隨著大數據時代來臨，資料存取、物聯網以及人工智慧等新興技術快速發展，下世代記憶元件的需求因此大幅增加。本論文主要研究應用於類神經計算之鹼金與鹵素材料二端人工突觸元件、可變電阻式記憶體以及電化學人工突觸電晶體，並針對其電性表現選擇適當的材料與元件結構上的優化。
第一章簡介人工突觸及可變電阻式記憶體之工作原理及研究發展，並針對用於人工突觸之鹵化鈣鈦礦特性及研究做進一步的介紹。統整元件電阻可調性之機制來源，並討論揮發性及非揮發性記憶體分別適合的類神經計算架構及其未來之應用與發展性。
第二章詳述人工突觸及記憶體元件完整的製備過程、儀器原理、參數設定及量測架設。
第三章以真空熱蒸鍍製程製備CsPbI2Br鹵化鈣鈦礦人工突觸，透過材料比例調整、上電極之選擇及元件結構改變，實現電阻變化明顯、操作電壓低、切換時間快及低能耗之Indium tin oxide (ITO)/MoO3/CsPbI2Br/MoO3/Ag元件。面積為1 × 1 mm2之封裝元件可實現40 µs內完成寫與讀的操作，每次驅動元件所需的最低切換能量為25.2 nJ，並以顯微材料分析技術證明Ag+及I-在電場驅動下遷移至CsPbI2Br/MoO3界面形成AgI複合物，使元件導電度呈類比變化。
第四章著重於開發用於類神經計算之新型金屬鹵化物人工突觸主動層材料，PbI2、MgI2、BiI3及CsI因具有容易移動之碘離子，且易與金屬電極產生電化學變化，電壓驅動之下能有連續多階之電阻變化，並針對有突觸行為的元件進行元件結構、電極選擇及薄膜厚度上的優化，以實現應用於類神經計算之低能耗元件。
第五章選用化學性質穩定且具有I-V遲滯特性之CsI及PbI2作為可變電阻式記憶體 (Resistive random-access memory, RRAM) 主動層材料，實現低驅動電壓(~0.1 V)、高開關比率(106)、可重複操作及長電流保留時間(>100秒)之記憶體，中間狀態也能有一定的電流保留時間，適合應用於類神經計算之類比/多階電流狀態憶阻器。
第六章為解決二端人工突觸元件之瓶頸，而開發全固相電化學人工突觸電晶體，以電池之可逆電化學反應為基礎設計含有可移動離子Li+、Na+及Cs+之固態絕緣層及PTCDA作為半導體層，透過鹼金離子摻雜改變通道之導電度。優化NaClO4-PEO固態電解質溶液之旋轉塗佈轉速及溶質濃度，並觀察其顯微結構特徵。最後對全固相電化學人工突觸電晶體進行電性量測及分析。

With the rapid development of data storage, Internet of things and artificial intelligence, the demand for next-generation memory devices increases significantly. In this thesis, two-terminal artificial synaptic device, resistive random-access memory and electrochemical synaptic transistor with alkali and halide materials were fabricated, which can be further utilized in neuromorphic computing. We also selected proper materials and modified the device structure to improve the electrical performance of artificial synapse and memory.
In the introduction section, we briefly introduced the working principles and the development of artificial synapse and resistive random-access memory, and then depicted the properties of perovskite materials and the recent researches on perovskite artificial synapses. Furthermore, we summarized the mechanism of resistive switching and the applicable neuromorphic computing network and future application of volatile and nonvolatile resistive switching memory.
The second chapter is the experimental section. We explicated the fabrication of synaptic and memory devices, the operation principle of the measurement instruments, the parameter setting and the setup of the electrical measurements.
In the third chapter, vacuum-thermal-deposited CsPbI2Br perovskite artificial synapses were studied. By tuning the material composition, selecting the suitable electrode and altering the device structure, we demonstrated the artificial synapse with ITO/MoO3/CsPbI2Br/MoO3/Ag structure that exhibited obvious resistive change, low operation voltage, fast switching time and low energy consumption. CsPbI2Br perovskite artificial synapses with 1 × 1 mm2 device area enabled total write-read duration within 40 µs and the minimal switching energy as low as 25.2 nJ per synaptic event. Finally, we found that the Ag+ and I- ions migrated under electrical field and formed a AgI layer at the CsPbI2Br/MoO3 interface. These AgI layers were responsible for the analogue change of the conductance.
In the fourth chapter, we were engaged in developing the metal halide materials as the active layer of artificial synapses. PbI2, MgI2, BiI3 and CsI with mobile iodide ions induced continuous multilevel resistive change under the electrical bias. We optimized the metal halide artificial synaptic devices by changing the device structures, selecting various electrodes, and tuning the thicknesses of the thin films and finally realized the neuromorphic electronic devices with low energy consumption.
In the fifth chapter, CsI-based and PbI2-based RRAM showed a low set voltage (~0.1 V), a high on/off ratio (106), a repeatable operation and a good retention time (>100 s). Some devices also exhibited multilevel switching behavior with a certain retention time.
The two-terminal memristors suffer from several deficiencies. Hence, we developed all-solid-state electrochemical transistors for neuromorphic computing and the results are shown in the sixth chapter. Based on the reversible electrochemical reaction of batteries, we used the insulator with mobile ion (Li+, Na+ and Cs+) and PTCDA semiconductor in our devices. By the application of a gate voltage, active ions are injected into the semiconductor channel and change the conductance of the channel. We first optimized the spin solution process parameters of the NaClO4-PEO solid electrolyte. Scanning electron microscope was used to investigate the microstructure of the thin films. Finally, we fabricated the all-solid-state electrochemical artificial synaptic transistors and analyzed their electrical properties.

