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CN105004698B - A kind of Biosensors Based on Surface Plasmon Resonance device - Google Patents

A kind of Biosensors Based on Surface Plasmon Resonance device Download PDF

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CN105004698B
CN105004698B CN201510313359.9A CN201510313359A CN105004698B CN 105004698 B CN105004698 B CN 105004698B CN 201510313359 A CN201510313359 A CN 201510313359A CN 105004698 B CN105004698 B CN 105004698B
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prism
graphene
plasmon resonance
surface plasmon
silicon dioxide
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CN105004698A (en
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石建平
查射曦
米佳佳
赵小童
黄万霞
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Shandong Weixin Medical Equipment Co ltd
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Anhui Normal University
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Abstract

一种表面等离激元共振生物传感器,由棱镜、纳米颗粒阵列、二氧化硅薄膜、石墨烯以及样品池组成,纳米颗粒阵列位于棱镜的下表面,二氧化硅薄膜覆盖在纳米颗粒阵列上,石墨烯覆盖在二氧化硅薄膜上,其特征在于:棱镜为高折射率材料,纳米颗粒阵列由聚苯乙烯纳米球外覆金属薄膜组成。本发明属于纳米科学领域,利用SPR原理在金属的下表面激发SPP,样品折射率的微小改变能够影响共振曲线,改变共振角。反之,由探测得到的共振角即可推出样品的折射率,进而可准确地获得待测物质的浓度。

A surface plasmon resonance biosensor consists of a prism, a nanoparticle array, a silicon dioxide film, graphene, and a sample cell. The nanoparticle array is located on the lower surface of the prism, and the silicon dioxide film covers the nanoparticle array. The graphene is covered on the silicon dioxide film, and it is characterized in that: the prism is a high refractive index material, and the nanoparticle array is composed of polystyrene nanospheres coated with a metal film. The invention belongs to the field of nano science, uses the principle of SPR to excite SPP on the lower surface of metal, and the small change of the sample refractive index can affect the resonance curve and change the resonance angle. On the contrary, the refraction index of the sample can be deduced from the detected resonance angle, and then the concentration of the substance to be measured can be obtained accurately.

Description

一种表面等离激元共振生物传感器A Surface Plasmon Resonance Biosensor

技术领域technical field

本发明涉及一种新型表面等离激元共振生物传感器,属于纳米技术、生物技术科学领域。The invention relates to a novel surface plasmon resonance biosensor, which belongs to the scientific fields of nanotechnology and biotechnology.

背景技术Background technique

近年来,对金属表面等离激元(SPP)的研究取得了长足的进展。SPP是指由外部电磁场(如光波)诱导金属微纳结构表面自由电子的集体振荡,它具有一个突出特点就是可以实现表面等离激元共振(Surface Plasmon Resonance,SPR),共振时局部电场可以增大上千倍。因此可以极大的提高电场与物质的作用效果,在生物传感领域应用十分广泛,已成为人们分析物质浓度的强有力的技术手段。本发明提出了一种新型的SPR传感技术,采用纳米球外覆金属薄膜作为传感单元,并用石墨烯封装,具有灵敏性高和适用范围广的特点。In recent years, the research on metal surface plasmons (SPPs) has made great progress. SPP refers to the collective oscillation of free electrons on the surface of metal micro-nano structures induced by an external electromagnetic field (such as light waves). It has a prominent feature that it can realize surface plasmon resonance (Surface Plasmon Resonance, SPR). Thousands of times bigger. Therefore, the interaction effect between the electric field and the substance can be greatly improved, and it is widely used in the field of biosensing, and has become a powerful technical means for people to analyze the concentration of substances. The invention proposes a new type of SPR sensing technology, which uses nanospheres covered with metal film as a sensing unit and is encapsulated with graphene, which has the characteristics of high sensitivity and wide application range.

发明内容Contents of the invention

本发明需要解决的技术问题是:克服现有技术的不足,提供一种灵敏度高、应用范围广泛、价格经济的一种新型表面等离激元共振生物传感器。The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a novel surface plasmon resonance biosensor with high sensitivity, wide application range and economical price.

本发明的技术解决方案是:Technical solution of the present invention is:

一种新型表面等离激元共振生物传感器,由棱镜(1)、纳米颗粒阵列(2)、二氧化硅薄膜(3)、石墨烯(4)以及样品池(5)组成,纳米颗粒阵列(2)位于棱镜(1)的下表面,二氧化硅薄膜(3)覆盖在纳米颗粒阵列(2)上,石墨烯(4)覆盖在二氧化硅薄膜(3)上,棱镜(1)为高折射率材料,纳米颗粒阵列(2)由聚苯乙烯纳米球(6)外覆金属薄膜(7)组成。A novel surface plasmon resonance biosensor consists of a prism (1), a nanoparticle array (2), a silicon dioxide film (3), graphene (4) and a sample cell (5), and the nanoparticle array ( 2) Located on the lower surface of the prism (1), the silicon dioxide film (3) covers the nanoparticle array (2), graphene (4) covers the silicon dioxide film (3), and the prism (1) is a high The refractive index material, the nanoparticle array (2) is composed of polystyrene nanospheres (6) coated with a metal film (7).

