CN115142062B - 一种自清洁复合sers基底及其制备方法 - Google Patents
一种自清洁复合sers基底及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种自清洁复合SERS基底及其制备方法，包括：在铜基石墨烯基底表面制备出四棱锥坑的阵列结构；将ZnO薄膜沉积在铜基石墨烯基底的四棱锥坑的阵列结构表面；将金纳米粒子溅射至ZnO薄膜的表面以获得自清洁复合SERS基底。与现有技术相比，本发明制得的复合SERS基底能实现自清洁功能，克服了传统SERS基底可回收性差的缺点，提高了SERS基底拉曼检测效率。
Description
技术领域
本发明涉及SERS基底制备领域，特别是一种自清洁复合SERS基底及其制备方法。
背景技术
表面增强拉曼散射(SERS)效应是指在特殊制备的一些金属良导体表面或溶胶中,在激发区域内,由于样品表面或近表面的电磁场的增强导致吸附分子的拉曼散射信号比普通拉曼散射(NRS)信号大大增强的现象。SERS增强主要包括化学增强(chemicalenhancement，CM)和电磁增强(electromagnetic enhancement，EM)，其中电磁增强起主导作用。EM是受表面等离子体共振(Surface plasmon resonance,SPR)现象，引起局域电磁场增强。SERS光谱技术有效地克服了常规拉曼光谱灵敏度低的缺点，因而被广泛地应用于表面科学、分析科学和生物科学等各个领域。自SERS技术问世以来，SERS基底的制备成为该领域研究的主要方面之一。基底的材料和多种表面微纳结构的制备(如采用纳米压痕技术在基底表面制备微纳结构)已应用于制作SERS基底。然而传统SERS基底存在成本高、效率低、可回收性差等问题，限制了其实际应用。
发明内容
本发明的目的是要解决现有技术中存在的不足，提供一种自清洁复合SERS基底及其制备方法。
为达到上述目的，本发明是按照以下技术方案实施的：
一种自清洁复合SERS基底的制备方法，包括以下步骤：
S1、在铜基石墨烯基底表面制备出四棱锥坑的阵列结构；
S2、将ZnO薄膜沉积在铜基石墨烯基底的四棱锥坑的阵列结构表面；
S3、将金纳米粒子溅射至ZnO薄膜的表面以获得自清洁复合SERS基底。
进一步地，所述步骤S1具体包括：
铜基石墨烯基底表面使用乙醇清洗去除杂质，并置于微纳加工实验装置的高精度位移台上，再使用四棱锥金刚石针尖以预设的二维平面水平方向f1和二维垂直方向f2控制高精度位移台的进给量f1A、f2B以及针尖和铜基石墨烯基底之间的法向力Fz在铜基石墨烯表面上加工出四棱锥坑的阵列结构，f1A表示在f1方向中，两个待加工出的相邻四棱锥坑的预设间距为Aμm，f2B表示在f2方向中，两个待加工出的相邻四棱锥坑的预设间距为Bμm，A为3-4，B为3-5，法向力Fz＝10mN。
进一步地，所述步骤S2具体包括：
S21、用吹气球去除四棱锥坑的阵列结构表面的杂质以及颗粒；
S22、打开原子层沉积系统的罗茨泵组合和分子泵将腔体抽真空至0.00001Torr；
S23、给腔体充气到常压下，迅速将清洗好的铜基石墨烯基底放入沉积室中并抽真空至0.00001Torr，然后关闭分子泵；
S24、设定管道温度为150℃、腔体温度为100℃、衬底温度为200℃，并热平衡两小时，以保证温度变化范围不超过设定温度值的±0.5℃；
S25、调节锌源二乙基锌和水源H2O两管路流量计的载气值，使工艺压力稳定在0.05Torr-0.07Torr，前驱体源的两管道载气值均设为30sccm；
