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研究生： 泰 拉
Thanmayee Shastry
論文名稱： 溶劑和熱退火聚苯乙烯共聚聚二甲基矽氧烷共聚物自組裝建構三維奈米圖案成型技術
3D Nanopatterning of Self-Assembled Polystyrene-block-Polydimethylsiloxane via Solvent and Thermal Annealing
指導教授： 何榮銘
Ho, Rong-Ming
口試委員: 蔣酉旺
孫亞賢
陳俊太
Shi, An-Chang
學位類別： 博士
Doctor
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2024
畢業學年度： 113
語文別： 英文
論文頁數： 151
中文關鍵詞： 聚苯乙烯嵌段共聚聚二甲基矽氧烷 、溶劑和熱退火 、三維奈米圖案
外文關鍵詞： Polystyrene-block-Polydimethylsiloxane, Solvent and Thermal Annealing, 3D Nanopatterning
相關次數： 點閱：2  下載：0 
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    • 具有取向控制的奈米微結構嵌段共聚物薄膜，尤其是垂直圓柱微結構，在奈米圖案化的領域具有極大潛力。然而，由於嵌段共聚物之組成鏈段間的表面張力差異較大，實現垂直取向控制非常具有挑戰性。為了使薄膜產生垂直的圓柱微結構，需平衡上下兩界面對於嵌段共聚物組成鏈段的親和力，即在上下兩界面各形成中性層，最終透過自對準機制形成貫穿薄膜的垂直圓柱微結構。
    本研究以聚苯乙烯-聚二甲基矽氧烷嵌段共聚物 (PS-b-PDMS) 為代表系統，探討溶劑退火對取向控制的影響。我們首先使用羥基封端的高分子刷PS-OH和PDMS-OH進行兩步驟基材修飾，將其接枝至晶圓的原生氧化層 (SiO2) 上。通過調整 PS-OH 和 PDMS-OH 接枝的比例，產生具溶劑響應性 (solvent responsive) 的基材粗糙度，以誘導垂直圓柱微結構的形成。此方法不同於傳統的中和基材對於兩組成嵌段的親和力，稱之為溶劑響應性官能基化基材。在溶劑退火過程中，官能基化基材提供適當的粗糙度，驅動 PS-b-PDMS 薄膜自底部形成垂直的 PDMS 圓柱體。同時，通過空氣電漿處理可在薄膜表面產生中性層，進而在溶劑退火後於薄膜頂部形成垂直的圓柱微結構。結合這兩個步驟，溶劑退火能夠通過自對準機制在官能基化基材上實現貫穿薄膜的垂直圓柱微結構。
    本研究提出利用溶劑退火進行序列式自組裝(sequential self-assembly) 來構建三維奈米圖案。通過調整溶劑的選擇性，PS-b-PDMS薄膜可形成六角穿孔層板、平行圓柱以及球體微結構。對這些微結構薄膜進行反應離子蝕刻 (RIE) 處理後，可獲得具有六角有序孔洞、平行線條及點陣列的SiO2拓樸結構。接著，透過逐層製備出點上孔 (hole-on-dot) 與孔上線 (line-on-hole) 的階層式結構，利用溶劑退火實現三維奈米圖案化的可行性，提供嵌段共聚物微影蝕刻的奈米微機電系統（nano-MEMS) 新技術。
    相較於溶劑退火，熱退火技術在工業中更易被接受。本實驗室意外發現，在高真空環境下，僅需熱退火即可實現嵌段共聚物奈米微結構薄膜的垂直取向。我們推測此現象與熔融態高分子表面張力與壓力之間的相依性有關。研究顯示，當溫度和壓力升高時，高分子熔體的表面張力呈線性下降關係。然而，在高真空條件下，我們卻觀察到不同的結果，其表面張力的變化趨勢卻相反，且相較於溫度，壓力在低壓環境下對表面張力的影響更為顯著。值得注意的是，在高溫高真空條件下，不同熔融態高分子的表面張力與壓力之間均呈現線性對數關係。此行為可用 Langmuir 吸附等溫線進行解析，該等溫線呈雙曲線形態，若在對數-常態圖中繪製，則呈現出S形曲線，中間區域表現出線性特徵，與觀察到的線性對數關係相似。本研究的發現，將為透過熱退火技術實現由二維到三維奈米圖案化的發展帶來新的契機。 

    Nanostructured block copolymer (BCP) thin films with controlled orientation, in particular, perpendicular cylinders, are appealing for nanopatterning. However, BCP with large discrepancy on the surface tensions of constituted blocks might cause difficulties for orientation control as expected. A neutral surface of BCP thin film is needed to give perpendicular cylinders from the top of the thin film. Also, it is necessary to create a neutral substrate with equivalent affinities for the constituted blocks to achieve perpendicular cylinders from the bottom of the thin film. Consequently, it is possible to create film-spanning cylinders through a self-alignment process.
