CN108707867B - 一种表面增强拉曼散射基片及其制备方法 - Google Patents
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Abstract
本发明公开了一种稳定的表面增强拉曼基片及其简便制备方法,属于痕量有机物检测技术领域。本发明采用双电子束共沉积的方法制备银铝固溶纳米棒阵列,在沉积腔室内原位退火,在银铝固溶纳米棒表面上自发形成一层均匀的非晶态氧化铝薄膜。超薄的氧化铝层不会大幅度衰减表面增强拉曼效应,基片具有良好的表面增强拉曼效应;同时自发形成的氧化铝薄膜使得银铝纳米棒同外界环境隔离,提高了银铝固溶纳米棒基片的抗硫化/抗氧化/抗腐蚀能力,从而大幅度提升了银铝固溶纳米棒基片的表面增强拉曼效应的稳定性。该基片在工业化批量生产和快速检测痕量有机物等方面具有广泛的应用前景。
Description
技术领域
本发明属于痕量有机物检测技术领域,涉及一种稳定的表面增强拉曼散射基片及其简便制备方法。
背景技术
表面增强拉曼效应作为一种痕量物质检测方法,具有灵敏度高、检测快速、费用低、无损分析等优点,广泛应用于化学、生物分子的痕量检测。通常采用金、银或铜等贵金属材料制备高灵敏度的表面增强拉曼基片,由于银纳米结构基底在环境中容易硫化/氧化/腐蚀,其化学不稳定性限制了表面增强拉曼效应的应用。
为了改善其不足,有报道的做法是通过化学方法、原子层沉积或复合石墨烯等工艺在已制备的银纳米结构上包裹一层极薄的惰性壳层,但这存在多次加工,工艺复杂,容易引进杂质,生产成本增加等缺点,不利于实际应用时批量生产。
通过原位退火在银铝固溶纳米棒表面形成一层非晶氧化铝可有效提高基底的稳定性。本发明制备工艺简单,同时超薄的氧化铝层不会大幅度衰减表面增强拉曼效应,基底具有良好的表面增强拉曼效应;氧化铝薄层可有效隔绝银铝固溶纳米棒同外界环境的接触,防止银铝固溶纳米棒的硫化/氧化/腐蚀,提高了基底的稳定性。
发明内容
本发明的目的在于,克服现有包覆技术工序繁复的不足,提供一种稳定的表面增强拉曼散射基片及其简便制备方法。本发明采用银铝固溶纳米棒基片,通过原位退火,在纳米棒的表面自发形成极薄的非晶氧化铝薄膜,制备工艺简单,在有效提高基片的稳定性的基础上,同时保持其良好的表面增强拉曼效应。
本发明通过以下技术方案来实现:
一种表面增强拉曼散射基片,在基片表面制备银铝固溶纳米棒,通过原位退火在纳米棒表面自发形成极薄的非晶氧化铝薄膜。
进一步,所述基片为单晶硅基片、石英片或玻璃基片。
进一步,所述银铝固溶纳米棒为斜棒或者圆柱阵列薄膜,其长度为300nm~500nm。
进一步,所述非晶态氧化物薄膜的厚度为1nm~5nm。
上述表面增强拉曼散射基片的制备方法,包括步骤如下:利用双电子束共沉积的方法,在基片表面沉积金属银和金属铝,得到银铝固溶纳米棒阵列薄膜;在沉积腔室内利用原位退火技术在银铝固溶纳米棒薄膜表面自发形成一层氧化铝薄膜,得到银铝固溶纳米棒@氧化铝复合纳米棒阵列薄膜作为表面增强拉曼效应基片。
其中,
步骤(1)中所述制备银铝固溶纳米棒阵列的方法为:将基片固定在电子束蒸发镀膜机的样品台上,调整电子束的入射角为85°~88°,并使样品台旋转或静止,以金属银和铝为靶材,在基片上垂直或倾斜共沉积长度为300nm~500nm的银铝固溶纳米棒阵列。
步骤(2)中所述采用原位退火技术的方法为:将银铝固溶纳米棒基片直接在沉积腔室内原位退火,控制退火温度为150℃~300℃,退火时间为1min~120min,真空度为1Pa~10-3Pa。
本发明通过在沉积腔室内原位退火在银铝固溶纳米棒阵列薄膜表面自发行成一层氧化铝薄膜,超薄的氧化铝薄膜厚度为1nm~5nm,基片具有良好的表面增强拉曼效应;同时氧化铝层可保护内部的银铝固溶纳米棒,防止其硫化/氧化/腐蚀,维持纳米棒状结构,大大提升了基片的稳定性。
本发明的有益效果:
本发明的银铝固溶氧化铝纳米棒基片,通过银铝固溶纳米棒在沉积腔内退火后在纳米棒表面自发形成氧化铝非晶层,大大简化了制备工艺。采用所述的银铝固溶纳米棒@氧化铝薄膜作为基底,在提供良好的表面增强拉曼效应的同时,可以有效隔绝外界环境,防止银铝固溶纳米棒的硫化/氧化/腐蚀,提高了基底的稳定性。银铝固溶氧化铝纳米棒基片具有良好稳定的表面增强拉曼效应,同时制备工艺简单,在工业化批量生产和快速检测痕量有机分子等方面具有广泛的应用前景。
附图说明
图1为本发明实施例1中制备的银铝固溶纳米棒@氧化铝表面增强拉曼基底的扫描电镜照片。
图2A为本发明实施例2中制备的银铝固溶纳米棒基底的透射电镜照片;图2B为实施例2中制备的银铝固溶纳米棒@氧化铝基底的透射电镜照片。
