WO2015135450A1 - 蘑菇形阵列表面增强拉曼光谱活性基底及制备方法 - Google Patents

蘑菇形阵列表面增强拉曼光谱活性基底及制备方法 Download PDF

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WO2015135450A1
WO2015135450A1 PCT/CN2015/073856 CN2015073856W WO2015135450A1 WO 2015135450 A1 WO2015135450 A1 WO 2015135450A1 CN 2015073856 W CN2015073856 W CN 2015073856W WO 2015135450 A1 WO2015135450 A1 WO 2015135450A1
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enhanced raman
raman scattering
mushroom
gold
active substrate
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PCT/CN2015/073856
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French (fr)
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周勇亮
樊海涛
杨防祖
张大霄
单洁洁
任斌
田中群
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厦门大学
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    • 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
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

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  • the invention belongs to the technical field of Raman spectroscopy, and in particular relates to a method for preparing a surface-enhanced Raman-active substrate.
  • the enhancement activity of the Raman spectral signal is closely related to the spacing between the nanostructures (or particles) and exponentially decays as the spacing increases. That is, theoretically, the smaller the pitch of the nanostructures is, the higher the enhancement activity is, and the nanometer spacing is usually required to be below 10 nm, and due to the limitations of the technology itself (the penetration of the photoresist into the nanostructure, the elimination of the bubbles, when the mold is released) Structural retention, etc., nanoimprint technology cannot produce arrays of structures spaced below 50 nm. That is, the enhancement effect of the SERS substrate prepared by simply using the nanoimprint technique is not satisfactory.
  • the object of the present invention is to overcome the disadvantages of the above method, and provide a mushroom-shaped metal nanostructure array surface-enhanced Raman scattering active substrate and a preparation method thereof.
  • a surface-enhanced Raman scattering active substrate characterized by:
  • the flat base layer is provided with a mushroom-shaped nanostructured metal array, and the diameter of the mushroom cap portion is 50-300 nm, and the distance between the caps is 0-50 nm.
  • the flat base layer of the present invention may be one of a conductive glass or a glass, a silicon wafer or a quartz wafer on which a metal layer is evaporated.
  • the metal layer may be one or more of gold, silver, and copper.
  • the metal of the metal nanostructure array of the present invention may be one or more of gold, silver, and copper.
  • a method for preparing a surface-enhanced Raman scattering active substrate comprising the steps of:
  • a flat substrate such as a glass, a silicon wafer or a quartz wafer on which a metal layer is vapor-deposited
  • Electrode deposition is performed on the nano-via holes to deposit metal gold, silver or copper, and overflowing the pores to form a cap. Together with the columnar shape at the through hole, the whole shape is like a mushroom;
  • step (2) preferably comprises: using a nanoimprinting system, first adopting a hot imprinting technique, using a nickel template as a master, and replicating the surface nanostructure thereof onto the surface of the polydimethylsiloxane soft film by hot stamping Then, using a UV imprint technique, using a spin coater, spin-coating the nanoimprintant on the surface of the silicon wafer on which the gold film is evaporated;
  • the surface of the nanoimprinted adhesive is UV-imprinted by using a polydimethylsiloxane soft film as a master to obtain a nanopore structure; and the UV-imprinted residual adhesive layer is removed by using a plasma etching machine in the nanopore The bottom is exposed to metal.
  • step (3) preferably comprises: the effective mass fraction of gold in the solution is 0.01-1%, the pH of the solution is 1-6, and the nanoimprint adhesive after ultraviolet imprinting is used as a template to block at 20-70 ° C.
  • the layer is subjected to constant current or constant potential electrodeposition, and the deposition time is 300-1200 s;
  • the nanoimprinting rubber barrier layer is removed by using a microwave plasma stripping machine to finally obtain a surface-enhanced Raman scattering substrate of the ordered gold nanostructure;
  • the nanoimprinting rubber barrier layer is removed, and an ordered gold nano mushroom array is obtained.
