Chloride, bromide, pyridinium and quinolinium homologues of 4-(N- hexadecylpyridinium-4-ylmethylidene-amino)-2,6-dichlorophenolate have been investigated in solution, Langmuir and Langmuir-Blodgett films. Techniques including spectroscopy, surface potential measurement, quartz crystal microbalance, surface plasmon resonance, atomic force microscopy, reectometry and X-ray diffraction have been used to characterise these molecular systems. In solution, solvatochroism was observed and Benisi-Hildebrand analysis revealed dimeric aggregation. Langmuir monolayers were compressed at the air/water interface and chromophore rotation was observed by surface potential measurement. Langmuir- Blodgett monolayers showed lm-thickness dependence on the deposition-pressure. Monolayer thicknesses between 6-24Ä were measured using SPR and molecular areas between 40-l25Ä2 were measured using a quartz crystal microbalance. Both the molecular/s/area)and monolayer thicknesses were deposition-pressure dependent. The high tilt phases were visually distinguishable from the low tilt phases using atomic force microscopy, The compounds showed phase behaviour that was predominantly alike for the bromide and chloride homologues but different for the pyridinium and quinolinum homologues. Multilayer Y-type films of the merocyanine dyes were analysed using reectometry and deposition-pressure dependent thicknesses were found. Alternate layer structures of NLO-active hemicyanine amphiphiles were used to achieve homogeneous. orientation ordering using active and inactive spacer layers. Ordering was achieved but the optical efficiency was reduced by high proportions of inactive material and interlayer dipole formation. Double chained hemicyanine molecules were used to form Z-type structures and subsequent layers were found to significantly interdigitate. Different chain lengths were found to interdigitate by the length of the shortest chain. Gas detection experiments were undertaken on the quinolinium, dichloro merocyanine using three optical geometries. The absorption method showed slow switching and poor sensitivity. The Kretschmann SPR geometry showed high sensitivity and rapid switching. The grating SPR geometry showed rapid switching but was less sensitive than the ATR method. Protonation of the monolayers was investigated using hydrochloric acid gas, acetic acid vapour and stearic acid immobilised within the lm.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of requirements for the degree of Master of Science. Johannesburg, 2015. / Organic Photovoltaic (OPVs) is a promising alternative technology to provide clean and inexhaustible energy due to their excellent optoelectronic properties of the active polymer blends. The organic polymers have low weight, tunable electrical and optical properties besides being relatively insensitive to film imperfections which in the long run enable low-cost high-throughput roll-to-roll processing. However, their photo-conversion efficiency (PCE) and instability to air remains their greatest drawback as these preclude their commercialization. Indeed the highest power-conversion efficiency reported in literature is between 10-12 % compared to their inorganic counterparts (40 %). Therefore there is great need for improvement to make them competitive with grid parity. In this thesis, the major factors limiting the efficiency of organic solar cells such as light absorption, exciton diffusion and dissociation as well as charge collection are investigated and discussed. Despite the high thickness dependent absorption coefficients (>105 cm-1) within the visible spectrum the materials exhibit short exciton diffusion lengths (10-20 nm) which limit the optimal active layer thickness to a few nanometers. Improving optical absorption within this thickness forms the basis of this project. We report the use of surface Plasmons synthesized by both thermal evaporation and Radio Frequency (RF) magnetron sputtering system to tune and enhance optical absorption and scattering using the surface Plasmon resonance effect. The NPs were annealed at various temperatures and for different times to reconstruct and modify their shapes, sizes as well as the inter-particle distance (coverage). Stability is of paramount importance in organic semiconductor devices. Serious degradation in air constrains their applications potential. The study further investigates the mechanisms that determine the stability of organic photovoltaic devices. Our results depict the degradation mechanisms and their circumvention through the use of high mobility pentacene to improve stability.

Malgré leurs contribution dans plusieurs domaines, les biopuces à lecture plasmonique conventionnelles basées sur l'utilisation d’un film métallique plan d'or, sont limitées en terme de sensibilité surtout quand il s'agit de détecter des molécules de faible masse molaire à l’état de trace.Dans ce cadre, nous étudions numériquement et expérimentalement le potentiel de détection d’interactions biomoléculaires d’une nouvelle génération de biopuces à lecture plasmonique intégrant un film métallique micro-nano-structurée en réseau rectangulaire 1D. L’étude numérique développée met en œuvre une méthode hybride, basée sur la combinaison de deux méthodes classiques : la méthode des éléments finis et la méthode modale de Fourier. Grâce à ce nouvel outil numérique, nous présentons une cartographie exhaustive du potentiel de détection d’une couche biologique, en variant les paramètres de la structuration liés aux dimensions du réseau. La réponse de la biopuce à l’accrochage de biomolécules est ensuite interprétée théoriquement par les différents phénomènes plasmoniques notamment les «points chauds» et les bandes plasmoniques interdites. Nos calculs soulignent l'importance de l’exploitation du confinement de la lumière à travers la structuration sub-longueur d’onde des surfaces plasmoniques. Ceci permet non seulement d’optimiser les paramètres géométriques afin d’améliorer la sensibilité vis-à-vis de la réponse d’une biopuce conventionnelle, mais aussi de mettre en évidence la transition entre le régime où les plasmons propagatifs dominent et le régime où les plasmons localisés dominent. De nouvelles figures de mérite sont introduites pour évaluer les performances des biopuces structurées.Cette étude montre également que de nouvelles opportunités pour améliorer davantage la bio-sensibilité sont offertes, si la localisation de biomolécules peut être effectuée dans les régions où le champ électrique est amplifié et confiné. / Surface plasmons resonance imaging with continuous thin metallic films have become a central tool for the study of biomolecular interactions. However, in order to extend the field of applications of surface plasmons resonance systems to the trace detection of biomolecules having low molecular weight, a change in the plasmonic sensing methodology is needed. In this study, we investigate theoretically and experimentally the sensing potential of 2D nano- and micro- ribbon grating structuration on the surface of Kretschmann-based surface plasmon resonance biosensors when they are used for detection of biomolecular binding events. Numerical simulations were carried out by employing a fast and novel model based on the hybridization of two classical methods, the Fourier Modal Method and the Finite Element Method. Our calculations confirm the importance of light manipulation by means of structuration of the plasmonic thin film surfaces on the nano- and micro- scales. Not only does it highlight the geometric parameters that allow the sensitivity enhancement, and associated figures of merit, compared with the response of the conventional surface plasmon resonance biosensor based on a flat surface, but it also describes the transition from the regime where the propagating surface plasmon mode dominates to the regime where the localized surface plasmon mode dominates. An exhaustive mapping of the biosensing potential of the nano- and micro- structured biosensors surface is presented, varying the structural parameters related to the ribbon grating dimensions. New figures of merit are introduced to evaluate the performance of the structured biosensors. The structuration also leads to the creation of regions on biosensor chips that are characterized by strongly enhanced electromagnetic fields. New opportunities for further improving the bio-sensitivity are offered if localization of biomolecules can be carried out in these regions of high electromagnetic fields enhancement and confined.

