seen that the G (~ 1591cm -1 ) and 2D (~ 2697cm -1 ) peaks are consistent with the standard Raman peaks of graphene, which proves that the film coated by PCF is indeed made of graphene. The relative intensity ratio of G and 2D peaks is less than 1, indicating that the graphene film has a single layer structure.
检测蔗糖溶液Detection of sucrose solution
使用具有不同浓度(0～233ppm)的蔗糖溶液作为用于折射率测量的折射率液体样品，它们的折射率从1.3338到1.3376，由传感器在室温300K下检测。Sucrose solutions with different concentrations (0 to 233 ppm) were used as refractive index liquid samples for refractive index measurement, and their refractive indices ranged from 1.3338 to 1.3376, which were detected by a sensor at 300K at room temperature.
为了研究石墨烯对于蔗糖溶液浓度的影响，进行了以下对照实验：制造对比光纤传感器，其与实施例1基本相同，不同之处在于，PCF表面没有包覆石墨烯层。利用该对比光纤传感器检测0ppm和230ppm的蔗糖溶液的最大偏移量，实验结果如图6(a)所示，两个浓度(0ppm和230ppm)之间的波长漂移仅为0.3nm。而利用石墨烯光纤传感器检测不同浓度的蔗糖溶液 的最大偏移量，实验结果如图6(b)所示，两个浓度(0ppm和230ppm)之间的波长漂移可以达到1nm。由此可见，石墨烯膜可以显著提高折射率传感器的灵敏度。In order to study the effect of graphene on the concentration of sucrose solution, the following control experiment was performed: a comparative optical fiber sensor was manufactured, which was basically the same as Example 1, except that the surface of the PCF was not coated with a graphene layer. Using this comparative fiber-optic sensor to detect the maximum offset of the sucrose solution at 0 ppm and 230 ppm, the experimental results are shown in Figure 6 (a). The wavelength drift between the two concentrations (0 ppm and 230 ppm) is only 0.3 nm. Using graphene fiber optic sensors to detect the maximum offset of sucrose solutions with different concentrations, the experimental results are shown in Figure 6 (b). The wavelength drift between the two concentrations (0 ppm and 230 ppm) can reach 1 nm. It can be seen that the graphene film can significantly improve the sensitivity of the refractive index sensor.
同时，随着蔗糖浓度的增加，波谷向较短的波长移动，原因如下：当蔗糖接触石墨烯传感层时，包层的有效折射率会增大，但纤芯的折射率不变，因此，差值(Δn eff)的折射率正在降低，从而，根据公式(3)，波长减小，表明随着蔗糖浓度的增加，折射仪的输出透射谱将发生蓝移。实验结果与理论结果非常吻合。波谷波长与浓度的值通过线性回归模型拟合，结果如图6所示，结果表明，校准曲线的相关系数R 2为0.98233，在给定的蔗糖溶液浓度范围内，石墨烯光纤传感器表现出相当好的线性响应，石墨烯对蔗糖溶液的敏感性为3.36pm/ppm。共振峰的波长位移与外部溶液的折射率之间的变化关系如图7所示，其中，离散点为实际测量点，直线为线性拟合曲线(R' 2＝0.98217)，实验结果表明，当外部折射率从1.3338变化到1.3376时，传感器的灵敏度可以达到205.26nm/RIU。 At the same time, as the sucrose concentration increases, the trough shifts to a shorter wavelength for the following reasons: When sucrose contacts the graphene sensing layer, the effective refractive index of the cladding will increase, but the refractive index of the core does not change, so The refractive index of the difference (Δn eff ) is decreasing. Therefore, according to formula (3), the wavelength decreases, indicating that as the sucrose concentration increases, the output transmission spectrum of the refractometer will undergo a blue shift. The experimental results are in good agreement with the theoretical results. The values of trough wavelength and concentration were fitted by a linear regression model. The results are shown in Figure 6. The results show that the correlation coefficient R 2 of the calibration curve is 0.98233. Within a given concentration range of sucrose solution, the graphene fiber optic sensor shows comparable performance. Good linear response. The sensitivity of graphene to sucrose solution is 3.36pm / ppm. The relationship between the wavelength shift of the resonance peak and the refractive index of the external solution is shown in Figure 7, where the discrete points are the actual measurement points and the straight line is a linear fitting curve (R ' 2 = 0.98217). The experimental results show that when When the external refractive index changes from 1.3338 to 1.3376, the sensitivity of the sensor can reach 205.26nm / RIU.
检测硫化氢气体Detection of hydrogen sulfide gas
