臺灣博碩士論文加值系統

由於採用電漿輔助化學氣相沉積(PECVD)之碳氮化矽薄膜方法開發的碳氮化矽的是極具潛力的電阻式記憶體（ReRAM） 候選。然而，由於PECVD方法難以沉積conformal 的薄膜在三維結構的電阻式記憶體。因此，為了開發適合應用於三圍結構電阻式記憶體必須開發適當的電漿輔助原子層沉積之碳氮化矽（PEALD）薄膜 並研究其電阻轉態行為。
在本論文中，使用矽氮烷前驅物，1,3,5-三甲基-1,3,5-三乙烯基環三矽氮烷（VSZ），通過PEALD用氮氣電漿在150-300℃下製備碳氮化矽膜。特別是，我們希望使用具有環狀Si-N-Si和3個乙烯基的矽氮烷前驅物來保持PEALD薄膜含有較高的碳含量。除此之外，本論文亦研究對基板表面之前處理，並控制電漿特性（功率，劑量）開發出新的電漿輔助原子層沉積方法。並同時研究了碳氮化矽薄膜的物理性質和化學結構。 電漿輔助原子層沉積之碳氮化矽薄膜顯示出更密集的Si-N結構，且沒有CHx鍵，Si-H鍵和CN-H帶，使得薄膜上產生高於電漿輔助化學氣相沉積之碳氮化矽薄膜的折射率和密度（1.81-1.94g / cm3）。
接下來為了研究電阻轉換行為，將SiCxNy薄膜製備在鋁的頂部和底部電極中。並在I-V測量中，30W 200℃製備的SiCxNy薄膜展示了雙極電阻開關特性而且不需要forming。50W 200℃製備的SiCxNy薄膜則呈現單極性選擇器的特性。因此以矽氮烷前騶物利用電漿輔助原子層沉積之碳氮化矽薄膜製備的元件展示出記憶體與選擇器的兩種功能有助於電路編程設計以及減少三圍結構的電阻式記憶體漏電流問題。，為製造三維結構非揮發性記憶體應用提供了途徑。

Plasma-enhanced chemical vapor deposited (PECVD) N-rich silicon carbonitride (SiCxNy) thin-films have been demonstrated as a promising candidate for resistive random-access memory (ReRAM) candidate owing to the conductive bridge random access memory (CBRAM). However, the PECVD method is not conformal and is difficult to meet the requirements of 3D ReRAM. It is, therefore, imperative to develop conformal SiCxNy film for 3D ReRAM structure using deposition technique such as atomic-layer-deposition (ALD). In this work, SiCxNy films were prepared by PEALD with N2 plasma at 150 to 300℃, using a silazane precursor, 1, 3, 5-trimethyl-1, 3, 5- trivinylcyclotrisilazane (VSZ), which contains cyclic Si-N-Si and 3 vinyl groups in hope to enhance carbon incorporation in the film.
Various surface treatments of native oxide/Si substrate were first explored to ensure linear ALD growth. The effects of plasma characteristics (power, dose) and deposition temperature on the ALD growth and the chemical structure and properties such as refractive index, density, and composition of SiCxNy films were studied. PEALD SiCxNy films show higher film density (1.81-1.94 g/cm3) and refractive index (1.62-1.67) than PECVD SiCxNy films, due to a denser Si-N structure and free of dangling bonds such as -CHx, -Si-H, and -CN-H bonds. PEALD SiCxNy films deposited at 200 ℃ illustrate excellent smoothness and layer-like stacking as verified by XRR and GISAXS.
To investigate resistive switching behavior, SiCxNy films were sandwiched by the top and bottom electrodes of aluminum. The SiCxNy cell demonstrates a bipolar resistive switching characteristic without forming and the unipolar selector performance, yet there is room for improvement in the durability. SiCxNy film (200℃, 30W) perform memory behavior and survive 37 cycles. Moreover, SiCxNy film (200℃, 50W) yield selector behavior with a 104 on/off ratio. PEALD SiCxNy films in this work demonstrate the feasibility to be used as memory and selector giving the pathway for the fabrication of 3D structure non-volatile memory application.

摘要 I
Abstract III
Acknowledgements V
Contents VI
Table captions IX
Figure captions X
Chapter 1 Introduction 15
1.1 Background 15
1.2 Overview 19
Chapter 2 Literature Review 20
2.1 Introduction of ALD technology 20
2.1.1 Plasma enhanced atomic layer deposition 21
2.2 Atomic Layer Deposition of Silicon Carbonitride 22
2.3 Emerging memory 24
2.3.1 Ferroelectric Random Access Memory (FeRAM) 26
2.3.2 Magnetoresistive Random Access Memory (MRAM) 26
2.3.3 Phase Change Memory (PCM) 27
2.3.4 Resistive Random Access Memory (ReRAM) 29
2.4 ReRAM options 30
2.4.1 Oxygen Migration 30
2.4.2 Oxygen vacancy migration 32
2.4.3 Metal filament 34
2.5 The switching mechanism of ReRAM 34
2.5.1 Filamentary model 35
2.5.1.1 Joule heating effect 36
2.5.1.2 Redox reaction 37
2.6 Carrier conduction mechanisms in ReRAM 38
2.6.1 Ohmic conduction 39
2.6.2 Schokkty emission 40
2.6.3 Poole-Frenkel emission 40
2.6.4 Tunneling conduction 41
2.6.5 Space charge limited current 43
2.6.6 Hopping conduction 44
Chapter 3 Experimental 69
3.1 Preparation of SiCxNy thin films 69
3.1.1 Precursor materials-1,3,5-trimethyl-1,3,5-trivinylcyclo-trisilazane (VSZ) 69
3.1.2 PEALD SiCxNy thin-films 70
3.2 Characterization of SiCxNy thin-films 70
3.2.1 Chemical characteristics 70
3.2.2 Film thickness measurement 71
3.2.3 Electrical characteristics 71
3.2.4 X-ray Reflectivity (XRR) 72
3.2.5 Gracing Incidence Small Angle X-ray Scattering (GISAXS) 72
Chapter 4 Results and discussion 78
4.1 PEALD of SiCxNy films 78
4.1.1 Effect of substrate pretreatment 78
4.1.2 PEALD Reaction Conditions- standard recipes for PEALD process 81
4.2 Chemical and Structural characterization of SiCxNy films 83
4.2.1 Infrared and XPS analyses of SiCxNy Films 83
4.2.2 Properties of SiCxNy films 87
4.2.3 Structure and morphology characterization 89
4.2.3 Summary 90
4.3 Study of the Resistive Switching of SiCxNy films 91
4.3.1 PEALD of SiCxNy films 91
4.4 Analyses of carrier transport mechanism of SiCxNy based ReRAM 94
4.4.1 Current-Voltage curve for fitting 94
4.4.2 Discussion for carrier transport mechanism 96
4.4.3 Interpretation of fitting results 97
4.4.4 Schottky barrier height and switch thickness 98
4.4.5 Set process 99
4.4.6 Reset process 101
4.4.7 Summary 102
Chapter 5 Conclusions 144
References 146
 

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