了解表面等子體和外部環境之間的相互作用對表面等子體應用的開發非常重要。我們的研究集中在表面等子體與遠場的耦合，以及表面等子體模之間的耦合。 / 首先，我們研究由表面等子體模式耦合所產生的射衰變的變化。我們以角分辨反射光譜測同孔大小的納米孔陣上的簡併表面等子體模的衰減。對於每個孔的大小，我們觀察到在發生共振耦合的光譜區，衰減速有很大的改變，顯示出暗模和模的形成。耦合模很好地解釋衰變的變化。推導出的耦合常隨著孔直徑的增加而增加。我們也對耦合模一些有趣的特性及衰減變化的微觀起源進探討。 / 第二，我們以偏振分辨反射光譜從二維屬陣射散射。我們發現，反射光譜遵循的法模型可以由耦合模和瓊斯矩陣演算推導出。通過用正交方向的偏光器和分析器，反射光譜上的谷翻轉成峰，從以能夠測定出射散射效。我們發現，射散射效與波長和孔直徑的依賴關係和單孔的瑞散射相符合。 / 最後，我們開發一個新的方法，以偏振分辨光譜在實驗中測射衰變。這方法的有效性通過時域有限差分計算得到證明。我們還將此方法應用在實驗據上作為示範。 / Understanding the interaction between surface plasmon and outer environment is crucial in development of plasmonic applications. Our study is focused on the coupling between surface plasmons and far field, and also the coupling between surface plasmon modes. / First, we studied the change in radiative decay rate due to coupling of degenerate surface plasmon modes. We measured the decay rates of two degenerate surface plasmon modes in Au nanohole arrays with different hole sizes by angle-resolved reflectivity spectroscopy. For each hole size, at the spectral region where resonant coupling occurs, we observed a large modification in decay rates, leading to the formation of dark and bright modes. The change in decay rates is well explained by coupled-mode theory. The deduced coupling constant is found to increase with increasing hole diameter. Interesting properties of the coupled modes and microscopic origin of the change in decay rate is also discussed. / Second, we measured the radiative scattering from two-dimensional metallic arrays by using polarization-resolved reflectivity spectroscopy. We found that the reflectivity spectra follow the Fano-like model which can be derived from coupled-mode theory and Jones matrix calculus. By orthogonally orienting the incident polarizer and the detection analyzer, reflectivity dips flip into peaks and the radiative scattering efficiency can be determined accordingly. The dependence of total radiative scattering efficiency on wavelength and hole diameter is found to agree well with Rayleigh scattering by single hole. / Finally, we developed a new method to measure radiative decay rates experimentally by polarization-resolved reflectivity spectroscopy. The validity of this method is proved by finite-difference time-domain simulation. We also applied this method on experimental data as a demonstration. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Lo, Hau Yung = 表面等離子體在金屬納米孔陣列的輻射衰減及耦合 / 羅孝勇. / "December 2012." / Thesis (M.Phil.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references (leaves 88-92). / Abstracts also in Chinese. / Lo, Hau Yung = Biao mian deng li zi ti zai jin shu na mi kong zhen lie de fu she shuai jian ji ou he / Luo Xiaoyong. / Chapter 1 --- Introduction --- p.1 / Chapter 2 --- Basic Theory and Techniques --- p.3 / Chapter 2.1 --- Macroscopic Maxwell Equations and Boundary Conditions --- p.3 / Chapter 2.2 --- Symmetries and Band Structure --- p.4 / Chapter 2.3 --- Coupled-mode Theory --- p.10 / Chapter 2.4 --- Finite-difference Time-domain Simulation --- p.12 / Chapter 2.5 --- Preparation of Metallic Nano-hole Arrays --- p.14 / Chapter 3 --- Fundamentals of Surface Plasmons on Metallic Nanohole Array --- p.18 / Chapter 3.1 --- Confinement and Propagation Nature of SPs --- p.18 / Chapter 3.2 --- Skin Depth and Propagation Length --- p.19 / Chapter 3.3 --- Dispersion Relation and Phase-matching Conditions --- p.21 / Chapter 3.4 --- Measurement of Band Structure: Angle-resolved Reflectivity Mapping --- p.23 / Chapter 3.5 --- Red Shift of Band Structure --- p.26 / Chapter 3.6 --- Comparison of Two Presentations of Band Structure: "ω against k" versus "λ against θ" --- p.28 / Chapter 3.7 --- Resonance Peak Shape: FanoModel and Wood's Anomalus --- p.30 / Chapter 3.8 --- Resonance Peak Shape: "Fano-like" Model --- p.34 / Chapter 3.9 --- Appendix A: Derivation of Eq(3.1) --- p.36 / Chapter 4 --- Decay Rates Modification though Coupling of Degenerate Surface Plasmon modes --- p.40 / Chapter 4.1 --- Introduction --- p.40 / Chapter 4.2 --- Measurements of Degenerate Surface Plasmon Modes --- p.42 / Chapter 4.3 --- Decay rates of Coupled Modes --- p.45 / Chapter 4.4 --- Hole Diameter Dependence of Coupling Constants --- p.47 / Chapter 4.5 --- Understanding the S-polarized Surface Plasmon Modes --- p.50 / Chapter 4.6 --- TE-like Surface Plasmon Modes --- p.53 / Chapter 4.7 --- Microscopic Origin of the Modification in Decay Rate --- p.54 / Chapter 4.8 --- Summary --- p.60 / Chapter 5 --- Direct Measurement of Radiative Scattering of Surface Plasmon Resonance from Metallic Arrays by Polarization-resolved Reflectivity Spectroscopy --- p.61 / Chapter 5.1 --- Introduction --- p.61 / Chapter 5.2 --- Theory of Direct Measurement of Radiative Scattering --- p.62 / Chapter 5.3 --- Comparison with Experiment --- p.65 / Chapter 5.4 --- Comparison with Rayleigh Scattering Model --- p.71 / Chapter 5.5 --- Summary --- p.74 / Chapter 6 --- A Method of Obtaining Radiative Decay Rates From Experiment --- p.76 / Chapter 6.1 --- Introduction --- p.76 / Chapter 6.2 --- Method --- p.77 / Chapter 6.3 --- Prove of Validity --- p.78 / Chapter 6.4 --- Experimental Demonstration --- p.82 / Chapter 6.5 --- Summary --- p.85 / Chapter 7 --- Conclusion --- p.86 / Chapter 8 --- Bibliography --- p.88 / Chapter 9 --- Curriculum Vitae --- p.93

Shao, Lei = 基於金納米棒組裝的寡聚體及陣列的表面等離子體共振特性研究 / 邵磊. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Shao, Lei = Ji yu jin na mi bang zu zhuang de gua ju ti ji zhen lie de biao mian deng li zi ti gong zhen te xing yan jiu / Shao Lei.