    Herein, polystyrene-block-polydimethylsiloxane (PS-b-PDMS) was used as a represented BCP system to demonstrate the aimed controlled orientation through solvent annealing. A two-step substrate functionalization of an intrinsic oxide layer (SiO2) wafer was carried out by using hydroxyl-terminated PS (PS-OH) followed by hydroxyl-terminated PDMS (PDMS-OH). By varying the grafting percentage of the PS and PDMS brushes on the substrate, it is possible to create roughness variation for the induction of perpendicular cylinders. In contrast to the neutralization of the affinities, this is referred to as a responsive functionalized substrate. With appropriate roughness of the functionalized substrate under solvent annealing, perpendicularly oriented PDMS cylinders can be driven from the bottom of the PS-b-PDMS thin film. By taking advantage of air plasma treatment, it is possible to generate a top-capped neutral layer on the film surface, giving the formation of perpendicular cylinders from the top surface after solvent annealing, giving film-spanning perpendicular cylinders via a self-alignment process.
    3D nanopatterning is challenging from solvent annealing. By simply tuning solvent selectivity, various nanostructures, including hexagonal perforated lamellae (HPL), parallel cylinders, and spheres, can be obtained from lamellae-forming PS-b-PDMS. After reactive ion etching (RIE) treatment of those solvent annealed PS-b-PDMS thin films with the use of various selective solvents, topographic SiO2 monoliths with an ordered arrays of hexagonally packed holes, parallel lines, and hexagonally packed dots can be fabricated. Subsequently, hole-on-dot and line-on-hole hierarchical textures can be created through a layer-by-layer process with RIE treatment, providing an appealing technique for nano-MEMS manufacturing based on BCP lithography.
    In contrast to solvent annealing, thermal annealing is currently more acceptable in industries. Our laboratory unexpectedly found that the formation of perpendicular orientation of nanostructured BCP thin films simply by thermal annealing under high vacuum. Herein, this work aims to in-depth examine the pressure dependence of surface tension for polymer melts under high vacuum. Increasing both temperature and pressure above the ambient condition results in a reduction in surface tension for polymer melts, showing a linear relationship. Surprisingly, an opposite trend for the reduction in surface tension can be observed under a high vacuum condition. In contrast to temperature, the influence of pressure on surface tension at low pressure is much more significant. Most interestingly, a linear log relationship between surface tension and pressure is evident across various polymer melts under a high vacuum at a high temperature. This behaviour can be correlated with the Langmuir adsorption isotherm that features a hyperbolic curve and appears as a sigmoidal curve on an equivalent log-normal plot with a linear mid-region, resembling the linear-log relationship. This finding will bring new opportunities to evolve from 2D to 3D nanopatterning via thermal annealing.