实施例1的石墨烯光纤传感器不单单局限于蔗糖溶液的实验，例如葡萄糖，氯化钠等溶液都可以进行实验，并且如果在石墨烯薄膜表面沉积一层其他的敏感物质，则可以用来检测其他溶液或者气体。本实验中，在实施例1的石墨烯光纤传感器的石墨烯薄膜表面沉积纳米铜，用来检测硫化氢气体。The graphene optical fiber sensor of Example 1 is not limited to the experiment of sucrose solution. For example, solutions such as glucose and sodium chloride can be tested, and if a layer of other sensitive substances is deposited on the surface of the graphene film, it can be used for detection. Other solutions or gases. In this experiment, nano-copper was deposited on the graphene film surface of the graphene fiber sensor of Example 1 to detect hydrogen sulfide gas.
使用集气袋分别配置0ppm，10ppm，20ppm，40ppm，60ppm，70ppm，80ppm这七种浓度的硫化氢气体并进行实验，得到如图8所示的光谱图。可见随着硫化氢气体浓度的增大，光谱的监测波谷发生了蓝移现象。其原因是：石墨烯薄膜表面的纳米铜吸附气体中的硫化氢分子后，自身折射率将发生改变，使光子晶体光纤的包层有效折射率发生改变，导致光子晶体光纤中纤芯与包层的光程差发生变化，因此可以从光谱仪上观察到透射光谱中的干涉波谷将发生偏移，从而将气体的浓度与波长的偏移联系起来，达到检测气体浓度的目的。Seven gas concentrations of 0 ppm, 10 ppm, 20 ppm, 40 ppm, 60 ppm, 70 ppm, and 80 ppm of hydrogen sulfide gas were arranged in the gas collecting bag and experiments were performed to obtain the spectrum shown in FIG. 8. It can be seen that with the increase of the concentration of hydrogen sulfide gas, a blue shift phenomenon occurs in the monitoring trough of the spectrum. The reason is that after the nano-copper on the surface of the graphene film adsorbs hydrogen sulfide molecules in the gas, its own refractive index will change, which will change the effective refractive index of the cladding of the photonic crystal fiber, resulting in the core and cladding of the photonic crystal fiber. The difference in optical path length changes, so it can be observed from the spectrometer that the interference valleys in the transmission spectrum will shift, thereby correlating the concentration of the gas with the shift in the wavelength to achieve the purpose of detecting the concentration of the gas.
实验结果表明，实施例1的石墨烯光纤传感器在硫化氢气体浓度为0～80ppm范围内呈现良好的线性响应，如图9所示。其中，离散点是实际测量点，直线是线型拟合曲线，可见其线性度极高(R 2＝0.9909)，且对硫化氢气体的灵敏度为8.5pm/ppm。该传感器易于制造，成本低，体积小，可用于低浓度硫化氢气体的检测。 The experimental results show that the graphene optical fiber sensor of Example 1 exhibits a good linear response in the range of a hydrogen sulfide gas concentration of 0 to 80 ppm, as shown in FIG. 9. Among them, the discrete point is the actual measurement point, and the straight line is a linear fitting curve. It can be seen that the linearity is extremely high (R 2 = 0.9909), and the sensitivity to hydrogen sulfide gas is 8.5pm / ppm. The sensor is easy to manufacture, has low cost and small size, and can be used for the detection of low-concentration hydrogen sulfide gas.
相对于现有技术，本发明将光纤与石墨烯相结合，利用石墨烯的特殊结构对溶液中的分子具有吸附性，由此改变光纤的折射率，提高其灵敏度。本发明的石墨烯光纤复合材料作为折射率传感器的传感材料，对于物质浓度(如硫化氢气体、蔗糖)检测具有高线性响应和优异的灵敏度，且具有成本低、制作方法简单、可重复性高的特点，可大量生产使用。Compared with the prior art, the present invention combines an optical fiber with graphene and utilizes the special structure of graphene to adsorb molecules in a solution, thereby changing the refractive index of the optical fiber and improving its sensitivity. The graphene optical fiber composite material of the present invention is used as a sensing material of a refractive index sensor, and has high linear response and excellent sensitivity for the detection of substance concentrations (such as hydrogen sulfide gas and sucrose), and has low cost, simple manufacturing method, and repeatability. High characteristics, can be used in mass production.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。The above-mentioned embodiments only express several implementation manners of the present invention, and their descriptions are more specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be noted that, for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, which all belong to the protection scope of the present invention.

