【摘要】：光學(xué)天線因其新穎的物理現(xiàn)象和對(duì)光場(chǎng)的收集、發(fā)射及調(diào)控能力受到研究人員的廣泛關(guān)注,在微納光場(chǎng)調(diào)控、增強(qiáng)拉曼散射和增強(qiáng)熒光、近場(chǎng)成像及近場(chǎng)光刻等領(lǐng)域都有重要應(yīng)用。金屬納米顆粒和納米結(jié)構(gòu)的局域表面等離子體(LSPs)效應(yīng)是決定光學(xué)天線性質(zhì)的基礎(chǔ),具有高度場(chǎng)局域和場(chǎng)增強(qiáng)特性。本文基于光學(xué)天線可調(diào)制分子發(fā)光性能的特性,設(shè)計(jì)了兩種耦合型天線結(jié)構(gòu),并應(yīng)用于表面增強(qiáng)拉曼散射(SERS)實(shí)驗(yàn)。研究了兩種耦合結(jié)構(gòu)的近遠(yuǎn)場(chǎng)光學(xué)性質(zhì)及其與結(jié)構(gòu)參數(shù)之間的關(guān)系。另外,根據(jù)光學(xué)天線的近場(chǎng)局域功能,使用蝴蝶結(jié)形光學(xué)天線進(jìn)行近場(chǎng)超分辨光刻研究�；谠撎炀�的近場(chǎng)光學(xué)性質(zhì),引入干涉式空間位相成像(ISPI)技術(shù)對(duì)掩膜板和光刻膠基底進(jìn)行測(cè)距、調(diào)平,最終實(shí)現(xiàn)大規(guī)模并行超分辨光刻。本論文工作對(duì)于發(fā)展制備簡(jiǎn)單、靈敏度高的SERS基底,及分辨率高、產(chǎn)率大、成本低廉、可靠性好的微納制造技術(shù)均有重要意義。 具體研究?jī)?nèi)容如下： 1.設(shè)計(jì)并制備了具有納米級(jí)間隙的銀納米球帽-納米小孔耦合型光學(xué)天線結(jié)構(gòu)并應(yīng)用于SERS實(shí)驗(yàn)。該結(jié)構(gòu)制備方法簡(jiǎn)單,成本低廉。將耦合結(jié)構(gòu)與非耦合的銀納米球帽單元結(jié)構(gòu)進(jìn)行對(duì)比研究,結(jié)合數(shù)值模擬手段分析知銀納米球帽和納米小孔邊緣的間隙中存在LSPs耦合效應(yīng),使能量高度局域在間隙區(qū)域內(nèi),增強(qiáng)電場(chǎng)強(qiáng)度,從而產(chǎn)生更多“熱點(diǎn)”和更高的SERS增強(qiáng)因子,導(dǎo)致SERS信號(hào)大幅增強(qiáng)。研究還發(fā)現(xiàn)耦合效應(yīng)強(qiáng)弱與耦合距離密切相關(guān),通過(guò)改變蒸鍍銀膜厚度可調(diào)節(jié)該結(jié)構(gòu)的耦合間隙大小,從而能改變SERS信號(hào)的強(qiáng)度,這為人為調(diào)控SERS基底的工作性能提供了有效途徑。 2.設(shè)計(jì)并制備了準(zhǔn)三維的銀納米立方體-銀納米小孔陣列耦合結(jié)構(gòu),并應(yīng)用于SERS實(shí)驗(yàn)。銀納米立方體通過(guò)化學(xué)合成法制備。銀納米小孔陣列結(jié)構(gòu)則通過(guò)在具有周期孔洞結(jié)構(gòu)的陽(yáng)極氧化鋁(AAO)模板上蒸鍍銀獲得。使用納米級(jí)厚度的PMMA薄膜作為間隔層,將銀立方體和銀小孔陣列結(jié)構(gòu)縱向疊加在一起獲得耦合結(jié)構(gòu)。SERS實(shí)驗(yàn)和數(shù)值模擬結(jié)果顯示,該結(jié)構(gòu)可將銀立方體和銀小孔陣列結(jié)構(gòu)的LSPs有效耦合并局域于PMMA間隔層中,影響摻雜在PMMA中的拉曼分子激發(fā)和輻射過(guò)程,從而可獲得1.1×108的SERS增強(qiáng)因子。一系列單變量對(duì)比實(shí)驗(yàn)證明耦合效應(yīng)對(duì)間隔層厚度、銀膜厚度、小孔孔徑及孔間距等特征結(jié)構(gòu)參數(shù)敏感,為該結(jié)構(gòu)今后的實(shí)際應(yīng)用提供了多樣化的調(diào)控手段。 3.研究基于蝴蝶結(jié)形光學(xué)天線的近場(chǎng)掃描超分辨光刻技術(shù)。根據(jù)蝴蝶結(jié)形光學(xué)天線的近場(chǎng)局域特性和光斑發(fā)散特性,設(shè)計(jì)掩膜板結(jié)構(gòu)、調(diào)平準(zhǔn)直體系和光刻工藝,建立了一套基于該天線的近場(chǎng)光刻系統(tǒng)。通過(guò)實(shí)驗(yàn)和理論分析,系統(tǒng)地研究了光刻膠特性、光源、掃描速度、潤(rùn)滑劑等各項(xiàng)實(shí)驗(yàn)條件對(duì)光刻效果的影響。經(jīng)過(guò)實(shí)驗(yàn)參數(shù)優(yōu)化,最終獲得可見(jiàn)光曝光條件下線寬分別為78nm和106nm的一維和二維任意圖形超分辨近場(chǎng)掃描光刻結(jié)果。 4.為提高近場(chǎng)光刻的生產(chǎn)效率,進(jìn)行大規(guī)模并行近場(chǎng)光刻研究。在光刻系統(tǒng)中引入ISPI技術(shù),用于對(duì)掩膜板與光刻膠基底進(jìn)行精密測(cè)距和調(diào)平。通過(guò)ISPI調(diào)平可獲得0.02mrad的掩膜板-基底空間平行度。建立了反饋控制機(jī)制,有效控制系統(tǒng)噪聲,提高光刻膠基底移動(dòng)過(guò)程中的系統(tǒng)穩(wěn)定性。利用ISPI技術(shù)精確控制光學(xué)天線的工作距離,可進(jìn)一步提高光刻分辨率,獲得最小19nm線寬的光刻圖形。使用改良的實(shí)驗(yàn)裝置及掩膜板,實(shí)現(xiàn)了5×5(25個(gè))和32×32(1024個(gè))蝴蝶結(jié)形光學(xué)天線陣列的大規(guī)模并行近場(chǎng)二維掃描光刻。所獲得的圖形形貌均一,表面質(zhì)量好,可靠性高。進(jìn)一步提高掃描速度,可將產(chǎn)率相對(duì)于傳統(tǒng)近場(chǎng)掃描光刻技術(shù)提高104倍以上。 本論文的創(chuàng)新點(diǎn)在于： 1.基于耦合型光學(xué)天線結(jié)構(gòu)增強(qiáng)局域場(chǎng)的光學(xué)效應(yīng),設(shè)計(jì)制備了一種新穎的銀納米球帽-納米小孔耦合天線結(jié)構(gòu),并應(yīng)用于SERS實(shí)驗(yàn)。該結(jié)構(gòu)的制備方法簡(jiǎn)單易行,可通過(guò)控制蒸鍍銀膜厚度的方法調(diào)節(jié)耦合間隙大小,從而對(duì)耦合效應(yīng)和SERS信號(hào)強(qiáng)度起調(diào)制作用。 2.提出一種新型的準(zhǔn)三維耦合天線結(jié)構(gòu)作為SERS基底。使用納米級(jí)PMMA薄膜作為間隔層,將銀納米立方體和銀納米小孔陣列結(jié)構(gòu)組裝到一起。利用銀小孔陣列結(jié)構(gòu)增強(qiáng)對(duì)入射光的吸收,利用LSPs耦合效應(yīng)將能量局域在耦合區(qū)域中,增強(qiáng)該區(qū)域內(nèi)拉曼分子的激發(fā)和輻射效率,通過(guò)銀立方體增強(qiáng)輻射,將近場(chǎng)拉曼信號(hào)發(fā)射至遠(yuǎn)場(chǎng),便于被探測(cè)器收集。該耦合結(jié)構(gòu)相比非耦合結(jié)構(gòu)具有更好的拉曼增強(qiáng)效應(yīng),可獲得1.1×108的SERS增強(qiáng)因子。 3.首次將ISPI技術(shù)引入基于蝴蝶結(jié)形光學(xué)天線的近場(chǎng)掃描光刻體系,對(duì)掩膜板與光刻膠基底進(jìn)行納米級(jí)精密測(cè)距和調(diào)平,獲得0.02mrad以上的掩膜板-基底平行度。系統(tǒng)地研究了近場(chǎng)掃描光刻過(guò)程中各技術(shù)參數(shù)對(duì)光刻結(jié)果的影響,使用ISPI技術(shù)精確控制天線工作距離,提高光刻分辨率,獲得線寬最小可達(dá)19nm的光刻圖形,并最終實(shí)現(xiàn)1024個(gè)天線陣列并行的大規(guī)模近場(chǎng)二維掃描超分辨光刻。該技術(shù)可將近場(chǎng)掃描光刻產(chǎn)率提高104倍。