由於表面等離子體激元可以將電磁場限制在金屬表面，從而產生強烈的場強增強效果，因此在納米光子學和生物光子學方面具有廣泛的應用價值，其中包括高性能發光二級管、光伏電池、超高分辨率光學成像和超靈敏分子檢測等。尤其在單分子和醫學診斷方面，基於表面等離子體共振的生物傳感器獲得了越來越多的青睞。本論文包括兩部份。第一部份著重討論二維週期性洞陣列的表面等離子體特性，而第二部份則是研究這種洞陣列結構在表面等離子體共振傳感方面的應用。 / 在第一部份中，表面等離子體模式被分為非簡並模式(m，O) 和簡並模式(m，±n)兩種情況分別加以討論。首先，結合實驗結果和理論模型，我們對非簡並模式的衰減壽命和激發效率進行了研究。通過光干涉光刻法和薄膜沉積技術，一系列不同幾何結構的洞陣列樣品被製備出來，且這些樣品具有很高的重複性。利用角分辨色散關係進行模式識別以及確定這些模式的衰減壽命和激發效率。通過調整起偏器和檢偏器的相對方向，表面等離子體模式的非輻射和輻射衰竭均可加以研究。結果發現，衰減壽命強烈依賴於單洞的幾何結構，而且這種行為可以用簡單的靜電模型并考慮高階修正加以解釋。從非輻射衰減和輻射衰減平衡的角度出發，激發效率對幾何結構和共振波長的依賴性也可以理解。對於簡并模式，由於存在稱合，對稱模式和反對稱模式分別被p 偏振激發和S偏振激發。它們的對稱性和對於衰減壽命和共振波長的修正可以用干涉法和模式耦合理論來理解。最後，利用多模耦合方程，我們對色散關係圖譜隨著洞深度增加而演化的情況也進行了探討。 / 第二部份對基於表面等離子體共振的生物傳感器與陣列幾何結構的關係進行了研究。結果發現，激發效率和衰減壽命對表面等離子體共振傳感器的分辨率都起到了關鍵性作用。在共振中，峰值高度和帶寬主要由表面等離子體的衰減速率控制。較低的衰減速率導致較清晰的峰值線型，從而產生較高的傳感器分辨率。因此，通過調整陣列的幾何結構以產生非常低得輻射衰減速率，表面等離于體共振傳感器的品質因數可高達104.8/RIU ，這已經超過了基於梭鏡和納米粒子對應器件的性能表現。 / Surface plasmon polaritons (SPPs) generate a strong localized electromagnetic field on metal surface and thus are promising for nano- and bio-photonics including high performing light-emitting diodes and photovoltaic cells, super-high resolution optical imaging, ultra-high sensitive bimolecular detection, etc. In particular, the application of SPPs on surface plasmon resonance (SPR) biosensor has drawn much more attention recently because of the attempt to realize single molecule detection in medical diagnosis. / This thesis contains two parts. The first part focuses on studying the basic plasmonic properties of two-dimensional periodic hole arrays while the second part concentrates on the application of hole arrays on SPR sensing. / In the first part, SPPs modes on hole arrays are classified into nondegenerate mode (m, 0) and degenerate mode (m, ±n). For nondegenerate mode, its decay lifetime and generation efficiency are studied both experimentally and theoretically. By combining interference lithography and thin film deposition, a set of arrays with a wide range of geometry has been fabricated with high reproducibility. The dispersion relations of arrays are studied by angle-dependent reflectivity for mode identification and detenninations of SPP decay lifetime and generation efficiency. In particular, through orienting the polarization of the specular reflection either parallel or orthogonal to that of the incidence, we can access both the nonradiative and radiative decays of SPPs at different resonance wavelengths. As a result, it is found that decay lifetime is strongly dependent on the geometry of single hole and its behaviors can be understood by using a simple quasi-static model taking into account of the higher order correction as well as numerical simulation deduced by finite-difference timedomain. The dependence of generation efficiency on hole geometry or resonance wavelength can be understood in tenns of trade-off between nonradiative and radiative decay rates. Once these two decay rates equals to each other, the optimum generation efficiency is realized and the field enhancement gets the maximum. And the optimum parameters can be achieved by adjusting the hole geometry or the resonance wavelength. For degenerate mode, due to the coupling between (m, +n) and (m, -n) modes, a symmetric and an anti-symmetric modes are excited under pand s-polarized excitation, respectively. Their symmetries and modifications to the decay lifetime and resonance wavelength can be understood by using the interference method and coupled mode theory. Finally, generalized coupled mode equations are employed to know about the evolution of dispersion relation as hole depth increases. / The dependence of SPR biosensor on the generation and decay of SPPs are studied in the second part. Both the generation efficiency and decay lifetime of SPPs are found to be critical in governing the resolution of SPR biosensor. In SPR, the peak height and linewidth are primarily controlled by the decay rate of SPPs. Lower decay rate leads to sharper peak profile, which results in higher SPR resolution. Therefore, by tailoring the geometry of hole arrays to achieve a very low radiative decay rate, a SPR biosensor with figure of merit (FOM) reaching l04.8/RIU can be realized, which surpasses those of prism and nanoparticle counterparts. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Zhang, Lei = 表面等離子體激元對於週期性金屬納米結構幾何形狀的依賴性及其在生物傳感中的應用 / 張磊. / "November 2011." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 116-125). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Zhang, Lei = Biao mian deng li zi ti ji yuan dui yu zhou qi xing jin shu na mi jie gou ji he xing zhuang de yi lai xing ji qi zai sheng wu chuan gan zhong de ying yong / Zhang Lei. / Chapter Chapter1 --- Introduction --- p.1 / Chapter Chapter2 --- Theoretical Background --- p.7 / Chapter 2.1 --- Maxwell's equations --- p.7 / Chapter 2.2 --- Classic electromagnetic theory for dielectric properties of matter --- p.9 / Chapter 2.3 --- Surface plasmon polaritons at the dielectric/metal interface --- p.11 / Chapter 2.4 --- Excitation of surface plasmon polaritons --- p.16 / Chapter 2.4.1 --- Prism coupling --- p.17 / Chapter 2.4.2 --- Grating coupling --- p.17 / Chapter 2.5 --- lones calculus --- p.19 / Chapter 2.6 --- Finite-difference time-domain method --- p.22 / Chapter Chapter 3 --- Sample Preparation --- p.25 / Chapter 3.1 --- Interference lithography --- p.25 / Chapter 3.1.1 --- Substrate preparation --- p.26 / Chapter 3.1.2 --- Exposure --- p.27 / Chapter 3.1.3 --- Pattern development --- p.30 / Chapter 3.2 --- Thin film deposition --- p.30 / Chapter Chapter 4 --- Experimental Setups and Calibration --- p.33 / Chapter 4.1 --- Experimental setup for measuring dispersion relation --- p.33 / Chapter 4.2 --- Experimental setup calibration --- p.35 / Chapter 4.2.1 --- Calibration of spectrometer --- p.36 / Chapter 4.2.2 --- Calibration of movement stages --- p.38 / Chapter 4.3 --- Data presentation for dispersion relation --- p.40 / Chapter 4.4 --- Summary --- p.41 / Chapter Chapter 5 --- Understanding of Fundamental Properties of SPPs --- p.43 / Chapter 5.1 --- Excitation of SPPs on 2D hole arrays --- p.44 / Chapter 5.2 --- Properties of non degenerate modes and theoretical explanation --- p.53 / Chapter 5.2.1 --- Dependence of lifetime on hole geometry and theoretical explanation --- p.55 / Chapter 5.2.2 --- Dependence of generation efficiency on hole geometry and theoretical explanation --- p.63 / Chapter 5.3 --- Properties of degenerate modes and theoretical explanation --- p.70 / Chapter 5.3.1 --- Dependence of properties of degeneration modes on hole geometry by FDTD --- p.72 / Chapter 5.3.1.1 --- (0, ±l)[subscript s,a] modes --- p.72 / Chapter 5.3.l.2 --- (-1, ±l)[subscript s,a] modes --- p.76 / Chapter 5.3.2 --- Understanding of excitation of degenerate modes by using interference method --- p.79 / Chapter 5.3.3 --- Understanding of coupling between degenerate modes by using coupled mode theory --- p.85 / Chapter 5.4 --- Evolution of dispersion relation as hole depth increases --- p.90 / Chapter 5.5 --- Summary --- p.95 / Chapter Chapter 6 --- Surface Plasmon Resonance Based Label Free Biosensor --- p.98 / Chapter 6.1 --- Basics of surface plasmon resonance (SPR) based biosensor --- p.98 / Chapter 6.2 --- State-of-the-art SPR biosensor --- p.101 / Chapter 6.3 --- SPR biosensor by using 2D metallic hole arrays --- p.102 / Chapter 6.4 --- Summary --- p.111 / Chapter Chapter 7 --- Conclusions --- p.112 / References --- p.116 / Publications --- p.126

