WO2016015599A1 - 一种大面积表面增强拉曼光谱单晶硅基底的快速制备方法 - Google Patents

一种大面积表面增强拉曼光谱单晶硅基底的快速制备方法 Download PDF

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WO2016015599A1
WO2016015599A1 PCT/CN2015/084989 CN2015084989W WO2016015599A1 WO 2016015599 A1 WO2016015599 A1 WO 2016015599A1 CN 2015084989 W CN2015084989 W CN 2015084989W WO 2016015599 A1 WO2016015599 A1 WO 2016015599A1
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crystal silicon
single crystal
substrate
laser
array
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French (fr)
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季凌飞
林真源
蒋毅坚
吴燕
吕晓占
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北京工业大学
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Priority claimed from CN201410361090.7A external-priority patent/CN104195644B/zh
Priority claimed from CN201510406413.4A external-priority patent/CN104949959A/zh
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon

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  • the invention belongs to the field of surface Raman enhanced spectral substrate preparation.
  • SERS Surface Raman Enhanced Spectroscopy
  • FIB ion beam etching
  • electron beam etching the morphology and size of the micro/nano structure can be precisely controlled, and the repeatability is good.
  • these methods also have the disadvantages of high preparation cost, high environmental requirements, and low preparation efficiency.
  • the Fangfengzhou team of Tianjin University used the FIB method to obtain an elliptical array with a minimum spacing of 15 nm on the silicon surface, and plated a 10-70 nm gold particle film on the surface to obtain a better SERS effect.
  • the maximum preparation area was 9.6 ⁇ m ⁇ 9.6 ⁇ m ("High Performance Surface-enhanced Raman Scattering Substrate of Si-based Au Film Developed by Focused Ion Beam Nanofabrication". Nanoscale research letters. 20127. Tingting Gao, et al).
  • Taiwan's Hai Pang Chiang team used a self-assembly effect to obtain dense arrays of microspheres by dropping polystyrene beads on a glass substrate. These microsphere arrays showed better deposition after deposition of silver particle films.
  • SERS effect Size Dependence of Nanoparticle-SERS Enhancement from Silver Film over Nanosphere (AgFON) Substrate. Plasmonics (2011) 6:201–206. Wenchi Lin et al.).
  • the Zhida Xu team at the University of Illinois in the United States prepared a polymer matrix with a positive pyramid and an inverted pyramid array using a silicon template of the inverted pyramid, and deposited a 200 nm gold particle film on it to obtain a SERS substrate with different enhancement effects.
  • the laser has the characteristics of high energy, easy operation, good controllability, and non-contact radiation heating, which is not easy to introduce pollution.
  • the laser irradiated single crystal silicon can modify its surface and form a microstructure.
  • the invention provides a rapid preparation method of a large-area surface-enhanced Raman spectroscopy single crystal silicon substrate. First, a microstructure array is prepared on a surface of a single crystal silicon, and the single crystal silicon substrate having a microstructure array is subjected to magnetron sputtering. After depositing silver nanofilm on the surface, it shows a good SERS effect. The regulation of the SERS effect of the substrate can be achieved by adjusting the size characteristics of the microstructure and the thickness of the silver film.
  • a method for rapidly preparing a large-area surface-enhanced Raman spectroscopy single crystal silicon substrate comprising the steps of:
  • the 2) treated single crystal silicon sample is ultrasonically cleaned to remove the microspheres, immersed in an aqueous solution of sodium hydroxide containing ethanol, and etched for 10-30 s in a water bath temperature of 70-80 ° C. Rinsing with deionized water to obtain a single crystal silicon wafer having a microstructured array; in the aqueous solution, the mass percentage of sodium hydroxide is 5%-10%, and the mass percentage of ethanol is 8%-10%;
  • the single crystal silicon substrate treated by 3) is subjected to magnetron sputtering deposition of a silver film, the magnetron sputtering time is 5-15 min, and the silver plating film thickness is 50-200 nm.