  • the effective mass fraction of gold in the solution is more preferably from 0.01 to 0.5%
  • the solution PH is more preferably from 2 to 5
  • the temperature is more preferably from 40 to 50 ° C
  • the deposition time is more preferably from 400 to 1,000 s.
  • the current density is 1-5 mA/cm 2 , and more preferably 1-3 mA/cm 2 .
  • the voltage of the constant potential is -2V to 2V, and more preferably -0.9V to 0.6V.
  • the invention has the following advantages:
  • the present invention prepares a nanostructured metal array having a mushroom cap portion having a diameter of 50-300 nm and a distance between the caps of 0-50 nm.
  • the preparation method of the invention combines the advantages of nanoimprinting capable of preparing nanostructure arrays on a large scale and at a low cost, and electrochemical deposition of controlled nanostructure size, thereby ensuring repeatability of the method and uniformity of the array, and large
  • the amplitude reduces the spacing of the metal nano-intervals, thereby greatly improving the enhancement effect of the Raman scattering signal.
  • the surface enhancement Raman spectrum of the prepared mushroom array substrate to 4-mercaptopyridine molecule was enhanced by 108.
  • FIG. 1 is a schematic view showing a process flow for preparing a surface-enhanced Raman scattering active substrate
  • FIG. 2 and FIG. 3 are SEM photographs of the nanoimprinting rubber barrier layer after removing the ultraviolet embossed residual adhesive of Example 2.
  • FIG. 4 and FIG. 5 are SEM photographs of the surface-enhanced Raman scattering active substrate prepared by using gold as an electrodeposited layer in Example 3;
  • Example 6 is a surface-enhanced Raman scattering active substrate prepared by using Example 1 with 1 mM 4-mercaptopyridine as a molecule to be tested and gold as an electrodeposited layer. a spectrum obtained by testing a portable Raman spectrometer that excites light;
  • FIG. 7 and FIG. 8 are SEM photographs of the surface-enhanced Raman scattering active substrate prepared by using gold as an electrodeposited layer in Example 5;
  • 9 and 10 are SEM photographs of the surface-enhanced Raman scattering active substrate prepared by using gold as an electrodeposited layer in Example 6.
  • the surface-enhanced Raman scattering active substrate (8) of the present invention is prepared as shown in Figure 1:
  • the first step coating the surface of the flat substrate such as glass, silicon wafer, quartz plate (4), etc. on which the metal layer (3) is evaporated on the surface, (2),
  • the second step using the template (1) nano-imprint process (5) and etching technology to prepare ordered nano-via structure (6) on the photoresist;
  • the third step deposition by electrochemical method (7) deposition of metal gold, silver or copper at the nano-via, and overflowing the pores to form a cap. Together with the columnar shape at the through hole, the whole shape is like a mushroom;
  • the fourth step removing the nanoimprint photoresist to obtain a surface-enhanced Raman scattering substrate (8) of an ordered mushroom-shaped nanostructured metal array, which is provided with a mushroom-shaped nanostructure metal array on the flat base layer, and a mushroom cap
  • the diameter of the part is 50-300 nm, and the distance between the caps is 0-50 nm.
  • a gold film was deposited on the surface of a circular wafer having a diameter of two inches after standard cleaning, and the thickness thereof was 200 nm.
  • Temescal 2000 electron beam evaporation system at a deposition rate of 0.2 ⁇ / s, a layer of 30nm thick chromium was deposited on the surface of the silicon wafer as a bonding layer; then a layer of evaporation on the surface of the chromium layer at a deposition rate of 0.5 ⁇ / s 200nm gold.
  • the nanopore structure has a diameter of 200 nm and a period of 400 nm:
  • the 6-type nanoimprinting system first uses hot imprint technology to copy the surface nanostructures to polydimethylsiloxane by hot stamping with a two-inch nickel template with a nanopore diameter of 200 nm and a period of 400 nm as the master. Film surface; then using UV imprint technology, using G3P-8 type spin coater, TU2-170 nano-imprinted adhesive was spin-coated on the surface of the above-mentioned vapor-deposited 200nm gold film, and the thickness of nano-imprinted adhesive was controlled at 200nm.
