【摘要】：表面增強拉曼散射(Surface-enhanced Raman Scattering,SERS)以高靈敏度、樣品前處理簡單、操作簡便等諸多優(yōu)點而受到廣泛關注,并且在近幾年的科學研究中發(fā)展迅速。通過SERS可以獲得待測物的增強拉曼光譜,從而解析其分子結構信息,因此SERS在生化檢驗、考古與藝術品鑒定、生物醫(yī)學、食品安全等領域中具有巨大應用潛力。表面增強拉曼散射基底的制備是SERS研究的重點問題�，F(xiàn)在常用的SERS基底大多為金、銀、銅等貴金屬制備而成的金屬納米陣列,這是因為金屬納米材料表面等離激元共振帶來的電磁場增強起到了拉曼增強的效果,但是金屬納米陣列制備過程相當復雜,且其造價昂貴,另外金屬的等離激元共振損耗較大,這就使得等離激元SERS基底的應用受到了一定的限制。近年來,一種基于無表面等離激元(plasmon-free)半導體材料二氧化鈦有序微納結構的SERS基底逐漸興起,二氧化鈦可以利用自身的電子轉移的特性來替代表面等離激元共振,并且有序的二氧化鈦微納結構可以使得激光在二氧化鈦有序微納結構中形成多重散射,增加了光與待測分子的作用時間,從而也可以有效地增強拉曼光譜,展現(xiàn)了很好的研究價值與應用前景�；诖�,本論文通過簡單且經(jīng)濟的方法制備出三維的二氧化鈦有序微納結構,探索了其SERS檢測性能。具體開展的工作如下:(1)使用模板法在毛細管內(nèi)制備了二氧化去鈦反蛋白石有序微納結構。通過將小粒徑二氧化鈦納米粒子填充到聚苯乙烯模板縫隙中,在毛細管內(nèi)組裝了三種不同結構色(反射峰分別為430 nm,551 nm,667 nm)的完整、均一、高質量的基底。(2)使用原子層沉積的方法制備了一種二氧化鈦/二氧化硅殼-核有序微納結構毛細管。首先在毛細管內(nèi)組裝二氧化硅正結構,然后通過原子層沉積在二氧化硅表面鍍上一層厚度可控的二氧化鈦薄膜,并對不同厚度二氧化鈦的樣本進行了反射峰位移和表面形貌結構變化的分析,隨著鍍膜厚度的增加,有序微納結構表面的縫隙逐漸被填充,反射峰發(fā)生紅移,反射峰的數(shù)值呈線性增長。(3)天然有序微納結構蝴蝶翅膀因其可以對光進行調制的優(yōu)良特性也可以用作SERS基底的模板,所以為了系統(tǒng)研究二氧化鈦有序微納結構基底的拉曼增強效果,我們用模板法和原子層沉積兩種方法制備出不同的二氧化鈦的蝶翅結構復制品,并且與之前同樣方法制備的兩種基于人工模板的二氧化鈦有序微納結構比較它們各自的拉曼增強效果。實驗發(fā)現(xiàn)這幾種基底均有拉曼增強效果。其中二氧化鈦反結構的靈敏性最高,二氧化鈦/二氧化硅殼-核結構次之,其次是原子層沉積法制備的二氧化鈦蝶翅結構,最后是模板法制備的二氧化鈦蝶翅結構,兩種二氧化鈦蝶翅結構均低于前者。與蝶翅結構這種平面基底相比,毛細管內(nèi)基底的SERS靈敏度,并且使用方便,顯示了較好的應用前景。
[Abstract]:Surface enhanced Raman scattering (Surface-enhanced Raman Scattering,SERS) has attracted much attention due to its high sensitivity, simple sample pretreatment and easy operation, and has been developed rapidly in recent years. The enhanced Raman spectra of the object to be tested can be obtained by SERS, and the information of its molecular structure can be analyzed. Therefore, SERS has great application potential in the fields of biochemical examination, archaeology and art identification, biomedicine, food safety and so on. The preparation of surface-enhanced Raman scattering substrates is an important issue in the study of SERS. Most of the current SERS substrates are metal nanoarrays made of precious metals such as gold, silver, copper, etc. This is because the enhancement of electromagnetic field caused by isoexciton resonance on the surface of metal nanomaterials has the effect of Raman enhancement. However, the fabrication process of metal nanoscale arrays is very complicated and expensive. In addition, the high resonance loss of metal isophosphors makes the application of SERS substrates limited to a certain extent. In recent years, a kind of SERS substrate based on the ordered micro and nano structure of titanium dioxide semiconductor material without surface isophosphorus (plasmon-free) has been gradually developed. Titanium dioxide can substitute for surface isoexciton resonance by using its own electron transfer characteristics. And the ordered TIO _ 2 structure can make the laser form multiple scattering in the ordered micro-nano structure of TIO _ 2, increase the time of interaction between the light and the molecule to be tested, so it can also effectively enhance the Raman spectrum. It shows good research value and application prospect. Based on this, the three-dimensional ordered micro-nano structure of titanium dioxide was prepared by a simple and economical method, and its SERS detection performance was explored. The main works are as follows: (1) the ordered nanostructures of detitanium dioxide reverse opal were prepared in capillary by template method. By filling the small particle size titanium dioxide nanoparticles into the polystyrene template slot, three different structure colors (the reflection peak is 430 nm,551 nm,667 nm) were assembled in the capillary tube. (2) A kind of TIO _ 2 / Sio _ 2 capillaries with ordered micro-nano structure was prepared by atomic layer deposition. First, the positive structure of silica was assembled in the capillary, and then a controllable thickness of titanium dioxide film was deposited on the surface of silica by atomic layer deposition. The change of reflection peak displacement and surface morphology of titanium dioxide samples with different thickness were analyzed. With the increase of coating thickness, the gap on the surface of ordered micro-nano structure was gradually filled, and the reflection peak was red-shifted. The value of the reflection peak increases linearly. (3) the natural ordered micro-nano structure butterfly wings can also be used as templates for SERS substrate because of their excellent properties of modulating light. So in order to study the Raman enhancement effect of titanium dioxide ordered micro-nano structure substrates, we prepared different replicas of titanium dioxide butterfly wings by template method and atomic layer deposition method. Their Raman enhancement effects were compared with two kinds of ordered TIO _ 2 microstructures based on artificial templates prepared by the same method. It is found that these substrates have Raman enhancement effect. Among them, titanium dioxide inverse structure is the most sensitive, titanium dioxide / silica shell-core structure is the second, the second is titanium dioxide butterfly wing structure prepared by atomic layer deposition, and the last is titanium dioxide butterfly wing structure prepared by template method. The structure of two titanium dioxide butterfly wings was lower than that of the former. Compared with the planar substrates, the SERS sensitivity of the capillary substrates is easy to use, which shows a good prospect of application.
【學位授予單位】：東南大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O657.37

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