所述的棱镜(1)为折射率大于二氧化硅薄膜(3)的材料,且相对于入射光为低损耗,优选为重火石玻璃或硒基氧硫玻璃或硅。The prism (1) is a material with a higher refractive index than the silicon dioxide film (3), and has low loss relative to incident light, preferably heavy flint glass or selenium oxysulfide glass or silicon.

所述聚苯乙烯纳米球(6)直径为50nm~80nm,单层紧邻排布。The polystyrene nanospheres (6) have a diameter of 50nm to 80nm and are arranged in a single layer next to each other.

所述金属薄膜(7)材料为金或银或铝,厚度为10nm~80nm。The material of the metal thin film (7) is gold, silver or aluminum, and the thickness is 10nm-80nm.

所述二氧化硅薄膜(3)厚度介于10nm与0.25倍入射波长之间。The thickness of the silicon dioxide film (3) is between 10 nm and 0.25 times the incident wavelength.

所述石墨烯(4)层数为1~8层。The number of layers of the graphene (4) is 1-8 layers.

本发明与现有技术相比具有如下优点:Compared with the prior art, the present invention has the following advantages:

1.超高的灵敏度。本发明设计的SPR生物传感器与传统的生物传感器相比灵敏度提高将近1个量级。1. Ultra-high sensitivity. Compared with the traditional biosensor, the sensitivity of the SPR biosensor designed by the invention is improved by nearly one order of magnitude.

2.待测物质检测范围种类广。本生物传感器克服待测样品物态受限的缺点,既能进行液态检测又可进行气态检测,应用范围广。2. The detection range of substances to be tested is wide. The biosensor overcomes the disadvantage of limited physical state of the sample to be tested, can detect both liquid state and gas state, and has a wide range of applications.

3.使用寿命长。石墨烯具有很强的抗氧化能力,可保护金属层不被氧化和腐蚀,增长传感器的使用寿命。3. Long service life. Graphene has a strong anti-oxidation ability, which can protect the metal layer from oxidation and corrosion, and increase the service life of the sensor.

4.操作波长宽。本发明选用的棱镜材料具有较宽的操作波长,可以在不同波段对样品进行检测。4. Wide operating wavelength. The prism material selected in the present invention has a wide operating wavelength and can detect samples in different wave bands.

附图说明Description of drawings

图1为本发明的结构示意图;Fig. 1 is a structural representation of the present invention;

图2表面等离激元共振峰Figure 2 Surface plasmon resonance peak

图3测试样品的共振峰移动Figure 3 The formant shift of the test sample

具体实施方式detailed description

下面结合附图和实施例对本发明作进一步说明。The present invention will be further described below in conjunction with drawings and embodiments.

如图1所示,本发明由棱镜(1)、纳米颗粒阵列(2)、二氧化硅薄膜(3)、石墨烯(4)以及样品池(5)组成,纳米颗粒阵列(2)位于棱镜(1)的下表面,二氧化硅薄膜(3)覆盖在纳米颗粒阵列(2)上,石墨烯(4)覆盖在二氧化硅薄膜(3)上。当棱镜(1)为重火石玻璃,金属薄膜(7)为银,厚度h为10nm,二氧化硅薄膜(3)厚度为25nm,石墨烯(4)厚度为0.34nm时,为入射波长700nm所用的表面等离激元共振传感器。As shown in Figure 1, the present invention is made up of prism (1), nanoparticle array (2), silicon dioxide film (3), graphene (4) and sample cell (5), and nanoparticle array (2) is positioned at prism On the lower surface of (1), the silicon dioxide film (3) is covered on the nanoparticle array (2), and the graphene (4) is covered on the silicon dioxide film (3). When the prism (1) is heavy flint glass, the metal film (7) is silver, the thickness h is 10nm, the silicon dioxide film (3) thickness is 25nm, and when the graphene (4) thickness is 0.34nm, it is used for incident wavelength 700nm surface plasmon resonance sensor.