S26、设置好前驱体源二乙基锌和H2O的暴露时间为150ms，多余反应物的吹扫时间为60s，运行程序，沉积氧化锌薄膜；
S27、待生长结束后，等待铜基石墨烯基底温度冷却至50℃以下，取出。
进一步地，所述步骤S3具体包括：
通过电子束蒸发系统(10kV,10-6mbar)在ZnO薄膜表面溅射金纳米粒子，其中电子束蒸发系统的压力设置为10-6mbar，高压电压为10kV，高压束电流为0.35A，溅射时间为10min。
优选地，所述A为3，B为3。
另外，本发明还提供了一种利用上述自清洁复合SERS基底的制备方法制得的自清洁复合SERS基底。
与现有技术相比，本发明采用维氏针尖法向力控制的方法在铜基石墨烯基底表面制备微纳结构，采用四棱锥针尖通过改变进给参数(f1、f2)及法向载荷对铜基石墨烯表面制备微纳阵列结构；随后，采用原子层沉积技术，以脉冲的形式将气相前驱体交替并反复地通入反应器中，在微纳结构表面发生化学吸附反应，在微纳结构表面沉积ZnO薄膜；最后，采用磁控溅射的方法将金纳米粒子溅射至ZnO薄膜的表面以获得自清洁复合SERS基底。本发明制得的复合SERS基底能实现自清洁功能，克服了传统SERS基底可回收性差的缺点，提高了SERS基底拉曼检测效率。
附图说明
图1为自清洁复合SERS基底的制备流程示意图。
图2为微纳加工实验装置在铜基石墨烯表面制备微纳结构的工作原理示意图。
图3为制备的加工参数为f13f23的铜基石墨烯表面微纳结构的原子力图。
图4为制备的加工参数为为f13f23的铜基石墨烯表面微纳结构的截面形貌图。
图5为制备的加工参数为f13f25的铜基石墨烯表面微纳结构的原子力图。
图6为制备的加工参数为f13f25的铜基石墨烯表面微纳结构的截面形貌图。
图7为制备的加工参数为f13f23的铜基石墨烯表面微纳结构的SEM形貌图。
图8为百草枯溶液在f13f23、f13f25、f14f25三组基底上的SERS光谱图。
图9为紫外光不同照射时间下SERS基底上百草枯的SERS光谱图。
图10为制备的SERS基底经过5个循环自清洗前后，其表面上的百草枯溶液的SERS光谱图。
具体实施方式
为使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步的详细说明。此处所描述的具体实施例仅用于解释本发明，并不用于限定发明。
实施例1
如图1所示，本实施例的自清洁复合SERS基底的制备方法，具体步骤如下：
S1、在铜基石墨烯基底表面制备出四棱锥坑的阵列结构：
铜基石墨烯基底表面使用乙醇清洗去除杂质，并置于微纳加工实验装置的高精度位移台上，如图2所示，再使用四棱锥金刚石针尖以预设的二维平面水平方向f1和二维垂直方向f2控制高精度位移台的进给量f1A、f2B以及针尖和铜基石墨烯基底之间的法向力Fz在铜基石墨烯表面上加工出四棱锥坑的阵列结构，f1A表示在f1方向中，两个待加工出的相邻四棱锥坑的预设间距为Aμm，f2B表示在f2方向中，两个待加工出的相邻四棱锥坑的预设间距为Bμm，A为3，B为3，法向力Fz＝10mN；为方便表达，铜基石墨烯基底在进行压痕处理时，在f1方向中，当两个相邻凹坑结构的预设间距为3μm时，简述为f13；在f2方向中，当两相邻结构的预设间距为3μm时，简述为f23，所以，在f1与f2方向上，两相邻凹坑结构预设间距都为3μm时，将其对应的拉曼增强结构名称简写为f13f23；
S2、将ZnO薄膜沉积在铜基石墨烯基底的四棱锥坑的阵列结构表面：
S21、用吹气球去除四棱锥坑的阵列结构表面的杂质以及颗粒；
S22、打开原子层沉积系统的罗茨泵组合和分子泵将腔体抽真空至0.00001Torr；