在本篇論文中，我們成功地在透明導電襯底上製備了一系列準一維納米材料陣列。我們首先製備了氧化鋅納米線陣列，然後把它們用作氧化鋅/硒化鎘核殼納米線纜陣列中的核以及合成硒化鎘和碲化鎘納米管陣列所需的犧牲模板。最後，金納米管陣列則是利用之前製備的硒化鎘納米管陣列為模板合成的。氧化鋅納米線陣列是通過高溫的熱蒸法和低溫的水熱法製備的。水熱法製備的氧化鋅納米線陣列的電導高於熱蒸法製備的氧化鋅納米線陣列，這使得水熱法製備的氧化鋅納米線更適合採用與電相關的後續處理方法。當氧化鋅納米線陣列被用作犧牲模板來製備納米管時，水熱法製備的氧化鋅納米線能被輕易地完全去除。基於這些認識，我們主要採用電化學沉積法在水熱法製備的氧化鋅納米線陣列表面沉積硒化鎘，得到了氧化鋅/硒化鎘核殼納米線纜陣列。接下來，我們將納米線纜陣列光電極和沉積了鉑催化劑的對電極組裝成三文治結構的太陽能電池。研究發現，採用多硫電解液的電池性能比碘基電解液的電池好，其中成分為1摩爾每升硫化鈉，1摩爾每升硫和1摩爾每升氫氧化鈉的多硫電解液的電池效率最高。當去除電化學沉積法生長的氧化鋅/硒化鎘和氧化鋅/碲化鎘核殼納米線纜陣列中的氧化鋅核以後，便在導電襯底上得到了硒化鎘和碲化鎘的納米管陣列。儘管兩種納米管陣列都對可見光有很強的吸收，但是，硒化鎘納米管陣列相比碲化鎘納米管陣列，表現出較高的光響應和較好的光催化降解亞甲基藍的活性。這是因為該樣品中的光生載流子能有效分離，同時能參與化學反應的表面積也較大。最後，我們選用硒化鎘納米管陣列作為模板，利用化學方法製備了金納米管陣列。金納米管的尺寸可以通過控制硒化鎘納米管模板來加以調節。當我們將具有拉曼活性的4-巰基苯甲酸分子吸附到金納米管的表面時，其拉曼散射相比未吸附時，顯著地增強了約四個數量級，如此大的提高來源於金納米管表面附近的局域電場增強效應。 / In this thesis, we demonstrated the synthesis of a series of pseudo-one-dimensional nanostructure arrays on transparent conducting substrates. We started with ZnO nanowire arrays, which were then served as the core for the ZnO/CdSe core/shell nanocable arrays formation. Further taking the ZnO as sacrificial templates led to the formation of CdSe (and CdTe) nanotube arrays. Finally, Au nanotube arrays were fabricated using the CdSe nanotube arrays as the template. ZnO nanowire arrays were synthesized via high-temperature thermal evaporation method (TE) and low temperature hydrothermal method (HT). The electrical conductivity of HT samples on the substrates was higher than that of the TE counterparts, making it attractive for further electrical-based processing. When serving as the sacrificial templates for nanotube fabrication, HT nanowires can be completely removed with ease. Based on these understanding, ZnO/CdSe core/shell nanocable arrays were obtained mainly via electrochemical deposition of CdSe on HT ZnO nanowire arrays. Nanocable-array-photoelectrode was assembled with a Pt-coated counter electrode into a sandwiched solar cell. Polysulfide electrolytes with various compositions were found to work better than iodine-based ones for such cells, and the cell with the polysulfide electrolyte containing 1 M Na₂S, 1 M S and 1 M NaOH showed highest efficiency. Removal of the ZnO cores in the electrodeposited ZnO/CdSe and ZnO/CdTe nanocable arrays left CdSe and CdTe nanotube arrays on the conducting substrate. Although strong visible-light absorption was observed from both two nanotube arrays, higher photocurrent and better photocatalytic degradation activity of methlyene blue were recorded from CdSe-nanotube-array samples (as compared to the CdTe ones), owing to effective charge separation and large surface area for chemical reactions. Lastly, Au nanotube arrays were synthesized via chemical method using CdSe nanotube arrays as the template. The dimensions of the Au nanotubes, as replicated from CdSe nanotubes, were tunable. When absorbed on the Au nanotube arrays surface, the Raman scattering of 4-mercaptobenzoic acid (a Raman-active molecule) was greatly enhanced for~4 orders of magnitude compared to the signals from the dry powder of the same molecule. Such large increase was due to the strong local electrical field enhancement near the Au nanotubes surface. / Detailed summary in vernacular field only. / Zhu, Haojun = 準一維納米結構在光伏、光催化及等離子體激元方面的應用 / 朱浩君. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 141-168). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Abstracts in English and Chinese. / Zhu, Haojun = Zhun yi wei na mi jie gou zai guang fu, guang cui hua ji deng li zi ti ji yuan fang mian de ying yong / Zhu Haojun. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgements --- p.iv / Contents --- p.v / List of Figures --- p.viii / List of Tables --- p.xviii / Chapter Chapter 1 --- Introductions --- p.1 / Chapter Chapter 2 --- Background --- p.4 / Chapter 2.1. --- Nanostructured Photovoltaic (PV) Solar Cells --- p.4 / Chapter 2.1.1. --- Fundamental physics of nanostructures for solar cell applications --- p.5 / Chapter 2.1.2. --- Inorganic nano-architectures for PV cells --- p.9 / Chapter 2.2. --- Nanostructures for Photocatalytic Degradation of Organic Pollutants --- p.18 / Chapter 2.2.1 --- Overview of photocatalytic degradation of organic pollutants --- p.19 / Chapter 2.2.2 --- Photocatalysis under visible light illumination --- p.24 / Chapter 2.3. --- Plamonic Noble Metal Nanostructures --- p.29 / Chapter 2.3.1 --- Surface plasmons of noble metal nanostructures --- p.29 / Chapter 2.3.2 --- Applications of plasmonic noble metal nanostructures in solar energy conversion and sensing --- p.35 / Chapter Chapter 3 --- Methodologies and Instrumentations --- p.45 / Chapter 3.1. --- Materials Growth Methodologies --- p.45 / Chapter 3.1.1. --- Thermal evaporation (TE) methods --- p.45 / Chapter 3.1.2. --- Hydrothermal (HT) methods --- p.47 / Chapter 3.1.3. --- Electrodeposition (ED) methods --- p.49 / Chapter 3.1.4. --- Prototype solar cells assemble --- p.52 / Chapter 3.2. --- Characterization Techniques --- p.53 / Chapter 3.2.1. --- Morphological, structural, and compositional analysis using electron microscopy based techniques --- p.53 / Chapter 3.2.2. --- Photoelectrochemical (PEC) performance test --- p.63 / Chapter 3.2.3. --- Photocatalytic degradation of organic pollutants --- p.65 / Chapter 3.2.4. --- Single-particle scattering imaging and spectroscopy --- p.67 / Chapter Chapter 4 --- ZnO Nanowire Arrays on Conducting Substrates -- A Comparison on the Growth Methodology --- p.71 / Chapter 4.1. --- Introduction --- p.71 / Chapter 4.2. --- Experimental --- p.72 / Chapter 4.3. --- Results and Discussions --- p.75 / Chapter 4.3.1 --- Morphologies, crystal structures and chemical compositions --- p.75 / Chapter 4.3.2 --- ZnO nanowire arrays used as electrodes --- p.80 / Chapter 4.3.3 --- ZnO nanowire arrays used as sacrificial templates in electroplating . --- p.85 / Chapter 4.4. --- Conclusions --- p.88 / Chapter Chapter 5 --- ZnO-core/CdSe-shell Nanocable Arrays for Photovoltaic Solar Cells --- p.89 / Chapter 5.1. --- Introduction --- p.89 / Chapter 5.2. --- Experimental --- p.90 / Chapter 5.3. --- Results and Discussions --- p.93 / Chapter 5.3.1 --- Synthesis of the ZnO-core/CdSe-shell