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研究生: 陳維德
Chen, Wei-De
論文名稱: 以射頻濺鍍法製備氧化鎂銦薄膜及其光電元件應用
Investigation of Magnesium Indium Oxide Thin Film Fabricated by RF Sputtering System and Their Optoelectronics Applications
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 - 微電子工程研究所
Institute of Microelectronics
論文出版年: 2020
畢業學年度: 108
語文別: 英文
論文頁數: 120
中文關鍵詞: 氧化鎂銦紫外光檢測器薄膜電晶體光電晶體同質緩衝層
外文關鍵詞: MgIn2O4, photodetector, thin film transistor, phototransistor, homogeneous buffer layer
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  • 本篇論文利用射頻濺鍍法沉積氧化鎂銦薄膜,探討不同製程條件下的薄膜特性,並將其應用於光感測器的感光層以及薄膜電晶體的通道層,並分析元件之光電特性。
    實驗的第一部分,我們以磁控濺鍍系統沉積不同氧流比的氧化鎂銦薄膜,並藉由在氬氣環境下進行熱退火改善薄膜特性。我們從薄膜結構、光學特性、元素分析等三大面向探討薄膜性質。在薄膜結構分析中,藉由XRD分析薄膜在高溫退火後擁有明顯的晶相,且較高氧流比的薄膜在700度退火後氧化鎂銦之晶相比氧化銦之晶相更為顯著,反之,低氧流比的薄膜在700度退火後呈現的晶相則相反。此外,藉由AFM佐證薄膜有均勻的表面,且在退火300度後擁有最低的粗糙度。在光學分析中,氧化鎂銦薄膜在可見光區擁有高於75%的穿透度,以及3.9電子伏特以上的能隙,顯示其具有作為紫外光感測材料的條件。在元素分析中,藉由EDS分析薄膜的元素比例,此外以XPS佐證提高濺鍍時的氧分壓可抑制氧化鎂銦薄膜中的氧空缺,進一步減少自由載子。
    實驗的第二部分,我們以氧化鎂銦薄膜作為紫外光感測器的感光層,並調變氧流比與熱退火溫度使元件光電特性最佳化。元件暗電流與響應隨著氧流比提高而下降,乃因氧空缺被填補。然而,氧空缺愈多反而會拉長上升與下降時間,因此響應大小與速度之間勢必存在著取捨。由於2%氧流比的元件在退火前有最好特性,我們進一步觀察退火溫度對元件的影響。在退火溫度300℃時,由於氧化鎂銦薄膜顯著提升的紫外光吸收度,大幅改善光暗電流比與響應值。在退火溫度400℃以上由於氧化鎂銦薄膜產生晶相,因而使暗電流大幅提升反而劣化元件整體特性。因此,透過製程參數優化找出製作氧化鎂銦光檢測器的最佳參數,發現氧流比2%並於氬氣環境中進行300℃熱退火的MgIn2O4光感測器有最佳特性,其光暗電流比大於107,響應值1.38 A/W,紫外光對可見光拒斥比為4.3×103。
    實驗的第三部分,我們以石英玻璃作為基板,以二氧化矽作為介電層,以氧化鎂銦薄膜作為通道層製作薄膜電晶體,並調變氧分壓與通道層厚度最佳化元件特性。實驗發現氧流比2%且30nm的氧化鎂銦通道層為最佳參數,其薄膜電晶體之臨界電壓為1.54 V,場效遷移率0.23 cm^2/V∙s,開關電流比5.88×104,次臨界擺幅0.61 V/decade。此外我們將特性最佳的氧化鎂銦薄膜電晶體擴展其應用至光電晶體,其在閘極偏壓為-3 V之下展現最大響應5.22×10-2 A/W及1.36×103的紫外光對可見光拒斥比。最後,我們驗證以5 nm 氧化鎂作為通道與絕緣層之間的緩衝層,可以大幅改善元件的遷移率與次臨界擺幅,以氧流比0%且50nm的氧化鎂銦通道層與5 nm 氧化鎂緩衝層製作的薄膜電晶體有臨界電壓為2.01 V,場效遷移率4.80 cm^2/V∙s,開關電流比9.68×103,次臨界擺幅0.76 V/decade。

    In this thesis, MgIn2O4 is deposited by RF sputtering system and the properties of MgIn2O4 thin films under different processing conditions were investigated and discussed. MgIn2O4 thin films were then applied for the active layer of optoelectronics devices including UV photodetectors (PDs) and thin-film transistors (TFTs). The electrical characteristics of devices were measured and compared, and the differences between each device were also discussed in detail.
