CN104568894A - Surface enhanced raman scattering substrate and manufacturing method thereof - Google Patents
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Abstract
Description
技术领域technical field
本发明涉及表面增强拉曼散射芯片技术领域，尤其涉及一种表面增强拉曼散射衬底及其制备方法。The invention relates to the technical field of surface-enhanced Raman scattering chips, in particular to a surface-enhanced Raman scattering substrate and a preparation method thereof.
背景技术Background technique
上世纪70年代，人们发现在银电极粗糙化表面吸附的几个分子层的吡啶的拉曼散射信号是正常拉曼光谱的105～106倍，并将这一现象命名为表面增强拉曼散射(SurfaceEnhancedRamanScattering)，简称SERS。由于SERS具有很高的表面灵敏度，因而在化学检测和生物分析中有着广发的应用。In the 1970s, it was found that the Raman scattering signal of several molecular layers of pyridine adsorbed on the roughened surface of the silver electrode was 10 5 to 10 6 times that of the normal Raman spectrum, and this phenomenon was named surface-enhanced Raman Scattering (SurfaceEnhancedRamanScattering), referred to as SERS. Due to the high surface sensitivity of SERS, it has been widely used in chemical detection and biological analysis.
但是拉曼散射的辐射强度与受到照射的分子数目成正比，而通常情况下入射光中只有极少数的光子会发生拉曼散射，因而使得散射信号非常微弱以至于难以检测和识别目标分子。为了能够增强信号达到正常检测的需要，人们通过各种方法制备规则排列的纳米银阵列结构。比如气相沉积法、电化学沉积法、光刻法、化学合成法、纳米阵列自组装、STM辅助纳米结构形成法、纳米球印刷法等等。但是由于衬底表面性质、加工工艺难度、加工环境条件和生产成本等限制因素，还很难获得精确控制纳米结构形态、尺寸、阵列化程度的SERS表面衬底。However, the radiation intensity of Raman scattering is proportional to the number of irradiated molecules, and usually only a very small number of photons in the incident light will undergo Raman scattering, which makes the scattering signal very weak and makes it difficult to detect and identify target molecules. In order to enhance the signal to meet the needs of normal detection, people have prepared regularly arranged nano-silver array structures by various methods. For example, vapor deposition, electrochemical deposition, photolithography, chemical synthesis, nanoarray self-assembly, STM-assisted nanostructure formation, nanosphere printing, etc. However, due to limiting factors such as substrate surface properties, processing difficulty, processing environmental conditions, and production costs, it is still difficult to obtain SERS surface substrates with precisely controlled nanostructure morphology, size, and arraying degree.
因此探究一种制备工艺简单方便，生产加工成本低廉，而且能够准确灵活地控制SERS衬底表面纳米阵列的方法具有十分重要的意义。Therefore, it is of great significance to explore a method that has a simple and convenient preparation process, low production and processing costs, and can accurately and flexibly control the nanoarrays on the surface of the SERS substrate.
发明内容Contents of the invention
针对上述提到的现有技术的不足，本发明提出了一种表面增强拉曼散射衬底及其制备方法，该衬底结构稳定，表面活性高；其制备方法工艺简单，降低了制作成本，容易控制纳米阵列结构的形态和位置，重复率高。Aiming at the deficiencies of the prior art mentioned above, the present invention proposes a surface-enhanced Raman scattering substrate and a preparation method thereof. The substrate has a stable structure and high surface activity; the preparation method has simple processes and reduces production costs. It is easy to control the shape and position of the nano-array structure, and the repetition rate is high.
为了实现上述目的，本发明采用了如下的技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种表面增强拉曼散射衬底，包括基底以及基底上的金属纳米单元阵列，其中，所述金属纳米单元是通过胶粘剂固定粘接金属粉末颗粒形成的，所述胶粘剂为无机胶粘剂或有机胶粘剂，所述金属纳米单元的高度为400～800nm，所述金属纳米单元的间距为1～2μm。A surface-enhanced Raman scattering substrate, comprising a substrate and a metal nanounit array on the substrate, wherein the metal nanounit is formed by fixing and bonding metal powder particles with an adhesive, and the adhesive is an inorganic adhesive or an organic adhesive, The height of the metal nano-units is 400-800 nm, and the distance between the metal nano-units is 1-2 μm.