nanocable arrays on ITO/glass --- p.93 / Chapter 5.3.2 --- The photovoltaic (PV) performance --- p.100 / Chapter 5.4. --- Conclusions --- p.107 / Chapter Chapter 6 --- CdSe and CdTe Nanotube Arrays as Visible-light-driven Photocatalyst for Organic Pollutant Degradation --- p.108 / Chapter 6.1. --- Introduction --- p.108 / Chapter 6.2. --- Experimental --- p.109 / Chapter 6.3. --- Results and Discussions --- p.112 / Chapter 6.3.1. --- Morphology, crystal structure, and chemical composition of the nanotube arrays --- p.112 / Chapter 6.3.2. --- Optical properties --- p.116 / Chapter 6.3.3. --- Photoelectrochemical (PEC) performance --- p.117 / Chapter 6.3.4. --- Photocatalytic activities --- p.120 / Chapter 6.4. --- Conclusions --- p.123 / Chapter Chapter 7 --- Fabrication of Au Nanotube Arrays and Their Plasmonic Properties --- p.124 / Chapter 7.1. --- Introduction --- p.124 / Chapter 7.2. --- Experimental --- p.125 / Chapter 7.3. --- Results and Discussions --- p.127 / Chapter 7.3.1. --- Morphology, crystalline structure, and chemical composition of Au nanotube arrays --- p.127 / Chapter 7.3.2. --- Au nanotube formation mechanism --- p.129 / Chapter 7.3.3. --- Plasmonic properties of Au nanotube arrays on ITO/glass substrates --- p.131 / Chapter 7.3.4. --- Plasmonic properties of single Au nanotubes --- p.133 / Chapter 7.3.5. --- Au nanotube arrays on ITO/glass as SERS substrates --- p.134 / Chapter 7.4. --- Conclusions --- p.138 / Chapter Chapter 8 --- Conclusions --- p.139 / Bibliography --- p.141

表面等離子共振 (SPR) 是受激發的電子的總體振動，一般在金屬、電介質界面上發生。我們能以振盪的電場去激發SPR。由於表面等離子共振時會產生巨大的增強電場，這令他在近場光學與納米光學中有著廣泛的應用。例如：微流控芯片、等離子波導、隱形裝置等等。 / 在這論文中，我們會研究納米金屬體之間的作用力。基於以下原因，這在納米技術中是一個重要課題。第一，當了解到物體之間的作用力後，我們可以以此開發出把納米尺寸的物體移動與放置的方法，有助於用自下而上式的方法製作納米器件。第二，物體之間的作用力會改變器件中納米顆粒的位置，因而會影響器件的特性。 / 在一般情況下，納米尺寸的物體的作用力都可以略去不理的，因為作用力是與體積成正比。但是，當表面等離子共振發生時，相互作用力會急速地增強。這增強是由於金屬顆粒的電偶會急速地增強的原故。我們稱這現象為「表面等離子共振增強光泳」 (SPREP). / 這論文由三個主要部份組成。第一部份，我們研究一帶梯度的金屬納米球與一振盪及旋進電偶之間的相互作用。我們以第一原理進路去解決這問題，並作了長波長假設。我們的解析解能夠處理多極效應，這效應在外場不均勻時是不可忽略的。我們探討了作用力、力矩、電場分佈。更發現了，當金屬納米球的梯度很高時，電偶與金屬納米球之間與有一穩定的力平衡。這研究有助於開發新型的光學鑷子。 / 第二部份，我們探討兩個金屬納米球之間的 SPREP，我們介紹了不同的計算方法。Bergman-Milton譜表示以及多重鏡象法。 兩個金屬納米球之間也有著穩定的平衡， 這表示在一群納米球中，可能有著穩定結構。這穩定的平衡，是由於表面等離子共振的頻率與相互距離有關，這是一種多體效應。這研究有助於了解納米簇的結構形成。 / 最後，我們以離散偶極子近似法(DDA)研究多體問題，雖然DDA並不是精確解，但當顆粒之間相距不太接近時，這依然是一個良好的近似。當顆粒的數量太多時，我們以等效介質理論去著手，不再考慮每一顆粒各自的位置，而只考慮顆粒的濃度。 / Surface plasmon resonance (SPR) is the collective electrons excitations, which occurred at the metal-dielectric interfaces and can be induced by an oscillating electric field. Because of the large field enhancement, SPR has a wide range of applications in near field optics and nano-optics, such as biosensors, lab-ona- chip devices, plasmonic waveguides, and cloaking devices. / In this thesis, we study the interparticle forces between metallic nanosized objects. It is an important topic in nanotechnology for at least two reasons. Firstly, the study of the interparticle forces may provide methods to control the motion and position of nano-size objects, which can be used to fabricate artificial nano-structure by bottom up approach. Secondly, the force can change the arrangement of the particles in the nanodevices and hence affecting the property of the devices. / The interparticle forces of nano-sized dielectric particles are negligible, since the force is proportional to the volume of the objects. However, the interparticle forces of metallic particles will be greatly enhanced when SPR occurs, which is able to compensate the volume effect. This phenomenon is called surface plasmon resonance enhanced photophoresis (SPREP), which is one of the consequences of the rapid increase in the dipole moment in the particles. / This thesis is consisted of three main parts. In the first part, we study the SPREP between a graded metallic nanosphere and a point dipole which is undergo oscillation and precession. A first principle approach is applied to handle this problem. Our analytic solutions are able to capture the multipole effect, which cannot be neglected in highly non-uniform fields. We have analyzed three important physical quantities: the induced force, the induced torque, and the field distribution. Furthermore, we find that there is a binding between the nanoparticle and the dipole source, when the gradation of the graded particles is large enough. This study has a potential application in developing a novel kind optical tweezers. / In the second part, we study the SPREP between two metallic nanoparticles. The force spectra are calculated by two different methods: Bergman- Milton spectral representation and multiple image method. The binding between two nanoparticles is observed, which indicates a possible stable structure among the metallic clusters. The binding is caused by the excitation of collective plasmon modes, and the consequence that the resonance poles sℓ are the functions of separation distances. This study may provide a better understanding in the structure formation of colloidal clusters in nano-scales. / Finally, we consider a many-particle system by the discrete dipole approximation (DDA) and effective medium theory. Although, the DDA is not an exact formalism, it is a suitable approximation for considering finite number of particles, if the distances among particles are not too close. When the number of particles in the host solution is large, we can use the effective medium theory to handle the problem. Instead of considering all discrete particles individually, we will consider the interaction between a single particle and a new effective host solution, where the dielectric function of the effective host solution is determined by the concentration of nanoparticles in the host solution. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Chan, Kin Lok = 納米金屬顆粒中的表面等離子共振增強光泳 / 陳建樂. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 90-94). