【摘要】：掠入射X射線散射是薄膜材料結(jié)構(gòu)表征的重要手段之一，具有測(cè)試過(guò)程中對(duì)樣品無(wú)損、能提供大面積表面結(jié)構(gòu)的統(tǒng)計(jì)信息等優(yōu)點(diǎn)，通過(guò)與同步輻射光源相結(jié)合可以實(shí)現(xiàn)對(duì)原位過(guò)程結(jié)構(gòu)演變的觀察，因此，掠入射X射線散射技術(shù)逐漸受到薄膜材料研究工作者的關(guān)注。然而，由于掠入射X射線散射的實(shí)驗(yàn)方法還不完整，理論分析較復(fù)雜，掠入射X射線散射的應(yīng)用領(lǐng)域還十分有限。本論文主要的工作是在上海光源小角散射線站發(fā)展和完善掠入射X射線散射實(shí)驗(yàn)方法，并應(yīng)用該技術(shù)研究自組裝介孔薄膜和自組裝聚電解質(zhì)多層膜的微觀結(jié)構(gòu)，推動(dòng)掠入射X射線散射技術(shù)在薄膜材料研究中的理論與實(shí)驗(yàn)發(fā)展。主要的工作內(nèi)容如下： 1.發(fā)展和完善掠入射X射線散射實(shí)驗(yàn)方法。通過(guò)理論建模和實(shí)驗(yàn)分析相結(jié)合，建立了廣角散射實(shí)驗(yàn)的角度校正方程，簡(jiǎn)化了校正過(guò)程。參與設(shè)計(jì)了小角散射線站首個(gè)掠入射原位控溫裝置，實(shí)現(xiàn)了真空或氣氛環(huán)境下對(duì)薄膜溫度變化過(guò)程的結(jié)構(gòu)研究。開發(fā)了數(shù)據(jù)預(yù)處理平臺(tái)，具備完整的數(shù)據(jù)預(yù)處理模塊，解決了數(shù)據(jù)分析的格式不兼容問(wèn)題，同時(shí)實(shí)現(xiàn)了對(duì)大批量數(shù)據(jù)的處理，提高了數(shù)據(jù)預(yù)處理的效率。 2.自組裝介孔薄膜的微觀結(jié)構(gòu)和模板劑去除過(guò)程研究。建立了介孔薄膜的掠入射X射線散射模型，實(shí)現(xiàn)了對(duì)薄膜內(nèi)部結(jié)構(gòu)的半定量分析，可以獲得內(nèi)部介孔通道的尺寸分布、取向、通道排列規(guī)整程度等結(jié)構(gòu)信息。應(yīng)用模型對(duì)三種不同有序度的介孔薄膜的結(jié)構(gòu)進(jìn)行了表征，三種薄膜在結(jié)構(gòu)上的主要差異表現(xiàn)為介孔通道偏離理想晶格位置的程度和介孔通道長(zhǎng)度的分布。另外，模板劑去除過(guò)程的原位實(shí)驗(yàn)實(shí)現(xiàn)了秒時(shí)間分辨的薄膜微觀結(jié)構(gòu)觀察，，薄膜內(nèi)部的介孔通道在模板劑去除過(guò)程經(jīng)歷了先膨脹再收縮的過(guò)程，在這一過(guò)程中形成了局部缺陷，當(dāng)介孔通道中的模板劑大量分解時(shí)，局部缺陷發(fā)展成區(qū)域性的結(jié)構(gòu)混亂，薄膜有序度降低，而升溫速率對(duì)介孔通道的形變量有著重要的影響，這些研究結(jié)果為優(yōu)化薄膜制備工藝提供了指導(dǎo)。 3.自組裝聚電解質(zhì)多層膜的微觀結(jié)構(gòu)和生長(zhǎng)機(jī)理研究。通過(guò)掠入射X射線散射、X射線反射率、原子力顯微鏡等技術(shù)觀察了自組裝不同階段的結(jié)構(gòu)變化，在薄膜生長(zhǎng)初期觀察到了表面有序結(jié)構(gòu)，這可以歸結(jié)為局部范圍內(nèi)聚電解質(zhì)分子復(fù)合所形成，這些有序結(jié)構(gòu)隨著薄膜層數(shù)增加逐漸消失，這與分子間的融合和穿插密切相關(guān)。另外，在薄膜生長(zhǎng)后期觀察到了共振彌散散射，這為三區(qū)域結(jié)構(gòu)模型提供了實(shí)驗(yàn)支持。共振彌散散射的臨界尺寸與有序結(jié)構(gòu)的尺寸相匹配，這表明有序的復(fù)合體可能是表面與內(nèi)部結(jié)構(gòu)傳播的基本單元。因此，薄膜表面大于臨界尺寸的結(jié)構(gòu)是由靠近基底的結(jié)構(gòu)所決定，而表面小于臨界尺寸的結(jié)構(gòu)主要與復(fù)合體內(nèi)的分子構(gòu)象相關(guān)�；诶碚摻Y(jié)構(gòu)模型，論文模擬了二維散射圖，模擬結(jié)果和實(shí)驗(yàn)結(jié)果基本相似，這為理論結(jié)構(gòu)框架的準(zhǔn)確性提供了依據(jù)。另外，本論文還應(yīng)用掠入射散射技術(shù)對(duì)聚電解質(zhì)薄膜熱處理過(guò)程中結(jié)構(gòu)演變進(jìn)行了探索，為實(shí)現(xiàn)通過(guò)熱處理方法實(shí)現(xiàn)薄膜結(jié)構(gòu)調(diào)控提供了理論與實(shí)驗(yàn)指導(dǎo)。 本論文的工作內(nèi)容以實(shí)驗(yàn)方法發(fā)展為起點(diǎn)，然后應(yīng)用散射技術(shù)對(duì)薄膜結(jié)構(gòu)進(jìn)行了深入的研究，解決了結(jié)構(gòu)分析中的重要問(wèn)題，這對(duì)完善和推動(dòng)掠入射X射線散射技術(shù)在自組裝材料研究中的應(yīng)用有著重要的借鑒意義。
[Abstract]:Grazing incidence X-ray scattering is one of the important means to characterize the structure of thin films. It has the advantages of nondestructive testing of samples and providing statistical information of large area surface structure. By combining grazing incidence X-ray scattering with synchrotron radiation source, in-situ structure evolution can be observed. Therefore, grazing incidence X-ray scattering technology is gradually thinned. However, the experimental methods of grazing incidence X-ray scattering are incomplete and the theoretical analysis is complicated, so the application fields of grazing incidence X-ray scattering are still very limited. The main work of this paper is to develop and improve the experimental methods of grazing incidence X-ray scattering at Shanghai Light Source Small Angle Scattering Line Station. The main work is as follows: 1. To study the microstructure of self-assembled mesoporous thin films and self-assembled polyelectrolyte multilayers, and to promote the theoretical and experimental development of grazing incidence X-ray scattering in thin film materials.