Claims (8)

  1. 一种石墨烯光纤复合材料的制备方法，其特征在于：包括以下步骤：A method for preparing a graphene optical fiber composite material is characterized in that it includes the following steps:
    S1：在铜箔上制备石墨烯和聚甲基丙烯酸甲酯的复合膜；S1: preparing a composite film of graphene and polymethyl methacrylate on a copper foil;
    S2：通过铜溶解法将所述复合膜转移到光子晶体光纤的表面；S2: transferring the composite film to the surface of a photonic crystal fiber by a copper dissolution method;
    S3：去除转移到所述光子晶体光纤表面的复合膜中的聚甲基丙烯酸甲酯，再进行煅烧，获得石墨烯光纤复合材料。S3: removing the polymethyl methacrylate transferred to the composite film on the surface of the photonic crystal optical fiber, and then calcining to obtain a graphene optical fiber composite material.
  2. 根据权利要求1所述的石墨烯光纤复合材料的制备方法，其特征在于：步骤S1中，先通过化学气相沉积法在铜箔上生长石墨烯，然后在长有石墨烯的铜箔上旋涂聚甲基丙烯酸甲酯前驱液，经烘干得到所述复合膜。The method for preparing a graphene optical fiber composite material according to claim 1, wherein in step S1, graphene is first grown on a copper foil by a chemical vapor deposition method, and then spin-coated on the copper foil having graphene grown thereon. The polymethyl methacrylate precursor is dried to obtain the composite film.
  3. 根据权利要求2所述的石墨烯光纤复合材料的制备方法，其特征在于：旋涂聚甲基丙烯酸甲酯前驱液时，先在500rpm转速下旋涂3s，再在5000rpm转速下旋涂40s。The method for preparing a graphene optical fiber composite material according to claim 2, characterized in that: when spin-coating the polymethyl methacrylate precursor, first spin-coat at 500 rpm for 3 s, and then spin-coat at 5000 rpm for 40 s.
  4. 根据权利要求3所述的石墨烯光纤复合材料的制备方法，其特征在于：所述烘干过程的温度为115～125℃，时间为8～12min。The method for preparing a graphene optical fiber composite material according to claim 3, wherein the temperature during the drying process is 115 to 125 ° C, and the time is 8 to 12 minutes.
  5. 根据权利要求1所述的石墨烯光纤复合材料的制备方法，其特征在于：步骤S2中，先将涂有复合膜的铜箔置于刻蚀液中，待铜箔溶解后，复合膜漂浮于刻蚀液中；然后用载玻片或PET片将该漂浮的复合膜转移至去离子水中，将光子晶体光纤浸入去离子水中并置于复合膜的底端；再将光子晶体光纤往上提，使复合膜转移到光子晶体光纤表面。The method for preparing a graphene optical fiber composite material according to claim 1, wherein in step S2, a copper foil coated with a composite film is first placed in an etching solution, and after the copper foil is dissolved, the composite film floats on In an etching solution; then use a glass slide or PET sheet to transfer the floating composite film to deionized water, immerse the photonic crystal fiber in deionized water and place it at the bottom of the composite film; then lift the photonic crystal fiber upward , So that the composite film is transferred to the surface of the photonic crystal fiber.
  6. 根据权利要求5所述的石墨烯光纤复合材料的制备方法，其特征在于：所述刻蚀液为硝酸铁溶液，其质量浓度为15～20g/ml。The method for preparing a graphene optical fiber composite material according to claim 5, wherein the etching solution is a ferric nitrate solution, and its mass concentration is 15-20 g / ml.
  7. 根据权利要求6所述的石墨烯光纤复合材料的制备方法，其特征在于：所述硝酸铁溶液中的溶剂为盐酸、双氧水与去离子水按1:1:20的比例配置的混合液。The method for preparing a graphene optical fiber composite material according to claim 6, wherein the solvent in the iron nitrate solution is a mixed solution of hydrochloric acid, hydrogen peroxide, and deionized water at a ratio of 1: 1: 20.
  8. 根据权利要求1所述的石墨烯光纤复合材料的制备方法，其特征在于：步骤S3中，所述煅烧的温度为280～320℃，时间为3.5～4.5h。The method for preparing a graphene optical fiber composite material according to claim 1, wherein in step S3, the calcination temperature is 280-320 ° C and the time is 3.5-4.5h.
PCT/CN2018/112900 2018-08-01 2018-10-31 Method for preparing graphene optical fibre composite material WO2020024466A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810864886.2 2018-08-01
CN201810864886.2A CN109030417B (en) 2018-08-01 2018-08-01 Preparation method of graphene optical fiber composite material

