臺灣博碩士論文加值系統

本研究通過射頻磁控濺鍍系統在玻璃基板上沉積一層磷與鈣摻雜氧化鋅薄膜，並使用水溶液法在氧化鋅薄膜上生長氧化鋅奈米片，藉由場發射掃描式電子顯微鏡、X光繞射儀和能量散射光譜儀來分析氧化鋅薄膜與氧化鋅奈米片之表面形貌、晶體結構與元素分析。製作出一種採用表面聲波模式和金屬-半導體-金屬模式的雙型紫外光感測器。本研究分別摻雜2、4莫耳%的磷與1、2、3、5莫耳%的鈣於氧化鋅薄膜中，並成長氧化鋅奈米片用來提高元件靈敏度，使用網路分析儀與Keithley 2450來進行紫外光感測元件頻率、相位、插入損耗與電流值的變化，並找出最佳靈敏度的元件。

Phosphorus and calcium doped ZnO thin films were grown on glass substrate through radio-frequency magnetron sputtering, and ZnO nanosheets were synthesized on ZnO thin films by using the hydrothermal method. The crystalline structure, surface morphology and composition of ZnO films and nanosheets were examined using X-ray diffraction, scanning electron microscope and energy-dispersive X-ray spectroscopy. We designed a dual type photodetector using surface acoustic wave mode and metal-semiconductor-metal mode and grew ZnO nanosheets on sensing area to increase the ultraviolet absorption rate. The concentrations of phosphorus-doped ZnO films included 2 and 4 mol% and calcium-doped ZnO films included 1, 2, 3 and 5 mol%. The influences of ZnO thin film thickness and phosphorus and calcium-doped amounts on ultraviolet sensitivity were investigated. The performance of the photodetector was evaluated using the variations in insertion loss, phase shift and output current. The maximum ultraviolet sensitivity of surface acoustic wave mode photodetector was obtained at 3.5µm-thick ZnO thin film with 3mol calcium-doped and metal-semiconductor-metal mode photodetector was obtained at 3.5µm-thick ZnO thin film with 4mol phosphorus-doped.

摘要...............................................i
Abstract...............................................ii
誌謝...............................................iii
目錄...............................................iv
表目錄...............................................vii
圖目錄...............................................viii
第一章 緒論...............................................1
1.1研究動機與目的...............................................1
1.2文獻探討...............................................1
1.3研究方法...............................................2
第二章 基礎理論...............................................3
2.1壓電理論...............................................3
2.1.1負壓電效應...............................................3
2.1.2正壓電效應...............................................4
2.1.3壓電材料...............................................4
2.1.4壓電基板...............................................5
2.2表面聲波...............................................6
2.2.1雷利波(Rayleigh Wave)...............................................6
2.2.2拉福波(Love Wave)...............................................6
2.3表面聲波元件概述與相關參數...............................................7
2.3.1表面聲波元件...............................................7
2.3.2指叉狀電極參數...............................................8
2.3.3插入損耗(Insertion Loss)...............................................9
2.3.4溫度頻率係數(Temperature Coefficients of Frequency, TCF)..................9
2.3.5中心頻率與波速...............................................9
2.3.6機電耦合係數(Electromechanical Coupling Coefficient,K2)..................10
2.4薄膜沉積方式...............................................10
2.4.1磁控濺鍍法...............................................11
2.4.2薄膜沉積機制...............................................12
2.5氧化鋅...............................................13
2.6氧化鋅奈米結構...............................................13
2.7紫外光感測原理...............................................14
2.7.1聲電效應(Acoustoelectric effect)........................................15
2.7.2質量負載效應(Mass-loading effect)........................................17
2.7.3光吸收...............................................18
2.7.4紫外光感測元件靈敏度...............................................19
2.8熱退火理論熱退火理論...............................................20
2.9COMSOL Multiphysic模擬軟體...............................................21
2.9.1有限元素法介紹...............................................21
2.9.2多重物理耦合概念...............................................21
