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研究生：	唐隆綾 Lung-Ling Tang
論文名稱：	微反應晶片應用於硒化鎘奈米微粒合成之研製 DEVELPMENT OF MEMS-BASED MICROREACTOR FABRICATED FOR SYNTHESIZING COMPOSITE CdSe NANOPARTICLES
指導教授：	楊啟榮 Yang, Chii-Rong 謝佑聖 Hsieh, Yu-Sheng
學位類別：	碩士 Master
系所名稱：	機電工程學系 Department of Mechatronic Engineering
論文出版年：	2005
畢業學年度：	93
語文別：	中文
論文頁數：	101
中文關鍵詞：	硒化鎘奈米微粒、微流體系統、微反應晶片、渾沌對流
英文關鍵詞：	CdSe nanoparticle, micro fluidic system, microreactor chip, chaotic advection
論文種類：	學術論文
相關次數：	點閱：278 下載：34
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奈米微粒(nanoparticles)由於粒子尺寸接近分子層級，受到強烈的量子侷限效應(quantum size confinement effect)規範，使其在各性質上顯現出截然不同於傳統塊材之特性，在眾多材料特性中，其吸收、放光光譜皆為粒子大小依憑性(size-dependent)最為顯而易見，此特性使得奈米微粒能廣泛應用於光電科技、生醫檢測方面的研究。因此近年來相關奈米微粒之製備，皆朝向高粒徑均勻度(monodispersity)、粒子大小可控性來發展。然而，透過化學藥品分散與包覆，奈米微粒的分佈寬度仍有一定極限，無法完全解決粒徑均勻度不佳之問題。
微流體系統具有快速質傳與熱傳特性的優點，應用於生化反應，如連鎖反應聚合脢(Polymerase Chain reaction, PCR)的微反應晶片，便有極優於傳統反應之表現。因此本研究目的即以微機電製程技術為基礎，製作一應用於合成硒化鎘奈米微粒之微反應晶片。與傳統巨觀反應器相較，微反應晶片因具有快速升溫降溫、溫度分佈均勻、濃度與反應時間容易控制等優點，預期能改善傳統合成法未能解決之粒徑分佈不均現象，並且精確的控制奈米粒子之粒徑大小；產量部分則藉由連續反應提升產量，達反應自動化與批次化生產的目的。本研究已建立一套製程，成功將微混合元件與微加熱元件，整合於全玻璃反應晶片上，並實際通入硒化鎘奈米微粒溶液進行合成，以驗證此微反應晶片之可行性。

Nanoparticles have been widely used in the fields of opto-electric and bio-inspecting technologies. The opto-electric characteristics of materials, e.g. absorbed and emitting spectrum, are significantly dependent to the size of the particles; therefore, the related techniques for preparing nanoparticle are requested to high monodispersity and controllability of particle diameters recently. However, the monodispersity of particle diameters is still a problem in present preparing techniques of nanoparticles.
Microfluidic system has the advantage of rapid mass transport and heat delivery. In this proposal, a MEMS-based microreactor chip will be developed to synthesize composite CdSe nanoparticles. This microreactor chip will integrate the functions of micro mixer, micro heater, continuous reaction. Compared with the traditional reactor, because microreactor has the merits of rapidly increasing and decreasing temperature, uniform temperature distribution, concentration and react time easily controlled, can significantly improve the drawbacks of poor monodispersity of particle diameters. Besides, the particle diameters can be precisely controlled by adjusting reaction parameters; batch production of nanoparticles will be also realized by continuous reaction and synthesis. We developed a glass deep-etching technique and integrated Pt micro heater and 3D micromixer on micro reactor devices. By using this device, CdSe nanoparticles can be produced and particle size can be adjusted by the temperature control.