    First, we deposited MgIn2O4 thin films with various oxygen flow ratios and annealed the films under different temperature in argon ambience to rearrange the atom in the films. Then, MgIn2O4 thin films were studied with a view to their structural, optical, and elemental properties. In the structural analysis, X-ray diffraction (XRD) results demonstrate that crystallization becomes more remarkable as the increasing annealing temperature. Besides, after high-temperature annealing, MgIn2O4 thin films with higher oxygen flow ratios show a more dominant MgIn2O4 crystalline phase than that of In2O3. The surface morphology MgIn2O4 thin films were investigated by AFM and all films display smooth surface roughness. In the optical analysis, MgIn2O4 thin film shows high transmittance in the visible region and a wide bandgap of above 3.9 eV which makes MgIn2O4 a potential material for UV sensing. In the elemental analysis, Energy-dispersive X-ray spectroscopy (EDS) was carried out to verify the elemental composition of the MgIn2O4 thin film. Furthermore, X-ray photoelectron spectroscopy (XPS) was conducted to prove the increasing oxygen partial pressure can effectively suppress oxygen vacancies in the MgIn2O4 thin film, indicating carrier concentration is certainly reduced.
    Second, the grown MgIn2O4 thin film was applied for the sensing layer of a UV photodetector. We optimized the optoelectronics characteristics of the MgIn2O4 UV photodetector by simply adjusting the oxygen flow ratio as well as post-annealing temperature. The dark current reduces with the increased oxygen flow ratio since more oxygen vacancies were compensated during the sputtering process, thus leading to a less carrier concentration. Similarly, responsivity drops with the rising oxygen flow ratio because oxygen vacancies, which can be contributed to a higher responsivity, were filled up when growing a MgIn2O4 thin film. Though the more oxygen vacancies bring about a higher responsivity, however, they also degrade the switching characteristics. Furthermore, we investigated the effect of post-annealed MgIn2O4 UV photodetector. Furthermore, the dark current increase dramatically after annealed under high temperature due to the atom rearrangement. The photo-to-dark current ratio and responsivity were notably improved because a suitable annealing condition can result in better film quality, and enhance the absorption in the UV region. The optimized MgIn2O4 visible-blind UV photodetector with an oxygen partial pressure of 2% and post-annealed under 300℃ in argon ambience for an hour was demonstrated, showing a responsivity of 1.38 A/W, a photo-to-dark current ratio of 1.82×107, and a UV to visible rejection ratio of 4.3×103.
    Third, MgIn2O4 TFTs with silicon dioxide as a gate insulator and quartz glass as the substrate were fabricated. We optimized MgIn2O4 TFT by changing the oxygen flow ratio and thickness of the channel layer. It is found that the MgIn2O4 TFT with an oxygen flow ratio of 2% and channel layer of 30 nm shows an optimal performance of a threshold voltage of 1.54 V, a field-effect electron mobility of 0.23 cm^2/V∙s, an on/off current ratio of 5.88×104, and a subthreshold swing of 0.61 V/decade. Moreover, we broaden the applicability of prepared MgIn2O4 TFT to the phototransistor, which exhibits a maximum responsivity of 5.22×10-2 A/W and a UV-to-visible rejection ratio of 1.36×103 at the gate bias voltage of -3 V. Moreover, we realized performance enhancement of MgIn2O4 TFTs by introducing a homogeneous MgO buffer layer. This buffer layer provides a superior interface quality and thus reduces interface scattering, resulting in improved mobility. Also, oxygen vacancies in the channel layer are suppressed by excessive amounts of oxygen resulted from the MgO buffer layer. As a consequence, the subthreshold swing is considerably ameliorated. The MgIn2O4 TFTs with a homogeneous MgO buffer layer shows a field-effect electron mobility of 4.80 cm^2/V∙s, a threshold voltage of 2.01 V, an on/off current ratio of 9.68×103, and a subthreshold swing of 0.76 V/decade.