图3A为用纯银基底在浸泡氯化钠溶液前后测试亚甲基蓝的表面增强拉曼信号;图3B为本发明实施例3中制备的银铝固溶纳米棒@氧化铝基底在浸泡氯化钠溶液前后测试痕量亚甲基蓝的表面增强拉曼信号;其中Ag表示银基底,Ag-Al@Al2O3表示银铝固溶氧化铝纳米棒复合基底。
具体实施方式
下面结合附图1~3和实施例1~3对本发明予以具体说明,但不能理解为对本发明保护范围的限制。任何熟悉该领域的技术人员根据上述本发明内容对本发明所做的一些非本质的改进和调整,都应该涵盖在本发明的保护范围之内。
实施例1
(1)将单面抛光的硅基片用丙酮、无水乙醇、去离子水逐一超声清洗并晾干;
(2)将预处理过的基片固定在双电子束蒸发镀膜机的样品台上;
(3)在室温下,采用金属银和金属铝为靶材,两个坩埚相距4cm,将双电子束蒸发镀膜机的腔室抽至真空度为9×10-5Pa;
(5)将步骤1~4制备的表面增强拉曼基片在沉积腔室内150℃退火5分钟,真空度为1Pa;
(6)将步骤1~5制备的表面增强拉曼基片取出,在扫描电镜下观察。电镜照片如图1所示。
上述方法制备的银铝固溶纳米棒@氧化铝纳米棒基片,纳米棒分立性良好,纳米棒直径约为40nm。
实施例2
(1)将单面抛光的硅基片用丙酮、无水乙醇、去离子水逐一超声清洗并晾干;
(2)将预处理过的基片固定在双电子束蒸发镀膜机的样品台上;
(3)在室温下,采用金属银和金属铝为靶材,两个坩埚相距4cm,将双电子束蒸发镀膜机的腔室抽至真空度为7×10-5Pa;
(5)将步骤1~4制备的表面增强拉曼基片取出,在透射电镜下观察。所制基片的透射电镜照片如图2A所示。
(6)将步骤1~4制备的表面增强拉曼基片在沉积腔室内200℃退火20分钟,真空度为0.1Pa;
(7)将步骤1~6制备的表面增强拉曼基片取出,在透射电镜下观察。退火后的基片的透射电镜照片如图2B所示。
对比图2A和图2B,制备的银铝固溶纳米棒基片在沉积腔室内退火后,在银铝固溶纳米棒表面自发形成了约2.0nm的均匀的非晶氧化铝薄膜。
实施例3
(1)将单面抛光的硅基片用丙酮、无水乙醇、去离子水逐一超声清洗并晾干;
(2)将预处理过的基片固定在双电子束蒸发镀膜机的样品台上;
(3)在室温下,采用金属银和金属铝为靶材,两个坩埚相距4cm,将双电子束蒸发镀膜机的腔室抽至真空度为5×10-5Pa;
(5)将步骤1~4制备的表面增强拉曼基片在沉积腔室内300℃退火120分钟,真空度为10-3Pa;
(6)配制0.02mol/L的NaCl水溶液;
(7)将步骤1~5制备的表面增强拉曼基片放入步骤6配制的待测溶液,浸泡1小时;
(8)配制10-5mol/L的亚甲基蓝溶液;
(9)分别将将步骤(1)~(5)制备的和步骤(7)处理过的表面增强拉曼基片放入步骤(8)配制的待测溶液,浸泡30分钟;
(10)将步骤(9)中吸附有痕量亚甲基蓝的表面增强拉曼基片放入拉曼光谱仪,选择波长为785nm的光源,进行拉曼光谱的测量;
图3A为用纯银基底在浸泡氯化钠溶液前后测试亚甲基蓝的表面增强拉曼信号;图3B为实施例3中制备的银铝固溶纳米棒@氧化铝基底在浸泡氯化钠溶液前后测试痕量亚甲基蓝的表面增强拉曼信号;其中Ag表示银基底,Ag-Al@Al2O3表示银铝固溶纳米棒@氧化铝复合基底。纯银基底在NaCl水溶液浸泡之后表面增强拉曼活性急剧下降,银铝固溶纳米棒@氧化铝复合基底在NaCl水溶液浸泡前后表面增强拉曼保持稳定。银铝固溶纳米棒@氧化铝基底表面的氧化铝层有效的隔离了溶液的腐蚀,大幅度提升了基片的稳定性。
Claims (7)
1.一种表面增强拉曼散射基片的制备方法,其特征在于,所述散射基片包括基片,基片表面的银铝固溶纳米棒,以及纳米棒表面的非晶态氧化铝薄膜;所述制备方法包括以下步骤:
1)利用双电子束共沉积的方法,在基片表面制备银铝固溶纳米棒阵列薄膜;
2)采用原位退火技术在银铝固溶纳米棒阵列薄膜表面自发形成非晶氧化铝薄膜。
2.根据权利要求1所述的制备方法,其特征在于,所述基片为单晶硅基片、石英片或光学玻璃片。
3.根据权利要求1所述的制备方法,其特征在于,所述银铝固溶纳米棒为斜棒或者圆柱阵列薄膜,其长度为300nm~500nm。
4.根据权利要求1所述的制备方法,其特征在于,所述非晶态氧化铝薄膜的厚度1nm~5nm。
6.根据权利要求5所述的制备方法,其特征在于,步骤(4)所得银铝固溶纳米棒阵列薄膜的长度为300nm~500nm,所述纳米棒直径约为40nm。
7.根据权利要求1所述的制备方法,其特征在于,步骤2)所述原位退火在沉积腔室内进行,退火温度为150℃~300℃,退火时间为1min~120min,真空度为1Pa~10-3Pa,在银铝固溶纳米棒薄膜表面自发形成非晶态氧化铝薄膜,所述氧化铝薄膜的厚度1nm-5nm。
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