金属纳米光学天线结构增强拉曼及近场超分辨光刻研究
发布时间：2019-03-24 14:58
【摘要】：光学天线因其新颖的物理现象和对光场的收集、发射及调控能力受到研究人员的广泛关注,在微纳光场调控、增强拉曼散射和增强荧光、近场成像及近场光刻等领域都有重要应用。金属纳米颗粒和纳米结构的局域表面等离子体(LSPs)效应是决定光学天线性质的基础,具有高度场局域和场增强特性。本文基于光学天线可调制分子发光性能的特性,设计了两种耦合型天线结构,并应用于表面增强拉曼散射(SERS)实验。研究了两种耦合结构的近远场光学性质及其与结构参数之间的关系。另外,根据光学天线的近场局域功能,使用蝴蝶结形光学天线进行近场超分辨光刻研究。基于该天线的近场光学性质,引入干涉式空间位相成像(ISPI)技术对掩膜板和光刻胶基底进行测距、调平,最终实现大规模并行超分辨光刻。本论文工作对于发展制备简单、灵敏度高的SERS基底,及分辨率高、产率大、成本低廉、可靠性好的微纳制造技术均有重要意义。 具体研究内容如下： 1.设计并制备了具有纳米级间隙的银纳米球帽-纳米小孔耦合型光学天线结构并应用于SERS实验。该结构制备方法简单,成本低廉。将耦合结构与非耦合的银纳米球帽单元结构进行对比研究,结合数值模拟手段分析知银纳米球帽和纳米小孔边缘的间隙中存在LSPs耦合效应,使能量高度局域在间隙区域内,增强电场强度,从而产生更多“热点”和更高的SERS增强因子,导致SERS信号大幅增强。研究还发现耦合效应强弱与耦合距离密切相关,通过改变蒸镀银膜厚度可调节该结构的耦合间隙大小,从而能改变SERS信号的强度,这为人为调控SERS基底的工作性能提供了有效途径。 2.设计并制备了准三维的银纳米立方体-银纳米小孔阵列耦合结构,并应用于SERS实验。银纳米立方体通过化学合成法制备。银纳米小孔阵列结构则通过在具有周期孔洞结构的阳极氧化铝(AAO)模板上蒸镀银获得。使用纳米级厚度的PMMA薄膜作为间隔层,将银立方体和银小孔阵列结构纵向叠加在一起获得耦合结构。SERS实验和数值模拟结果显示,该结构可将银立方体和银小孔阵列结构的LSPs有效耦合并局域于PMMA间隔层中,影响掺杂在PMMA中的拉曼分子激发和辐射过程,从而可获得1.1×108的SERS增强因子。一系列单变量对比实验证明耦合效应对间隔层厚度、银膜厚度、小孔孔径及孔间距等特征结构参数敏感,为该结构今后的实际应用提供了多样化的调控手段。 3.研究基于蝴蝶结形光学天线的近场扫描超分辨光刻技术。根据蝴蝶结形光学天线的近场局域特性和光斑发散特性,设计掩膜板结构、调平准直体系和光刻工艺,建立了一套基于该天线的近场光刻系统。通过实验和理论分析,系统地研究了光刻胶特性、光源、扫描速度、润滑剂等各项实验条件对光刻效果的影响。经过实验参数优化,最终获得可见光曝光条件下线宽分别为78nm和106nm的一维和二维任意图形超分辨近场扫描光刻结果。 4.为提高近场光刻的生产效率,进行大规模并行近场光刻研究。在光刻系统中引入ISPI技术,用于对掩膜板与光刻胶基底进行精密测距和调平。通过ISPI调平可获得0.02mrad的掩膜板-基底空间平行度。建立了反馈控制机制,有效控制系统噪声,提高光刻胶基底移动过程中的系统稳定性。利用ISPI技术精确控制光学天线的工作距离,可进一步提高光刻分辨率,获得最小19nm线宽的光刻图形。使用改良的实验装置及掩膜板,实现了5×5(25个)和32×32(1024个)蝴蝶结形光学天线阵列的大规模并行近场二维扫描光刻。所获得的图形形貌均一,表面质量好,可靠性高。进一步提高扫描速度,可将产率相对于传统近场扫描光刻技术提高104倍以上。 本论文的创新点在于： 1.基于耦合型光学天线结构增强局域场的光学效应,设计制备了一种新颖的银纳米球帽-纳米小孔耦合天线结构,并应用于SERS实验。该结构的制备方法简单易行,可通过控制蒸镀银膜厚度的方法调节耦合间隙大小,从而对耦合效应和SERS信号强度起调制作用。 2.提出一种新型的准三维耦合天线结构作为SERS基底。使用纳米级PMMA薄膜作为间隔层,将银纳米立方体和银纳米小孔阵列结构组装到一起。利用银小孔阵列结构增强对入射光的吸收,利用LSPs耦合效应将能量局域在耦合区域中,增强该区域内拉曼分子的激发和辐射效率,通过银立方体增强辐射,将近场拉曼信号发射至远场,便于被探测器收集。该耦合结构相比非耦合结构具有更好的拉曼增强效应,可获得1.1×108的SERS增强因子。 3.首次将ISPI技术引入基于蝴蝶结形光学天线的近场扫描光刻体系,对掩膜板与光刻胶基底进行纳米级精密测距和调平,获得0.02mrad以上的掩膜板-基底平行度。系统地研究了近场扫描光刻过程中各技术参数对光刻结果的影响,使用ISPI技术精确控制天线工作距离,提高光刻分辨率,获得线宽最小可达19nm的光刻图形,并最终实现1024个天线阵列并行的大规模近场二维扫描超分辨光刻。该技术可将近场扫描光刻产率提高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
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TN820
本文编号：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
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TN820
【参考文献】
相关博士学位论文 前1条
1 易明芳;银纳米立方体及其与银膜耦合结构增强的荧光与拉曼研究[D];中国科学技术大学;2011年
，本文编号：2446425
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