2.10紫外光感測元件靈敏度...............................................22
第三章 實驗步驟與分析...............................................23
3.1實驗流程...............................................23
3.2摻雜磷或鈣氧化鋅粉靶...............................................24
3.3製作表面聲波元件...............................................25
3.3.1氧化鋅薄膜濺鍍流程與濺鍍參數...........................................25
3.3.2黃光微影製程...............................................27
3.3.3生長氧化鋅奈米片...............................................29
3.4模擬流程...............................................31
3.5分析儀器介紹...............................................32
3.5.1場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscopy, FE-SEM)...............................................32
3.5.2X光繞射儀(X-ray Diffraction, XRD)........................................32
3.5.3網路分析儀(Network Analyzer)............................................33
3.5.4I-V特性曲線量測儀器...............................................34
3.6表面聲波元件於紫外光量測...............................................34
3.7實驗藥品及耗材介紹...............................................35
3.7.1實驗耗材及藥品...............................................35
3.7.2實驗儀器...............................................36
第四章 實驗結果與驗證...............................................37
4.1氧化鋅材料表面分析...............................................37
4.1.1氧化鋅XRD分析...............................................37
4.1.2氧化鋅薄膜SEM與EDS元素組成分析............................................ 38
4.1.3氧化鋅奈米片SEM表面形貌分析...............................................41
4.2模擬結果...............................................45
4.2.1模擬表面聲波頻率與S11...............................................45
4.3氧化鋅材料頻率響應分析...............................................48
4.3.1沉積不同時間的純氧化鋅薄膜頻率響應分析......................................48
4.3.2不同摻雜磷與鈣氧化鋅薄膜與純氧化鋅薄膜頻率響應分析...........................53
4.3.3摻雜磷與鈣氧化鋅薄膜成長純氧化鋅奈米片頻率響應分析...........................67
4.4表面聲波元件紫外光感測變化比較...............................................72
4.4.1不同厚度純氧化鋅薄膜之紫外光感測變化........................................76
4.4.2退火不同摻雜濃度磷氧化鋅薄膜之紫外光感測變化.................................79
4.4.3退火不同摻雜濃度鈣氧化鋅薄膜之紫外光感測變化.................................85
4.4.4奈米片成長於不同摻雜濃度磷薄膜之紫外光感測變化...............................91
4.4.5奈米片成長於3mol%鈣摻雜薄膜之紫外光感測變化.................................94
4.5氧化鋅薄膜與奈米片紫外光感測電流變化量........................................97
4.5.1I-V特性...............................................97
4.5.2I-T特性...............................................99
4.5.3氧化鋅奈米片成長於4mol%磷氧化鋅薄膜不同功率密度之電流變化...................103
4.5.4氧化鋅奈米片成長於3mol%鈣氧化鋅薄膜不同功率密度之電流變化...................105
第五章 結論...............................................107
參考文獻...............................................109
Extended Abstract...............................................115
1.Introduction...............................................116
2.Research methods...............................................116
3.Conclusion...............................................117

[1] Uday Muhsin Nayef, Kadhim A. Hubeatir, Zahraa J. Abdulkareem, 2016 “Ultraviolet photodetector based on TiO2 nanoparticles/porous silicon hetrojunction”, Optik, 127, pp. 2806-2810
[2] Lei Liu, et al., 2017, “High-detectivity ultraviolet photodetectors based on laterally mesoporous GaN”, Nanoscale, 9, pp. 8142-8148
[3] Ali Aldalbahi, et al., 2016, “A new approach for fabrications of SiC based photodetectors”,Sci. Rep”, 6, 23457
[4] Basavaraj S. Sannakashappanavar, Aniruddh Bahadur Yadav, Kunal Singh, Talapati Akhil Sai, 2023, “Fabrication and characterization of ultra-thin ZnO based bottom gate thin film transistor for UV detection Micro and Nanostructures” 179, 207581
[5] Yen-Lin Chu, et al., 2020, “Fabrication and Characterization of Ni-Doped ZnO Nanorod Arrays for UV Photodetector Application”, J. Electrochem. Soc , 167 , 067506
[6] Z. L. Wang, 2004, “Zinc oxide nanostructures: growth, properties and applications”, Journal of Physics: Condensed Matter, vol.16.