  • the surface of the nanoimprinted adhesive was UV-imprinted with a polydimethylsiloxane soft film as the master to obtain a nanopore structure with a diameter of 200 nm and a period of 400 nm.
  • the layer of residual glue reveals gold at the bottom of the nanopore.
  • the electron micrograph is shown in Figures 2 and 3.
  • the effective area of the nanostructure is about 20 square centimeters.
  • the gold is deposited by electrochemical method, and the deposition current is controlled by the galvanostatic method.
  • Gold is deposited on the basis of Example 2, so that the electrodeposited gold grows out of the nanopore and has a shape like a mushroom, specifically:
  • a saturated sodium sulfite solution containing sodium gold sulfite is used as a plating additive with potassium dihydrogen phosphate (9% by mass) and sodium citrate (4% by mass).
  • the effective mass fraction of gold in the solution is 0.2%, and the solution pH is 4.5.
  • the current density is 2 mA/cm 2
  • the nano-imprinted adhesive after UV imprinting is used as a template barrier layer
  • CU760E is used for constant current electrodeposition
  • the deposition time is 660 s.
  • the nano-imprinted rubber barrier is removed using an Alpha microwave plasma stripper to finally obtain a surface-enhanced Raman scattering substrate of ordered gold nanostructures;
  • the nanoimprinting rubber barrier layer is removed, the power is 300W, the process pressure is 20Pa, and the time is 2min, and an ordered gold nano mushroom array is obtained.
  • the diameter of the mushroom cap portion prepared in this embodiment is about 50-300 nm, and the distance between the caps is about 0-50 nm.
  • the "stalk" height is approximately 10-200 nanometers.
  • the electron micrograph is shown in Figures 4 and 5.
  • the effective area of the mushroom array is about 20 square centimeters.
  • the gold was deposited by electrochemical method, and the deposition potential was controlled by the potentiostatic method, so that the gold deposited in Example 2 grew into a nanopore, and the shape was like a mushroom, specifically.
  • a saturated sodium sulfite solution containing sodium gold sulfite is used as a plating additive with potassium dihydrogen phosphate (9% by mass) and sodium citrate (4% by mass).
  • the effective mass fraction of gold in the solution is 0.2%, and the solution pH is 4.5.
  • the diameter of the mushroom cap portion prepared in this embodiment is about 50-300 nm, and the distance between the caps is about 0-50 nm.
  • the "stalk" height is approximately 10-200 nanometers.
  • the electron micrograph is shown in Figures 7 and 8.
  • the effective area of the mushroom array is about 20 square centimeters.
  • the diameter of the mushroom cap portion prepared in this embodiment is about 50-300 nm, and the distance between the caps is 0-50 nm.
  • the "stalk" height is approximately 10-200 nanometers.
  • the electron micrograph is shown in Figures 9 and 10.
  • Electrodeposition, deposition potential was 0.6V, UV imprinted nanoimprint adhesive as template barrier, CHI760E for constant potential electrodeposition, deposition time of 560s.
  • the diameter of the mushroom cap portion prepared in this embodiment is about 50-300 nm, and the distance between the caps is 0-50 nm.
  • the "stalk" height is approximately 10-200 nanometers.
  • the pH of the solution is about 2, and the effective mass fraction of gold in the solution is 0.02%.
  • the current density is 1.6 mA/cm 2
  • the nanoimprinted adhesive after UV imprinting is a template barrier layer, and CU760E is used for constant current electrodeposition with a deposition time of 1000 s.
  • the diameter of the mushroom cap portion prepared in this embodiment is about 50-300 nm, and the distance between the caps is 0-50 nm.
  • the "stalk" height is approximately 10-200 nanometers.
