WO2016015599A1 - Fast preparation method for large area monocrystalline silicon substrate with surface-enhanced raman spectrum - Google Patents

Fast preparation method for large area monocrystalline silicon substrate with surface-enhanced raman spectrum Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
crystal silicon
single crystal
substrate
laser
array
Prior art date
Application number
PCT/CN2015/084989
Other languages
French (fr)
Chinese (zh)
Inventor
季凌飞
林真源
蒋毅坚
吴燕
吕晓占
Original Assignee
北京工业大学
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
Priority claimed from CN201410361090.7A external-priority patent/CN104195644B/en
Priority claimed from CN201510406413.4A external-priority patent/CN104949959A/en
Application filed by 北京工业大学 filed Critical 北京工业大学
Publication of WO2016015599A1 publication Critical patent/WO2016015599A1/en

Links

Images

Classifications

    • 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

Definitions

  • 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.

Abstract

Provided is a fast preparation method for a large area monocrystalline silicon substrate with a surface-enhanced raman spectrum, which belongs to SERS substrate preparation field. In present invention the method comprises: a monocrystalline silicon surface is covered with a periodic closed microsphere array; the residual microspheres on the surface is removed by using laser scanning or radiation; then the silicon is immerged into a sodium hydroxide aqueous solution containing ethanol to erode for 10-30 seconds in a water bath temperature environment of 70-80 ℃, and it is took out and cleaned with deionized water, so as to obtain a monocrystalline silicon wafer with microstructure array. In the aqueous solution, the mass percent of sodium hydroxide is 5%-10% and the mass percent of ethanol is 8%-10%. And a silver thin film with a deposition thickness of 50-200 nm deposited on the post-eroded monocrystalline silicon surface is carried out by using magnetic controlled sputtering. The present inventioncan produce a periodic and uniform microstructure array in a fast and easy way, and can adjust the performance of the SERS substrate by controlling the appearance and dimension characters of the microstructure array and the thickness of the silver film. At the same time, the method has advantages of high repeatability and low cost, and the SERS substrate obtained has stable performance and can be utilized repeatedly.