  • the ultra-short pulse of ultraviolet wavelength with pulse width ⁇ 10 -11 s is scanned with positive defocusing single line.
  • the scanning interval is laser spot size, the repetition frequency is 200-400 kHz, and the scanning speed is 800-1200 mm. /s, power density is 5-25W/mm 2 .
  • the laser When the laser is irradiated, the 1) treated single crystal silicon sample is placed on the target stage, the optical path is adjusted, and the uniform beam spot is adapted to the sample size for single pulse irradiation, and the laser has a wavelength of 248 nm.
  • Molecular laser using a pulse energy density of 100 mJ/cm 2 to 400 mJ/cm 2 and a frequency of 1-3 Hz.
  • the SERS effect of the substrate is regulated by changing the size or morphology of the microstructure array.
  • the SERS effect of the substrate is enhanced; when the size of the microstructure array is increased, the substrate SERS is increased. The effect is enhanced.
  • the SERS effect of the substrate is controlled by changing the thickness of the silver film.
  • the thickness of the silver film is between 50 and 160 nm, the SERS effect of the substrate increases as the film thickness increases, and the thickness of the silver film is 160.
  • the SERS effect of the substrate decreases as the film thickness increases.
  • the laser irradiation microsphere processing can accurately position the position of the microstructure formation, and the size of the microsphere can be precisely controlled to accurately control the density of the microstructure array, and ensure good periodicity and Uniformity.
  • the Raman enhancement effect can be adjusted by adjusting the surface microstructure size characteristics and the thickness of the silver film, and has high controllability.
  • the prepared single crystal silicon SERS substrate having a microstructure array has good stability and can be reused.
  • the ultraviolet ultrashort pulse laser adopts a small laser power, has a simple process, and can realize large-area processing; the alkali etching time is 10-30s, and the magnetron sputtering time is 5-15min.
  • the overall preparation cycle is short; at the same time, the equipment cost is low, the structure reproducibility is high, and the raw materials used are low. Has a high practicality.
  • Example 1 is a microstructure array diagram prepared in Example 1;
  • Example 2 is a microstructured array diagram prepared in Example 2;
  • Example 3 is a microstructure array diagram prepared in Example 3.
  • Figure 4 is a Raman spectrum of a sample prepared with different parameters.
  • the cleaning of the following examples is specifically: ultrasonic cleaning of single crystal silicon in acetone solution for 6-10 minutes; immersion in HF solution of 5%-20% mass fraction for 6-10 minutes; ultrasonic cleaning by immersion in ethanol solution for 6-10 minutes, washing , dry; but not limited to this cleaning method.
  • a single layer of hexagonal close-packed SiO 2 microspheres was arranged on the surface of the cleaned single crystal silicon wafer by direct drop coating, and the size of the microspheres used was 1.5 ⁇ m; the single crystal silicon sample was placed on the target table and adjusted.
  • Optical path using ultra-short pulse (10ps) laser with ultraviolet wavelength for positive defocus single-line scanning, scanning interval is laser spot size, repetition frequency is 400kHz, scanning speed is 1200mm/s, power density is 5W/mm 2 ;
  • the cleaned single crystal silicon sample is immersed in an aqueous solution of sodium hydroxide containing ethanol, etched for 10 s in a water bath temperature of 75 ° C, and taken out and rinsed with deionized water to obtain a monocrystalline silicon wafer having a microstructured array.
  • the mass percentage of sodium hydroxide is 10%, and the mass percentage of ethanol is 8%.
  • the silver nano-film deposition on the surface of the single crystal silicon wafer with microstructured array on the surface is performed by magnetron sputtering, and the deposition time is 8 min.
  • the film thickness was 100 nm.
  • the prepared structure has a pore-like shape and has good periodicity and uniformity.
  • a single layer of hexagonal close-packed SiO 2 microspheres was arranged on the surface of the cleaned single crystal silicon wafer by direct drop coating, and the size of the microspheres used was 1 ⁇ m; the single crystal silicon sample was placed on the target table to adjust the optical path.