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Chan, Kin Lok = Na mi jin shu ke li zhong de biao mian deng li zi gong zhen zeng qiang guang yong / Chen Jianle. / Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Nanoparticles and nanotechnology --- p.1 / Chapter 1.2 --- The history of nanoparticles and nano-optics --- p.1 / Chapter 1.3 --- Applications of nanoparticles --- p.2 / Chapter 1.3.1 --- Optical applications --- p.2 / Chapter 1.3.2 --- Biological and medical applications --- p.3 / Chapter 1.4 --- Electrokinetics of nanoparticles --- p.4 / Chapter 1.4.1 --- Review on recent work on electrokinetics --- p.5 / Chapter 1.5 --- Objectives of the thesis --- p.6 / Chapter 2 --- Basic Principles --- p.8 / Chapter 2.1 --- Drude model --- p.8 / Chapter 2.2 --- Complex dielectric function --- p.9 / Chapter 2.2.1 --- Electric field in an imperfect conductor --- p.10 / Chapter 2.3 --- Effective medium theory --- p.11 / Chapter 2.3.1 --- Maxwell-Garnett approximation --- p.12 / Chapter 2.3.2 --- Bruggeman approximation --- p.13 / Chapter 2.3.3 --- Bergman-Milton spectral representation (BMSR) --- p.13 / Chapter 2.3.4 --- Effective dielectric function of shelled sphere --- p.17 / Chapter 2.4 --- Surface plasmon resonance (SPR) --- p.18 / Chapter 2.5 --- Surface plasmon resonance enhanced photophoresis (SPREP) --- p.20 / Chapter 2.6 --- Justification of long wavelength limit --- p.23 / Chapter 3 --- Manipulation of Nanoparticles by a Single Dipole Source --- p.25 / Chapter 3.1 --- Introduction --- p.25 / Chapter 3.2 --- Formalism --- p.26 / Chapter 3.2.1 --- Electrostatic potential of a dipole --- p.27 / Chapter 3.2.2 --- Electrostatic potential of a dipole in terms of multipole expansion --- p.27 / Chapter 3.2.3 --- Laplace's equation of graded sphere --- p.30 / Chapter 3.2.4 --- Boundary value problem --- p.31 / Chapter 3.2.5 --- Force --- p.33 / Chapter 3.2.6 --- Torque --- p.35 / Chapter 3.3 --- Result and discussion --- p.36 / Chapter 3.3.1 --- Force --- p.38 / Chapter 3.3.2 --- Torque --- p.45 / Chapter 3.3.3 --- Electric field distribution --- p.46 / Chapter 3.4 --- Conclusion --- p.48 / Chapter 4 --- Interaction between Two Objects --- p.49 / Chapter 4.1 --- Introduction --- p.49 / Chapter 4.2 --- Interaction between two particles --- p.50 / Chapter 4.2.1 --- Dipole approximation --- p.50 / Chapter 4.2.2 --- Multiple images method --- p.52 / Chapter 4.2.3 --- Bergman-Milton spectral representation for collection of grains --- p.58 / Chapter 4.2.4 --- Equation of motion --- p.61 / Chapter 4.2.5 --- Result and discussion --- p.62 / Chapter 4.3 --- Particle near a conducting plane --- p.67 / Chapter 4.3.1 --- Dipole approximation --- p.67 / Chapter 4.3.2 --- Multiple image method --- p.69 / Chapter 4.3.3 --- Result and discussion --- p.70 / Chapter 5 --- Many-particle Systems --- p.72 / Chapter 5.1 --- Introduction --- p.72 / Chapter 5.2 --- Discrete dipole approximation --- p.72 / Chapter 5.2.1 --- 2-particle system --- p.73 / Chapter 5.2.2 --- 4-particle system --- p.74 / Chapter 5.2.3 --- Result and discussion --- p.75 / Chapter 6 --- Concentration Effect --- p.80 / Chapter 6.1 --- Introduction --- p.80 / Chapter 6.2 --- Formalism --- p.81 / Chapter 6.2.1 --- Result and discussion --- p.83 / Chapter 7 --- Summary --- p.88 / Bibliography --- p.90 / Chapter A --- Eigenfunctions, Eigenvalues, and Green's function --- p.95 / Chapter A.1 --- Isolated sphere --- p.95 / Chapter A.1.1 --- Eigenfunctions and eigenvalues --- p.96 / Chapter A.1.2 --- Green's function --- p.98 / Chapter A.2 --- Planar interface --- p.98 / Chapter A.2.1 --- Eigenfunctions and eigenvalues --- p.99 / Chapter A.2.2 --- Green's function --- p.100 / Chapter B --- Property of Spherical Harmonics and Associated Legendre Polynomials --- p.101 / Chapter B.1 --- Complex conjugate of Yℓm(Ω): --- p.102 / Chapter B.2 --- Differential Property --- p.102 / Chapter B.3 --- Limiting value --- p.102

Nous utilisons un microscope à effet tunnel (STM) associé à un microscope optique inversé pour l’excitation et la détection des plasmons de surface propagatifs et/ou localisés. L’excitation de ces plasmons est assurée par passage d’un courant tunnel inélastique entre la pointe du STM et la surface d’un film métallique mince (épaisseur de 50 nm) d’or ou d’argent déposé sur une lamelle de verre. Les fuites radiatives des plasmons de surface propagatifs et la lumière émise par les plasmons localisés dans le substrat de verre sont collectées par un microscope optique via un objectif à immersion. Il est alors possible de déterminer à la distribution spatiale et angulaire des émissions issues de ces plasmons de surface excités par STM, ainsi qu’à leur distribution en longueurs d’onde. Dans cette thèse, nous nous sommes intéressés au fonctionnement et à l’émission de lumière sous la pointe d’un microscope à effet tunnel fonctionnant à l’air. Nous montrons que la présence d’eau adsorbée au sein de la jonction tunnel, associée à la boucle d’asservissement du STM induit un mode de fonctionnement oscillant et périodique du STM sans lequel il serait difficile d’exciter les plasmons de surface. Ensuite, nous avons montré qu’il est possible de contrôler la directivité des plasmons de surface propagatifs excités par STM en excitant localement un nanofil d’or déposé sur le film d’or. L’étude détaillée de cette directivité nous a permis de démontrer que, contrairement au cas du nanofil d’or déposé sur verre, un nanofil d’or déposé sur film d’or ne se comporte pas comme un résonateur Fabry Pérot. Nous avons proposé un modèle simple dans lequel le nanofil est assimilé à un réseau linéaire d’antennes. Ce modèle permet de rendre compte des structurations spectrales et spatiales des plasmons de surface sur le film d’or résultant de l’ajout du nanofil d’or. Puis, nous avons étudié le couplage entre des nanofibres organiques fluorescentes (structures excitoniques) et les plasmons de surface propagatifs d’un film métallique d’or ou d’argent sur lequel ces nanofibres sont déposées. Nous avons ainsi montré que (i) la fluorescence de la nanofibre peut exciter des plasmons de surface à la surface du film d’or, (ii) la nanofibre organique agit comme un guide d’onde plasmonique et (iii) qu’il est possible d’injecter des plasmons de surface propagatifs du film excités par STM dans ces modes guidés par la nanofibre. D’autre part, en étudiant la figure d’interférences dans le plan de Fourier, nous avons pu confirmer que l’émission du dipôle sous la pointe STM et les plasmons de surface propagatifs excités par STM sont cohérents, donc issus du même événement tunnel. Enfin, nous discutons les effets du couplage entre des nanocristaux semiconducteurs (quantum dots) individuels et un monofeuillet de graphène. Nous montrons que la présence du graphène réduit d’un facteur ~10 la durée de vie de l’état excité des quantum dots déposés sur graphène par rapport aux quantum dots déposés sur verre. Pour les quantum dots déposés sur graphène, il résulte de cette réduction de la durée de vie de l’état excité, une baisse de l’intensité de fluorescence et une réduction du phénomène de scintillement avec un temps de résidence dans un état brillant globalement plus long que pour les quantum dots déposés sur verre. Les différents résultats obtenus au cours de cette thèse permettent de mieux comprendre l’excitation de plasmons de surface avec un microscope à effet tunnel, le couplage entre nanostructures plasmoniques et le couplage entre une structure plasmonique et une nanostructure excitonique. Ils ouvrent des perspectives intéressantes pour le développement de nanodispositifs hybrides plus complexes liants plasmons et excitons et contrôlés électriquement / We use a scanning tunnelling microscope (STM) to