本論文中，藉由陽極氧化鋁來限制有機無機鈣鈦礦晶體的成長方向，使在奈米孔洞中的有機無機鈣鈦礦依照特定方向結晶，以形成有優選方向的鈣鈦礦薄膜，並運用在電阻式記憶體元件應用上，希望載子在指向性奈米結晶鈣鈦礦中有更好的電阻切換效果。
本論文主要分為三大部分，第一個部分是陽極氧化鋁AAO模板的製作，實驗中改變陽極氧化製程參數及條件，藉此探討陽極氧化後AAO氧化鋁模板的表面形貌與孔洞密度之差異。其中調變的陽極氧化參數包含電解液種類、工作電壓以及電流、一次陽極氧化與二次陽極氧化的時間、擴孔的時間等；經實驗結果可知陽極氧化電解液種類影響孔洞的尺寸，為了達到有效陽極氧化效果，工作電壓與電解液需匹配，電流的改變則會影響電化學輔助溶解效應的速度，並使孔洞成核的速度加快，來提升孔洞密度。為了後續元件的製作，測試了不同基板之AAO陽極氧化鋁膜的穩定性，得到在矽基板上做陽極氧化較其他透明導電基板穩定，所以最後以矽基板作為後續實驗的基板，並得到最佳以及最穩定陽極氧化的參數。再來是阻擋層移除的探討，陽極氧化後期在AAO底層會形成一層Al2O3阻擋層，是良好絕緣體而阻礙載子在電子元件的傳輸，我們以感應耦合電漿蝕刻來將多餘的阻擋層去除，主要實驗參數包含蝕刻功率、時間、氣氛等，實驗結果得到最佳ICP條件為雙功率下以大功率搭配短時間，再以小功率搭配長時間，並在氬氣氛中加入氯化硼以增加垂直性蝕刻率，環境副產物由氬氣帶走。最後以不同四吋陽極氧化後的試片、不同位置去做重複性實驗，確認每片的阻擋層都能完全去除以獲得足夠均勻性。
第二個部分是陽極氧化鋁模輔助有機鈣鈦礦成長，以不同條件將鈣鈦礦填入AAO模板，改變的參數有孔洞表面改質、鈣鈦礦濃度的改變、旋塗轉速改變、溶劑蒸氣法改變鈣鈦礦表面形貌、烤溫持溫時間長短、不同孔洞大小的陽極氧化鋁模板等，並與平面鈣鈦礦薄膜特性作比較。經實驗了解，表面性質對奈米尺寸孔洞基板較平面影響較大，經由APTMS塗佈在基板上使鈣鈦礦可以與基板有更好接觸特性。藉由改變鈣鈦礦濃度以及轉速，可使填入陽極氧化鋁模板後，於模板上方不受限制成長的鈣鈦礦比例減少，更能展現孔洞中鈣鈦礦的特性，藉由溶劑蒸氣法改變薄膜的品質，改變持溫時間控制薄膜結晶特性與晶粒尺寸。結果顯示AAO奈米孔不僅提升鈣鈦礦結晶特性，也抑制δ-FAPbI3二次相生成，而退火持溫時間縮短可導致高織構性。
第三個部分是在AAO基板上成長有機鈣鈦礦並製作成電阻式記憶體結構，並討論四種不同基板上的元件製程，本研究最終成功以重摻雜矽基板製備AAO孔洞陣列，並比較APTMS塗佈後鈣鈦礦記憶體元件特性。由結果得知，添加APTMS除了具有介面改質功能外，也能夠增加鈣鈦礦與基板的親和性，改善鈣鈦礦材料的結晶度以及提升元件性能。記憶體元件開關比可達3個數量級，操作電壓從原本2V降為1.8V，優於沒添加APTMS元件之特性。綜合上述結果，說明了APTMS對於AAO模板與有機鈣鈦礦電阻式記憶體發展所具備的潛力。

In this paper, anodized aluminum is used to limit the growth direction of organic and inorganic perovskite crystals, so that the organic and inorganic perovskite in the nanopores could crystallize in a specific direction to form a preferential perovskite film. As used in the resistive memory devices, it is predicted that the directional nanocrystalline perovskite could exhibit a better resistance switching effect.
This paper is mainly divided into three parts. The first part is the production of an anodized alumina AAO template. In the experiment, some parameters and conditions of the anodization process were tested to explore the relationship between the surface morphology and the port density of the AAO alumina template after anodization. Among them, the adjustable anodizing parameters include electrolyte type, working voltage and current, primary anodizing and secondary anodizing time, hole expansion time, etc. The experimental results show that the type of anodizing electrolyte affects the size of the pores. Based on the effective anodic oxidation effect, the working voltage and electrolyte need to be matched; and the applied current will affect the speed of electrochemical assisted dissolution effect, accelerating the speed of pore nucleation to increase the port density. For the issue of integration process, the stability of the AAO anodized aluminum film on different substrates was tested. It was found that the anodization on the silicon substrate was more stable than on other transparent conductive substrates. Therefore, the silicon substrate was used as the substrate for the device application and the best results were obtained. Next is to examine the barrier layer removal process. In the later stage of anodization, an Al2O3 barrier layer will orm on the bottom of AAO, which is a good insulator and hinders the transport of carriers. We use inductively coupled plasma (ICP) etching to remove the excess barrier layer. The etching parameters include etching power, time, atmosphere, etc. The best ICP conditions were obtained by a dual power process with a high power for a short time, then a low power for a long time. During etching, boron chloride was incorporated into an argon atmosphere to increase vertical etching rate, then environmental by-products were drained off by the argon gas. A good uniformity was obtained by repeating tests of different four-inch anodized wafers to confirm that the barrier layer of each wafer was completely removed everywhere.
The second part is to investigate the AAO assisted organic perovskite growth. The perovskite was filled into the AAO by spin coating the perovskite precursors onto the template under different conditions. The experiment parameters include the surface modification of the the nanopore, the the concentrations of the perovskite precursors, the spin coating speed, and the solvent vapor annealing method. According to the results, the ((3-aminopropyl) trimethoxysilane) (APTMS) surface treatment helped the perovskite to have better contact characteristics with the substrate. By optimizing the concentration and spin speed of the perovskite precursor, the proportion of perovskite layer above the AAO template can be reduced, and the characteristics of the AAO perovskite clearly appeared. The solvent vapor annealing method is used to improve the quality of the film by changing the holding time to control the crystalline properties and the grain size of the film. The results show that AAO nanopores not only improve the crystalline properties of the perovskite, but also inhibit the formation of the secondary phase of δ-FAPbI3. In addition, we found that a short annealing temperature led to the development of a high texture of perovskite.
The third part is established an AAO-organic perovskite resistive memory device and investigate the device substrate effects. A bipolar resistive switching behavior of AAO-organic perovskite device was successfully developed on on a heavily doped silicon substrate. It was found that the APTMS surface treatment could improve the affinity between the perovskite and the substrate, enhancing the crystallinity of the perovskite as well as the performance of the device. The on-off ratio of the memory device achieved 3 orders of magnitude, and the operating voltage is reduced from 2V to 1.8V, which is better than that without APTMS. Based on the above results, APTMS could act an important role for the development of AAO-organic perovskite resistive switching memories.

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