  • the invention greatly improves the enhancement effect of the Raman scattering signal.
  • the surface enhancement Raman spectrum of the prepared mushroom array substrate for the 4-mercaptopyridine molecule has an enhancement factor of 10 8 .

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Abstract

一种蘑菇形阵列表面增强拉曼光谱活性基底（8）及制备方法。该活性基底为金或银蘑菇形纳米结构阵列，其制备方法为首先使用纳米压印工艺（5）在具有金薄膜的硅或玻璃基片表面的光胶压印制备有序纳米通孔结构（6），然后利用电化学沉积（7）在纳米通孔处沉积金属并使其溢出孔外，形成蘑菇纳米结构阵列，蘑菇菌盖部分的直径为50-300纳米，菌盖之间的距离为0-50纳米。该基底可大幅度提高拉曼散射信号的增强效果。

Description

蘑菇形阵列表面增强拉曼光谱活性基底及制备方法 技术领域
本发明属于拉曼光谱检测技术领域，特别涉及表面增强拉曼活性基底的制备方法。
背景技术
1928年印度科学家C. V. Raman 利用太阳光观察到散射光发生频率改变的非弹性散射现象。这种现象是由于入射光子与介质分子发生能量交换造成的，这种能量交换和分子中的电子云或化学键有关。Raman光谱是用途广泛的无损检测和分子识别技术, 它能够提供化学和生物分子结构的指纹信息。拉曼现象的发现对科学界有着重大的意义，但是拉曼信号极其微弱，这种内在低灵敏度的缺陷曾制约了Raman光谱应用于痕量检测和表面科学领域，想要对拉曼信号进行研究几乎都要利用一定的增强效应。20世纪70年代中期, Fleischmann, VanDuyne, Creighton领导的3个研究组分别观测和确认了表面增强拉曼现象, 即在粗糙银电极表面的吡啶分子的Raman信号比其在溶液中增强了约106倍。人们将这种由于分子等物种吸附或非常靠近具有某种纳米结构的表面, 其Raman信号强度比其体相分子显著增强的现象称作表面增强拉曼散射( Surface enhanced Raman Scattering, SERS)效应。 SERS效应的发现有效地解决了Raman光谱在表面科学和痕量分析中存在的低灵敏度问题。纳米科技的发展给SERS技术的应用注入了新活力,溶胶纳米粒子体系的SERS信号可以放大至百万亿倍, 已成为单分子科学中的重要检测工具(Shu MingNie et al.Science, 1997, 275, 1102–1106)，但是溶胶纳米粒子基底的稳定性和制备的重复性较差。因此，制备出稳定性好、增强效果好、有可重复性的SRES 衬底，是当前研究的重点。近年来，人们开始尝试使用纳米压印技术制备有序结构的SERS 基底，这样可以实现SERS基底的批量、低成本生产，又能很好的满足SERS基底对稳定性和制备的重复性的要求（中国专利CN 103091983 A）。但拉曼光谱信号的增强活性与纳米结构（或粒子）之间的间距有密切关系，并随着间距的增大，呈指数衰减。即，从理论上，纳米结构的间距越小，增强活性越高，通常要求纳米间隔在10纳米以下，而由于技术本身的局限（光刻胶对纳米结构的渗入，气泡的排除，脱模时结构的保持等），纳米压印技术无法制备间隔在50纳米以下的结构阵列。即，单纯利用纳米压印技术制备的SERS基底的增强效果并不理想。