excite propagating and/or localised surface plasmons on a thin metallic film (50 nm thick) made of gold or silver deposited on a glass substrate. The leakage radiation of these STM-excited propagating surface plasmons, and the light emitted by localized plasmons into the glass substrate are collected by an inverted optical microscope equipped with an oil immersion objective. Using this setup, it is possible to image both the spatial and angular distribution of the light emitted into the glass substrate on a cooled-CCD. Sending this light to a spectrometer, it is also possible to obtain the wavelength distribution of these STM-excited plasmons. In this manuscript, we discuss the different operation modes of an STM in air. We show that the thin water layers adsorbed on both the STM tip and sample, along with the STM feedback loop, may give rise to an oscillatory mode of operation. Moreover, this mode turns out to be the most efficient one for plasmon excitation with a STM in air. We then show that, when the STM tip is used to locally excite plasmons on a gold nanowire deposited on a gold film, propagating surface plasmons may be preferentially launched along the nanowire axis. Precise understanding of this directivity allows us to demonstrate that, when deposited on a gold film, gold nanowires do not behave as Fabry-Perot resonators, but may be described quite accurately with a one dimensional antenna array model. With this model, it is thereby possible to explain the complex spatial and spectral characteristics of the STM-excited plasmons on the gold film after the addition of the nanowire. Next, we focus on the coupling between fluorescent organic nanofibres (excitonic nanostructures) and propagating surface plasmons on a metallic film (either gold or silver). We show that when the nanofibres are deposited on the metallic film, (i) their fluorescence can excite propagating surface plasmon, (ii) the nanofibre can act as a plasmonic waveguide, and (iii) it is possible to inject surface plasmons propagating onto the metallic film into the guided plasmonic modes of the nanofibre. Moreover, by studying Fourier space images, we confirmed that the vertical dipole localised under the STM tip and the STM-excited propagating surface plasmons are coherent. We finally study the coupling between individual semiconducting nanocrystals (quantum dots) and a graphene monolayer deposited on a glass substrate. We show that, when deposited on graphene, the fluorescence lifetime of the quantum dots is about 10 times shorter than for the quantum dots deposited on bare glass. This leads to a weaker fluorescence signal and reduced blinking behaviour with longer time spent into a bright state. These results improve our understanding of the STM excitation of surface plasmons. They also provide information on the coupling between plasmonic nanostructures and between plasmonic and excitonic entities. in particular, these results are a promising step toward the conception and the realisation of complex electrically driven hybrid plasmonic/excitonic nanodevices

基於表面等離子體的納米器件已經在近幾十年引起了十分廣泛的興趣因為其對於半波長光子器件，光學傳感，光譜學以及光學捕獲有著廣大的應用前景。表面等離子體是一種被限定於金屬和介質介面上的一種光子-電子混合模式，而且它具有許多吸引人的特質，比如對金屬表面周圍環境極其敏感，納米尺度範圍的光學電磁場局域和場增強，以及對鄰近物體極強的場強梯度捕獲力。雖然這些特性都已經分別被廣泛的研究過，但從光學捕獲的角度去實現光學傳感的方案並還沒有引起大量的關注。很明顯，在納米尺度範圍內操縱目標的可能性將使得新的納米器件具有高的光學探測性能和多功能性。為了涉及這個論題，本項目包括新穎的等離子體納米器件的研究，這些納米器件將能夠提供獨特的功能，在光學傳感，表面增強拉曼散射，以及光學捕獲方面。 / 在第一部分設計中，構建了一種基於雙層金屬納米條陣列的耦合系統。這樣的系統具有簡單的結構，易於加工和集成於微流系統的優點。由於這個系統內的光場耦合，場強可以進一步的被加強，這樣的特點有助於提高系統的敏感特性，尤其是通過強的光場來捕獲一些金屬的納米顆粒後。這個系統的光學共振條件可以從理論上進行模式分析得到。然後二維時域有限差分法證實了理論的分析而且進一步證明了利用該系統於光學傳感和捕獲的可能性。結果表明此系統的光學敏感度約為200nm/RIU，通過光學捕獲的金屬納米顆粒引起的近場調製和場增強可以使得表面增強拉曼散射的增強因數達到10⁹ 到10¹° 的高度。 / 在第二部分的設計裡，金納米環結構被證實了可以成為一個強大的工具作為表面等離子體納米光鑷來抓獲金屬納米顆粒。首先，金屬納米環具有很多優點比如對入射光的偏振不敏感，很寬的可調的共振範圍，有環的內腔周圍和內部有著均勻的光學場增強，以及很容易製備。這裡的設計著重于納米環在入射波長為785nm 的新穎的光學捕獲特性以及表面增強拉曼散射的性能。三維的時域有限差分法被用來計算結構的光學回應，以及麥克斯韋應力張量法被用來計算光學受力分佈情況。計算結果表明對於一個有20nm 大小的金納米顆粒球，納米環結構有最大的光學捕獲勢阱約32 KgT 。由於納米環結構周圍存在多個捕獲勢阱，使得其對目標捕獲顆粒具有約10⁶nm³ 的非常之大的有效體積。而且，被捕獲的顆粒會進一步的導致一些納米間隙的形成，這些納米間隙又會使得近場增強達到約160 倍的高度，這使得在實際應用中10⁸ 的表面增強拉曼散射的增強因數成為可能。 / 在第三部分的設計裡，全光納米操縱的概念被提出並證實，因為這樣的概念拓展了等離子體光鑷的一個極其重要的功能，那就是被捕獲的分子可以在捕獲和區域內被任意的操縱和轉移，而且這個區域是納米尺度的。設計的系統由梯度形金屬納米盤組成，這些納米盤具有不同的直徑，這使得它們支援不同波長的表面等離子體共振。通過改變入射光的波長和旋轉入射光的偏振態，就可以將捕獲的目標從一個納米盤轉移到另一個納米盤。三維的時域有限差分法和麥克斯韋應力張量法被用來證實了所提出的觀點。計算結果表明被捕獲的目標感受到的捕獲勢阱深度高達5000kgT/W/μm²，最大的光學轉矩約為336pN·nm/W/μm²，而且總的有效捕獲體積可達到10⁶nm³ 。在這部分的結尾，討論了所設計的系統在光學傳感方面潛在的應用前景。 / 在最後的部分裡，展示了一個實驗的證明來說明等離子體納米光鑷對目標捕獲的觀測問題，因為這樣的觀測對往後近期的相關實驗來說是首先要關心的問題。雖然兩種途徑已經在別處被證實了，分別是通過觀測系統的透射光的強度變化和系統共振波長的改變，來監測表面等離子體納米光鑷近場捕獲行為的發生，但是在這個部分裡，等離子體納米光鑷和表面增強拉曼傳感技術被結合在了一起並且被證實了這是另一種有效的方法用於觀測捕獲行為的發生。在本實驗中兩束鐳射光束被為別用來激發等離子體納米光鑷和表面增強拉曼信號，一束是633nm 的鐳射，另一束是785nm 的鐳射。表面等離子體納米光鑷簡單地由熱蒸鍍並熱退光的金顆粒納米島墊底構成，這個墊底的共振峰被調製到緊靠633nm 的位置。目標顆粒是由光化學生長合成的銀納米十面體，這些十面體被綁定了4-巰基苯甲酸分子的單分子層，且具有遠離633nm 和785nm 的共振峰。由於當等離子體納米光鑷被激勵的時候目標顆粒會被捕獲到近場的熱點內，這時近場的光場就會被極大的增強，所以表面增強拉曼的信號就會出現。這個過程也被用數值模擬的方法（三維時域有限差分法和麥克斯韋應力張量法）闡明了。更進一步的，當等離子體納米光鑷不被激勵的時候，被捕獲的目標顆粒可以被釋放掉，那樣表面增強拉曼的信號就會消失掉。所以，本設計不僅提供了一種強有力的探測等離子體光鑷捕獲行為的方法，而且能夠成為一種在生物探測方面可重複利用的“捕獲并傳感“的平臺。 / Surface plasmons (SPs) based nanodevices have attracted much research interest in recent decades due to their powerful application potentials for subwavelength optical circuits, optical sensing, spectroscopy, and optical trapping. SPs are the hybrid photon-electron modes bound at the interface of conductors and transparent materials, and they have lots of attractive properties such as sensitive to the changes of environment around the interface, strong optical field localization and enhancement in nanoscale domain, and strong field intensity gradient forces to trap the adjacent objects. Even though these properties have been widely investigated, their application in optical sensing based on the plasmonic optical trapping strategy remains largely unexplored. Clearly, the possibility of manipulating objects within the nanometer regime will enable new nanodevices that offer high optical detection performance and multiple-functionality. With the aim to address this issue, this project involves the study of novel plasmonic nanodevices that provide unique functionality in optical sensing, surface-enhanced Raman scattering (SERS), and optical trapping. / The first design is based on a coupling system involving double-layered metal nano-strips arrays. This system has the advantages of simple geometry and direct integration with microfluidic chips. The intense optical localization due to field coupling within the system can enhance detection sensitivity of target molecules, especially by virtue of the optical trapping of plasmonic nanoparticles. The optical resonant condition is obtained theoretically through analyzing the SPs modes. Numerical modeling based on two-dimensional (2D) finite-difference time-domain (FDTD) is consistent with