[7] B.P. Zhang, N.T. Binh, Y. Segawa, K. Wakatsuki, N. Usami, 2003, “Optical properties of ZnO rods formed by metalorganic chemical vapor deposition” Appl. Phys. Lett., 83, pp. 1635-1637
[8] K.M. Sandeep, Shreesha Bhat, S.M. Dharmaprakash, 2017, “Structural, optical, and LED characteristics of ZnO and Al doped ZnO thin films”, Journal of Physics and Che mistry of Solids, 104, pp. 36-44
[9] A. Orlov, V. Ulianova, Y. Yakimenko, O. Bogdan and G. Pashkevich, 2015, “SAW UV
sensor based on ZnO and Al-doped ZnO nanorods”, 2015 IEEE 35th International Conference on Electronics and Nanotechnology (ELNANO)
[10] Dong Chan Kim, et al., 2011, “Highly Sensible ZnO Nanowire Ultraviolet Photodetectors Based on Mechanical Schottky Contact”, J. Electrochem. soc, 159, K10
[11] Ruey-Chi Wang, et al., 2018, “Differentiating Ammonia from Other Reducing Gases via Response Reversal Phenomena by Varied ZnO/CuxO Nanorod Arrays”, J. Electrochem.
Soc, 165, B484
[12] Sheng-Joue Young, Kuo-Wei Yuan, 2019, “Self-Powered ZnO Nanorod Ultraviolet
Photodetector Integrated with Dye-Sensitised Solar Cell”, J. Electrochem. Soc, 166,
B1034
[13] Sheng-Joue Young, Tsan-Hua Wang, 2018, “ZnO Nanorods Adsorbed with Photochemical Ag Nanoparticles for IOT and Field Electron Emission Application”, J. Electrochem. Soc, 165 B3043
[14] M. Boujnah, et al., 2016, “High efficiency of transmittance and electrical conductivity of V doped ZnO used in solar cells applications”, Journal of Alloys and Compounds, 671, pp. 560-565
[15] Ahmed Mishaal Mohammed,Ibraheem Jaleel Ibraheem, A.S.Obaid M.Bououdina, 2017, “Nanostructured ZnO-based biosensor: DNA immobilization and hybridizationbased”, Sensing and Bio-Sensing Research, 15, pp.46-52
[16] A. Mauder, 1995, “SAW gas sensors: comparison between delay line and two port resonator”, Sensors and Actuators B: Chemical, 26, pp. 187-190
[17] Qin peng Liu, et al., 2020, “Temperature-insensitive optical fiber reflective micro-liquid level sensor base on the drop shape quasi-Mach Zehnder interferometer”, Optik, 216, 164893
[18] Hong Li, et al., 2023, “UV-durable superhydrophobic ZnO/SiO2 nanorod arrays on an aluminum substrate using catalyst-free chemical vapor deposition and their corrosion performance”, Applied Surface Science, 623, 157085
[19] Xiangdong Meng, et al., 2022, “UV luminescence enhancement of Cu-doped ZnO
nanorods grown by hydrothermal treatment”, Journal of Luminescence, 252, 119364
[20] Nafiseh Memarian, et al., 2021, “Effect of the seed layer on the UV photodetection properties of ZnO nanorods”, Materials Science and Engineering: B, 272, 115332
[21] L.-T. Lai, S.-J. Young, Y.-H. Liu, Z.-D. Lin and S.-J. Chang, 2015, “UV Enhanced Field Emission Properties of ZnO Nanosheets With Different NaOH Concentration”, IEEE
Transactions on Nanotechnology, 14, pp. 776-781
[22] Jing Wang, et al., 2021, “Mesoporous ZnO nanosheets with rich surface oxygen vacancies for UV-activated methane gas sensing at room temperature”, Sensors and Actuators B: Chemical, 333, 129547
[23] Dong Jin Lee, et al., 2021, “Piezo-phototronic effect triggered flexible UV photodetectors based on ZnO nanosheets/GaN nanorods arrays”, Applied Surface Science, 558, 149896
[24] Hongye Guan, et al., 2021, “A self-powered UV photodetector based on the hydrovoltaic and photoelectric coupling properties of ZnO nanowire arrays”, Journal of Alloys and Compounds, 867, 159073
