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研究生： 王郁鈞
Wang, Yu-Chun
論文名稱： 氧空缺效應調控鐵電錫酸鋅奈米線之材料特性暨其壓光電子學之水分解應用
Effects of Oxygen Vacancy on Material Properties of Ferroelectric ZnSnO3 Nanowires and Its Application on Water Splitting through Piezo-phototronic Mechanism
指導教授： 吳志明
Wu, Jyh-Ming
口試委員: 杜正恭
Duh, Jenq-Gong
翁錦成
Weng, Chin-Cheng
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學工程學系
Materials Science and Engineering
論文出版年： 2019
畢業學年度： 107
語文別： 英文
論文頁數： 108
中文關鍵詞： 錫酸鋅 、不對稱中心結構 、壓電光電子效應 、氧空缺 、降解 、光催化水分解 、產氫反應
外文關鍵詞： ZnSnO3 nanowires, non-centrosymmetric structure
相關次數： 點閱：2  下載：0 
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    • 本研究利用水熱法合成出屬於R3c空間群之錫酸鋅奈米線 (ZnSnO3 nanowires) 鐵電材料，其晶體結構具有特殊的非對稱中心特性，由於材料內部鋅原子和錫原子在z軸方向上相較於中心有著較大的偏移，故受到一外加應力時會沿著z軸方向產生自發性極化的現象，並誘導出高密度的電荷累積在材料的兩側，形成一個電位差，稱之為壓電勢。在Comsol模擬中明確指出奈米線在受到z軸方向的外力時所誘導出的壓電勢會高過於受到其他方向外力的情況。將錫酸鋅之壓電特性以及半導體特性耦合可以有效地提升光觸媒的效率。
    目前為止少有文獻詳細探討氧空缺濃度對於錫酸鋅奈米線之光觸媒活性和壓電性質的影響，本實驗透過簡單快速的氫氣退火製程，在錫酸鋅奈米線的晶格中引入氧空缺，而氧缺陷的濃度會隨著退火時間的拉長而增加。進一步利用時間解析光致發光光譜 (TRPL) 發現在退火時間為0到3小時的區間內，光激發電子的存活時間會明顯的提高，代表電子電洞對再結合的機率降低，但是在經過4及5小時退火後電子的存活時間下降，此結果和光致發光光譜 (PL) 的結果相吻合；而極化對電場之作圖為一電滯曲線，符合錫酸鋅之鐵電特性，隨著退火時間的增長殘餘極化量的下降代表氧空缺的引入會破壞錫酸鋅之壓電表現，另外在霍爾量測當中發現經過3小時退火的錫酸鋅奈米線有著適當的載子濃度以及載子遷移率。在壓電輔助光電子的協同效應上，結果顯示最佳條件為經過3小時退火處理的錫酸鋅，其能夠在1小時內降解92 %的若丹明 (RhB) 染料，此外，產氫量在1小時內可以達到3882.5 mumol g-1 ，相較於未經退火處理的錫酸鋅提高了1.5倍，綜觀以上結果指出適當的氧空缺濃度可以降低錫酸鋅奈米線之光激發電子電洞對的複合藉此提高載子利用率，再透過壓電效應的輔助更進一步的提升觸媒效能，使其成為在再生能源以及永續產氫領域上的一個新選擇。

    This work, the ferroelectric ZnSnO3 nanowires (NWs) with LiNbO3 structure were successfully synthesized through the hydrothermal method, which belongs to the R3c space group and possesses a non-centrosymmetric structure. In the comsol simulation, it clearly demonstrated that the piezoelectric potential of the nanowire induced by the external force in the z-axis direction is higher than the external force applied in other directions. Also, to improve the catalyst efficiency of ZnSnO3, the oxygen vacancies were introduced into the crystal lattice through a rapid and straightforward hydrogen annealing process, and the concentration of oxygen defects increases with the annealing time. According to the time-resolved photoluminescence (TRPL) results, the lifetime of carriers was increased in the annealing time interval from 0 to 3 hours and achieved 8.05 ns in the case of three hours annealing. After three hours annealing time, with increasing the annealing time, the lifetime was decreased. The piezoelectric properties of ZnSnO3 NWs can couple its semiconductor characteristics to effectively enhance the efficiency of photocatalyst in dye degradation and hydrogen production, which is called piezophototronic effect. By three hours post-annealed ZnSnO3 nanowires, the RhB dye degradation test illustrates that it can decompose 92 % dye molecules in an hour. Besides, the hydrogen evolution reaction reaches 3882.5 mumol g-1, which is 150 % times and 3500 % times higher than that of pristine ZnSnO3 NWs and blank control sample (without nanowires). The results indicate that oxygen vacancies play an important role in hydrogen evolution through the synergistic effect of piezoelectric characteristics and photocatalytic activity of LN-type ZnSnO3 NWs.