S23、给腔体充气到常压下，迅速将清洗好的铜基石墨烯基底放入沉积室中并抽真空至0.00001Torr，然后关闭分子泵；
S24、设定管道温度为150℃、腔体温度为100℃、衬底温度为200℃，并热平衡两小时，以保证温度变化范围不超过设定温度值的±0.5℃；
S25、调节锌源二乙基锌和水源H2O两管路流量计的载气值，使工艺压力稳定在0.06Torr，前驱体源的两管道载气值均设为30sccm；
S26、设置好前驱体源二乙基锌和H2O的暴露时间为150ms，多余反应物的吹扫时间为60s，运行程序，沉积氧化锌薄膜；
S27、待生长结束后，等待铜基石墨烯基底温度冷却至50℃以下，取出；
S3、将金纳米粒子溅射至ZnO薄膜的表面以获得自清洁复合SERS基底：
通过电子束蒸发系统(10kV,10-6mbar)在ZnO薄膜表面溅射金纳米粒子，其中电子束蒸发系统的压力设置为10-6mbar，高压电压为10kV，高压束电流为0.35A，溅射时间为10min。
实施例2
与实施例1的主要不同在于，A为3，B为5，法向力Fz＝10mN；将其对应的拉曼增强结构名称简写为f13f25。
实施例3
与实施例1的主要不同在于，A为4，B为5，法向力Fz＝10mN；将其对应的拉曼增强结构名称简写为f14f25。
使用原子力显微镜(AFM)对上述实施例1和实施例2制备得到的铜基石墨烯基底的四棱锥坑的阵列结构进行表征，得到原子力图像及其相应的截面图。其中图3为f13f23的原子力图像，图5为f13f25的原子力图像，从图中可以看出，在不同进给参数(f1、f2)下，阵列结构都具有良好的均匀性和周期性。并且由两组基底截面图(图4，图6)可以看出，单个结构保持着高度完整的四棱锥形状。其中，f13f23基底单一四棱锥坑的深度(H)为170.686nm，宽度(L)为3.033μm，f13f25单一四棱锥坑的深度(H)为225.443nm，宽度(L)为2.824μm。
为了更加清晰的观察SERS基底的形貌情况，使用扫描电子显微镜镜(SEM)对实施例1制备得到的铜基石墨烯基底的四棱锥坑的阵列结构进行表征，得到SEM图像。其中图7为f13f23的SEM图，由图可知，整体结构呈现出整齐的四棱锥状形貌排列。上述所制备的四棱锥坑的阵列结构能够使基底表面产生更多的热点，引起局域表面等离激元共振(LSPR)使局域电磁场增强，从而增强拉曼信号。
使用百草枯(浓度为10-6mol/L)探针分子对上述实施例1、实施例2、实施例3所制备的上述SERS基底的四棱锥坑的阵列结构进行拉曼强度检测，如图8，得到百草枯溶液的SERS光谱图。由图8可知，通过上述三组不同加工参数制备的微纳结构检测百草枯溶液的拉曼强度对比，f13f23结构的SERS基底拉曼增强效果最好。
实施例4
SERS基底的自清洁性能对实际的SERS光谱检测应用具有重要意义，为了验证本发明制备的自清洁复合SERS基底自清洁性能，本实施例选用百草枯溶液(浓度为10-6mol/L)作为探针分子，检测实施例1所制备的SERS基底的自清洁性能，具体步骤如下：
(1)将百草枯附着在所制备的SERS基底上，通过拉曼光谱仪测得百草枯溶液的SERS光谱图；
(2)将附着了百草枯溶液的SERS基底放置在氙灯(功率300W)下进行紫外光照射，每隔5min使用拉曼光谱仪检测百草枯的拉曼信号，得到百草枯溶液的SERS光谱图。图9为紫外光不同照射时间下百草枯的SERS光谱图，由图可知，随着光照时间的增加，百草枯的拉曼特征峰强度在不断减小，表明随着光催化反应不断进行，百草枯不断被分解，在经过紫外光照射25min后，百草枯溶液的拉曼特征峰完全消失，表明百草枯溶液被完全分解，证明所制备的自清洁复合SERS基底具有良好的自清洁性能；