摘要     Ⅰ
總目錄      Ⅲ
圖目錄      Ⅴ
表目錄      Ⅹ
符號對照表      XI
第一章  緒論      1
1.1  微機電系統與微反應晶片       1
1.2  奈米微粒簡介      5
1.2.1  奈米微粒之特性      5
1.2.2  奈米微粒之應用      6
第二章  文獻回顧      13
2.1  硒化鎘奈米微粒之合成      13
2.2  應用於化學合成之微反應器      19
2.3  研究動機與目的      24
第三章 微反應器之分析與設計      25
3.1  微管道之流體力學      25
3.1.1 微混合原理      26
3.1.2 微加熱與微溫度感測原理      28
3.2  微反應器晶片之設計      32
3.2.1 微混合器之設計      32
3.2.2 微溫控模組之設計      33
3.3  微混合區域之特性模擬      40
3.4  微混合區域之模擬結果      43
第四章 實驗製程與檢測規劃      49
4.1  微反應晶片之製程規劃      49
4.1.1 製程規劃      49
4.1.2 微反應晶片之特性檢測      51
4.1.3 奈米微粒之合成與粒徑分析      52
4.2  實驗設備與檢測系統      55
第五章 實驗結果與討論      65
5.1  微反應晶片製程      65
5.1.1 雷射加工玻璃流道製程      65
5.1.2 玻璃流道蝕刻製程      66
5.1.2.1 蝕刻罩幕之選擇      67
5.1.2.2 三種玻璃基材蝕刻特性之比較      68
5.1.2.3 退火處理抑制玻璃基材側蝕比      69
5.1.3 玻璃熔融接合      69
5.1.4 金屬加熱器與溫度感測電極製作      70
5.2  微反應晶片特性量測      87
5.2.1 混合效率測試      87
5.2.2 熱電阻加熱特性測試      87
5.2.3 微反應晶片合成硒化鎘奈米微粒      88
第六章 結論      95
6.1  本文結論      95
6.2  未來展望      96
參考文獻     97