[Abstract]:Because of the novel physical phenomena and the collection, emission and control ability of the optical field, the optical antenna is widely concerned by the researchers, and has an important application in the fields of micro-nano-field control, enhanced Raman scattering and enhanced fluorescence, near-field imaging and near-field lithography. The local surface plasma (lsps) effect of metal nanoparticles and nanostructures is the basis for determining the properties of the optical antenna and has a high field local area and field enhancement properties. In this paper, based on the characteristics of the light-emitting performance of the optical antenna, two coupling-type antenna structures are designed and applied to the surface-enhanced Raman scattering (SERS) experiment. The near-field optical properties of the two coupling structures and their relationship with the structural parameters are studied. In addition, according to the near-field local function of the optical antenna, a bow-shaped optical antenna is used for near-field super-resolution lithography. Based on the near-field optical property of the antenna, the interference-type spatial phase imaging (ISPI) technology is introduced to range and level the mask plate and the photoresist base, and the large-scale parallel super-resolution lithography is finally realized. The work of this paper is of great significance to the development of micro-nano-fabrication technology with simple preparation, high sensitivity, high resolution, high yield, low cost and good reliability. The specific content of the study is as follows: Lower:1. A silver nanosphere cap-nano-hole-coupled optical antenna structure with nano-scale gap is designed and prepared and applied to SER The preparation method of the structure is simple, The structure of the coupling structure and the non-coupled silver nano-ball cap unit is compared and researched, and the coupling effect of the LSPs exists in the gap between the silver nano-ball cap and the nano-hole edge in combination with the numerical simulation method, so that the energy height is locally in the gap area, and the power is enhanced. Field strength, resulting in more "hot spot" and higher SERS enhancement factors, resulting in a large SERS signal It is also found that the coupling effect is closely related to the coupling distance, and the coupling gap size of the structure can be adjusted by changing the thickness of the deposited silver-plated film, so that the intensity of the SERS signal can be changed, which provides for the man-made regulation of the working performance of the SERS substrate. 2. The coupling structure of a quasi-three-dimensional silver nano-cube-silver nanopore array is designed and prepared and applied to the S ERS experiment. Silver nanocubes are chemically The silver nano-hole array structure is prepared by using an anode alumina (AAO) template with a periodic hole structure, the silver cube and the silver small hole array structure are longitudinally stacked together by using a nano-scale PMMA film as a spacer layer, The results of SERS and numerical simulation show that the structure of the structure can effectively couple the LSPs of the silver cube and the silver small-hole array structure to the PMMA spacer layer, and influence the excitation and radiation process of the Raman molecules doped in the PMMA, so that the SER of 1.1-108 can be obtained. A series of single-variable contrast experiments show that the coupling effect is sensitive to the thickness of the spacer layer, the thickness of the silver film, the aperture of the small hole and the hole spacing, and provides a variety of practical applications in the future 3. Research on the