    Abstract............................................................................................................................ii Acknowledgements..................................................................................................viii Contents..........................................................................................................................xi List of Figures...............................................................................................................xiv List of Tables................................................................................................................xxx Abbreviations.............................................................................................................xxxi Chapter 1. Introduction...............................................................................................1 1.1 Patterning Techniques..........................................................................................1 1.2 Block Copolymer (BCP) Lithography...............................................................3 1.3 Self-Assembly of Block Copolymers (BCPs)..................................................5 1.4 Self-Assembly of BCP Thin Films.......................................................................7 1.4.1 Confinement Effects on BCP Thin Films......................................................7 1.5 Various Techniques for Controlled Orientation in BCP Thin Films.......8 1.6 Silicon-Based BCPs...............................................................................................28 1.7 3D Nanopatterning..............................................................................................30 1.7.1 Layering of Block Copolymers Patterns....................................................30 1.7.2 Cross-linking and Sequential Deposition of BCP thin film................31 1.7.3 Formation of BCP Pattern via Iterative Self-Assembly.........................34 1.8 Surface Tension of Polymers.............................................................................37 1.8.1 Material Dependence of Surface Tension................................................37 1.8.2 Temperature Dependence of Surface Tension.......................................38 1.8.3 Pressure Dependence of Surface Tension................................................40 1.8.4 Molecular-Weight Dependence of Surface Tension............................42 1.8.4 Effect of High Vacuum Degree on Surface Tension..............................44 Chapter 2. Objectives..................................................................................................47 Chapter 3. Experimental............................................................................................50 3.1 Synthesis of PS-b-PDMS BCPs.........................................................................50 3.2 Sample Preparation..............................................................................................52 3.2.1 Sample Preparation for PS-b-PDMS Bulk Samples...............................52 3.2.2 Controlled Orientation of BCP Thin Film under Solvent Annealing...............................................................................................................52 3.2.3 Preparation of PS-b-PDMS Thin Film for 3D Nanopatterning..........53 3.2.4 Thin Film Morphology of PS-b-PDMS in Solvent Annealing........54 3.2.5 Hierarchical Self-Assembly of PS-b-PDMS on Topographic Patterned SiO2.....................................................................................................56 3.3 Instrumentation.....................................................................................................56 3.3.1 Transmission Electron Microscopy (TEM).................................................56 3.3.2 Small-Angle X-ray Scattering (SAXS).........................................................57 3.3.3 Spectral Reflectometer (SR)...........................................................................57 3.3.4 Reactive Ion Etching (RIE)...............................................................................58 3.3.5 Field-Emission Scanning Electron Microscopy (FESEM).....................58 3.3.6 Scanning Probe Microscope (SPM)............................................................58 3.3.7 Grazing Incidence Small-Angle X-ray Scattering (GISAXS)...............59 3.3.8 Home-made high vacuum oven..................................................................59 Chapter 4. Results and Discussion.........................................................................61 4.1 Induced orientation through solvent annealing.......................................61 4.1.1 Schematic Illustration of Induced Orientation.......................................62 4.1.2 Intrinsic Phase Morphology of Self-Assembled PS-PDMS................64 4.1.3 Induced orientation from the bottom of thin film................................65 4.1.4 Perpendicular orientation from air plasma-treated top surface.....81 4.1.5 Self-alignment mechanism for induced perpendicular orientations from the bottom and top................................................................................83 4.2 Three-dimensional (3D) Nanopatterning....................................................88 4.2.1 Schematic Illustration of 3D Nanopatterning.........................................88 4.2.2 Self-assembled PS-b-PDMS in bulk...........................................................91 4.2.3 Controlled PS-b-PDMS self-assembly.......................................................93 4.2.4 Fabrication of 3D Nanopatterns................................................................103 4.2.5Theoretical Framework: Self-Consistent Field Theory (SCFT).........107 4.2.6 Wall-Profile Construction............................................................................110 4.2.7 SCFT Simulation Results for 3D Nanopatterning...............................112 4.3 Pressure dependence of surface tension of polymeric melt.............117 4.3.1 Measurement of surface tension for polymeric melt.......................118 4.3.2 Temperature dependence of surface tension.....................................120 4.3.3 Pressure dependence of surface tension..............................................121 4.3.4 Molecular weight dependence on surface tension..........................124 4.3.5 Theoretical Model......................................................................................... 125 4.3.6 Discussion.........................................................................................................127 Chapter 5. Conclusions and Perspective..........................................................131 Chapter 6. References.............................................................................................136 Publications................................................................................................................150  

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