[25] Feng Yang, et al., 2020, “Tuning oxygen vacancies and improving UV sensing of ZnO nanowire by micro-plasma powered by a triboelectric nanogenerator”, Nano Energy, 67, 104210
[26] Lei Li, et al., 2017, “Optimizing growth of ZnO nanowire networks for high-performance UV detection Ceramics International”, 43, pp. 15978-15985
[27] Hao Wu, et al., 2021, “Synthesis of single-crystalline ZnO nanoflowers for a superhigh sensitivity ultraviolet photodetector application”, Optical Materials, 122, 111683
[28] Mohan Reddy Pallavolu, et al., 2023, “High responsivity self-powered UV photodetector performance of pristine and V-doped ZnO nano-flowers”, Optics & Laser Technology, 157, 108776
[29] Z.-S. Hu, F.-Y. Hung, S.-J. Chang and K.-J. Chen, 2012, “The crystallization characteristics and photoluminescence properties of ZnO/Ag nanoflower arrays”, 25th International Vacuum Nanoelectronics Conference, pp.1-6
[30] Shaivalini Singh, Si-Hyun Park, 2017, “Fabrication and properties of ZnO nanorods based MSM UV detectors on silicon substrates”, Optik, 137, pp.96-100
[31] Shahad S. Khudiar, et al., 2021, “Synthesis of ZnO nanostructures by hydrothermal method deposited on porous silicon for photo-conversion application”, Optik, 247, 167903
[32] Khaldoon N. Abbas, et al., 2016, “Structures and emission features of high-density ZnO micro/nanostructure grown by an easy hydrothermal method”, Materials Chemistry and Physics, 182, pp. 298-307
[33] Bing Cheng, et al., 2008, “Growth mechanism and morphology dependent luminescence properties of ZnO nanostructures prepared in aqueous solution”, Materials Letters, 62, pp. 3099-3102
[34] M. Mazilu, et al., 2012, “Optical properties of undoped and Al-doped ZnO nanostructures grown from aqueous solution on glass substrate”, Optical Materials, 34, pp. 1833-1838
[35] N.H. Erdogan, N. Sedefoglu, H. Kavak, 2021, “Effect of Na doping on microstructures, optical and electrical properties of ZnO thin films grown by sol-gel method”, J. Alloys Compd, 881, 160554
[36] F.K. Shan, et al., 2004, “Substrate effects of ZnO thin films prepared by PLD technique”, Journal of the European Ceramic Society, 24, pp. 1015-1018
[37] J B Kim, et al., 2008, “Cu-doped ZnO-based p-n hetero-junction light emitting diode”, Semiconductor Science and Technology, 23, 095004
[38] Maria Losurdo, et al., 2008, “Tailoring nanostructure of ZnO thin films by plasma assisted and Au-catalyst assisted MOCVD”, Journal of Non-Crystalline Solids, 354, pp. 2821-2825
[39] G. Jimenez-Cadena, et al., 2010, “Synthesis of different ZnO nanostructures by modified PVD process and potential use for dye-sensitized solar cells”, Materials Chemistry and Physics, 124, pp. 694-698
[40] Colin Campbell, 1989, “Surface Acoustic Wave Devices and Their Signal Processing Applications”, pp. 1-7
[41] K.Hashimoto, 2012, “11-Surface acoustic wave (SAW) devices”, Ultrasonic Transducers, pp. 331-373
[42] ChunliZhang, et al., 2014, “Two-dimensional theory of piezoelectric shells considering surface effect”, European journal of Mechanics-A/solids, pp. 109-117
[43] D. S. Ballantine, et al., 1997, “Acoustic Wave Sensors: Theory, Design and
Physicochemical Applications”, Academic Press
[44] S.K. Panda, C. Jacob, 2012, “Preparation of transparent ZnO thin films and their application in UV sensor devices”, Solid-State Electronics, 73, pp. 44-50