发明内容
本发明的目的在于克服上述方法的缺点，提供一种蘑菇状金属纳米结构阵列表面增强拉曼散射活性基底及其制备方法,
本发明的技术方案如下：
一种表面增强拉曼散射活性基底，其特征在于: 其为平整基础层上设有蘑菇形纳米结构金属阵列，蘑菇菌盖部分的直径为50-300纳米，菌盖之间的距离为0-50纳米。
本发明所述平整基础层可以为导电玻璃或表面蒸镀有金属层的玻璃、硅片、石英片中的一种。所述的金属层可以为金、银、铜中的一种或两种以上。
本发明所述金属纳米结构阵列的金属可以为金、银、铜中的一种或两种以上。
本发明的又一技术方案为：
一种表面增强拉曼散射活性基底的制备方法，包括如下步骤：
1）在表面蒸镀有金属层的玻璃、硅片、石英片等平整基片表面涂覆光刻胶，
2）采用纳米压印技术及刻蚀技术在光刻胶上制备有序纳米通孔结构；
3）利用电化学方法沉积在纳米通孔处沉积金属金，银或铜，并使其溢出孔外，形成菌盖状。连同通孔处的柱状，整体形如蘑菇；
4）除去纳米压印光刻胶，获得有序蘑菇状纳米结构金属阵列的表面增强拉曼散射基底。
其中：步骤（2）优选包括：使用纳米压印***，先采用热压印技术，以镍模板为母版，通过热压印将其表面纳米结构复制到聚二甲基硅氧烷软膜表面；然后采用紫外压印技术，使用旋涂仪，将纳米压印胶旋涂在蒸镀金膜的硅片表面；
以聚二甲基硅氧烷软膜为母版在纳米压印胶表面紫外压印，即得到纳米孔结构；再使用等离子体刻蚀机去除紫外压印后的残胶层，在纳米孔的底部裸露出金属。
其中，步骤（3）优选包括：溶液中金的有效质量分数在0.01-1%，溶液PH为1-6，在20-70℃条件下，以紫外压印后的纳米压印胶为模板阻挡层进行恒电流或恒电位电沉积，沉积时间为300-1200s；
使用微波等离子去胶机除去纳米压印胶阻挡层，最终获得有序金纳米结构的表面增强拉曼散射基底；
采用微波等离子刻蚀机，在蘑菇阵列电沉积制备完成后，除去纳米压印胶阻挡层，即得到有序的金纳米蘑菇阵列。
其中，溶液中金的有效质量分数更优选为0.01-0.5%，溶液PH更优选为2-5，温度更优选为40-50℃，沉积时间更优选为400-1000s。
恒电流时，电流密度为1-5mA/cm2，更优选为1-3 mA/cm2。
恒电位的电压为-2V-2V，更优选为-0.9V-0.6V。
本发明与现有技术相比，具有如下优点:
1、本发明制备出了蘑菇菌盖部分的直径为50-300纳米，菌盖之间的距离为0-50纳米的纳米结构金属阵列。
2、本发明制备方法结合了可大规模、低成本制备纳米结构阵列的纳米压印和可控制纳米结构大小的电化学沉积优点，既保证了方法的可重复性和阵列的均匀性，又大幅度缩小了金属纳米间隔的间距，从而大幅度提高了拉曼散射信号的增强效果。所制备蘑菇阵列基底对4-巯基吡啶分子的表面增强拉曼光谱的增强因子为108。
附图说明
下面结合附图和实施例对本发明作进一步描述。
图1 为表面增强拉曼散射活性基底制备工艺流程示意图；
图2和图3为实施例2去除紫外压印残胶后纳米压印胶阻挡层的SEM照片；
图4和图5为实施例3以金为电沉积层制备出表面增强拉曼散射活性基底的SEM照片；
图6为实施例4以1mM4-巯基吡啶为待测分子，以金为电沉积层制备出表面增强拉曼散射活性基底，通过785nm 激发光的便携式拉曼光谱仪进行测试获得的光谱图；
图7和图8为实施例5以金为电沉积层制备出表面增强拉曼散射活性基底的SEM照片；
图9和图10为实施例6以金为电沉积层制备出表面增强拉曼散射活性基底的SEM照片。