  • the ultra-short pulse (10ps) laser with ultraviolet wavelength is used for positive defocus single-line scanning.
  • the scanning interval is laser spot size, the repetition frequency is 200kHz, the scanning speed is 1000mm/s, and the power density is 20W/mm 2 ;
  • the sample of single crystal silicon is immersed in an aqueous solution of sodium hydroxide containing ethanol, etched in an environment of a bath temperature of 75 ° C for 30 s, and taken out and rinsed with deionized water to obtain a monocrystalline silicon wafer having a microstructured array.
  • the mass percentage of sodium hydroxide is 10%
  • the mass percentage of ethanol is 10%
  • silver thin film deposition is performed on the single crystal silicon wafer having a microstructure array on the surface by magnetron sputtering, and the deposition time is 12 min, and the film is obtained.
  • the thickness is 160 nm.
  • the prepared structure is a mound structure with good periodicity and uniformity.
  • a single layer of hexagonal close-packed SiO 2 microspheres was arranged on the surface of the cleaned single crystal silicon wafer by direct drop coating, and the size of the microspheres used was 0.5 ⁇ m; the single crystal silicon sample was placed on the target table and adjusted.
  • Optical path using ultra-short pulse (10ps) laser with ultraviolet wavelength for positive defocus single-line scanning, scanning interval is laser spot size, repetition frequency is 200kHz, scanning speed is 1200mm/s, power density is 25W/mm 2 ;
  • the cleaned single crystal silicon sample is immersed in an aqueous solution of sodium hydroxide containing ethanol, etched for 30 s in a water bath temperature of 70 ° C, and taken out and rinsed with deionized water to obtain a monocrystalline silicon wafer having a microstructured array.