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Rapid preparation method of large area surface enhanced Raman spectroscopy single crystal silicon substrate 技术领域Technical field
本发明属于表面拉曼增强光谱衬底制备领域。The invention belongs to the field of surface Raman enhanced spectral substrate preparation.
背景技术Background technique
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)。Surface Raman Enhanced Spectroscopy (SERS) has been widely used as a powerful detection and analysis tool since its discovery. Compared with the ordinary Raman signal, in theory, when the target molecule to be tested is located between the gaps of the metal nanoparticles, the enhancement factor of the SERS signal can reach 10 14 times. This enhancement can make the original weak Raman signal detectable, and even a clear Raman fingerprint at a single molecule level. The strong anti-interference ability of Raman scattering itself, combined with SERS technology, enables it to be used in a wide variety of complex environments. SERS substrates are typically prepared by depositing metal nanoparticles on a solid substrate by chemical synthesis or self-assembly effects, which results in a stronger enhancement factor. However, its uniformity and stability of metal particles limit its application expansion in large area detection. Therefore, it has been proposed to prepare a micro/nano structure on a SERS substrate to improve its uniformity and stability. By focusing ion beam etching (FIB) or electron beam etching, the morphology and size of the micro/nano structure can be precisely controlled, and the repeatability is good. At the same time, 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. Meanwhile, the maximum preparation area was 9.6 μm × 9.6 μm ("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.)。In recent years, efforts have been made to explore a method for preparing a SERS substrate at a lower cost and more efficiently. 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. ("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。Therefore, improving the uniformity and stability of the SERS substrate while ensuring high efficiency and low cost is a problem faced by the current SERS substrate preparation.
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。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.
发明内容Summary of the invention
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。It is an object of the present invention to provide a rapid preparation method for a large area surface enhanced Raman spectroscopy single crystal silicon substrate.
本发明的目的是通过以下技术方案实现的：The object of the invention is achieved by the following technical solutions:
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：A method for rapidly preparing a large-area surface-enhanced Raman spectroscopy single crystal silicon substrate, comprising the steps of:
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；1) arranging a single layer of hexagonal close-packed SiO 2 microsphere array on the surface of the cleaned single crystal silicon wafer by direct drop coating;
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；2) placing the 1) treated single crystal silicon sample on the target stage, adjusting the optical path, and irradiating or scanning with an ultrashort pulse laser of ultraviolet wavelength;
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％； 3) 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%;
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。4) 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.
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。When the laser is scanned, 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 .
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。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.
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。Further, the SERS effect of the substrate is regulated by changing the size or morphology of the microstructure array. When the spacing of the microstructure array is reduced, 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.
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。Further, the SERS effect of the substrate is controlled by changing the thickness of the silver film. When 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. When between -200 nm, the SERS effect of the substrate decreases as the film thickness increases.
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：The rapid preparation method of the large-area surface-enhanced Raman spectroscopy single crystal silicon substrate proposed by the invention has the following advantages:
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。1. In the method of the invention, 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.
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。2. In the method of the invention, 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.
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。3. In the method of the present invention, the prepared single crystal silicon SERS substrate having a microstructure array has good stability and can be reused.
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。4. In the method of the invention, 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.
附图说明DRAWINGS
图1是实施例1制备的微结构阵列图；1 is a microstructure array diagram prepared in Example 1;
图2是实施例2制备的微结构阵列图；2 is a microstructured array diagram prepared in Example 2;
图3是实施例3制备的微结构阵列图；3 is a microstructure array diagram prepared in Example 3;
图4是不同参数制备的样品的拉曼图谱。Figure 4 is a Raman spectrum of a sample prepared with different parameters.
具体实施方式detailed description
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。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.
实施例1：Example 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。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 μm; 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. In the aqueous solution, 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.
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。It can be seen from Fig. 1 that the prepared structure has a pore-like shape and has good periodicity and uniformity.
实施例2：Example 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。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 μm; 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. In the aqueous solution, the mass percentage of sodium hydroxide is 10%, and 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.
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。It can be seen from Fig. 2 that the prepared structure is a mound structure with good periodicity and uniformity.
实施例3：Example 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；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 μm; 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. In the aqueous solution, 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;
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。It can be seen from Fig. 3 that the prepared structure is a cluster structure with good periodicity and uniformity.
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。 4 is a Raman spectrum of a SERS substrate prepared by using different microsphere sizes and etching times. It can be seen that the enhancement effect of the SERS substrate prepared by the method and the morphology of the microstructure array and Size related.

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：A rapid preparation method for a large-area surface-enhanced Raman spectroscopy single crystal silicon substrate, comprising the steps of:
    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；1) arranging a single layer of hexagonal close-packed SiO 2 microsphere array on the surface of the cleaned single crystal silicon wafer by direct drop coating;
    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；2) placing the 1) treated single crystal silicon sample on the target stage, adjusting the optical path, and irradiating or scanning with an ultrashort pulse laser of ultraviolet wavelength;
    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％；3) 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%;
    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。4) 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.
  2. 根据权利要求1所述的方法，其特征在于：The method of claim 1 wherein:
    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。When the laser is scanned, 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 .
  3. 根据权利要求1所述的方法，其特征在于：The method of claim 1 wherein:
    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。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.
  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。The method for rapidly preparing a large-area surface-enhanced Raman spectroscopy single crystal silicon substrate according to claim 1, wherein the SERS effect of the substrate is controlled by changing the size or morphology of the microstructure array, when the microstructure array is As the spacing decreases, the SERS effect of the substrate increases; as the size of the microstructure array increases, the substrate SERS effect increases.
  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。 The method for rapidly preparing a large-area surface-enhanced Raman spectroscopy single crystal silicon substrate according to claim 1, wherein the SERS effect of the substrate is controlled by changing the thickness of the silver film, and the thickness of the silver film is 50-160 nm. The SERS effect of the substrate increases with the increase of the film thickness. When the thickness of the silver film is between 160-200 nm, the SERS effect of the substrate decreases with the increase of the film thickness.
PCT/CN2015/084989 2014-07-27 2015-07-24 Fast preparation method for large area monocrystalline silicon substrate with surface-enhanced raman spectrum WO2016015599A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201410361090.7 2014-07-27
CN201410361090.7A CN104195644B (en) 2014-07-27 2014-07-27 A kind of monocrystalline substrate submicron pyramid structure laser-chemical preparation process
CN201510406413.4 2015-07-12
CN201510406413.4A CN104949959A (en) 2015-07-12 2015-07-12 Quick preparing method for large-area surface Raman spectrum enhancing monocrystalline silicon substrate

