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研究生：	呂嘉輝 Lu, Chia-Hui
論文名稱：	相異結構之氧化鋅薄膜微機電氣體感測器之研究 Zinc Oxide Thin Film MEMS Gas Sensor with Different Structure
指導教授：	張守進 Chang, Shoou-Jinn
學位類別：	碩士 Master
系所名稱：	電機資訊學院 - 奈米積體電路工程碩士博士學位學程 MS Degree/Ph.D. Program on Nano-Integrated-Circuit Engineering
論文出版年：	2019
畢業學年度：	107
語文別：	英文
論文頁數：	97
中文關鍵詞：	微機電系統、氧化鋅、矽穿孔、氣體感測器
外文關鍵詞：	MEMS, ZnO, TSV, Gas sensors
相關次數：	點閱：89 下載：1
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在這篇論文中製作了三種不同 MEMS 結構的氧化鋅薄膜，第一種主
要利用磁控濺鍍法沈積 4%氬氧比的氧化鋅薄膜作為氣體感測膜，製作了微機電氣體感測器。第二種也是利用磁控濺鍍法沉積純氬氣的二氧化錫薄膜，並與 4%氬氧比的氧化鋅薄膜做結合形成雙面感應式異質接面氧化鋅/二氧化錫薄膜微積電氣體感測器，最後利用銅電鍍所製作之矽穿孔基版與微機電氣體感測器做結合形成第三種結構，取代傳統的打線手法，達成垂直整合的功用。
第一個部分主要探討單層氧化鋅薄膜微積電氣體感測器的材料特性、電性與氣體量測特性。在結構特性方面，磁控濺鍍法沈積的氧化鋅薄膜呈現多晶型態，在組成分析上則確認了成功沈積未摻雜的氧化鋅薄膜。在氣體感測器的電性方面，以電子束蒸鍍系統沈積之鎳電極微加熱器的功耗在感測膜溫度 150 度到 350 度分別是 130mW 到 317mW，而操作溫度在 150 度以下氧化鋅薄膜阻值約為 2 GΩ，在 180 度以上才會出現半導體特性。在氣體量測部分針對乙醇、硫化氫與一氧化氮氣體進行感測，在最佳的操作溫度下，對於 5ppm 的酒精會有 52.59 的感測特性，而對於 200ppb 的硫化氫及一氧化氮則分別有 23.7%及 143.41%的響應。
第二個部分則是在探討雙面感應式異質接面氧化鋅/二氧化錫薄膜微積電氣體感測器的材料特性、電性與氣體量測特性。在結構特性方面，磁控濺鍍法沈積的二氧化錫薄膜呈現非晶狀態，而組成分析上確立了成功沈積了未摻雜的二氧化錫薄膜，在氣體感測器的電性方面，以電子束蒸鍍系統沈積之鎳電極微加熱器的功耗在感測膜溫度 50 度到 250 度分別是 37mW 到 392mW，氣體量測方面，在低溫下就能感測一氧化氮氣體，且在最佳的操作溫度情況下對於 200 ppb 的一氧化氮有 898.27%的響應，特別的是此氣體感測器僅可用於一氧化氮的量測，具有絕佳的選擇性。
第三個部分製作了銅電鍍矽穿孔基版，目的是取代傳統的封裝打線技術，透過結合銅電鍍矽穿孔與氣體感測器成功進行量測，之後對於銅電鍍矽穿孔結構進行表面分析，可以知道矽穿孔表面孔徑為 469 微米，蝕刻深度約為 700 微米。

In this paper, three different zinc oxide thin film MEMS structure were fabricated. The first one mainly used a magnetron sputtering system to deposit a 4% argon-oxygen ratio of zinc oxide as a gas sensing film to fabricate a MEMS gas sensor. The second is to deposit tin dioxide film by magnetron sputtering system and combine it with a 4% argon-oxygen ratio of zinc oxide thin film to form a bifacial sensing sides ZnO/SnO2 MEMS gas sensor. Finally, we combine the electroplating copper TSV structure with the MEMS gas sensor to form a third structure, which replaces the conventional wire bonding method and achieves the function of vertical integration.
In the first part of the experiment, we discuss the material properties, electrical properties and gas measurement characteristics of single-layer zinc oxide thin film MEMS gas sensors. The zinc oxide thin film deposited by magnetron sputtering system shows polycrystalline, and the elemental analysis confirmed the successful deposition of undoped zinc oxide. The power consumption of the micro-heater deposited by the E-beam evaporation system is 130mW to 317mW at a sensing film temperature of 150 to 350 degrees, respectively. The zinc oxide has a resistance of about 2 GΩ in 150 degrees, and its semiconductor characteristic occurs above 180 degrees. For C2H5OH, H2S and NO gas sensing, we found that the gas sensors made by us
have the best sensitivity at the temperature of 350°C, 250°C, 250°C ,
respectively.
In the second part of the experiment, we discuss the material properties, electrical properties and gas measurement characteristics of bifacial sensing sides ZnO/SnO2 MEMS gas sensors. The tin dioxide thin film deposited by magnetron sputtering system shows amorphous, and the elemental analysis confirmed the successful deposition of undoped tin dioxide. The power consumption of the micro-heater deposited by the E-beam evaporation system is 37mW to 392mW at a sensing film temperature of 50 to 250 degrees, respectively. For gas sensing, bifacial sensing sides ZnO/SnO2 MEMS gas sensors can detect low concentration of NO gas (5ppb) and work at low temperature (100°C).
In the third part of the experiment, we discuss the MEMS gas sensor with Cu TSV structure which can replace conventional wire bonding technique. The diameter and length of Cu TSV structure is about 470μm and 700μm, respectively. Sensing performance is also investigated in this study.