  • the mass percentage of sodium hydroxide is 10%, and the mass percentage of ethanol is 10%; silver nano-film deposition on a single crystal silicon wafer having a microstructured array on the surface by magnetron sputtering is performed, and the deposition time is 12 min.
  • the film thickness is 160 nm;
  • the prepared structure is a cluster structure with good periodicity and uniformity.

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Abstract

一种大面积表面增强拉曼光谱单晶硅基底的快速制备方法，属于SERS衬底制备领域。本发明在单晶硅表面覆盖周期密排的微球阵列；采用激光扫描或辐照后去除表面残留的微球；然后浸入含有乙醇的氢氧化钠水溶液中，水浴温度70-80℃环境中，腐蚀10-30s，取出使用去离子水清洗，得到具有微结构阵列的单晶硅片，水溶液中，氢氧化钠的质量百分比为5％-10％，乙醇的质量百分比为8％-10％；利用磁控溅射在刻蚀后的单晶硅表面进行银薄膜沉积，沉积厚度为50-200nm。本发明能够快速、简便的制备具有周期性及均一性的微结构阵列，通过对微结构阵列形貌尺寸特征及银膜厚度的控制，可以对SERS衬底的性能进行调控。同时，该方法重现性高，成本较低，所制备出的SERS衬底性能稳定，可重复利用。

Description

一种大面积表面增强拉曼光谱单晶硅基底的快速制备方法 技术领域
本发明属于表面拉曼增强光谱衬底制备领域。
背景技术
表面拉曼增强光谱(SERS)自被发现以来，已经作为一种强大的检测分析工具得到了广泛的关注。相较于普通的拉曼信号，理论上，当待测的靶分子位于金属纳米颗粒的间隙之间时，其SERS信号的增强因子可以达到1014倍。这种增强可以使原本微弱的拉曼信号变得可探测，甚至在单分子水平也能得到清晰的拉曼指纹谱。而拉曼散射本身所具有的强抗干扰能力，结合SERS技术使得其能在各式各样复杂的环境中得以应用。SERS衬底的制备通常是通过化学合成或者自组装效应在固体衬底上沉积金属纳米颗粒，这种方法可以获得较强的增强因子。然而，其均匀性及金属颗粒的稳定性限制了其在大面积探测的应用扩展。因此，人们提出在SERS衬底上制备微纳结构以提高其均匀性及稳定性。通过聚焦离子束刻蚀(FIB)或者电子束刻蚀的方法，可以精确控制微纳结构的形貌及尺寸，并且具有较好的重复性。同时，这些方法也存在制备费用和环境要求较高，制备效率较低等缺点。天津大学的房丰洲小组利用FIB的方法在硅表面获得最小间距为15nm的椭圆阵列，并在其表面镀上10-70nm的金颗粒薄膜，获得了较好的SERS效果。同时，其最大制备面积为9.6μm×9.6μm(“High Performance Surface-enhanced Raman Scattering Substrate of Si-based Au Film Developed by Focused Ion Beam Nanofabrication”.Nanoscale research letters.20127.Tingting Gao,et al)。
近年来，人们致力于探索能够更低成本并且更高效的制备SERS衬底的方法。台湾的Hai Pang Chiang小组通过在玻璃衬底上滴涂聚苯乙烯小球，利用其自组装效应获得密排的微球阵列，这些微球阵列在沉积了银颗粒薄膜后，表现出了较好的SERS效应(“Size Dependence of Nanoparticle-SERS Enhancement from Silver Film over Nanosphere(AgFON)Substrate”. Plasmonics(2011)6:201–206.Wenchi Lin et al.)。美国伊利诺大学的Zhida Xu小组利用倒金字塔的硅模板制备了具有正金字塔及倒金字塔阵列的高分子聚合物基底，同时在上面沉积了200nm的金颗粒薄膜，从而获得不同增强效果的SERS衬底(“Nanoreplicated positive and inverted submicrometer polymer pyramid array for surface-enhanced Raman spectroscopy”.Journal of Nanophotonics Vol.5,2011.Xu et al.)。