Publications (1)

Publication Number Publication Date
WO2016015599A1 true WO2016015599A1 (en) 2016-02-04

Family

ID=55216763

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/084989 WO2016015599A1 (en) 2014-07-27 2015-07-24 Fast preparation method for large area monocrystalline silicon substrate with surface-enhanced raman spectrum

Country Status (1)

Country Link
WO (1) WO2016015599A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111876734A (en) * 2020-07-16 2020-11-03 贵州大学 Preparation method of nano Ag-Zn double-layer lattice coating
CN112499581A (en) * 2020-11-12 2021-03-16 西安交通大学 Preparation method of surface-enhanced Raman scattering substrate
CN113046707A (en) * 2021-02-09 2021-06-29 杭州电子科技大学 Preparation method and application of nanoflower array structure
CN114231929A (en) * 2021-12-22 2022-03-25 杭州电子科技大学 Method for preparing nano conical honeycomb structure
CN114231928A (en) * 2021-12-22 2022-03-25 杭州电子科技大学 Preparation method of annular stepped nanostructure

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101672786A (en) * 2009-03-12 2010-03-17 中国科学院理化技术研究所 Active substrate with surface provided with enhanced raman scattering effect and production method and application thereof
US20110128536A1 (en) * 2009-12-02 2011-06-02 Bond Tiziana C Nanoscale array structures suitable for surface enhanced raman scattering and methods related thereto
CN102590179A (en) * 2012-03-28 2012-07-18 上海大学 Silver nano lattice surface enhanced raman active substrate and preparation method thereof
CN103361601A (en) * 2013-05-22 2013-10-23 南开大学 Method for manufacturing surface enhancement Raman scatting substrate
CN103398996A (en) * 2013-08-07 2013-11-20 苏州扬清芯片科技有限公司 Rapid preparation method of regular triangular pyramid SERS active substrate
CN104195644A (en) * 2014-07-27 2014-12-10 北京工业大学 Laser-chemical preparation method of monocrystal silicon substrate sub-micron pyramid structure
CN104949959A (en) * 2015-07-12 2015-09-30 北京工业大学 Quick preparing method for large-area surface Raman spectrum enhancing monocrystalline silicon substrate

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101672786A (en) * 2009-03-12 2010-03-17 中国科学院理化技术研究所 Active substrate with surface provided with enhanced raman scattering effect and production method and application thereof
US20110128536A1 (en) * 2009-12-02 2011-06-02 Bond Tiziana C Nanoscale array structures suitable for surface enhanced raman scattering and methods related thereto
CN102590179A (en) * 2012-03-28 2012-07-18 上海大学 Silver nano lattice surface enhanced raman active substrate and preparation method thereof
CN103361601A (en) * 2013-05-22 2013-10-23 南开大学 Method for manufacturing surface enhancement Raman scatting substrate
CN103398996A (en) * 2013-08-07 2013-11-20 苏州扬清芯片科技有限公司 Rapid preparation method of regular triangular pyramid SERS active substrate
CN104195644A (en) * 2014-07-27 2014-12-10 北京工业大学 Laser-chemical preparation method of monocrystal silicon substrate sub-micron pyramid structure
CN104949959A (en) * 2015-07-12 2015-09-30 北京工业大学 Quick preparing method for large-area surface Raman spectrum enhancing monocrystalline silicon substrate