优选地，以质量百分比计算，所述有机胶粘剂中含有60～75%的甲基丙烯酸酯，15～25%的乙烯和丙烯混合物，8.5～17.5%的环氧乙烷，0.5～1.0%的过氧化物引发剂，0.2～0.5%乙酰丙酮铜。Preferably, calculated by mass percentage, the organic adhesive contains 60-75% of methacrylate, 15-25% of ethylene and propylene mixture, 8.5-17.5% of ethylene oxide, 0.5-1.0% of Oxide initiator, 0.2-0.5% copper acetylacetonate.
优选地，以质量百分比计算，所述无机胶粘剂中含有3～4%氯化钠，5～6%的碳酸钠，2～3%的碳酸氢钠，6～9%的硅酸，20～30%的木糖醇，48～64%的水。Preferably, calculated by mass percentage, the inorganic adhesive contains 3-4% sodium chloride, 5-6% sodium carbonate, 2-3% sodium bicarbonate, 6-9% silicic acid, 20-30 % xylitol, 48-64% water.
优选地，所述金属粉末颗粒为Au、Ag和Cu粉末颗粒中的任意一种。Preferably, the metal powder particles are any one of Au, Ag and Cu powder particles.
优选地，所述金属粉末颗粒的粒径是1nm～10nm。Preferably, the particle size of the metal powder particles is 1 nm˜10 nm.
优选地，所述基底包括硅、金属板、塑料板或玻璃。Preferably, the substrate comprises silicon, a metal plate, a plastic plate or glass.
优选地，所述金属纳米单元为金属纳米柱结构。Preferably, the metal nano-unit is a metal nano-column structure.
如上所述的表面增强拉曼散射衬底的制备方法，包括步骤：The preparation method of the surface-enhanced Raman scattering substrate as described above comprises the steps of:
（a）在所述基底上敷设一层金属粉末颗粒层，并将所述基底放置于3D打印设备的工作台上；所述金属粉末颗粒层的厚度为200～600nm；(a) laying a layer of metal powder particles on the substrate, and placing the substrate on the workbench of a 3D printing device; the thickness of the metal powder particle layer is 200-600nm;
（b）在3D打印设备的控制系统上设定金属纳米单元阵列化图案；(b) Set the metal nano unit array pattern on the control system of the 3D printing device;
（c）按照设定的阵列化图案，通过3D打印设备的喷头将所述无机胶粘剂或有机胶粘剂滴加在金属粉末颗粒层上，粘接固定对应位置的金属粉末颗粒；(c) According to the set array pattern, the inorganic adhesive or organic adhesive is dripped on the metal powder particle layer through the nozzle of the 3D printing equipment, and the metal powder particles at the corresponding positions are bonded and fixed;
（d）去除未粘接固定的金属粉末颗粒，在基底上形成金属纳米单元阵列结构；(d) removing unbonded and fixed metal powder particles to form a metal nano-unit array structure on the substrate;
（e）将步骤（d）得到的金属纳米单元阵列进行烧结处理，获得所述的表面增强拉曼散射衬底。(e) Sintering the metal nano unit array obtained in step (d) to obtain the surface-enhanced Raman scattering substrate.
优选地，该方法还包括步骤：将烧结处理的表面增强拉曼散射衬底进行退火处理，退火处理的温度为200～300℃，时间为20～40分钟。Preferably, the method further includes the step of annealing the sintered surface-enhanced Raman scattering substrate at a temperature of 200-300° C. for 20-40 minutes.
优选地，所述烧结处理采用激光烧结，激光功率200～300瓦，烧结的温度为700～1000℃，时间为20～60秒。Preferably, the sintering treatment adopts laser sintering, the laser power is 200-300 watts, the sintering temperature is 700-1000° C., and the time is 20-60 seconds.
优选地，所述烧结处理采用烧结炉高温烧结，烧结的温度为50～500℃，时间为60～100分钟。Preferably, the sintering process adopts high-temperature sintering in a sintering furnace, the sintering temperature is 50-500° C., and the sintering time is 60-100 minutes.