摘要	I
Abstract	III
誌謝	V
Contents	VI
Figure Captions	IX
Table Captions	XII
Chapter 1	Introduction	1
1.1	Background and Motivation	1
1.2 Background of Zinc Oxide	5
1.3 Overview of Through Silicon via	6
1.4 Overview of Gas Sensor	8
1.5 Organization of Thesis	11
Chapter 2	Relevant Theory and Experimental System	13
2.1 Theory of Gas Sensors	13
2.2 Important Parameters of Gas Sensors	15
2.2.1	Sensitivity	15
2.2.2	Response Time & Recovery Time	16
2.2.3	Working Temperature	17
2.2.4	Selectivity	17
2.3 Related Mechanism of MEMS gas sensors	18
2.3.1 	Bosch DRIE and Cryogenic DRIE	18
2.3.2	Resistive Microheater	22
2.4 Fabrication Systems of Gas Sensors	24
2.4.1	The RCA wet bench system	24
2.4.2	The Furnace Tube System	26
2.4.3	Photolithography and Mask Aligner	27
2.4.4	Plasma-Enhanced Chemical Vapor Deposition & Inductively Coupled Plasma Etching System	28
2.4.5	The RF Magnetron Sputter System	30
2.4.6	E-beam and Thermal Evaporation System	31
2.5 Analyst Systems	33
2.5.1	Scanning Electron Microscope (SEM)	33
2.5.2 	X-ray Diffraction Analysis (XRD)	34
2.5.3	Infrared Thermal Imager	35
Chapter 3 Fabrication and Characteristics of single ZnO Thin Film MEMS Gas Sensors	37
3.1 Growth of Sample	37
3.1.1	Growth of ZnO thin film Sample	37
3.2	Characteristics of ZnO thin film	38
3.2.1	Structural Characteristics	38
3.2.2	Elemental Analysis	39
3.3 Fabrication of ZnO Thin Film MEMS Gas Sensor with Cr/Ni as Electrodes	41
3.4	Basic Characteristics of ZnO Thin Film MEMS Gas Sensor	48
3.4.1	Electrical Characteristic of the Microheater	48
3.5	Sensing Characteristic of ZnO Thin Film MEMS Gas Sensors	50
3.5.1	Measurement Setup	50
3.5.2	Operating Temperature Influence	51
Chapter 4	Fabrication and Characteristics of Bifacial Sensing Sides ZnO/SnO2 MEMS Gas Sensor	57
4.1 Growth of Sample	57
4.1.1	Growth of SnO2 thin film Sample	57
4.2	Characteristics of SnO2 thin film	58
4.2.1	Structural Characteristics	58
4.2.2	Elemental Analysis	59
4.3 Fabrication of Bifacial Sensing Sides ZnO/SnO2 MEMS Gas Sensor	61
4.4 Basic Characteristics of Bifacial Sensing Sides ZnO/SnO2 MEMS Gas Sensor	69
4.4.1	Electrical Characteristic of the Microheater	69
4.4.2	Analysis of the gas sensor structure	71
4.5	Sensing Characteristic of bifacial sensing sides ZnO/SnO2 MEMS Gas Sensor	73
4.5.1	Operating Temperature Influence	73
4.5.2	Concentration Influence	75
Chapter 5	Fabrication and Characteristics of gas sensor with TSV structure	78
5-1 Fabrication of Electroplating Cu TSV Structure	78
5.2	Characteristics of Electroplating Cu TSV Structure	83
5.2.1	Structural Characteristics	83
5.2.2	Elemental Analysis	85
5.2.3	Reliable Analysis	88
Chapter 6	Conclusion and Future Work	89
6.1 Conclusion	89
6.2 Future Work	90
Reference	92