[45] L.Le Brizoua, et al., 2006, “High frequency SAW devices based on thired harmonic generation”, Ultrasonics , pp. 100-103
[46] AyanaA, et al., 2006, “Microstructural and piezoelectric properties of ZnO thin films”, Materials Science in Semiconductor Processing, 106680
[47] Sourav Mondal, Shuvaraj Ghosh, Durga Basak, 2021, “Extraordinarily high ultraviolet photodetection by defect tuned phosphorus doped ZnO thin film on flexible substrate”, Materials Research Bulletin, 144, 111490
[48] Sourav Mondal, Durga Basak, 2022, “Photophysical investigation of the formation of defect levels in P doped ZnO thin films”, Ceramics International, 48, pp. 20000-20009
[49] K. P. Misra, K. C. Dubey, R. K. Shukla and A. Srivastava, 2009, “Reduction in carrier concentration by calcium doping in ZnO thin films”, 2009 International Conference on Emerging Trends in Electronic and Photonic Devices & Systems, pp. 495-496
[50] H. Mahdhi, et al., 2015, “Effect of sputtering power on the electrical and optical properties of Ca-doped ZnO thin films sputtered from nanopowders compacted target”, Optical Materials, 45, pp. 97-103
[51] A. J. Slobodnik, 1978, “Material and their inlluence on performance”, Chapter 6 in Acoustic Surface Waves, pp. 226-303
[52] Changshuai Yin, et al., 2021, “Enhancing the sensitivity of flexible acoustic wave ultraviolet photodetector with graphene-quantum-dots decorated ZnO nanowires”, Sensors and Actuators A: Physical, 321, 112590
[53] Duy-Thach Phan, Gwiy-Sang Chung, 2012, “Characteristics of SAW UV sensors based on a ZnO/Si structure using third harmonic mode”, Current Applied Physics, 12, pp. 210-213
[54] Kuo-Sheng Kao, et al., 2016, “Photoluminescence of ZnO thin films deposited at various substrate temperatures”, Thin Solid Films, 605, pp. 77-83
[55] Kourosh Kalantar Zadeh, et al., 2002, “A novel Love-mode device based on a ZnO/ST-cut quartz crystal structure for sensing applications”, Sensors and Actuators A: Physical, 100, pp. 135-143
[56] Y.J. Guo, et al., 2013, “Characterization and humidity sensing of ZnO/42° YX LiTaO3 Love wave devices with ZnO nanorods”, Materials Research Bulletin, 48, pp. 5058-5063
[57] G.A Athanasopoulos, et al., 2000, “Effect of soil stiffness in the attenuation of Rayleigh-wave motions from field measurements”, Soil Dynamics and Earthquake Engineering, 19, pp. 277-288
[58] C. S. Hartmann, D. T. Bell,R. C. Rosenfeld, 1973, “Impulse Model Design of Acoustic Surface-Wave Filters”, IEEE Transactions on Microwave Theory and Techniques, 21, pp.162-175
[59] A. Jaakkola, M. Prunnila,T. Pensala, 2012, “Temperature compensated resonance modes of degenerately n-doped silicon MEMS resonators”, 2012 IEEE International Frequency Control Symposium Proceedings, pp. 1-5
[60] Xi Chen, Dali Liu, 2009, “Temperature stability of ZnO-based Love wave biosensor with SiO2 buffer layer”, Sensors and Actuators A: Physical, 156, pp.317-322
[61] Rui Wang, et al., 2023, “Enhanced secondary electron emission properties of Zn doped MgO thin films prepared by aerosol assisted chemical vapor deposition”, Materials Science in Semiconductor Processing, 157, 107323
[62] Israrul Haq, et al., 2023, “Linkage of thermoelectric properties with the structural parameters in zinc indium oxide (ZnInO) thin films grown by physical vapor deposition (PVD)”, Inorganic Chemistry Communications, 149, 110438