有益效果：Beneficial effect:
本发明通过3D打印设备使用胶粘剂将金属粉末颗粒粘接，在基底上形成金属纳米单元阵列结构，再通过烧结和退火工艺得到表面增强拉曼散射衬底，该衬底结构稳定，表面活性高。与气相沉积法、纳米结构组装、纳米球印刷等方法相比，本发明的方法对衬底表面性质要求低，容易控制纳米阵列结构的形态和位置；与刻蚀方法相比，本发明的方法不需要繁重且昂贵的平版印刷图案化掩膜和蚀刻终止层，能够显著降低生产成本；与电化学沉积和化学合成等方法相比，本发明获得的衬底尺寸大，工艺条件控制方便，节省原料和能源。In the present invention, a 3D printing device is used to bond metal powder particles with an adhesive to form a metal nano-unit array structure on a substrate, and then a surface-enhanced Raman scattering substrate is obtained through sintering and annealing processes, and the substrate has a stable structure and high surface activity. Compared with methods such as vapor deposition, nanostructure assembly, and nanosphere printing, the method of the present invention has lower requirements on the properties of the substrate surface, and is easy to control the shape and position of the nanoarray structure; compared with the etching method, the method of the present invention There is no need for heavy and expensive lithographic patterned masks and etching stop layers, which can significantly reduce production costs; compared with methods such as electrochemical deposition and chemical synthesis, the size of the substrate obtained by the present invention is large, and the control of process conditions is convenient, saving Raw materials and energy.
附图说明Description of drawings
图1为本发明一实施例中提供的表面增强拉曼散射衬底的主视图。Fig. 1 is a front view of a surface-enhanced Raman scattering substrate provided in an embodiment of the present invention.
图2为本发明一实施例中提供的表面增强拉曼散射衬底的俯视图；其中图2a所示为金属纳米单元的横截面为圆形，图2b所示为金属纳米单元的横截面为方形。Figure 2 is a top view of the surface-enhanced Raman scattering substrate provided in an embodiment of the present invention; wherein Figure 2a shows that the cross-section of the metal nano-unit is circular, and Figure 2b shows that the cross-section of the metal nano-unit is square .
图3为本发明一实施例中制备表面增强拉曼散射衬底的示意图。Fig. 3 is a schematic diagram of preparing a surface-enhanced Raman scattering substrate in an embodiment of the present invention.
具体实施方式Detailed ways
下面将结合附图用实施例对本发明做进一步说明。The present invention will be further described below with reference to the accompanying drawings.
如前所述，鉴于现有技术存在的不足，本发明提出了一种表面增强拉曼散射衬底，如图1所示，该衬底包括基底1以及基底1上的金属纳米单元2阵列，其中，所述金属纳米单元2是通过胶粘剂22固定粘接金属粉末颗粒21形成的，所述胶粘剂21为无机胶粘剂或有机胶粘剂，所述金属纳米单元2的高度为400～800nm，所述金属纳米单元的间距为1～3μm。如图2a和2b所示，在纳米单元阵列中，所述金属纳米单元2的形状可以为圆柱形或者是方状条形，当然，所述金属纳米单元2的形状也可以是其他不规则的形状。该衬底结构稳定，表面活性高。As mentioned above, in view of the deficiencies in the prior art, the present invention proposes a surface-enhanced Raman scattering substrate, as shown in Figure 1, the substrate includes a substrate 1 and an array of metal nano-units 2 on the substrate 1, Wherein, the metal nano unit 2 is formed by fixing and bonding metal powder particles 21 with an adhesive 22, the adhesive 21 is an inorganic adhesive or an organic adhesive, the height of the metal nano unit 2 is 400-800 nm, and the metal nano unit The pitch of the cells is 1 to 3 μm. As shown in Figures 2a and 2b, in the nano-unit array, the shape of the metal nano-unit 2 can be cylindrical or square, and of course, the shape of the metal nano-unit 2 can also be other irregular shape. The substrate has a stable structure and high surface activity.