the theoretical analysis and demonstrates the feasibility of using this system for optical sensing and trapping. Simulation results show that the refractive index sensitivity can reach ~200 nm/RIU, and a maximum SERS enhancement factor (EF) of 10⁹-10¹° is possible because of the near-field modulation and enhancement from optically trapped metal nanoparticles. / In the second design, a gold nano-ring structure is demonstrated to be an effective approach for plasmonic nano-optical tweezers (PNOTs) for trapping metallic nanoparticles. The plasmonic nano-ring structure has many interesting merits such as polarization insensitivity, wide tunable resonance range, uniform field enhancement around and inside the ring cavity, and ease of fabrication. This design has a unique feature of having large active volume for trapping. In our demonstration example, we have optimized a device for SERS operation at the wavelength of 785 nm. Three-dimensional (3D) FDTD techniques have been employed to calculate the optical response, and the optical force distribution have been derived using the Maxwell stress tensor (MST) method. Simulation results indicate that the nano-ring produces a maximum trapping potential well of ~32 kgT on a 20 nm gold nanoparticle. The existence of multiple potential well results in a very large active trapping volume of ~10⁶ nm³ for the target particles. Furthermore, the trapped gold nanoparticles further lead to the formation of nano-gaps that offer a near-field enhancement of ~160 times, resulting in an achievable EF of 10⁸ for SERS. / In the third design, we propose a concept of all-optical nano-manipulation. We show that target molecules, after being trapped, can be transferred between the trapping sites within a linear array of PNOTs. The system consists of an array of graded plasmonic nano-disks (NDs) with individual elements coded with different resonant wavelengths according to their dimensions. Thus, by switching the wavelength and rotating the polarization of the excitation source, the target nanoparticles trapped by the device can be manipulated from one ND to another. 3D FDTD simulation and MST calculation are utilized to demonstrate the operation of this idea. Our results reveal that the target experiences a trapping potential strength as high as 5000 kgT/W/μm², maximum optical torque of ~336 pN·nm/W/μm², and the total active volume may reach ~10⁶ nm³. The potential applications in terms of optical sensing are also discussed. / In the final design, for which experimental demonstration has been conducted, we show that PNOTs are achievable with random plasmonic nano-islands. Operation of the random PNOTs can be monitored by measuring the SERS enhancement factor in real time. Two laser beams having wavelengths of 633 nm and 785 nm are utilized to stimulate the PNOTs and excite the Raman signals simultaneously. The PNOTs are formed by annealing of a thermal evaporated gold film. This so-called nano-island substrate (Au-NIS) has a resonant peak close to 633 nm. The target is photochemical synthesized silver nanodecadedrons (AgNDs) functionalized with 4-Mercaptobenzoic acid (4-MBA) and the resonant peak of these AgNDs is far away from 633 nm and 785 nm. As the target is trapped to the hot-spots when the PNOTs are active, the near-field intensity is enhanced significantly, which results in the emergence of SERS signals, i.e. confirming the expected outcome of SERS upon nanotrapping by the PNOTs. This process is also elucidated numerically through 3D FDTD simulation and MST calculation. Furthermore, the target can be released as the PNOTs become inactive, i.e. disappearance of the SERS signal. Therefore, this design offers not only a robust avenue for monitoring trapping events in PNOTs, but also a reproducible “trap-and-sense“ platform for bio-detection. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Kang, Zhiwen. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references (leaves 146-170). / Abstracts also in Chinese. / Abstract --- p.I / Acknowledgements --- p.VIII / List of Illustrations --- p.XIII / Chapter Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- Surface Plasmon Polaritons and Localized Surface Plasmons --- p.1 / Chapter 1.2 --- Relevant Applications Based on Surface Plasmons --- p.3 / Chapter 1.3 --- Plasmonic Nano-Optical Tweezers and Relevant Applications --- p.7 / Chapter 1.4 --- Literatures Review and Objectives of this Thesis --- p.12 / Chapter 1.5 --- Structure of this Thesis --- p.17 / Chapter Chapter 2. --- Research Methodologies --- p.20 / Chapter 2.1 --- Theoretical Background of Surface Plasmons --- p.20 / Chapter 2.2 --- Numerical Simulation Techniques for Studying Complex Nanostructures --- p.30 / Chapter 2.3 --- Optical Force Calculation with the Maxwell Stress Tensor Method --- p.38 / Chapter 2.4 --- Nanostructure Fabrication and Characterization --- p.40 / Chapter Chapter 3. --- Optical Sensing Based on Double-Layered Metal Nano-Strips --- p.43 / Chapter 3.1 --- Introduction --- p.43 / Chapter 3.2 --- Theoretical Model and Analysis --- p.46 / Chapter 3.3 --- Numerical Verification and Discussion --- p.50 / Chapter 3.4 --- Optical Sensing Evaluation --- p.54 / Chapter 3.5 --- Near-Field Modulation by Optically Trapped Metal Nanoparticles --- p.58 / Chapter 3.6 --- Discussion --- p.61 / Chapter 3.7 --- Conclusion --- p.62 / Chapter Chapter 4. --- Gold Nano-Ring as Plasmonic Nano-Optical Tweezer --- p.64 / Chapter 4.1 --- Introduction --- p.64 / Chapter 4.2 --- Design and Optical Response --- p.67 / Chapter 4.3 --- Optical Force Calculation and Evaluation of Trapping Performance --- p.73 / Chapter 4.4 --- Stable Trapping Sites and Active Trapping Volume --- p.76 / Chapter 4.5 --- Near-Field Variation and Discussion --- p.81 / Chapter 4.6 --- Conclusion --- p.84 / Chapter Chapter 5. --- Graded Plasmonic Nano-Disks for Near-Field Nano-Manipulation --- p.86 / Chapter 5.1 --- Introduction --- p.86 / Chapter 5.2 --- Modeling and Optical Response --- p.89 / Chapter 5.3 --- Optical Force Distribution in the Structure --- p.91 / Chapter 5.4 --- Optical Trapping Potential and Rotational Energy --- p.96 / Chapter 5.5 --- Optical Trapping Volume and Discussion --- p.101 / Chapter 5.6 --- Conclusion --- p.104 / Chapter Chapter 6. --- Monitoring Plasmonic Nano-Optical Trapping through Detection of Surface-Enhanced Raman Scattering --- p.106 / Chapter 6.1 --- Introduction --- p.106 / Chapter 6.2 --- Numerical Investigation --- p.110 / Chapter 6.3 --- Sample Preparation and Characterization --- p.112 / Chapter 6.4 --- Experimental Implementation and Results --- p.122 / Chapter 6.5 --- Discussion --- p.134 / Chapter 6.6 --- Conclusion --- p.137 / Chapter Chapter 7. --- Conclusion and Outlook --- p.139 / References --- p.146 / Publications from this Work --- p.171