具体实施方式
实施例1
本发明表面增强拉曼散射活性基底（8）其制备方法流程如附图1：
第一步：在表面蒸镀有金属层（3）的玻璃、硅片、石英片（4）等平整基片表面涂覆光刻胶（2），
第二步：利用模板（1）采用纳米压印工艺（5）及刻蚀技术在光刻胶上制备有序纳米通孔结构（6）；
第三步：利用电化学方法沉积(7)在纳米通孔处沉积金属金，银或铜，并使其溢出孔外，形成菌盖状。连同通孔处的柱状，整体形如蘑菇；
第四步：除去纳米压印光刻胶，获得有序蘑菇状纳米结构金属阵列的表面增强拉曼散射基底（8），其为平整基础层上设有蘑菇形纳米结构金属阵列，蘑菇菌盖部分的直径为50-300纳米，菌盖之间的距离为0-50纳米。
实施例2
利用电子束蒸镀技术，在经过标准清洗后的直径为两英寸的圆形硅片表面沉积一层金膜，其厚度为200nm。标准清洗步骤：1.配制H2SO4：H2O2=1：4溶液，将硅片用石英舟乘载放入，浸煮15分钟。热去离子水清洗，后换冷去离子水清洗。2.将硅片置于HF溶液（HF：H2O=1：1）中浸泡30秒，取出后冲去离子水15分钟。3.用溶液（NH4OH：H2O2：H2O=1：1：5）煮沸清洗：先把烧杯中去离子水加热至85℃，倒入相应比例的NH4OH和H2O2溶液，煮15分钟，取出用热去离子水清洗，后换冷去离子水清洗。4.将硅片置于稀释的HF溶液（HF：H2O=1：20）中浸泡20秒，冲热去离子水15分钟。5.用溶液（HCl：H2O2：H2O=1：1：5）煮沸清洗：先把去离子水加热至85℃，倒入相应比例的HCl和H2O2溶液，煮15分钟，取出用热去离子水清洗，后换冷去离子水清洗。6.用氮气把洗干净的硅片吹干。
采用Temescal 2000电子束蒸发***，以0.2Å/s的沉积速率，在硅片表面蒸镀一层30nm厚的铬作为粘结层；然后以0.5Å/s的沉积速率，在铬层表面蒸镀一层200nm金。
实施例3
采用复合式纳米压印技术在金膜表面压印出有序纳米孔状结构图案，纳米孔结构直径为200nm，其周期为400nm：
使用Obducat Eitre 6型纳米压印***，先采用热压印技术，以纳米孔直径200nm，周期400nm的两英寸镍模板为母版，通过热压印将其表面纳米结构复制到聚二甲基硅氧烷软膜表面；然后采用紫外压印技术，使用G3P-8型旋涂仪，将TU2-170纳米压印胶旋涂在上述蒸镀200nm金膜的硅片表面，纳米压印胶厚度控制在200nm，以聚二甲基硅氧烷软膜为母版在纳米压印胶表面紫外压印，即得到直径为200nm，周期为400nm的纳米孔结构；再使用AMS200等离子体刻蚀机去除紫外压印后的残胶层，在纳米孔的底部裸露出金。其电镜图见图2和图3，纳米结构的有效面积约为20平方厘米。
实施例4
利用电化学方法沉积金，使用恒电流法，控制沉积电量，在实施例2基础上沉积金，使电沉积的金长出纳米孔，形状如蘑菇，具体为：
采用亚硫酸金钠的饱和亚硫酸钠溶液，以磷酸二氢钾（9%质量分数）、柠檬酸钠（4%质量分数）为电镀添加剂，溶液中金的有效质量分数在0.2%，溶液PH为4.5，在45℃条件下，电流密度大小为2mA/cm2，以紫外压印后的纳米压印胶为模板阻挡层，使用CHI760E进行恒电流电沉积，沉积时间为660s。
使用Alpha微波等离子去胶机除去纳米压印胶阻挡层，最终获得有序金纳米结构的表面增强拉曼散射基底；
采用Q240 Alpha微波等离子刻蚀机，在蘑菇阵列电沉积制备完成后，除去纳米压印胶阻挡层，功率300W，工艺压力20Pa，时间2min，即得到有序的金纳米蘑菇阵列。