因此，提高SERS衬底的均匀性及稳定性，同时保证高效性和低成本性，是现今SERS衬底制备所面临的问题。
激光具有能量高、易操作、可控性好、以及非接触辐照加热不易引入污染等特点，激光辐照单晶硅可以对其表面进行改性并形成微结构。本发明提出一种大面积表面增强拉曼光谱单晶硅基底的快速制备方法，首先在单晶硅表面进行微结构阵列制备，该具有微结构阵列的单晶硅衬底在进行磁控溅射表面沉积银纳米薄膜后，表现出较好的SERS效应。通过对微结构形貌尺寸特征及银膜厚度的调节，可以实现对衬底的SERS效应的调控。
发明内容
本发明的目的在于提供一种大面积表面增强拉曼光谱单晶硅基底的快速制备方法。
本发明的目的是通过以下技术方案实现的：
1、一种大面积表面增强拉曼光谱单晶硅基底的快速制备方法，其特征在于，包括以下步骤：
1)采用直接滴涂法在清洗过的单晶硅片样品表面上排布单层六角密排分布的SiO2微球阵列；
2)将经1)处理过的单晶硅样品放置于靶台上，调整光路，采用紫外波长的超短脉冲激光器进行辐照或扫描；
3)将经2)处理过的单晶硅样品进行超声清洗去除微球，浸入含有乙醇的氢氧化钠水溶液中，在水浴温度为70-80℃的环境中，腐蚀10-30s，腐蚀后取出使用去离子水冲洗，得到具有微结构阵列的单晶硅片；所述的水溶液中，氢氧化钠的质量百分比为5％-10％，乙醇的质量百分比为8％-10％；
4)将经3)处理的单晶硅衬底进行磁控溅射沉积银膜，磁控溅射时间为5-15min，所镀银膜厚为50-200nm。
当激光器采用扫描时，采用脉宽≤10-11s的紫外波长的超短脉冲用正离焦单次线扫描，扫描间隔为激光光斑大小，重复频率为200-400kHz，扫描速度为800-1200mm/s，功率密度为5-25W/mm2。
当激光器采用辐照时，将经1)处理过的单晶硅样品放置于靶台上，调整光路，使均束光斑与样品大小相适应，进行单脉冲辐照，激光器为波长为248nm的准分子激光器；采用脉冲能量密度100mJ/cm2-400mJ/cm2，频率为1-3Hz。
进一步，通过改变微结构阵列的尺寸或形貌对衬底的SERS效应进行调控，当微结构阵列的间隔减小时，衬底的SERS效应增强；当微结构阵列的尺寸增大时，衬底SERS效应增强。
进一步，通过改变银薄膜的厚度对衬底的SERS效应进行调控，当银膜厚度在50-160nm之间时，衬底的SERS效应随膜厚的增大而增大，当银膜厚度在160-200nm之间时，衬底的SERS效应随膜厚的增大而减小。
本发明提出的一种大面积表面增强拉曼光谱单晶硅基底的快速制备方法，具有以下优点：
1、本发明方法中，激光辐照微球加工可以对微结构形成的位置进行精准定位，只需改变微球的尺寸就能精确控制微结构阵列的疏密程度，并且保证良好的周期性和均一性。
2、本发明方法中，通过对表面微结构形貌尺寸特征及银膜厚度的调节，可以实现拉曼增强效应的调节，具有较高的可控性。
3、本发明方法中，所制备出的具有微结构阵列的单晶硅SERS衬底稳定性较好，可以重复利用。
4、本发明方法中，紫外超短脉冲激光器所采用的激光功率较小，工艺简单，并且可以实现大面积加工；碱刻蚀的时间为10-30s，磁控溅射时间为5-15min，总体制备周期短；同时，设备成本较低，结构重现性高，所用原料低廉， 具有较高的实用性。
附图说明
图1是实施例1制备的微结构阵列图；
图2是实施例2制备的微结构阵列图；
图3是实施例3制备的微结构阵列图；
图4是不同参数制备的样品的拉曼图谱。
具体实施方式
以下实施例子清洗具体为：将单晶硅浸入丙酮溶液超声清洗6-10分钟；在质量分数5％-20％的HF溶液中浸泡6-10分钟；浸入乙醇溶液超声清洗6-10分钟，冲洗，干燥；但不局限于此清洗方式。
实施例1：
采用直接滴涂法在清洗过的单晶硅片样品表面上排布单层六角密排分布的SiO2微球，所用微球尺寸为1.5μm；将单晶硅样品置于靶台上，调整光路，采用紫外波长的超短脉冲(10ps)激光器进行正离焦单次线扫描，扫描间隔为激光光斑大小，重复频率为400kHz，扫描速度为1200mm/s，功率密度为5W/mm2；将清洗过的单晶硅样品浸入含有乙醇的氢氧化钠水溶液中，在水浴温度为75℃的环境中，腐蚀10s，取出使用去离子水冲洗，得到具有微结构阵列的单晶硅片，所述的水溶液中，氢氧化钠的质量百分比为10％，乙醇的质量百分比为8％；利用磁控溅射对表面具有微结构阵列的单晶硅片进行银纳米薄膜沉积，沉积时间为8min，获得膜厚为100nm。