Fig. 1-1. 2014-2021 gas sensor forecast 	3
Fig. 1-2. Kaohsiung gas explosion [8]	3
Fig. 1-3. The schematic diagram of wurtzite structure of ZnO	5
Figure 1-4. Schematic diagram of two-dimensional packing and three-dimensional packaging 	7
Figure 1-5. conventional wire bonding 	7
Figure 1-6. Comparison of TSV and traditional packing	8
Fig 1-7. History of different kinds of gas sensors	11
Fig. 2-1. The schematic diagram of sensing mechanism.	15
Fig. 2-2. The schematic diagram of suspended structure.	19
Fig. 2-3. The schematic diagram of Bosch DRIE.	20
Fig. 2-4. The schematic diagram of Cryogenic DRIE.	22
Fig .2-5 Wet bench	25
Fig. 2-6. High temperature and low pressure furnace tubes	27
Fig. 2-7 The mask aligner system	28
Fig. 2-8. The plasma enhanced chemical vapor deposition & ion coupled plasma etching system	29
Fig. 2-9. The schematic diagram of RF sputtering system	31
Fig. 2-10 Thermal Evaporation System	32
Fig. 2-11 E-beam Evaporation System	32
Fig. 2-12. The schematic diagram of SEM system.	34
Fig. 2-13. The X-ray diffraction plots	35
Fig. 2-14. The Infrared Thermal Imager System	36
Fig. 3-1. The schematic diagram of ZnO thin film sample.	38
Fig. 3-2. XRD spectrum of ZnO thin film which ratio of argon flow and oxygen flow is 48:2	39
Fig. 3-3. Energy-dispersive X-ray spectroscopy spectrum of ZnO thin film	40
Fig. 3-4. ZnO thin film MEMS gas sensor experiment and parameter	46
Fig. 3-5. ZnO thin film MEMS gas sensor	47
experimental process	47
Fig. 3-6. Infrared thermal image of MEMS gas sensor at 350℃	49
Fig. 3-7. Schematic diagram of gas sensing measurement system.	51
Fig. 3-8. Sensing transient response of 5 ppm ethanol at different operating temperature	54
Fig. 3-9. Comparison response of 5 ppm ethanol at different operating temperature	54
Fig. 3-10. Sensing transient response of 200 ppb hydrogen sulfide at different operating temperature	55
Fig. 3-11. Comparison response of 200 ppb hydrogen sulfide at different operating temperature	55
Fig. 3-12. Sensing transient response of 200 ppb nitric oxide at different operating temperature.	56
Fig. 3-13 Comparison response of 200 ppb nitric oxide at different operating temperature	56
Fig. 4-1. The schematic diagram of SnO2 thin film sample.	58
Fig. 4-2. XRD spectrum of SnO2 thin film which ratio of argon flow and oxygen flow is 100:0	59
Fig. 4-3. Energy-dispersive X-ray spectroscopy spectrum of SnO2 thin film	60
Fig. 4-4. Bifacial Sensing Sides ZnO/SnO2 MEMS Gas Sensor	67
experiment and parameter	67
Fig. 4-5. Bifacial Sensing Sides ZnO/SnO2 MEMS Gas Sensor experimental process	68
Fig. 4-6. Infrared thermal image of bifacial sensing sides ZnO/SnO2 MEMS gas sensor at 150℃	69
Fig. 4-7 Sensor of micro-heater power consumption with different temperatures	70
Fig. 4-8 OM of (a) micro-heater and electrodes	72
(b)fail electrodes(c) top view of the suspend structure	72
(d) backside of the suspend structure	72
Fig. 4-9 OM of (a)over etching (b)incomplete etching (c) Infrared thermal image of incomplete etching	72
Fig. 4-10 Sensing transient response of 200 ppb nitric oxide at different operating temperature	74
Fig. 4-11 Comparison response of 200 ppb nitric oxide at different operating temperature	74
Fig. 4-12 Response of nitric oxide with different concentration at 100℃	76
Fig. 4-13 Comparison response of nitric oxide with different concentration at 100℃	76
Fig. 4-14 Response of nitric oxide with different low concentration at 100℃	77
Fig. 4-15 Comparison response of nitric oxide with different low concentration at 100℃	77
Fig. 5-1. Electroplating Cu TSV structure experiment and parameter	82
Fig. 5-2. Electroplating Cu TSV structure experimental process	83
Fig. 5-3. SEM image of (a) top-view electroplating Cu TSV structure	84
(b) cross-section electroplating Cu TSV structure (c) top-view of electroplating Cu and Sn TSV structure (d) cross-section gas sensor bonding on electroplating Cu TSV structure	84
Fig. 5-4. Energy-dispersive X-ray spectroscopy spectrum of Cu TSV structure	86
Fig. 5-5. Energy-dispersive X-ray spectroscopy spectrum of tin ball	87
Fig. 5-6 Sensing transient response of 200 ppb nitric oxide at 200℃	88

Table 1-1. Allowable concentration criteria for hazardous substances	4
Table 1-2. Comparison of each type gas sensor	10
Table 1-3. Comparison between MEMs gas sensors and conventional gas sensors	10
Table.2-1. The system and parameter of RCA clean.	25
Table 3-1. Weight percentage and atomic percentage of ZnO thin film	40
Table 3-2. Corresponding applied voltage and power consumption at different temperatures.	49
Table 4-1. Weight percentage and atomic percentage of SnO2 thin film	60
Table 4-2. Corresponding applied voltage and power consumption at different temperatures.	70
Table 5-1. Weight percentage and atomic percentage of Cu TSV structure	86
Table 5-2. Weight percentage and atomic percentage of tin ball	87

                                    

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