如上所述的表面增强拉曼散射衬底的制备方法，参阅图3，首先在所述基底1上敷设一层金属粉末颗粒层4，并将所述基底1放置于3D打印设备3的工作台上；所述金属粉末颗粒层4的厚度为200～600nm；然后在3D打印设备3的控制系统上设定金属纳米单元阵列化图案，并按照设定的阵列化图案，通过3D打印设备3的喷头将胶粘剂22滴加在金属粉末颗粒层4上，粘接固定对应位置的金属粉末颗粒21；去除未粘接固定的金属粉末颗粒，在基底1上形成金属纳米单元阵列2的结构；最后将得到的金属纳米单元阵列进行烧结处理，获得所述的表面增强拉曼散射衬底。该制备方法采用3D打印技术，其工艺简单，降低了制作成本，容易控制纳米阵列结构的形态和位置，重复率高。The preparation method of the surface-enhanced Raman scattering substrate as described above, referring to FIG. 3 , first lays a layer of metal powder particle layer 4 on the substrate 1, and places the substrate 1 on the workbench of the 3D printing device 3 Above; the thickness of the metal powder particle layer 4 is 200-600nm; then set the metal nano unit array pattern on the control system of the 3D printing device 3, and according to the set array pattern, through the 3D printing device 3 The nozzle drips the adhesive 22 on the metal powder particle layer 4, and bonds and fixes the metal powder particles 21 at the corresponding positions; removes the unbonded and fixed metal powder particles, and forms the structure of the metal nano-unit array 2 on the substrate 1; The obtained metal nano unit array is sintered to obtain the surface-enhanced Raman scattering substrate. The preparation method adopts 3D printing technology, the process is simple, the production cost is reduced, the shape and position of the nano-array structure can be easily controlled, and the repetition rate is high.
实施例1Example 1
本实施例使用德国Voxeljet公司的VX500型3D打印机作为加工设备。在3D打印机控制系统的计算机上设计SERS衬底表面的金属纳米单元阵列化图案。将基片放入3D打印机工作台，在基底上敷设粒子粒径为1nm的Au粉末层，Au粉末层的厚度为400nm；按照设定的阵列化图案，通过3D打印机喷头在预设图案上方向Au粉末层滴加Voxeljet公司配套的胶粘剂，并使用3D打印机所带的激光设备对胶粘剂粘附的Au粉末颗粒进行烧结，激光功率为200W，烧结的温度为1000℃，时间为60秒；烧结完毕后，用N2气体吹除未粘接固定的Au粉末颗粒，在基底上形成Au纳米单元阵列的结构，其中Au纳米单元的间距为1μm。将上述得到的Au纳米单元阵列放入300℃的高温炉中退火20min，即制得本发明所述的表面增强拉曼散射衬底。In this embodiment, the VX500 3D printer of German Voxeljet Company is used as the processing equipment. The metal nanounit array pattern on the surface of the SERS substrate is designed on the computer of the 3D printer control system. Put the substrate into the 3D printer workbench, lay a layer of Au powder with a particle size of 1nm on the substrate, and the thickness of the Au powder layer is 400nm; according to the set array pattern, the nozzle of the 3D printer is directed on the preset pattern. Add the matching adhesive of Voxeljet to the Au powder layer, and use the laser equipment attached to the 3D printer to sinter the Au powder particles adhered to the adhesive. The laser power is 200W, the sintering temperature is 1000°C, and the time is 60 seconds; the sintering is completed Finally, the unbonded and fixed Au powder particles were blown off with N 2 gas, and a structure of an Au nanounit array was formed on the substrate, wherein the pitch of the Au nanounits was 1 μm. Put the Au nano unit array obtained above into a high-temperature furnace at 300° C. for 20 minutes and anneal for 20 minutes to obtain the surface-enhanced Raman scattering substrate of the present invention.
