臺灣博碩士論文加值系統

非等向性濕式矽蝕刻製程是體型矽微加工關鍵技術之一，而其技術發展重點在於如何提升蝕刻面的蝕刻速率與表面粗糙度。由於傳統的磁石攪拌方式有無法均勻地改善蝕刻速率與蝕刻粗糙度的缺點，而超音波震盪的方式雖可改善蝕刻表面粗糙度，但蝕刻速率改善的幅度卻不大，亦不適用於製作薄膜微結構。因此為改善以上機械攪拌式的缺點，本研究擬利用高壓高溫的方式，來進行快速非等向性濕式矽蝕刻，利用壓力輔助機制，可將蝕刻面的表面張力降低，並增加蝕刻液的氣體溶解度。最後，使氫氣泡附著現象得到有效解決，並增加蝕刻液的質傳效果，可降低蝕刻表面的粗糙度並大幅度地提升蝕刻速率。
在應用方面，本研究將使用高壓高溫輔助蝕刻機制，結合快速的蝕刻速率、良好的表面粗糙度與非機械式攪拌方式等特性，用於製作各式薄膜微結構，達到大幅降低製程時間，並增加製作薄膜微結構之良率。
本研究將以KOH與TMAH溶液為蝕刻液，整合薄膜沉積、微影(lithography)、電漿蝕刻等製程技術來進行研究計劃，並購裝具高壓控制、高溫控制、抗侵蝕及高強度等特色之高壓暨高溫濕式矽蝕刻系統，進而改善矽蝕刻特性。研究中所獲得的最佳參數，將應用於高精度矽微結構與薄膜微結構的製作，以達到批次量產的目的，實現低成本微機電系統的製造與應用技術。

Anisotropic wet etching is one of the key technologys for the microstructure fabrication in Micro Electro Mechanical Systems(MEMS). In the study, for improving the roughness quality and etching rate of etched surface, high pressure and high temperature enhanced fast anisotropic etching of mono-crystalline silicon, the methods will be used to evaluate the etching properties of (100) silicon plane in KOH or TMAH solutions. The anisotropic etching parameters will be optimized adequately and employed to fabricate the high precise silicon microstructures.
For the study of batch production, the silicon structures will be formed the metallic mold insert by the electroforming process, and then the molding process, including hot embossing or injection molding, will be applied to produce mass plastic microstructure, and then the low-cost MEMS applications will be realized. Four key techniques will be focused as followed: (1) To setup the apparatus of high pressure and high temperature suitable to anisotropic fast wet etching of single silicon; (2) To build up the optimized fast etching process parameters, (3) To fabricatie the silicon-microstructure and Silicon nitride membrane microstructure.
The results of carrying out project will be predicted to promote the domestic silicon etching technique in MEMS , and also facilitate the international competitive power of the related companies in the market of micro-systems, which have been demonstrated as the highest valued industry in the future.

總 目 錄
摘 要 Ⅰ
總目錄 Ⅱ
圖目錄 Ⅳ
表目錄 Ⅷ
第一章 緒論 1
1.1 前言 1
1.2 非等向性濕式蝕刻技術之重要性 4
1.3 非等向性濕式蝕刻技術之應用 5
1.4 論文架構 7
第二章 文獻回顧 16
2.1 濕式蝕刻概論 16
2.2 改良蝕刻特性之重要性 18
2.3 濕式蝕刻特性之改良方式 19
2.3.1 磁石攪拌與超音波震盪 19
2.3.2 微波輔助蝕刻 19
2.3.3 添加劑的運用 20
2.4 研究動機 21
第三章 應用理論與技術 31
3.1 單晶矽非等向性濕式蝕刻 31
3.1.1 矽的晶體結構 31
3.1.2 非等向性濕式蝕刻之基本概念 31
3.1.2.1 蝕刻終止技術 33
3.1.2.2 蝕刻保護技術 34
3.1.2.3 薄膜殘留應力問題 34
3.2 非等向性濕式蝕刻之影響因素 36
3.2.1非等向性濕式蝕刻的反應機制 36
3.2.2 蝕刻液的選用 37
3.2.3 非等向性濕式蝕刻之物理模型 39
3.3 快速非等向性濕式蝕刻之理論基礎 42
3.3.1 高壓物理之反應特性 42
3.3.2 高溫化學之蝕刻機制 43
3.3.3 蝕刻表面改質方法 44
第四章 研究設計與實驗方法 53
4.1 研究設計法則 53
4.1.1 實驗步驟設計 53
4.1.2 結構設計 54
4.2 實驗規劃與方法 55
4.3 實驗設備 57
第五章 實驗結果與討論 69
5.1 壓力輔助蝕刻 69
5.1.1 表面粗糙度 69
5.1.2 蝕刻速率 73
5.2 高溫高壓輔助蝕刻 75
5.2.1 表面粗糙度 75
5.2.2 蝕刻速率 78
5.3 蝕刻應用與性質 81
第六章 結論 114
參考文獻 116