当用TM偏振的700nm激光光源入射时,经过棱镜(1)折射后到达纳米颗粒阵列(2)。当入射角度大于全反射临界角后,在棱镜(1)和纳米颗粒阵列(2)的界面处产生消逝波,该消逝波将激发表面等离激元共振模式。当覆盖于聚苯乙烯纳米球(6)上的金属薄膜(7)厚度h为10nm~80nm时,可以显著增强这种共振模式,其作用类似于纳米球壳。共振发生时,局部电场增大,入射光被吸收,使反射光能量急剧下降,在反射光谱上出现表面等离激元共振峰,如图2所示。该共振峰对样品折射率的改变十分敏感,当被石墨烯(4)吸附的样品折射率改变时,共振峰位置将发生改变,实现对样品的检测,如图3所示。石墨烯(4)介电常数具有较大的虚部,在可见光波段比Ag要大一个数量级。这会导致表面等离激元共振时损耗增大,引起共振峰变宽,使得传感器的准确度降低。在金属薄膜(7)与石墨烯(4)之间添加二氧化硅薄膜(3)调节膜系的等效介电常数,厚度介于10nm与0.25倍入射波长之间。When incident with a TM polarized 700nm laser light source, it reaches the nanoparticle array (2) after being refracted by the prism (1). When the incident angle is greater than the critical angle of total reflection, an evanescent wave is generated at the interface of the prism (1) and the nanoparticle array (2), and the evanescent wave will excite a surface plasmon resonance mode. When the thickness h of the metal thin film (7) covered on the polystyrene nanosphere (6) is 10nm-80nm, the resonance mode can be significantly enhanced, and its effect is similar to that of a nanosphere shell. When the resonance occurs, the local electric field increases, the incident light is absorbed, the energy of the reflected light drops sharply, and the surface plasmon resonance peak appears on the reflection spectrum, as shown in Figure 2. The resonance peak is very sensitive to the change of the refractive index of the sample. When the refractive index of the sample adsorbed by graphene (4) changes, the position of the resonance peak will change to realize the detection of the sample, as shown in Figure 3. The dielectric constant of graphene (4) has a large imaginary part, which is an order of magnitude larger than that of Ag in the visible light band. This leads to increased loss at surface plasmon resonance, causing a broadening of the resonance peak, which reduces the accuracy of the sensor. A silicon dioxide film (3) is added between the metal film (7) and the graphene (4) to adjust the equivalent dielectric constant of the film system, and the thickness is between 10 nm and 0.25 times the incident wavelength.

本发明的具体制作步骤如下:Concrete manufacturing steps of the present invention are as follows:

a.将聚苯乙烯纳米球分散液均匀涂覆在棱镜下表面,形成紧邻的单层纳米球阵列;b.真空环境下采用磁控溅射在棱镜下表面的纳米球阵列上镀金属薄膜,厚度为10nm~80nm;c.采用液相沉积技术法(LPD)在金属银或铝膜上生长二氧化硅薄膜,膜厚为10nm~0.25倍入射波长;d.采用化学气相沉积法(CVD)生长石墨烯,厚度为0.34nm~2.72nm;e.清洗、烘干,完成制作。a. uniformly coating the polystyrene nanosphere dispersion on the lower surface of the prism to form a single-layer nanosphere array next to each other; b. using magnetron sputtering in a vacuum environment to coat a metal film on the nanosphere array on the lower surface of the prism, Thickness is 10nm~80nm; c. Using liquid phase deposition (LPD) to grow silicon dioxide film on metal silver or aluminum film, the film thickness is 10nm~0.25 times the incident wavelength; d. Using chemical vapor deposition (CVD) Grow graphene with a thickness of 0.34nm to 2.72nm; e. Clean and dry to complete the production.

Claims (3)

  1. A kind of 1. Biosensors Based on Surface Plasmon Resonance device, by prism (1), nano-grain array (2), silica membrane (3), graphene (4) and sample cell (5) composition, nano-grain array (2) are located at the lower surface of prism (1), and silica is thin Film (3) is covered on nano-grain array (2), and graphene (4) is covered on silica membrane (3), it is characterised in that:Prism (1) it is high-index material, nano-grain array (2) is cladded with metallic film (7) by polystyrene nanospheres (6) and formed;
    A diameter of 50nm~the 80nm of the polystyrene nanospheres (6), individual layer is close to arrangement;
    The metallic film (7) is covered on polystyrene nanospheres (6), is 10nm~80nm apart from nanosphere top thickness h, Material is gold or silver or aluminium;
    Silica membrane (3) thickness is between 10nm and 0.25 times of incident wavelength.
  2. 2. Biosensors Based on Surface Plasmon Resonance device according to claim 1, it is characterised in that:Described prism (1) It is more than the material of silica membrane (3) for refractive index, and is low-loss relative to incident light, is dense flint glass or seleno oxygen Sulphur glass or silicon.
  3. 3. Biosensors Based on Surface Plasmon Resonance device according to claim 1, it is characterised in that:The graphene (4) The number of plies is 1~8 layer.
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