实施例2Example 2
本实施例使用美国Stratasys公司的Objet350Connex型3D打印机作为加工设备。在3D打印机控制系统的计算机上设计SERS衬底表面的金属纳米单元阵列化图案。将基片放入3D打印机工作台，在基底上敷设粒子粒径为5nm的Ag粉末层，Ag粉末层的厚度为500nm；按照设定的阵列化图案，通过3D打印机喷头在预设图案上方向Ag粉末层滴加有机胶粘剂。其中，以质量百分比计算，所述有机胶粘剂含有65%的甲基丙烯酸酯，22%的乙烯和丙烯混合物，12%的环氧乙烷，0.8%的过氧化物引发剂，0.2%乙酰丙酮铜；并使用该打印机的UV装置使胶粘剂迅速固化，然后用N2气体吹除未粘接固定的Ag粉末颗粒，在基底上形成Ag纳米单元阵列的结构，其中Ag纳米单元的间距为2μm。将上述得到的Ag纳米单元阵列放入500℃的高温炉中烧结60min，即制得本发明所述的表面增强拉曼散射衬底。This embodiment uses the Objet350Connex type 3D printer of Stratasys Company of the United States as the processing equipment. The metal nanounit array pattern on the surface of the SERS substrate is designed on the computer of the 3D printer control system. Put the substrate into the 3D printer workbench, lay an Ag powder layer with a particle size of 5nm on the substrate, and the thickness of the Ag powder layer is 500nm; according to the set array pattern, the nozzle of the 3D printer is directed on the preset pattern. The Ag powder layer is dripped with an organic adhesive. Wherein, calculated by mass percentage, the organic adhesive contains 65% methacrylate, 22% ethylene and propylene mixture, 12% ethylene oxide, 0.8% peroxide initiator, 0.2% copper acetylacetonate and use the UV device of the printer to quickly cure the adhesive, and then use N2 gas to blow off the unbonded and fixed Ag powder particles to form a structure of Ag nanounit arrays on the substrate, wherein the spacing of Ag nanounits is 2 μm. Put the Ag nano unit array obtained above into a high-temperature furnace at 500° C. for sintering for 60 minutes to obtain the surface-enhanced Raman scattering substrate of the present invention.
需要说明的是，以上实施例中给出的有机胶粘剂中各个组分的具体数值，仅仅是作为例子进行说明。在本发明中，所述有机胶粘剂中各个组分的含量，以质量百分比计算，甲基丙烯酸酯可以选择的范围是60～75%，乙烯和丙烯混合物可以选择的范围是15～25%，环氧乙烷可以选择的范围是8.5～17.5%，过氧化物引发剂可以选择的范围是0.5～1.0%，乙酰丙酮铜可以选择的范围是0.2～0.5%。It should be noted that the specific numerical values of each component in the organic adhesive given in the above examples are only used as examples for illustration. In the present invention, the content of each component in the organic adhesive is calculated by mass percentage, the selectable range of methacrylate is 60-75%, the selectable range of ethylene and propylene mixture is 15-25%, and the cyclic The selectable range of oxyethane is 8.5-17.5%, the selectable range of peroxide initiator is 0.5-1.0%, and the selectable range of copper acetylacetonate is 0.2-0.5%.
实施例3Example 3
本实施例使用美国Stratasys公司的Objet350Connex型3D打印机作为加工设备。在3D打印机控制系统的计算机上设计SERS衬底表面的金属纳米单元阵列化图案。将基片放入3D打印机工作台，在基底上敷设粒子粒径为10nm的Cu粉末层，Cu粉末层的厚度为800nm；按照设定的阵列化图案，通过3D打印机喷头在预设图案上方向Cu粉末层滴加无机胶粘剂。其中，以质量百分比计算，所述无机胶粘剂含有4%氯化钠，6%的碳酸钠，3%的碳酸氢钠，7%的硅酸，25%的木糖醇，55%的水；并使用该打印机的UV装置使胶粘剂迅速固化，然后用N2气体吹除未粘接固定的Cu粉末颗粒，在基底上形成Cu纳米单元阵列的结构,其中Cu纳米单元的间距为2μm。将上述得到的Cu纳米单元阵列衬底放入500℃的高温炉中烧结、退火50min，即制得本发明所述的表面增强拉曼散射衬底。This embodiment uses the Objet350Connex type 3D printer of Stratasys Company of the United States as the processing equipment. The metal nanounit array pattern on the surface of the SERS substrate is designed on the computer of the 3D printer control system. Put the substrate into the 3D printer workbench, and lay a Cu powder layer with a particle size of 10nm on the substrate. The Cu powder layer is dripped with an inorganic adhesive. Wherein, in terms of mass percentage, the inorganic adhesive contains 4% sodium chloride, 6% sodium carbonate, 3% sodium bicarbonate, 7% silicic acid, 25% xylitol, and 55% water; and The UV device of the printer was used to quickly cure the adhesive, and then the unbonded and fixed Cu powder particles were blown off with N2 gas to form a Cu nanounit array structure on the substrate, where the Cu nanounit spacing was 2 μm. Put the above-obtained Cu nano unit array substrate into a high temperature furnace at 500° C. for sintering and annealing for 50 minutes to obtain the surface-enhanced Raman scattering substrate of the present invention.