Publications (1)

Publication Number Publication Date
WO2020024466A1 true WO2020024466A1 (en) 2020-02-06

Family

ID=64648396

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/112900 WO2020024466A1 (en) 2018-08-01 2018-10-31 Method for preparing graphene optical fibre composite material

Country Status (2)

Country Link
CN (1) CN109030417B (en)
WO (1) WO2020024466A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109030417B (en) * 2018-08-01 2020-08-25 广州特种承压设备检测研究院 Preparation method of graphene optical fiber composite material
CN110736722B (en) * 2019-10-29 2022-04-08 广州特种承压设备检测研究院 Manufacturing method of graphene quantum dot composite material optical fiber gas sensor
CN110749572B (en) * 2019-10-29 2022-04-12 广州特种承压设备检测研究院 Graphene optical fiber gas sensor measuring system and method for measuring hydrogen sulfide gas by using same
CN114453023A (en) * 2021-12-14 2022-05-10 中国科学院深圳先进技术研究院 Luminescent optical fiber composite catalytic material and plasma preparation method thereof
CN115036144A (en) * 2022-05-12 2022-09-09 蚌埠学院 Preparation method and application of iron oxide/graphene composite material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103954590A (en) * 2014-04-30 2014-07-30 电子科技大学 Micro optical fiber gas sensor covered by adopting graphene
CN104198389A (en) * 2014-09-22 2014-12-10 上海理工大学 Preparation method of copper-based suspended sample stage used for ultrahigh resolution fluorescence imaging
CN106596418A (en) * 2016-12-21 2017-04-26 重庆理工大学 Graphene photonic crystal fiber gas sensor manufacturing method, gas sensor and hydrogen sulfide gas concentration detection method
CN107782709A (en) * 2016-08-24 2018-03-09 北京大学 A kind of method of isotope pulse calibration graphene growth speed
CN109030417A (en) * 2018-08-01 2018-12-18 广州特种承压设备检测研究院 A kind of preparation method of graphene Fiber Composites

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103954590A (en) * 2014-04-30 2014-07-30 电子科技大学 Micro optical fiber gas sensor covered by adopting graphene
CN104198389A (en) * 2014-09-22 2014-12-10 上海理工大学 Preparation method of copper-based suspended sample stage used for ultrahigh resolution fluorescence imaging
CN107782709A (en) * 2016-08-24 2018-03-09 北京大学 A kind of method of isotope pulse calibration graphene growth speed
CN106596418A (en) * 2016-12-21 2017-04-26 重庆理工大学 Graphene photonic crystal fiber gas sensor manufacturing method, gas sensor and hydrogen sulfide gas concentration detection method
CN109030417A (en) * 2018-08-01 2018-12-18 广州特种承压设备检测研究院 A kind of preparation method of graphene Fiber Composites