圖   目   錄
Figure 1-1    Schematic of the lab on a chip function      4
Figure 1-2    Schematic successive fragmentation of a block of metal      9
Figure 1-3    Density of states as a function of energy in systems with different number of spatial dimensions      9
Figure 1-4    Pictures showing how three different quantum dots can produce 24 unique codes      11
Figure 1-5    (a) Quantum-dot LEDs; (b) The structure contains a single layer of CdSe quantum dots sandwiched between two organic thin films s     11
Figure 1-6    Cell labeling with quantum dots and illustration of quantum dot photostability, compared with the dye Alexa 488      12
Figure 2-1    Schematic of the nanoparticles preparation      16
Figure 2-2        Schematic of nucleation and growth during the preparation of monodisperse nanoparticles      17
Figure 2-3    Schematic of the nanoparticles preparation      17
Figure 2-4    Process of nanoparticles size selection      18
Figure 2-5    A microfluidic procedure for the production of CdS nanoparticles     22
Figure 2-6    Schematic of the flow reaction for CdSe nanoparticles      22
Figure 2-7    Microreactor channels in a 100 mm diameter glass wafer: (a) react directly in a serpentine 4.7 L channel; (b) be diluted before reacting in a 12.5 L channel. The nanoparticle product is diluted and quenched before exiting to a capillary flow cell      23
Figure 3-1    Transition mode of fluid      30
Figure 3-2    (Top) schematic of the three-dimensional serpentine channel, (middle) schematic of square-wave channel, (bottom) schematic of straight channel      30
Figure 3-3    Fabricating flow chart of microreactor and synthesis of CdSe nanoparticles      35
Figure 3-4    Schematic of microreactor      36
Figure 3-5        Schematic of 3-D micromixer      36
Figure 3-6        Entire view of five inch mask pattern layout      37
Figure 3-7    Schematic diagram of micromixer patterns      38
Figure 3-8    Schematic diagram of microheater position      38
Figure 3-9        Schematic diagram of microheater patterns      39
Figure 3-10    Solid model of 3-D micromixer      42
Figure 3-11    Mixing index in etch cross-section of the 3D serpentine channel for various cell number      45
Figure 3-12    Spatial variation of the ethanol concentration for various cell number with inlet flow rate 100 &micro;l/min      46
Figure 3-13    Spatial variation of the ethanol concentration for various flow rate      47
Figure 3-14    Spatial variation of the ethanol concentration with an inlet flow rate of 50、100、200、600 and 1000 &micro;l/min      48
Figure 4-1        Fabrication process of microreactor (laser ablation)     54
Figure 4-2    Fabrication process of microreactor (wet etching)     54
Figure 4-3    Lithography process equipments      59
Figure 4-4    Three target-gun with dual DC & RF power sputter      60
Figure 4-5        Optical microscope and image measurement system      61
Figure 4-6    Surface profiler      61
Figure 4-7    Zoom-variable optical microscope      62
Figure 4-8    Scanning electron microscope      62
Figure 4-9        Box furnace      63
Figure 4-10    Power supply      63
Figure 4-11        Dual-syringe infusion pump      64
Figure 5-1        Microchannel defined by laser ablation     72
Figure 5-2        SEM image of the laser-ablating channel      73
Figure 5-3    Microchannel defined by wet etching; (a) Upper microchannel     73
Figure 5-3    Microchannel defined by wet etching; (b) Lower microchannel     74
Figure 5-4    Pinholes were formed in Pyrex7740 when only Cr/Au was used as mask      74
Figure 5-5    Pinholes were formed in Pyrex7740 when S1813/Cr/Au was used as mask      75
Figure 5-6    No pinholes appear in the Pyrex7740 when AZ4620/Cr/Au was used as mask      75
Figure 5-7        SEM image of channels etched in Soda-lime      76
Figure 5-8    SEM image of channels etched in Pyrex 7740      76
Figure 5-9   SEM image of channels etched in Corning 1737      77
Figure 5-10  SEM image of channels etched in annealed Pyrex 7740      77
Figure 5-11  SEM image of channels wet etched in annealed Soda-lime      78
Figure 5-12  SEM image of channels wet etched in annealed Corning 1737     78
Figure 5-13  SEM image of microchannels defined by wet etching      79
Figure 5-14  Two glass flats aligned and clung to each other by DI water      80
Figure 5-15  Newton’s rings were formed after fusion bonding      81
Figure 5-16  A sealed microchannel was formed after fusion bonding      81
Figure 5-17  SEM micrograph of the bonding layer     82
Figure 5-18  Ripples formed by residual potoresist exist in Pt/Ti film      83
Figure 5-19  Pt/Ti was completely defined on rough surface      83
Figure 5-20  Pt/Ti was completely defined on smoother surface      84
Figure 5-21  Pt/Ti was completely defined on microractor      85
Figure 5-22  Photograph of mixing test      88
Figure 5-23  OM image of mixing test      88
Figure 5-24  IR image of microreactor      89
Figure 5-25  The highest temperature of microreactor      90
Figure 5-26  Distribution of temperature at microreactor      91
Figure 5-27  3D thermal distribution of microreactor      92
Figure 5-28  Congealed CdSe raw solution at room temperature      92
Figure 5-29  CdSe solution collected at 220 ℃, 240 ℃ and 260℃     93
Figure 5-30  Top view of microeactor      93
Figure 5-31  CdSe products blocked up the microchannel      94
Figure 5-32  UV-Vis absorption spectra of obtained in CdSe products     94

表   目   錄
Table 1-1        Microfabrication technologies in MEMS field      3
Table 1-2    Changes of material properties      10
Table 1-3        Application of nanoparticle      10
Table 2-1        Method for preparation of nanoparticles      16
Table 3-1    Temperature coefficient of resistivity and thermal expansion coefficient of common metal      31
Table 3-2        Physical properties of ethanol and water      42
Table 3-3    Standard deviation of ethanol concentration for various cell number     44
Table 3-4        Standard deviation of ethanol concentration decreasing by chaotic advection      44
Table 4-1    Experimental facilities      57
Table 5-1    Wet etching results for three different material      71
Table 5-2    Wet etching results for three different materials with and without annealing      71
Table 5-3    Experimental parameters of sputtering Pt/Ti      71
                                

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