圖 目 錄
Figure 1-1 Illustration of bulk micromachining on (100) silicon wafer 9
Figure 1-2 Different structure types producible on a (100) wafer 9
Figure 1-3 (a) Different structure types producible on (110) wafer; (b) SEM pictures of anisotropic wet etching structures on (110) wafer 10
Figure 1-4 Different excitation and detection principles for resonant vibration. Cantilever beams have been used to fabricate various sensing elements 11
Figure 1-5 (a) Three basic resonant structures; (b) two plate structures with mass-balanced vibration modes. The plate supports twist torsionally d 11
Figure 1-6 Photographs of several sensors fabricated using anisotropic wet etching: (a) force sensor; (b) flow sensor; (c) pressure sensor; (d) accelerometer; (e) vapor sensor; (f) double plate sensor 13
Figure 1-7 (a) Illustration of V-groove fabricated using anisotropic wet etching; (b) SEM picture of fiber switch based on bulk micromachining 14
Figure 1-8 Bulk micromachining platform integrated with V-groove, cavity and mesa on the substrate 14
Figure 1-9 (a) SEM photograph of portion 16-nozzle print head.fabricated using anisotropic wet etching; (b) SEM picture of a three-barrel neural microprobe 15
Figure 2-1 Illustrations of isotropic etching 23
Figure 2-2 Diagrams of hemispherical specimen of single-crystal silicon:(a) before etching; (b) after etching 23
Figure 2-3 Figure 2-3. Contour diagram of surface roughness at various oriented single crystal Silicon: (a) KOH; (b) TMAH 24
Figure 2-4 Contour diagram of etching rate at various oriented single crystal silicon: (a) KOH; (b) TMAH 24
Figure 2-5 Comparison between samples etched at various concentrations with and without IPA 25
Figure 2-6 Experimental setup for ultrasonic assisted anisotropic etching 25
Figure 2-7 SEM micrographs of ultrasonic assisted anisotropic etching structures: (a) broken cantilever beam; (b) sidewall damage 26
Figure 2-8 Microwave etching system: (1) microwave generator, (2) power supplying unit, (3) connector, (4) single or multimode resonator, (5) reaction chamber, (6) silicon substrate, (7) temperature sensor, (8) pressure sensor, (9) cooling water, (10) I/O 27
Figure 2-9 Microwave assisted etching process parameter: typical characteristics vs. time 27
Figure 2-10 Surface morphologies of silicon wafers etched in KOH and KOH+IPA solution 28
Figure 2-11 Surface morphologies of silicon wafers etched in TMAH and TMAH+IPA solution 29
Figure 2-12 Average roughness against etching temperature in pure and surfactant-added 10 wt. % TMAHW solutions 30
Figure 2-13 Average etching rate of (100) silicon plane against etching temperature in pure and surfactant-added 10 wt. % TMAH solutions 30
Figure 3-1 Illustration of diamond structure of silicon 47
Figure 3-2 Miller index of silicon crystal 47
Figure 3-3 Reactions of suspended bond and OH- at silicon atomic: (a) (111) crystal face; (b) (100) crystal face 48
Figure 3-4 Grooves fabricated using anisotropic etching on different directions of silicon crystal 48
Figure 3-5 SEM photography of micro cantilever beams 49
Figure 3-6 Various micro membrane structure fabricated using anisotropic etching technique 49
Figure 3-7 Illustration of etching stop technique 50
Figure 3-8 Diagram of heavy dope etching stop technique 50
Figure 3-9 Schematic diagram of electro chemical etching stop technique 51
Figure 3-10 Illustration of component protected by acrylic or teflon clamping 51
Figure 3-11 Illustrates of sidewall etching 52
Figure 3-12 Schematic diagram of wet etching reaction and formed H2 bubbles 52
Figure 4-1 Schematic diagram of anisotropic wet etching test patterns 61
Figure 4-2 Schematic mask patterns of micro membrane structure 61
Figure 4-3 Fabrication processes of the etching test pattern 62
Figure 4-4 Fabrication processes of micro membrane structures 62
Figure 4-5 Precise balance 63
Figure 4-6 Ultrasonic cleaner 63
Figure 4-7 Hot plate 64
Figure 4-8 Spin coater 64
Figure 4-9 UV mask aligner 65
Figure 4-10 Equipment with high pressure and temperature control for fast silicon anisotropic etching process 65
Figure 4-11 Reactive ion etching system 66