本实施例制备出的蘑菇菌盖部分的直径约为50-300纳米，菌盖之间的距离约为0-50纳米。“菌柄”高度约为10-200纳米。其电镜图见图4和图5，蘑菇阵列的有效面积约为20平方厘米。
实施例5
取5uL 1mM4-巯基吡啶水溶液滴在实施例3所制备的表面增强拉曼散射基底表面，干燥后使用大量超纯水冲洗，氮气吹干，通过785nm 激发光的便携式拉曼光谱仪进行测试。其结果见图6，所制备蘑菇阵列基底对4-巯基吡啶分子的表面增强拉曼光谱的增强因子为108。
实施例6
利用电化学方法沉积金，使用恒电位法，控制沉积电量，使实施例2沉积的金长出纳米孔，形状如蘑菇，具体为。
采用亚硫酸金钠的饱和亚硫酸钠溶液，以磷酸二氢钾（9%质量分数）、柠檬酸钠（4%质量分数）为电镀添加剂，溶液中金的有效质量分数在0.2%，溶液PH为4.5，在45℃条件下，恒电位-0.9V电沉积，以紫外压印后的纳米压印胶为模板阻挡层，使用CHI760E进行恒电位电沉积，沉积时间为400s。
本实施例制备出的蘑菇菌盖部分的直径约为50-300纳米，菌盖之间的距离约为0-50纳米。“菌柄”高度约为10-200纳米。其电镜图见图7和图8，蘑菇阵列的有效面积约为20平方厘米。
实施例7
和实施例6基本相同，所不同的是
采用3g/L的氰化金钾溶液为电镀液，质量分数为1%的柠檬酸钠为添加剂，溶液PH值约为4.0，溶液中金的有效质量分数为0.2%，在55℃条件下，恒电流电沉积，电流密度大小为3mA/cm2，以紫外压印后的纳米压印胶为模板阻挡层，使用CHI760E进行恒电流电沉积，沉积时间为300s。
本实施例制备出的蘑菇菌盖部分的直径为约50-300纳米，菌盖之间的距离为0-50纳米。“菌柄”高度约为10-200纳米。其电镜图见图9和图10。
实施例8
和实施例6基本相同，所不同的是
采用1mM氯金酸水溶液为电镀液，以质量分数为1.5%的高氯酸钠为添加剂，溶液中金的有效质量分数为0.02%，溶液PH值约为2，在50℃条件下，恒电位电沉积，沉积电位为0.6V，以紫外压印后的纳米压印胶为模板阻挡层，使用CHI760E进行恒电位电沉积，沉积时间为560s。
本实施例制备出的蘑菇菌盖部分的直径为约50-300纳米，菌盖之间的距离为0-50纳米。“菌柄”高度约为10-200纳米。
实施例9
和实施例6基本相同，所不同的是
采用1mM氯金酸水溶液为电镀液，溶液PH值约为2，溶液中金的有效质量分数为0.02%，在50℃条件下，恒电流电沉积，电流密度大小为1.6mA/cm2，以紫外压印后的纳米压印胶为模板阻挡层，使用CHI760E进行恒电流电沉积，沉积时间为1000s。
本实施例制备出的蘑菇菌盖部分的直径为约50-300纳米，菌盖之间的距离为0-50纳米。“菌柄”高度约为10-200纳米。
最后说明的是，以上实施例仅用以说明本发明的技术方案而非限制，参照实施例对本发明进行了详细说明，本领域的普通技术人员应当理解。对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的宗旨和范围，其均应涵盖在本发明的权利要求范围当中。
工业实用性
本发明大幅度提高了拉曼散射信号的增强效果。所制备蘑菇阵列基底对4-巯基吡啶分子的表面增强拉曼光谱的增强因子为108。

Claims (10)

  1. 一种表面增强拉曼散射活性基底，其特征在于: 其为平整基础层上设有蘑菇形纳米结构金属阵列，蘑菇菌盖部分的直径为50-300纳米，菌盖之间的距离为0-50纳米。
  2. 按权利要求1所述的表面增强拉曼散射活性基底，其特征在于：所述平整基础层为导电玻璃或表面蒸镀有金属层的玻璃、硅片、石英片中的一种。