中文摘要---------------------------------------I
Abstract------------------------------------III
致謝------------------------------------------V
目錄------------------------------------------VI
圖目錄----------------------------------------IX
表目錄-------------------------------------XVIII
第一章 序論------------------------------------1
1-1 前言---------------------------------------1
1-2 人工突觸簡介-------------------------------3
1-2-1 大腦結構與突觸可塑性----------------------3
1-2-2 人工突觸之研究發展------------------------4
1-2-3 用於人工突觸之鹵化鈣鈦礦------------------6
1-3 RRAM簡介----------------------------------15
1-3-1 RRAM之研究發展---------------------------15
1-3-2 RRAM之工作原理---------------------------16
1-4 電阻變化機制-------------------------------19
1-5 用於類神經計算之揮發性及非揮發性元件---------23
第二章 人工突觸與RRAM之元件製備與量測分析--------29
2-1 元件製備-----------------------------------29
2-1-1 有機材料之純化----------------------------29
2-1-2 基板清洗---------------------------------29
2-1-3 薄膜製備---------------------------------29
2-1-4 元件封裝---------------------------------31
2-2 薄膜分析與元件電性量測-----------------------33
2-2-1 薄膜分析----------------------------------33
2-2-2 元件電性量測------------------------------35
第三章 CsPbI2Br鹵化鈣鈦礦人工突觸----------------36
3-1前言-----------------------------------------36
3-2 以Au作為電極之CsPbI2Br人工突觸---------------37
3-3 以Ag作為電極之CsPbI2Br人工突觸---------------39
3-3-1 短期記憶到長期記憶-------------------------39
3-3-2 插入有機薄膜層以延長電流保留時間------------40
3-3-3 最短驅動脈衝與切換能量---------------------41
3-3-4 不同元件面積之電流與切換時間----------------42
3-4 以Ag作為電極之CsPbI2Br人工突觸機制探討--------50
3-4-1 短期記憶/長期記憶之促進/抑制過程------------51
3-4-2 穿透式電子顯微鏡及能量色散X射線譜證明--------52
3-5 結論----------------------------------------56
第四章 金屬鹵化物人工突觸-------------------------57
4-1前言-----------------------------------------57
4-2 以Au作為電極之氯化物/溴化物/碘化物人工突觸-----58
4-2-1 電性量測----------------------------------58
4-2-2 電極變化與能量色散X射線譜分析---------------59
4-3 以Au作為電極之BiI3人工突觸--------------------62
4-4 以Cu/Ag作為電極之CsI人工突觸------------------64
4-5 以Au作為電極之PbI2人工突觸--------------------66
4-5-1 主動層厚度優化------------------------------66
4-5-2 元件結構優化--------------------------------67
4-6 結論-----------------------------------------70
第五章 金屬鹵化物RRAM-----------------------------71
5-1 前言-----------------------------------------71
5-2 CsI金屬鹵化物RRAM-----------------------------72
5-2-1 以Ag作為上及下電極之CsI記憶體----------------72
5-2-2 以Au/Ag作為上及下電極之CsI記憶體-------------74
5-2-3 以Au作為上及下電極之CsI記憶體----------------75
5-2-4 以Ag作為上電極之CsI記憶體--------------------77
5-3 PbI2金屬鹵化物RRAM----------------------------89
5-4 結論------------------------------------------92
第六章 全固相電化學人工突觸電晶體-------------------94
6-1 前言------------------------------------------94
6-2 濺鍍氧化銦鋅薄膜之特性量測----------------------95
6-3 電化學電晶體元件設計及原理----------------------97
6-4 固態電解質薄膜特性分析及元件電性量測-------------99
6-4-1 NaClO4-PEO固態電解質薄膜特性分析--------------99
6-4-2 全固相電化學人工突觸電晶體之電性量測----------103
6-5 結論-----------------------------------------108
第七章 未來展望-----------------------------------109
參考文獻------------------------------------------111

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