从图1可以看出所制备出的结构为孔状形状，具有较好的周期性及均一性。
实施例2：
采用直接滴涂法在清洗过的单晶硅片样品表面上排布单层六角密排分布的SiO2微球，所用微球尺寸为1μm；将单晶硅样品置于靶台上，调整光路，采用紫外波长的超短脉冲(10ps)激光器进行正离焦单次线扫描，扫描间隔为激光光斑大小，重复频率为200kHz，扫描速度为1000mm/s，功率密度为20W/mm2；将清洗过的单晶硅样品浸入含有乙醇的氢氧化钠水溶液中，在水浴 温度为75℃的环境中，腐蚀30s，取出使用去离子水冲洗，得到具有微结构阵列的单晶硅片，所述的水溶液中，氢氧化钠的质量百分比为10％，乙醇的质量百分比为10％；利用磁控溅射对表面具有微结构阵列的单晶硅片进行银纳米薄膜沉积，沉积时间为12min，获得膜厚为160nm。
从图2可以看出所制备出的结构为丘状结构，具有较好的周期性及均一性。
实施例3：
采用直接滴涂法在清洗过的单晶硅片样品表面上排布单层六角密排分布的SiO2微球，所用微球尺寸为0.5μm；将单晶硅样品置于靶台上，调整光路，采用紫外波长的超短脉冲(10ps)激光器进行正离焦单次线扫描，扫描间隔为激光光斑大小，重复频率为200kHz，扫描速度为1200mm/s，功率密度为25W/mm2；将清洗过的单晶硅样品浸入含有乙醇的氢氧化钠水溶液中，在水浴温度为70℃的环境中，腐蚀30s，取出使用去离子水冲洗，得到具有微结构阵列的单晶硅片，所述的水溶液中，氢氧化钠的质量百分比为10％，乙醇的质量百分比为10％；利用磁控溅射对表面具有微结构阵列的单晶硅片进行银纳米薄膜沉积，沉积时间为12min，获得膜厚为160nm；
从图3可以看出制备出的结构为团状结构，具有较好的周期性及均一性。
图4为利用不同微球尺寸及刻蚀时间所制备出的SERS衬底拉曼图谱，可以看出，采用该方法制备出的SERS衬底所表现出的增强效果与微结构阵列的形貌及尺寸有关。

Claims (5)

  1. 一种大面积表面增强拉曼光谱单晶硅基底的快速制备方法，其特征在于，包括以下步骤：
    1)采用直接滴涂法在清洗过的单晶硅片样品表面上排布单层六角密排分布的SiO2微球阵列；
    2)将经1)处理过的单晶硅样品放置于靶台上，调整光路，采用紫外波长的超短脉冲激光器进行辐照或扫描；
    3)将经2)处理过的单晶硅样品进行超声清洗去除微球，浸入含有乙醇的氢氧化钠水溶液中，在水浴温度为70-80℃的环境中，腐蚀10-30s，腐蚀后取出使用去离子水冲洗，得到具有微结构阵列的单晶硅片；所述的水溶液中，氢氧化钠的质量百分比为5％-10％，乙醇的质量百分比为8％-10％；
    4)将经3)处理的单晶硅衬底进行磁控溅射沉积银膜，磁控溅射时间为5-15min，所镀银膜厚为50-200nm。
  2. 根据权利要求1所述的方法，其特征在于：
    当激光器采用扫描时，采用脉宽≤10-11s的紫外波长的超短脉冲用正离焦单次线扫描，扫描间隔为激光光斑大小，重复频率为200-400kHz，扫描速度为800-1200mm/s，功率密度为5-25W/mm2。
  3. 根据权利要求1所述的方法，其特征在于：
    当激光器采用辐照时，将经1)处理过的单晶硅样品放置于靶台上，调整光路，使均束光斑与样品大小相适应，进行单脉冲辐照，激光器为波长为248nm的准分子激光器；采用脉冲能量密度100mJ/cm2-400mJ/cm2，频率为1-3Hz。
  4. 根据权利要求1所述大面积表面增强拉曼光谱单晶硅基底的快速制备方法，其特征在于：通过改变微结构阵列的尺寸或形貌对衬底的SERS效应进行调控，当微结构阵列的间隔减小时，衬底的SERS效应增强；当微结构阵列的尺寸增大时，衬底SERS效应增强。
  5. 根据权利要求1所述大面积表面增强拉曼光谱单晶硅基底的快速制备方法，其特征在于：通过改变银薄膜的厚度对衬底的SERS效应进行调控，当银膜厚度在50-160nm之间时，衬底的SERS效应随膜厚的增大而增大，当银膜厚度在160-200nm之间时，衬底的SERS效应随膜厚的增大而减小。
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