Figure 4-12 Optical microscope 66
Figure 4-13 Scanning electronic microscope 67
Figure 4-14 Surface profiler 67
Figure 4-15 Contact angle meter 68
Figure 5-1 SEM micrographs and average roughness of etched surfaces in 30 wt. % KOH solutions at 100 C 83
Figure 5-2 Surface roughness of etched surfaces in 30 wt. % KOH solution at 100 C 84
Figure 5-3 Average roughness against etching temperature in 30 wt. % KOH solution with pressure enhanced etching mechanism 85
Figure 5-4 Surface roughness of etched surfaces against etching temperature in pressure enhanced etching mechanism at 60, 80 and 100 C 86
Figure 5-5 AFM images of an Si(100) surface etched in 30 wt. % KOH solution at 100 C and 40 Kg/cm2 87
Figure 5-6 SEM micrographs and average roughness of etched surfaces in 10 wt. % TMAH solutions at 100 C 88
Figure 5-7 Surface roughness of etched surfaces in 10 wt. % TMAH solution at 100 C 89
Figure 5-8 Average roughness against etching temperature in 10 wt. % TMAH　solution with pressure enhanced etching mechanism 90
Figure 5-9 Surface roughness of etched surfaces against etching pressure in 10 wt. % TMAH solution at 60, 80 and 100 C 91
Figure 5-10 AFM images of an Si(100) surface etched in 10 wt. % TMAH solution at 100 C and 40 Kg/cm2 92
Figure 5-11 Average etching rate of (100) silicon plane against etching temperature in 30 wt. % KOH solutions with pressure enhanced etching mechanism 93
Figure 5-12 Average etching rate of (100) silicon plane against etching pressure in 30 wt. % KOH solutions with pressure enhanced etching mechanism 94
Figure 5-13 Average etching rate of (100) silicon plane against etching temperature in 10 wt. % TMAH solutions with pressure enhanced etching mechanism 95
Figure 5-14 Average etching rate of (100) silicon plane against etching pressure in 10 wt. % TMAH solutions with pressure enhanced etching mechanism 96
Figure 5-15 SEM micrographs of microstructure fabricated by KOH solution 98
Figure 5-16 Dependence of the boiling point on etching pressure in high temperature and high pressure enhanced etching mechanism 99
Figure 5-17 SEM micrographs and average roughness of etched surfaces in 30 wt. % KOH solutions 100
Figure 5-18 Surface roughness of etched surfaces in 30 wt. % KOH solution 101
Figure 5-19 Average roughness against etching temperature in 30 wt. % KOH　solution with high temperature and high pressure enhanced etching mechanism 102
Figure 5-20 SEM micrographs and average roughness of etched surfaces in 10 wt. % TMAH solutions 103
Figure 5-21 Surface roughness of etched surfaces in 10 wt. % TMAH solution 104
Figure 5-22 Average roughness against etching temperature in 10 wt. % TMAH　solution with high temperature and high pressure enhanced etching mechanism 105
Figure 5-23 Average etching rate of (100) silicon plane against etching temperature in 30 wt. % KOH solutions with high temperature and high pressure enhanced etching mechanism 106
Figure 5-24 Etching ratio against etching temperature in 30 wt. % KOH solutions with high temperature and high pressure enhanced etching mechanism 107
Figure 5-25 Average etching rate of (100) silicon plane against etching temperature in 10 wt. % TMAH solutions with high temperature and high pressure enhanced etching mechanism 108
Figure 5-26 Etching ratio against etching temperature in 10 wt. % TMAH solutions with high temperature and high pressure enhanced etching mechanism 109
Figure 5-27 SEM micrographs of microstructure fabricated by KOH solution in high temperature and high pressure enhanced etching mechanism at 140 °C 110
Figure 5-28 Silicon nitride membrane microstructure fabricated by KOH solution in high temperature and high pressure enhanced etching mechanism. 112
Figure 5-29 SEM of a thickness of membrane microstructures fabricated by KOH solution in high temperature and high pressure enhanced etching mechanism. 113








表 目 錄
Table 1-1 Microfabrication technologies in MEMS field 8
Table 4-2 Experimental facilities 59
Table 4-2 Information of experimental materials 60
Table 4-3 Various surfactants added to KOH and TMAH solution 60

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