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TAN, Y. C. ET AL.: "Graphene-deposited Photonic Crystal Fibers for Continuous Refractive Index Sensing Applications", OPTICS EXPRESS, vol. 23, no. 24, 30 November 2015 (2015-11-30), pages 31286 - 31294, XP055684074 *
XU, FENG: "Hydrogen Sulfide Gas Sensor Based on Graphene-coated Tapered Photonic Crystal Fiber Interferometer", SENSORS AND ACTUATORS B-CHEMICAL, vol. 247, 31 December 2017 (2017-12-31), pages 540 - 545, XP055684079 *

Also Published As

Publication number Publication date
CN109030417B (en) 2020-08-25
CN109030417A (en) 2018-12-18

Similar Documents

Publication Publication Date Title
WO2020024466A1 (en) Method for preparing graphene optical fibre composite material
WO2020024467A1 (en) Graphene optical fibre sensor and preparation method therefor and use thereof
CN208568590U (en) A kind of refractive index detection system of index sensor and its composition
US6785432B2 (en) Target molecules detection by waveguiding in a photonic silicon membrane
US10725373B1 (en) Nano-patterning methods including: (1) patterning of nanophotonic structures at optical fiber tip for refractive index sensing and (2) plasmonic crystal incorporating graphene oxide gas sensor for detection of volatile organic compounds
Zhang et al. A visual film sensor based on silole-infiltrated SiO 2 inverse opal photonic crystal for detecting organic vapors
KR101090430B1 (en) Optical Fiber Containing Carbon Nanostructure Layer, Optical Fiber Chemical Sensor and Method of Forming Carbon Nanostructure Layer on Optical Fiber Core
KR101237990B1 (en) Surface plasmon resonance sensor using metallic graphene, preparing method of the same, and surface plasmon resonance sensor system
Arasu et al. Fiber Bragg grating assisted surface plasmon resonance sensor with graphene oxide sensing layer
Samavati et al. Comprehensive investigation of evanescent wave optical fiber refractive index sensor coated with ZnO nanoparticles
Azad et al. Fast response relative humidity clad-modified multimode optical fiber sensor with hydrothermally dimension controlled ZnO nanorods
KR101297325B1 (en) Surface plasmon resonance sensor containing prism deposited metallic carbon nanostructure layer, and preparing method of the same
Harith et al. Relative humidity sensor employing tapered plastic optical fiber coated with seeded Al-doped ZnO
Brigo et al. Xylene sensing properties of aryl-bridged polysilsesquioxane thin films coupled to gold nanoparticles
Tahhan et al. Fabrication of fiber bragg grating coating with TiO 2 nanostructured metal oxide for refractive index sensor
Subramanian et al. Room temperature fiber optic gas sensor technology based on nanocrystalline Ba3 (VO4) 2: Design, spectral and surface science
Sun et al. Surface Plasmon Resonance Alcohol Sensor with Ni (OH) 2 Nanoflowers/Au Structure
Miao et al. Optofluidic sensor: Evaporation kinetics detection of solvents dissolved with Cd3P2 colloidal quantum dots in a Rolled‐Up microtube
Zhao et al. Graphene oxide modified surface plasmon resonance sensor based on side-polished fiber
Dong et al. Design and analysis of surface plasmon resonance sensor based on multi-core photonic crystal fiber
KR101733751B1 (en) Bio-sensor and manufacturing Method thereof
Sun et al. Free-space coupled silicon photonic crystal refractometric membrane sensors
Han et al. Asymmetrical photonic crystal fiber based on the surface plasmon resonance sensor and analysis by the lower-birefringence peak method
Gifford et al. Sensitivity control of optical fiber biosensors utilizing turnaround point long period gratings with self-assembled polymer coatings
Park et al. High performance label-free biosensing by all dielectric metamaterial

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18928899

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18928899

Country of ref document: EP

Kind code of ref document: A1