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111876734A (en) * 2020-07-16 2020-11-03 贵州大学 Preparation method of nano Ag-Zn double-layer lattice coating
CN111876734B (en) * 2020-07-16 2022-05-17 贵州大学 Preparation method of nano Ag-Zn double-layer lattice coating
CN112499581A (en) * 2020-11-12 2021-03-16 西安交通大学 Preparation method of surface-enhanced Raman scattering substrate
CN112499581B (en) * 2020-11-12 2023-07-04 西安交通大学 Preparation method of surface-enhanced Raman scattering substrate
CN113046707A (en) * 2021-02-09 2021-06-29 杭州电子科技大学 Preparation method and application of nanoflower array structure
CN113046707B (en) * 2021-02-09 2023-04-28 杭州电子科技大学 Preparation method and application of nanoflower array structure
CN114231929A (en) * 2021-12-22 2022-03-25 杭州电子科技大学 Method for preparing nano conical honeycomb structure
CN114231928A (en) * 2021-12-22 2022-03-25 杭州电子科技大学 Preparation method of annular stepped nanostructure
CN114231928B (en) * 2021-12-22 2023-12-29 杭州电子科技大学 Preparation method of annular stepped nano structure

Similar Documents

Publication Publication Date Title
WO2016015599A1 (en) Fast preparation method for large area monocrystalline silicon substrate with surface-enhanced raman spectrum
TWI692457B (en) Method for introducing at least one recess into a material by means of electromagnetic radiation and a subsequent etching process
Bushunov et al. Review of surface modification technologies for mid‐infrared antireflection microstructures fabrication
CN104949959A (en) Quick preparing method for large-area surface Raman spectrum enhancing monocrystalline silicon substrate
Zavestovskaya Laser nanostructuring of materials surfaces
CN106975841A (en) One-step method prepares metal Raman substrate in femtosecond double pulses air
CN106119804A (en) A kind of method based on short annealing metallic film self-assembled nanometer particle
CN111496384A (en) Device and method for processing nano-pore array on surface of brittle material
CN113206005A (en) Laser manufacturing method for two-dimensional material tensile strain engineering
CN111001939B (en) Method for processing multiple nano patterns by femtosecond laser
Li et al. High period frequency LIPSS emerging on 304 stainless steel under the irradiation of femtosecond laser double-pulse trains
Li et al. Deepening of nanograting structures on Si by a two-step laser spatial-selective amorphization strategy combined with chemical etching
Havryliuk et al. Formation of periodic structures on the solid surface under laser irradiation
CN106970068B (en) A kind of method of quick preparation wide area surface enhancing Raman scattering substrate
Wang et al. A low-damage copper removal process by femtosecond laser for integrated circuits
CN113113289A (en) Method for preparing silicon controlled nanowire by using femtosecond laser with remote/near field cooperative shaping
Saikiran et al. Ultrafast laser induced subwavelength periodic surface structures on semiconductors/metals and application to SERS studies
Ahsan et al. Femtosecond Laser Induced Nanostructures in Soda-lime Glass.
CN113247859B (en) Method for preparing crack type nano gap structure based on femtosecond laser
Shen et al. Fabrication of novel structures on silicon with femtosecond laser pulses
Liu et al. Evolution and mechanism of the periodical structures formed on Ti plate under femtosecond laser irradiation
Li et al. Formation of micro-/nano-surface structures on stainless steel by ultrafast lasers
Mizeikis et al. Fabrication of Frequency-Selective Surface Structures by Femtosecond Laser Ablation of Gold Films.
Song et al. High-performance antireflection nanostructure arrays on aluminum-doped zinc oxide film fabricated with femtosecond laser near-field processing
CN111333024A (en) Ge2Sb2Te5Metal-column-sphere heterogeneous nano structure and preparation method thereof

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: 15826567

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 07.07.2017)

122 Ep: pct application non-entry in european phase

Ref document number: 15826567

Country of ref document: EP

Kind code of ref document: A1