1. Developing and perfecting the experimental method of grazing incidence X-ray scattering. By combining theoretical modeling with experimental analysis, the angle correction equation of wide angle scattering experiment is established, and the correction process is simplified. The first grazing incidence in-situ temperature control device of small angle scattering line station is designed, which realizes the junction of temperature change process of thin film in vacuum or atmosphere. A data pre-processing platform is developed, which has a complete data pre-processing module, and solves the incompatibility of data analysis format. At the same time, it realizes the processing of a large number of data and improves the efficiency of data pre-processing.
2. Microstructure and template removal process of self-assembled mesoporous thin films were studied. Grazing incidence X-ray scattering model of mesoporous thin films was established. Semi-quantitative analysis of the internal structure of the films was realized. The size distribution, orientation and channel arrangement regularity of the internal mesoporous channels were obtained. The structure of mesoporous films was characterized by the degree of the deviation of mesoporous channels from the ideal lattice position and the distribution of the length of mesoporous channels. The removal process of the agent undergoes a process of expansion and shrinkage, in which local defects are formed. When a large number of templates are decomposed in the mesoporous channel, the local defects develop into regional structural disorder and the ordering degree of the film decreases. The heating rate has an important effect on the morphological variables of the mesoporous channel. These results are optimized. The film preparation process provides guidance.
3. Study on the microstructure and growth mechanism of self-assembled polyelectrolyte multilayers. The structural changes at different stages of self-assembly were observed by grazing incidence X-ray scattering, X-ray reflectance, atomic force microscopy and other techniques. The ordered surface structure was observed at the initial stage of film growth, which can be attributed to the local range of polyelectrolyte molecular recombination. As a result, these ordered structures gradually disappear with the increase of the number of layers, which is closely related to the intermolecular fusion and interpolation. In addition, resonance dispersion scattering was observed at the late growth stage of the films, which provides experimental support for the three-region structure model. The ordered complex may be the basic unit of surface-to-internal structure propagation. Therefore, the structure with a surface larger than the critical size is determined by the structure near the substrate, while the structure with a surface smaller than the critical size is mainly related to the molecular conformation in the complex. In addition, the grazing incidence scattering technique was used to investigate the structure evolution of polyelectrolyte films during heat treatment, which provides theoretical and experimental guidance for realizing the structure control of polyelectrolyte films by heat treatment.
In this paper, the experimental method is used as the starting point, and then the scattering technique is applied to study the structure of thin films. The important problems in structure analysis are solved. It is of great significance to perfect and promote the application of grazing incidence X-ray scattering technique in the study of self-assembled materials.
【學(xué)位授予單位】：中國(guó)科學(xué)院研究生院（上海應(yīng)用物理研究所）
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB383.2

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本文編號(hào)：2203003