金屬納米光學天線結構增強拉曼及近場超分辨光刻研究
發(fā)布時間：2019-03-24 14:58
【摘要】：光學天線因其新穎的物理現(xiàn)象和對光場的收集、發(fā)射及調(diào)控能力受到研究人員的廣泛關注,在微納光場調(diào)控、增強拉曼散射和增強熒光、近場成像及近場光刻等領域都有重要應用。金屬納米顆粒和納米結構的局域表面等離子體(LSPs)效應是決定光學天線性質(zhì)的基礎,具有高度場局域和場增強特性。本文基于光學天線可調(diào)制分子發(fā)光性能的特性,設計了兩種耦合型天線結構,并應用于表面增強拉曼散射(SERS)實驗。研究了兩種耦合結構的近遠場光學性質(zhì)及其與結構參數(shù)之間的關系。另外,根據(jù)光學天線的近場局域功能,使用蝴蝶結形光學天線進行近場超分辨光刻研究。基于該天線的近場光學性質(zhì),引入干涉式空間位相成像(ISPI)技術對掩膜板和光刻膠基底進行測距、調(diào)平,最終實現(xiàn)大規(guī)模并行超分辨光刻。本論文工作對于發(fā)展制備簡單、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均有重要意義。 具體研究內(nèi)容如下： 1.設計并制備了具有納米級間隙的銀納米球帽-納米小孔耦合型光學天線結構并應用于SERS實驗。該結構制備方法簡單,成本低廉。將耦合結構與非耦合的銀納米球帽單元結構進行對比研究,結合數(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,使能量高度局域在間隙區(qū)域內(nèi),增強電場強度,從而產(chǎn)生更多“熱點”和更高的SERS增強因子,導致SERS信號大幅增強。研究還發(fā)現(xiàn)耦合效應強弱與耦合距離密切相關,通過改變蒸鍍銀膜厚度可調(diào)節(jié)該結構的耦合間隙大小,從而能改變SERS信號的強度,這為人為調(diào)控SERS基底的工作性能提供了有效途徑。 2.設計并制備了準三維的銀納米立方體-銀納米小孔陣列耦合結構,并應用于SERS實驗。銀納米立方體通過化學合成法制備。銀納米小孔陣列結構則通過在具有周期孔洞結構的陽極氧化鋁(AAO)模板上蒸鍍銀獲得。使用納米級厚度的PMMA薄膜作為間隔層,將銀立方體和銀小孔陣列結構縱向疊加在一起獲得耦合結構。SERS實驗和數(shù)值模擬結果顯示,該結構可將銀立方體和銀小孔陣列結構的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)和輻射過程,從而可獲得1.1×108的SERS增強因子。一系列單變量對比實驗證明耦合效應對間隔層厚度、銀膜厚度、小孔孔徑及孔間距等特征結構參數(shù)敏感,為該結構今后的實際應用提供了多樣化的調(diào)控手段。 3.研究基于蝴蝶結形光學天線的近場掃描超分辨光刻技術。根據(jù)蝴蝶結形光學天線的近場局域特性和光斑發(fā)散特性,設計掩膜板結構、調(diào)平準直體系和光刻工藝,建立了一套基于該天線的近場光刻系統(tǒng)。通過實驗和理論分析,系統(tǒng)地研究了光刻膠特性、光源、掃描速度、潤滑劑等各項實驗條件對光刻效果的影響。經(jīng)過實驗參數(shù)優(yōu)化,最終獲得可見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掃描光刻結果。 4.為提高近場光刻的生產(chǎn)效率,進行大規(guī)模并行近場光刻研究。在光刻系統(tǒng)中引入ISPI技術,用于對掩膜板與光刻膠基底進行精密測距和調(diào)平。通過ISPI調(diào)平可獲得0.02mrad的掩膜板-基底空間平行度。建立了反饋控制機制,有效控制系統(tǒng)噪聲,提高光刻膠基底移動過程中的系統(tǒng)穩(wěn)定性。利用ISPI技術精確控制光學天線的工作距離,可進一步提高光刻分辨率,獲得最小19nm線寬的光刻圖形。使用改良的實驗裝置及掩膜板,實現(xiàn)了5×5(25個)和32×32(1024個)蝴蝶結形光學天線陣列的大規(guī)模并行近場二維掃描光刻。所獲得的圖形形貌均一,表面質(zhì)量好,可靠性高。進一步提高掃描速度,可將產(chǎn)率相對于傳統(tǒng)近場掃描光刻技術提高104倍以上。 本論文的創(chuàng)新點在于： 1.基于耦合型光學天線結構增強局域場的光學效應,設計制備了一種新穎的銀納米球帽-納米小孔耦合天線結構,并應用于SERS實驗。該結構的制備方法簡單易行,可通過控制蒸鍍銀膜厚度的方法調(diào)節(jié)耦合間隙大小,從而對耦合效應和SERS信號強度起調(diào)制作用。 2.提出一種新型的準三維耦合天線結構作為SERS基底。使用納米級PMMA薄膜作為間隔層,將銀納米立方體和銀納米小孔陣列結構組裝到一起。利用銀小孔陣列結構增強對入射光的吸收,利用LSPs耦合效應將能量局域在耦合區(qū)域中,增強該區(qū)域內(nèi)拉曼分子的激發(fā)和輻射效率,通過銀立方體增強輻射,將近場拉曼信號發(fā)射至遠場,便于被探測器收集。該耦合結構相比非耦合結構具有更好的拉曼增強效應,可獲得1.1×108的SERS增強因子。 3.首次將ISPI技術引入基于蝴蝶結形光學天線的近場掃描光刻體系,對掩膜板與光刻膠基底進行納米級精密測距和調(diào)平,獲得0.02mrad以上的掩膜板-基底平行度。系統(tǒng)地研究了近場掃描光刻過程中各技術參數(shù)對光刻結果的影響,使用ISPI技術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19nm的光刻圖形,并最終實現(xiàn)1024個天線陣列并行的大規(guī)模近場二維掃描超分辨光刻。該技術可將近場掃描光刻產(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
【學位授予單位】：中國科學技術大學
【學位級別】：博士
【學位授予年份】：2014
【分類號】：TN820
本文編號：2446425
[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
【學位授予單位】：中國科學技術大學
【學位級別】：博士
【學位授予年份】：2014
【分類號】：TN820
【參考文獻】
相關博士學位論文 前1條
1 易明芳;銀納米立方體及其與銀膜耦合結構增強的熒光與拉曼研究[D];中國科學技術大學;2011年
，本文編號：2446425
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