需要说明的是，以上实施例中给出的无机胶粘剂中各个组分的具体数值，仅仅是作为例子进行说明。在本发明中，所述无机胶粘剂中各个组分的含量，以质量百分比计算，氯化钠可以选择的范围是3～4%，碳酸钠可以选择的范围是5～6%，碳酸氢钠可以选择的范围是2～3%，硅酸可以选择的范围是6～9%，木糖醇可以选择的范围是20～30%，水可以选择的范围是48～64%。It should be noted that the specific numerical values of each component in the inorganic adhesive given in the above examples are only used as examples for illustration. In the present invention, the content of each component in the inorganic adhesive is calculated by mass percentage. The range that can be selected for sodium chloride is 3-4%, the range that can be selected for sodium carbonate is 5-6%, and the range for sodium bicarbonate can be The selected range is 2-3%, the optional range of silicic acid is 6-9%, the optional range of xylitol is 20-30%, and the optional range of water is 48-64%.
以上实施例中退火处理和烧结处理给出的具体参数只是作为具体的例子进行说明，可根据不同的材料设计不同的烧结和退火温度。The specific parameters given in the annealing treatment and sintering treatment in the above embodiments are only described as specific examples, and different sintering and annealing temperatures can be designed according to different materials.
综上所述，本发明通过3D打印设备使用胶粘剂将金属粉末颗粒粘接，在基底上形成金属纳米单元阵列结构，再通过烧结和退火工艺得到表面增强拉曼散射衬底，该衬底结构稳定，表面活性高。与气相沉积法、纳米结构组装、纳米球印刷等方法相比，本发明的方法对衬底表面性质要求低，容易控制纳米阵列结构的形态和位置；与刻蚀方法相比，本发明的方法不需要繁重且昂贵的平版印刷图案化掩膜和蚀刻终止层，能够显著降低生产成本；与电化学沉积和化学合成等方法相比，本发明获得的衬底尺寸大，工艺条件控制方便，节省原料和能源。In summary, the present invention uses adhesives to bond metal powder particles through 3D printing equipment to form a metal nano-unit array structure on the substrate, and then obtains a surface-enhanced Raman scattering substrate through sintering and annealing processes, and the substrate has a stable structure , high surface activity. Compared with methods such as vapor deposition, nanostructure assembly, and nanosphere printing, the method of the present invention has lower requirements on the properties of the substrate surface, and is easy to control the shape and position of the nanoarray structure; compared with the etching method, the method of the present invention There is no need for heavy and expensive lithographic patterned masks and etching stop layers, which can significantly reduce production costs; compared with methods such as electrochemical deposition and chemical synthesis, the size of the substrate obtained by the present invention is large, and the control of process conditions is convenient, saving Raw materials and energy.
需要说明的是，在本文中，诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply that there is a relationship between these entities or operations. There is no such actual relationship or order between them. Furthermore, the term "comprises", "comprises" or any other variation thereof is intended to cover a non-exclusive inclusion such that a process, method, article, or apparatus comprising a set of elements includes not only those elements, but also includes elements not expressly listed. other elements of or also include elements inherent in such a process, method, article, or device. Without further limitations, an element defined by the phrase "comprising a ..." does not exclude the presence of additional identical elements in the process, method, article or apparatus comprising said element.
以上所述仅是本申请的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本申请的保护范围。The above description is only the specific implementation of the present application. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present application, some improvements and modifications can also be made. It should be regarded as the protection scope of this application.
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