[63] Cristian L. Terán, et al., 2021, “Optical properties and bipolar resistive switching of ZnO thin films deposited via DC magnetron sputtering”, Chinese Journal of Physics, 74, pp. 1-8
[64] F Chaabouni, M Abaab, B Rezig, 2004, “Effect of the substrate temperature on the properties of ZnO thin films grown by RF magnetron sputtering”, Materials Science and Engineering: B, 109, pp. 236-240
[65] R.S. Gonçalves, et al., 2018, “The effect of thickness on optical, structural and growth mechanism of ZnO thin film prepared by magnetron sputtering”, Thin Solid Films, 661, pp. 40-45
[66] Dilawar Ali, et al., 2021, “Synthesis, characterization and antibacterial performance of transparent c-axis oriented Al doped ZnO thin films”, Surfaces and Interfaces, 27, 101452
[67] Fayyaz Hussain, et al., 2020, “An insight of Mg doped ZnO thin films: A comparative experimental and first-principle investigations”, Physica E: Low-dimensional Systems and Nanostructures, 115, 113658
[68] M. Hjiri, et al., 2019, “Study of defects in Li-doped ZnO thin films”, Materials Science in Semiconductor Processing, 89, pp. 149-153
[69] M.A.Borvsiewicz, 2019, “ZnO as Functional Material,A Review”, Crystals 2019, 505
[70] S. -J. Young and Y. -H. Liu, 2017, “High Response of Ultraviolet Photodetector Based on Al-Doped ZnO Nanosheet Structures”, IEEE Journal of Selected Topics in Quantum Electronics, 23, pp. 1-5
[71] R. H. Parmenter, 1953, “The Acousto-electric effect”, Phys Rev, pp. 990-998
[72] A. Wixforth, et al., 1989, “Surface acoustic waves on GaAs/AlxGal-xAs heterostructures”, Phy Rev B, pp. 7874-7887
[73] M. Rotter, et al., 1998, “Giant acoustoelectric effect in GaAs/LiNbO3 hybrids”, Appl Phys Lett, pp. 2128-2130
[74] D.S. Ballantine, R.M. White, 1997, “Acoustic Wave Sensors-Theory, Design and Physico- chemical Applications”, Academic Press
[75] J.D.N. Cheeke, Z. Wang, 1999, “Acoustic wave gas sensors”, Sens Actuator B-Chem, 59, pp.146-153
[76] BenG. Streetman, Sanjay Kumar Banerjee, 2000, “Soild state electronic devices”, 6th ed
[77] Y. J. Guo, et al., 2015, “Ultraviolet sensing based on nanostructured ZnO/Si surface acoustic wave devices”, Smart Materials and Structures, 24, 125015
[78] Quang Chieu Bui, et al., 2021, “Effects of thermal annealing on the structural and electrical properties of ZnO thin films for boosting their piezoelectric response”, Journal of Alloys and Compounds, 870, 159512
[79] 皮托科技股份有限公司，2014， “comsol 有限要素分析快易通”
[80] Sanjeev Kumar, Gil-Ho Kim, K. Sreenivas and R. P. Tandon, 2009, “ZnO based surface acoustic wave ultraviolet photo sensor”, Journal of Electroceramics, 22, pp. 198–202
[81] Parmanand Sharma, 2003, “Highly Sensitive Ultraviolet Detector Based on ZnO/LiNbO3 Hybrid Surface Acoustic Wave Filter”, Applied Physics Letters, 83(17)
[82] Y J Guo, C Zhao, X S Zhou, Y Li, X T Zu, D Gibson and Y Q Fu, “Ultraviolet sensing based on nanostructured ZnO/Si surface acoustic wave devices”, Smart Materials and Structures, 24, 12
[83] Duy-Thach Phan, Gwiy-Sang Chung, 2012, “Characteristics of SAW UV sensors based on a ZnO/Si structure using third harmonic mode”, Current Applied Physics, 12, pp. 210-213
[84] Ching-Liang Wei, Ying-Chung Chen, Chien-Chuan Cheng, Kuo-Sheng Kao, Da-Long Cheng, Po-Shu Cheng, 2010, “Highly sensitive ultraviolet detector using a ZnO/Si layered SAW oscillator”, Thin Solid Films, 518, pp. 3059-3062