(3)取上述经过自清洁过程的SERS基底，用去离子水和乙醇洗涤5次，烘箱60℃烘干，将百草枯溶液(浓度为10-6mol/L)重新吸附在SERS基底表面，检测百草枯溶液的SERS信号，为了研究SERS信号的重现性和稳定性，重复5次该步骤进行对比。图10为制备的SERS基底经过5次自清洗循环前后，其表面上百草枯溶液的SERS光谱图，由图可知，在紫外光照射25min后，百草枯溶液在SERS基底上没有表现出任何拉曼信号。然而，当SERS基底重新作为底物检测百草枯分子的SERS信号时，可以明显观察到百草枯溶液的强拉曼峰。此外，自清洗过程重复5次后，SERS基底上的百草枯溶液的SERS信号与新的SERS基底上检测到的信号一样强。测试结果表明，所制备的自清洁复合SERS基底具有良好的可重用性。
综上所述，本发明制得的复合SERS基底能实现自清洁功能，克服了传统SERS基底可回收性差的缺点，提高了SERS基底拉曼检测效率。
本发明的技术方案不限于上述具体实施例的限制，凡是根据本发明的技术方案做出的技术变形，均落入本发明的保护范围之内。
Claims (4)
1.一种自清洁复合SERS基底的制备方法，其特征在于，包括以下步骤：
S1、在铜基石墨烯基底表面制备出四棱锥坑的阵列结构；
所述步骤S1具体包括：
铜基石墨烯基底表面使用乙醇清洗去除杂质，并置于微纳加工实验装置的高精度位移台上，再使用四棱锥金刚石针尖以预设的二维平面水平方向f1和二维垂直方向f2控制高精度位移台的进给量f1A、f2B以及针尖和铜基石墨烯基底之间的法向力Fz在铜基石墨烯表面上加工出四棱锥坑的阵列结构，f1A表示在f1方向中，两个待加工出的相邻四棱锥坑的预设间距为Aμm，f2B表示在f2方向中，两个待加工出的相邻四棱锥坑的预设间距为Bμm，A为3-4，B为3-5，法向力Fz＝10mN；
S2、将ZnO薄膜沉积在铜基石墨烯基底的四棱锥坑的阵列结构表面；
所述步骤S2具体包括：
S21、用吹气球去除四棱锥坑的阵列结构表面的杂质以及颗粒；
S22、打开原子层沉积系统的罗茨泵组合和分子泵将腔体抽真空至0.00001Torr；
S23、给腔体充气到常压下，迅速将清洗好的铜基石墨烯基底放入沉积室中并抽真空至0.00001Torr，然后关闭分子泵；
S24、设定管道温度为150℃、腔体温度为100℃、衬底温度为200℃，并热平衡两小时，以保证温度变化范围不超过设定温度值的±0.5℃；
S25、调节锌源二乙基锌和水源H2O两管路流量计的载气值，使工艺压力稳定在0.05Torr-0.07Torr，前驱体源的两管道载气值均设为30sccm；
S26、设置好前驱体源二乙基锌和H2O的暴露时间为150ms，多余反应物的吹扫时间为60s，运行程序，沉积氧化锌薄膜；
S27、待生长结束后，等待铜基石墨烯基底温度冷却至50℃以下，取出；
S3、将金纳米粒子溅射至ZnO薄膜的表面以获得自清洁复合SERS基底。
2.根据权利要求1所述的自清洁复合SERS基底的制备方法，其特征在于，所述步骤S3具体包括：
通过电子束蒸发系统(10kV,10-6mbar)在ZnO薄膜表面溅射金纳米粒子，其中电子束蒸发系统的压力设置为10-6mbar，高压电压为10kV，高压束电流为0.35A，溅射时间为10min。
3.根据权利要求2所述的自清洁复合SERS基底的制备方法，其特征在于：所述A为3，B为3。
4.一种如根据权利要求1所述的自清洁复合SERS基底的制备方法制得的自清洁复合SERS基底。
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