主題一實驗研究高介電常數材料ZrTiO4(k=45)在未經過及經過N2O電漿處理100秒後，做為電荷捕陷層應用於TaN/Al2O3/ZrTiO4/SiO2/Si記憶體電容元件的電荷捕陷表現。實驗發現：
1.XRD顯示，兩樣品在高溫700 oC退火後皆呈現orthorhombic的晶相性；XPS顯示，經過N2O處理者相較於未摻入氮者，其Zr 3d軌域的峰值往低鍵結能方向位移0.3 eV，此可被歸因於有些N原子的摻入取代原先O的位置，另外，N 1s軌域的XPS光譜亦可驗證N原子確實摻入ZrTiO4中並形成O-N的鍵結。
2.使用經過N2O的電漿處理的ZrTiO4作為電荷捕陷層實現快閃式記憶體有相當不錯的表現。包含在+/-7 V電壓掃描下磁滯的記憶視窗高達5.0 V、施加+7 V, 100 μs的脈衝具大的平帶電壓位移3.2 V及優異的保持性(104 s後在85 oC下電荷流失=79 %)。另外該元件的溫度相依性電流密度對電壓曲線分析，證實元件操作於普爾-法朗克機制，此被認為常發生於陷阱數目多的介電層中。這些佳化的參數歸功於使用N2O電漿處理摻入氮帶來更多且更深的陷阱能階所致。
主題二實驗研究有無氮氣通入於腔體的高介電常數材料HfZrO(k=20)做為電荷捕陷層，應用於TaN/SiO2/HfZrO/SiO2/Si記憶體電容元件的電荷捕陷表現。實驗發現：
1.XPS光譜顯示，相較於HfZrO，HfZrON的Hf 4f軌域有額外的峰值產生，此被證實為Hf-N的鍵結形成。另外，N 1s軌域的XPS光譜亦可驗證Hf-N鍵結發生。
2.使用HfZrON作為電荷捕陷層強化了HfZrO在記憶體的電性表現。包含+/-10 V電壓掃描下磁滯記憶視窗由2.7 V提升至5.0 V、施加+10 V,1 ms的脈衝具更大的平帶電壓位移2.6 V，同時也具有優異的保持性(104 s後在85 oC下電荷流失=86 %)。另外，該元件溫度相依性的電流密度對電壓曲線證實元件操作於躍遷機制，此被認為發生於缺陷密度高的薄膜。此優化特性歸因於同腔體通入氮氣帶來更多且更深的陷阱能階。

From the experiment of topic 1, the charge trapping characteristics were investigated by using high-k ZrTiO4(k=45) with and without N2O plasma treatment for 100 sec as charge trapping layer based on the TaN/Al2O3/ZrTiO4/SiO2/Si (MONOS) capacitors.
1. By XRD spectroscopy, both samples exhibit orthorhombic phase after 700 oC high temperature annealing. From XPS analysis, the N2O treated ZrTiO4 presents the peaks shift to lower binding energy by 0.3 eV than untreated one, which should be mainly due to the occurrence of few replacements of O by N, as the Zr-O bond is stronger than Zr-N bond. Moreover, the presence of O-N compound can be further confirmed by the N 1s spectrum.
2.The ZrTiO4 after N2O treatment as charge trapping layer displayed promising performance in terms of a large hysteresis window (5 V) by +-/7 V sweeping voltage, large flat band voltage (VFB) shift (3.2 V) at a low gate voltage of +7 V for 100 μs, a low charge loss=79 % after 104 sec even at 85 oC. Based on the temperature dependent current density versus electric field measurement, the dominate conduction mechanisms in N2O treated ZrTiO4 film is Poole-Frenkel emission which is also confirmed high density of traps in the film. These advantages can be associated with higher trap density and generated deep-level traps due to nitrogen incorporation by N2O plasma.
From the experiment of topic 2, charge trapping characteristics of HfZrO(k=20) with and without in-situ nitrogen incorporation were investigated based on the TaN/SiO2/HfZrO/SiO2/Si (MONOS) capacitors.
1. Compared with the HfZrO film, the additional peak of Hf 4f spectrum for the HfZrON can be observed due to the formation of Hf-N compound. Moreover, the presence of Hf-N compound can be further confirmed by the N 1s spectrum.
2. The HfZrON as charge trapping layer displayed promising performance than using HfZrO in terms of larger hysteresis window (3.8 V) by +-/10 V sweeping voltage, larger flat band voltage (VFB) shift (2.6 V) at a low gate voltage of +10 V for 1 ms, a lower charge loss=86 % after 104 sec even at 85 oC. Based on the temperature dependent current density versus electric field measurement, the dominate conduction mechanisms in HfZrO and HfZrON film are hopping conduction which is also confirmed high density of traps in the film. These advantages can be associated with higher trap density and generated deep-level traps due to nitrogen incorporation by introduced nitrogen in-situ deposition.