    中文摘要 I Abstract III 誌謝 IV Contents V List of figures VII Chapter 1 Introduction 1 1.1 Preface 1 1.2 Motivation 2 Chapter 2 Literature review 4 2.1 Photocatalyst 4 2.1.1 Non-metal doping engineering for modification of photocatalyst 5 2.1.2 Metal doping engineering 6 2.1.3 Heterojunction composites 8 2.1.4 Defect engineering 11 2.1.5 Photocatalytic water splitting 13 2.2 Piezocatalyst 15 2.2.1 Principle 15 2.2.2 Mechanism of piezocatalyst 18 2.2.3 Two-dimensional transition metal dichalcogenide 19 2.2.4 Molybdenum disulfide (MoS2) 20 2.2.5 Molybdenum diselenide (MoSe2) 22 2.2.6 Tungsten disulfide (WS2) 23 2.3 Piezo-assisted photocatalytic effect 26 2.4 Effect of oxygen vacancies on ferroelectric properties of materials 29 2.5 ZnSnO3 with R3c space group 32 2.5.1 Preparation of LN-type ZnSnO3 33 2.5.2 Crystal structure and piezoelectricity of LN-type ZnSnO3 35 2.5.3 Ferroelectric behavior and spontaneous polarization 37 Chapter 3 Experimental methods 41 3.1 Materials 41 3.2 Experimental procedures 43 3.2.1 Seed layer sputtering 43 3.2.2 Precursor preparation 44 3.2.3 Hydrothermal process 44 3.3 Material characteristics analysis method 45 3.3.1 Cold field emission scanning electron microscope (SEM) 45 3.3.2 Scanning transmission electron microscope (STEM) 46 3.3.3 Wide angle X-ray diffraction (XRD) 47 3.3.4 Raman spectrometer and photoluminescence spectrometer 48 3.3.5 Time-resolved photoluminescence spectroscopy 49 3.3.6 X-ray photoelectron spectroscopy (XPS) 50 3.3.7 Piezoelectric force microscope (PFM) 51 3.3.8 Electron paramagnetic resonance spectroscopy 52 3.3.9 Ferroelectric analyzer 54 3.3.10 Hall effect measurement 56 3.4 Degradation test 58 3.5 Hydrogen evolution reaction (HER) test 58 Chapter 4 Results and discussion 61 4.1 Surface morphology analysis 61 4.2 XRD analysis 63 4.3 TEM analysis 65 4.4 Raman spectroscopy analysis 67 4.5 Lattice structure analysis 68 4.6 Piezoelectric properties analysis 71 4.7 X-ray photoelectron spectroscopy 75 4.8 Electron paramagnetic resonance spectroscopy 78 4.9 Effects of oxygen vacancies on the optical properties of the ZnSnO3 80 4.9.1 Photoluminescence analysis 81 4.9.2 Interpretation of the PL spectra 83 4.10 Ferroelectric properties 85 4.11 Hall effect measurement 87 4.12 Piezo-phototronic effect 88 4.12.1 Dye degradation test 89 4.12.2 Reaction constant for the dye degradation experiments 91 4.12.3 Water splitting and hydrogen evolution reaction 93 4.12.4 Working mechanism for water splitting of H:ZnSnO3 NWs 96 Chapter 5 Conclusion and future prospects 99 5.1 Conclusion 99 5.2 Future prospects 101 Chapter 6 Reference 103

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