    摘要 I Abstract IV 致謝 VIII Content IX Table Captions XII Figure Captions XIV Chapter 1 Introduction 1 1.1 Background and Motivation 1 1.2 Background of MgIn2O4 Material 3 1.3 Overview of Ultraviolet Photodetectors 4 1.4 Overview of Thin Film Transistor 6 1.5 Organization of This Thesis 7 Reference 8 Chapter 2 Relevant Theory and Experimental Equipment 13 2.1 Theory of Photodetector 13 2.1.1 Responsivity of the Photodetector 14 2.1.2 Rejection Ratio of the Photodetector 15 2.1.3 Rise Time & Recovery Time of the Photodetector 15 2.2 Theory of Thin Film Transistor 16 2.2.1 Threshold Voltage (Vth) 18 2.2.2 Field-Effect Mobility 18 2.2.3 On/Off Current Ratio (Ion/Ioff) 19 2.2.4 Subthreshold Swing (SS) 20 2.2.5 Interface Trap Density (Nit) 20 2.3 Experimental Equipment 21 2.3.1 RF Sputtering System 21 2.3.2 Plasma-Enhanced Chemical Vapor Deposition 24 2.3.3 Thermal Evaporation 25 2.3.4 X-ray Diffraction Analysis 26 2.3.5 Atomic Force Microscopes 29 2.3.6 Transmission Electron Microscope 30 2.3.7 Energy-Dispersive X-ray Spectroscopy (EDS) 30 2.3.8 X-ray Photoelectron Spectroscopy 32 2.3.9 Measurement Systems 33 Reference 34 Chapter 3 Characteristics of MgIn2O4 Thin Film 38 3.1 Growth of MgIn2O4 Thin Film 38 3.2 Structural Characteristics 40 3.2.1 X-ray Diffraction (XRD) Analysis 40 3.2.2 Atomic Force Microscopy (AFM) Analysis 43 3.2.3 Transmission Electron Microscope (TEM) Analysis 48 3.3 Optical Characteristics 50 3.4 Elemental Analyses 55 3.4.1 X-ray Photoelectron Spectroscopy (XPS) 55 3.4.2 Energy Dispersive X-ray Spectroscopy (EDS) 57 Reference 64 Chapter 4 Fabrication and Characteristics of MgIn2O4 MSM Photodetector 68 4.1 Fabrication of MgIn2O4 MSM Photodetector 68 4.2 Characteristics of MgIn2O4 MSM Photodetector 70 4.2.1 Characteristics of Different Oxygen Flow Ratios 70 4.2.2 Characteristics of Different Annealing Temperatures 77 4.3 Summary 81 Reference 82 Chapter 5 Fabrication and Characteristics of MgIn2O4 Thin Film Transistor 84 5.1 Fabrication and Measurement of MgIn2O4 Thin Film Transistor 84 5.2 Characteristics of the MgIn2O4 Thin Film Transistor 86 5.2.1 Characteristics of Different Oxygen Flows Ratios 86 5.2.2 Characteristics of Different Active Layer Thicknesses 91 5.3 Characteristics of the MgIn2O4 Phototransistor 97 5.4 Introduction of MgIn2O4 TFT with an MgO Buffer Layer 103 5.5 Fabrication of MgIn2O4 TFT with an MgO Buffer Layer 104 5.6 Characteristics of the MgIn2O4 TFT with an MgO Buffer Layer 107 5.7 Summary 112 Reference 114 Chapter 6 Conclusion and Future Work 117 6.1 Conclusion 117 6.2 Future Work 119

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    Chapter 4
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    Chapter 5
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    [13] Liu, G. X., et al. "High-performance fully amorphous bilayer metal-oxide thin film transistors using ultra-thin solution-processed ZrOx dielectric." Applied Physics Letters 105.11 (2014): 113509.
    [14] Na, So-Yeong, et al. "Improvement in negative bias illumination stress stability of In-Ga-Zn-O thin film transistors using HfO2 gate insulators by controlling atomic-layer-deposition conditions." Journal of Physics D: Applied Physics 50.49 (2017): 495109.
    [15] Jiang, Guixia, et al. "Solution-processed high-κ magnesium oxide dielectrics for low-voltage oxide thin-film transistors." Applied Physics Letters 109.18 (2016): 183508.
    [16] Lee, Jong Hoon, et al. "Characterization of magnesium oxide gate insulators grown using RF sputtering for ZnO thin-film transistors." Current Applied Physics 14.5 (2014): 794-797.
    [17] Huang, H. Q., et al. "Effect of MgO buffer layer thickness on the electrical properties of MgZnO thin film transistors fabricated by plasma assisted molecular beam epitaxy." Applied surface science 257.24 (2011): 10721-10724.

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