摘要..................................................i
Abstract.............................................ii
致謝.................................................iv
總目錄................................................v
圖目錄...............................................viii
表目錄...............................................xiii

第一章 緒論.............................................1
1-1 研究背景............................................1
1-2 研究動機............................................3
1-2-1 【主題一】實驗研究動機..............................3
1-2-2 【主題二】實驗研究動機..............................5
1-3 文獻回顧…............................................6
1-3-1 新型高介電常數材料作為電荷捕陷層應用於非揮發性記憶體之研究.....................................................6
1-3-2 透過氮摻入於高介電常數材料增強其捕陷能力之研究........10

第二章 快閃記憶體原理與操作..............................20
2-1 快閃式記憶體元件結構.................................20
2-2 磁滯曲線的順逆時針操作與記憶視窗大小...................21
2-3 頻率相依性的電容-電壓曲線及電導-電壓曲線...............22
2-4 寫入及抹除速度與機制討論..............................23
2-4-1 寫入操作..........................................24
2-4-2 抹除操作..........................................25
2-5 資料耐久性..........................................26
2-6 資料保持性..........................................26

第三章 實驗規劃與製程流程................................31
3-1【主題一】 TaN/SiO2/N2O:ZrTiO4/SiO2/Si元件製程流程.....................................................32
3-2【主題二】 TaN/SiO2/HfZrON/SiO2/Si元件製程流程.....................................................34

第四章 實驗結果與討論....................................43
4-1【主題一】以N2O電漿處理結晶態ZrTiO4作為電荷捕陷層應用於低電壓操作的非揮發性記憶體......................................43
4-1-1 X光繞射儀........................................43
4-1-2 X光光電子能譜儀...................................44
4-1-3 電容-電壓曲線與記憶視窗............................46
4-1-4 儲存陷阱密度......................................47
4-1-5 頻率相依性的電容-電壓曲線及電導-電壓曲線.............47
4-1-6 電流密度-電壓曲線..................................48
4-1-7 溫度相依性的電流密度-電壓曲線.......................49
4-1-8 普爾-法蘭克散射機制................................49
4-1-9 寫入/抹除速度.....................................49
4-1-10 耐久性..........................................50
4-1-11 保持性...........................................51
4-2【主題二】氮摻入結晶態HfZrO作為電荷捕陷層應用於低電壓操作的非揮發性記憶體..............................................52
4-2-1 X光光電子能譜儀...................................52
4-2-2 電容-電壓曲線與記憶視窗............................53
4-2-3 儲存陷阱密度......................................54
4-2-4 頻率相依性的電容-電壓曲線及電導-電壓曲線.............54
4-2-5 電流密度-電壓曲線.................................55
4-2-6 溫度相依性的電流密度-電壓曲線......................56
4-2-7 躍遷機制.........................................56
4-2-8 寫入/抹除速度.....................................57
4-2-9 耐久性...........................................58
4-2-10 保持性..........................................58

第五章 結論與未來展望....................................82

參考文獻................................................83

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