  3. 按权利要求1所述的表面增强拉曼散射活性基底，其特征在于：所述金属纳米结构阵列的金属为金、银、铜中的一种或两种以上。
  4. 一种表面增强拉曼散射活性基底的制备方法，包括如下步骤：
    1）在表面蒸镀有金属层的平整基片表面涂覆光刻胶，
    2）采用纳米压印技术及刻蚀技术在光刻胶上制备有序纳米通孔结构；
    3）利用电化学方法在纳米通孔处沉积金属金，银或铜，并使其溢出孔外，形成菌盖状，连同通孔处的柱状，整体形如蘑菇；
    4）除去纳米压印光刻胶，获得有序蘑菇状纳米结构金属阵列的表面增强拉曼散射基底。
  5. 如权利要求4所述的一种表面增强拉曼散射活性基底的制备方法，其特征在于：步骤（2）包括：使用纳米压印***，先采用热压印技术，以镍模板为母版，通过热压印将其表面纳米结构复制到聚二甲基硅氧烷软膜表面；然后采用紫外压印技术，使用旋涂仪，将纳米压印胶旋涂在蒸镀金膜的硅片表面；
    以聚二甲基硅氧烷软膜为母版在纳米压印胶表面紫外压印，即得到纳米孔结构；再使用等离子体刻蚀机去除紫外压印后的残胶层，在纳米孔的底部裸露出金属。
  6. 如权利要求4所述的一种表面增强拉曼散射活性基底的制备方法，其特征在于：步骤（3）包括：用于电沉积的溶液中金的有效质量分数在0.01-1%，溶液PH为1-6，在20-70℃条件下，以紫外压印后的纳米压印胶为模板阻挡层进行恒电流或恒电位电沉积，沉积时间为300-1200s；
    使用微波等离子去胶机除去纳米压印胶阻挡层，最终获得有序金纳米结构的表面增强拉曼散射基底；
    采用微波等离子刻蚀机，在蘑菇阵列电沉积制备完成后，除去纳米压印胶阻挡层，即得到有序的金纳米蘑菇阵列。
  7. 按权利要求6所述的表面增强拉曼散射活性基底的制备方法，其特征在于：恒电流时，电流密度为1-5mA/cm2。
  8. 按权利要求6所述的表面增强拉曼散射活性基底的制备方法，其特征在于：恒电位的电压为-2V-2V。
  9. 按权利要求4所述的表面增强拉曼散射活性基底的制备方法，其特征在于：所述平整基础层为导电玻璃或表面蒸镀有金属层的玻璃、硅片、石英片中的一种。
  10. 按权利要求4所述的表面增强拉曼散射活性基底的制备方法，其特征在于：所述金属纳米结构阵列的金属为金、银、铜中的一种或两种以上。
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CN112014375B (zh) * 2020-09-03 2023-06-16 鲁东大学 一种金属圆环内六角星三聚体纳米阵列及其制备方法和应用
CN113720826A (zh) * 2021-08-30 2021-11-30 南通大学 基于v型腔阵列表面的可控电镀法在制备高灵敏sers基底中的应用
CN113720826B (zh) * 2021-08-30 2024-05-10 南通大学 基于v型腔阵列表面的可控电镀法在制备高灵敏sers基底中的应用
CN115011932A (zh) * 2022-07-01 2022-09-06 吉林大学 一种具有宽带、全方位表面增强拉曼散射的多孔锥阵列及其制备方法
WO2024104104A1 (zh) * 2022-11-15 2024-05-23 华东师范大学 一种基于等离子共振增强的电荷转移拉曼增强基底材料、制备及其应用

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