全球能源消耗的增加使得能源需求將達到每天1GW的使用量，龐大的能源消耗，對目前的能源基礎設施造成巨大壓力。加上傳統化石燃料能源的枯竭和氣候變遷的威脅，使得可再生能源的發展和利用成為迫在眉睫的挑戰。在眾多的可再生能源技術當中，太陽能電池有望成為取代傳統化石燃料能源並大幅减少二氧化碳的排放。近年來，因為鈣鈦礦材料具有廣泛的光吸收範圍、低的非輻射發射和低的製造成本，使得鈣鈦礦材料在太陽能電池中的應用引起了學術界的廣泛關注。如今，鈣鈦礦太陽能電池的光電轉換效率已大幅提高到25.2%，可以與矽晶太陽能電池相媲美。除了將鈣鈦礦材料應用在太陽能電池中，鈣鈦礦材料在發光二極管（LED）和光催化領域也具有相當亮眼的表現。然而，鈣鈦礦材料很容易受到大氣環境的影響，例如光，氧氣，水氣，進而降低鈣鈦礦電池的穩定性且限制了鈣鈦礦太陽能電池的產品商業化。因此，本論文的研究方向是利用密度泛函理論（DFT）和分子動力學模擬（AIMD）探討環境因素對於鈣鈦礦材料結構穩定性的影響，並將研究結果用來開發新一代太陽能電池和光催化的鈣鈦礦材料。
有機-無機金屬鹵化物鈣鈦礦作為鈣鈦礦眾多種類之一，由於其良好的晶體結構和光電性質，在光電領域中獲得了高度的關注。一般來說，有機-無機鹵化物鈣鈦礦(例如, CH3NH3PbI3(MAPbI3))的有機陽離子容易與氧氣或水氣反應，進而加速鈣鈦礦結構的光降解。但是，對於MAPbI3鈣鈦礦同時暴露於水和氧時的光降解機制，計算上並沒有太多的深入探討。因此，我們利用密度泛函理論 (DFT) 探討照光條件下，水氣和氧氣對四方晶相的MAPbI3鈣鈦礦穩定性的影響。計算結果顯示MAPbI3(110)在水氣和氧氣共吸附的條件下，其光降解速度和表面崩壞程度比單獨水氣或氧氣的系統下來的快速和嚴重。此外，由AIMD可知PbI2表面的結構降解比MAI表面更明顯。因此，製備富含MAI的MAPbI3薄膜可以有效降低鈣鈦礦的不穩定性。
另外，全無機鹵化物鈣鈦礦(AIHPs)材料近年來也被廣泛得使用在光催化領域來降低環境的汙染。然而，由於氧氣在光下的相互作用，AIHPs結構變得相當不穩定且嚴重阻礙了其工業化和商業化。因此，本研究利用第一原理計算探討了CsPbX3（其中X=Cl、Br和I）在光照下接觸氧氣時的穩定性。計算結果顯示，照光會增加了鈣鈦礦表面與氧氣的靜電相互作用力。此外，分子動力學結果揭示，吸附在CsPbBr3和CsPbI3表面上的氧氣很容易被活化，在照光產生電子極化子系統下，氧氣比較容易與表面的Pb自發形成Pb-O鍵。基於上述結果我們可預期CsPbCl3在結構上更加的穩定，因此CsPbCl3鈣鈦礦有機會為高潛力的光催化材料。

Increases in global energy demand, which are expected to reach 1 GW/day, will significantly strain the current energy infrastructure. This impending challenge, together with the depletion of traditional fossil-fuel-based energy sources and the threat of climate change, necessitates the development of renewable energy technologies. Of the possible renewable energy approaches, solar cells represent a promising route. Perovskite materials have attracted widespread academic interest in recent years due to their broad range of light absorption, low non-radiative emission, and low manufacturing cost. The photovoltaic conversion efficiency of perovskite solar cells has now been significantly increased to 25.2%, comparable to silicon solar cells. Perovskite has a strong track record in light-emitting diodes (LEDs) and photocatalysis, and its use in solar cells. Despite their many advantages, the perovskite materials are easily affected by environmental factors such as light, oxygen, and water vapor, which reduce the stability of perovskite cells and limit the commercialization of perovskite solar cell products. Therefore, the focus of this thesis is to investigate environmental effects on the perovskite materials structural stability using density functional theory (DFT) and ab initio molecular dynamic calculations (AIMD) develop novel perovskite-based materials for solar cells and photocatalysis applications.
Organic-inorganic halide perovskites (OIHPs), one of the many types of perovskites, have been widely used in optoelectronics due to their good crystalline structure and photoelectric properties. In general, the organic cations in OIHPs (for example, CH3NH3PbI3 (MAPbI3)) tend to react with oxygen or water vapor, which accelerates the photodegradation of the perovskite structures. The detailed photodegradation mechanism of MAPbI3 perovskite upon simultaneous exposure to water and oxygen in the presence of light, however, was not thoroughly investigated. Therefore, the role of light in the structural stability of MAPbI3 perovskite after exposure to water and oxygen is investigated, with a particular emphasis on the effects of surface termination. The coexistence of H2O and O2 molecules causes both the MAI and PbI2 terminated MAPbI3 perovskite surfaces to degrade faster than the presence of either monomer on the surface, with the structural degradation being more noticeable in the PbI2 terminated surface than in the MAI terminated surface. Therefore, it is concluded that preparing MAI-rich MAPbI3 films can reduce perovskite instability.
Furthermore, in recent years, all-inorganic halide perovskite materials (AIHPs) have been widely used in photocatalytic applications to reduce environmental pollution. However, the inherent instability of AIHPs due to the interaction of O2 in the presence of light severely impedes their industrialization and commercialization. Hence, the stability of CsPbX3 (where X=Cl, Br, and I) upon O2 exposure in the presence of light is explored in this study using first-principles calculations. The results show that the presence of light increases the electrostatic interactions of these perovskite surfaces with O2. AIMD simulations clearly show that adsorbing O2 is readily activated on the surfaces of CsPbBr3 and CsPbI3, and Pb-O bonds form spontaneously in the presence of light. Based on the results, CsPbCl3 is structurally more stable, suggesting that the CsPbCl3 perovskite could be the potential catalyst material for the photocatalyst applications.

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