near-field scanning based on the bow-shaped optical antenna The invention designs a mask plate structure, a leveling quasi-direct system and a photoetching process according to the near-field local characteristic and the light spot divergence characteristic of the bow-shaped optical antenna, Based on the experimental and theoretical analysis, the characteristics of the photoresist, the light source, the scanning speed, the lubricant and other experimental conditions are systematically studied. Through the optimization of the experimental parameters, a two-dimensional, two-dimensional arbitrary graphic super-resolution of 78 nm and 106 nm, respectively, was obtained. and 4. for improving the production efficiency of the near-field photoetching, in a lithography system, an ISPI technique is introduce, which is used for etching a mask plate and a photoresist base, Precision ranging and leveling are performed. A mask of 0.02 mrad can be obtained by ISPI leveling The parallel degree of the board-base space is established. The feedback control mechanism is established, the noise of the control system is effectively controlled, and the movement of the photoresist base is improved. System stability during the process. The working distance of the optical antenna can be accurately controlled by using the ISPI technique, and the photoetching resolution can be further improved to obtain the minimum 19. by using the improved experimental device and the mask plate, a large-scale parallel optical antenna array of 5 to 5 (25) and 32-32 (1024) bow-shaped optical antenna arrays is realized, the method comprises the following steps of: performing two-dimensional scanning and photoetching in a near-field, wherein the obtained pattern is uniform in shape, the surface quality is good, the reliability is high, the scanning speed is further improved, the yield can be compared with the traditional near-field scanning and photoetching technology, And the operation is improved by more than 104 times. The innovation point of this thesis is:1. Based on the optical effect of the coupling type optical antenna structure to enhance the local field, a novel silver nanosphere cap-nano-hole coupling antenna is designed The preparation method of the structure is simple and feasible, and the size of the coupling gap can be adjusted by controlling the thickness of the silver-plated film, so that the coupling effect and the coupling effect can be adjusted, to modulate the signal strength of SERS.2. Put forward a new kind of quasi-three the nano-scale PMMA film is used as the spacer layer, and the silver nano-cube and the excitation and the radiation efficiency of the Raman molecules in the region are enhanced, the radiation is enhanced by the silver cube, The coupling structure has better Raman enhancement effect compared with the non-coupling structure, and can be obtained .3. First, the ISPI technology is introduced to the near-field scanning lithography system based on the bow-shaped optical antenna, and the mask plate and the photoresist base are subjected to nano-scale precision ranging and leveling to obtain 0.0. the influence of the technical parameters on the photoetching result in the near-field scanning and photoetching process is systematically studied, the working distance of the antenna is controlled by using the ISPI technology, the photoetching resolution is improved, obtaining a photoetching pattern with a minimum line width of up to 19 nm, and finally realizing 1024 antenna arrays Parallel large-scale near-field two-dimensional scanning super-resolution lithography
【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：TN820

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本文編號(hào)：2446425