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研究生： 盧麒竣
Lu, Chi-Chun
論文名稱： 應用微波電漿化學氣相沉積法合成奈米鑽石之非揮發性電阻式記憶體
Nonvolatile Resistive Random Access Memory Based on Microwave Plasma Chemically Vapor Deposited Nanodiamond Films
指導教授： 曾永華
Tzeng, Yon-Hua
學位類別： 碩士
Master
系所名稱： 電機資訊學院 - 微電子工程研究所
Institute of Microelectronics
論文出版年： 2013
畢業學年度： 101
語文別： 英文
論文頁數： 113
中文關鍵詞： 電阻式記憶體 、奈米鑽石 、微波電漿化學氣相沉積
外文關鍵詞： Resistive random access memory (RRAM), Nanodiamond, Microwave plasma vapor deposition (MPCVD)
相關次數： 點閱：153  下載：5 
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    • 在本論文中, 我們成功地將微波電漿化學氣相沉積法合成之奈米鑽石薄膜應用於非揮發性電阻式記憶體中之介電質層並且以銅及鎢分別作為上、下電極，所以其結構為銅-奈米鑽石薄膜-鎢。藉由外部提供電場，此記憶體可在其高、低阻態間來回切換而其高、低阻態之電流值可經由一個較小的讀取電壓得知。另外，指叉式之上、下電極結構也被用來呈現此記憶體。
    此應用奈米鑽石薄膜之記憶體具有大的開關電流值比( >100000)、40次以上的開關切換次數，而且此記憶體在高、低阻態之電流值分別都可以保持長時間的穩定性( >10000 秒)。另外，在本論文中，藉由電壓電流特性及二次離子質譜儀之分析，此記憶體之導通操作以及其高、低阻態切換機制也被討論與研究，由電壓電流特性分析可得之，此記憶體在其高、低阻態之導通機制分別為空間電荷侷限電流(Space charge limit current)理論及歐姆定律，而此現象也可說明此記憶體之開關特性是由燈絲傳導機制(Filamentary conduction)所造成。而二次離子質譜儀分析之結果更可以說明此記憶體之高、低阻態切換機制為燈絲傳導機制。
    奈米鑽石薄膜擁有良好的化學惰性、散熱性以及低的銅之固體溶解度，因此，在奈米鑽石薄膜中，銅離子藉由電場形成之燈絲導通路徑非常穩定，所以奈米鑽石薄膜很適合作為電阻式記憶體之介電質層，在未來，此奈米鑽石電阻式記憶體可以應用其良好的特性，操作於艱困的環境中。

    In this thesis, the nanodiamond thin film, deposited by the microwave plasma vapor deposition (MPCVD) system, is utilized as the dielectric film for the fabrication of resistive random access memory (RRAM) with copper (Cu) layer as top electrodes and the tungsten (W) counter electrodes. The RRAM with the metal-insulator-metal (MIM) structure of Cu/Nanodiamond/W is switched between the high resistance state (HRS; OFF state) and its low resistance state (LRS; ON state) by the external electrical stimulation. The HRS or LRS can be probed by a low applied voltage across two counter electrodes and measure its conduction current.
    It is observed that the Cu/Nanodiamond/W structure shows good performance with the ON/OFF conduction current ratio >100000 and retention time >10000 s; switching cycle times is up to 40. Besides, the conduction and resistive switching mechanism are also researched and discussed in the thesis. For the conduction mechanism, the trap-controlled space charge limit current (SCLC) might dominate the conduction current of the HRS while the conduction current of the LRS might be dominated by the Ohmic conduction. As for the resistive switching mechanism, the results of secondary ion mass spectrometry (SIMS), it is the food agreement that the switching mechanism might be the filamentary model.
    Nanodiamond is known to be chemically inert, good heat dissipation and has very low solid solubility in copper. That is, the conductive filamentary channel composed of copper ion is very stable in the nanodiamond thin film. It is, therefore, a suitable dielectric material to fabricate the RRAM for harsh environments.

    中文摘要 I ABSTRACT II 致謝 III CONTENTS IV TABLE CAPTIONS VII FIGURE CAPTIONS VIII CHAPTER 1 INTRODUCTION 1 1.1 MOTIVATION 1 1.2 DIAMONDS 2 1.2.1 INTRODUCTION TO DIAMOND 2 1.2.2 CHARACTERISTICS OF DIAMOND 7 1.2.3 DIAMOND APPLICATIONS 19 1.3 NONVOLATILE MEMORIES FOR NEXT GENERATION 24 1.3.1 INTRODUCTION TO MEMORIES 24 1.3.2 PHASE CHANGE MEMORY 27 1.3.3 FERROELECTRIC RANDOM ACCESS MEMORY 29 1.3.4 MAGNETORESISTIVE RANDOM ACCESS MEMORY 30 1.3.5 RESISTIVE RANDOM ACCESS MEMORY 30 CHAPTER 2 BACKGROUND 31 2.1 CHEMICALLY VAPOR DEPOSITED DIAMOND FILMS 31 2.1.1 THEORY AND MECHANISM OF CHEMICAL VAPOR DEPOSITION 32 2.1.2 GROWTH OF CVD DIAMOND FILMS 33 2.1.3 INTRODUCTION TO CVD DIAMOND FILMS 35 2.1.4 GASES FOR CHEMICALLY VAPOR DEPOSITED REACTION 38 2.1.5 DOPED CVD DIAMOND FILMS 40 2.2 RESISTIVE RANDOM ACCESS MEMORY 41 2.2.1 TYPICAL STRUCTURE OF RRAM 41 2.2.2 RESISTIVE SWITCHING CURRENT-VOLTAGE CURVES OF RRAM 42 2.2.3 CONDUCTION MECHANISMS OF RRAM 43 2.2.4 RESISTIVE SWITCHING MECHANISMS OF RRAM 45 2.3 CARBON-BASED RESISTIVE RANDOM ACCESS MEMORY 46 CHAPTER 3 INSTRUMENTS 47 3.1 MICROWAVE PLASMA CHEMICAL VAPOR DEPOSITION SYSTEM 47 3.2 RADIO FREQUENCY SPUTTERING SYSTEM 48 3.3 RAMAN SPECTROSCOPE SYSTEM 49 3.4 ATOM FORCE MICROSCOPE 49 3.5 SCANNING ELECTRON MICROSCOPE 50 CHAPTER 4 EXPERIMENTAL 51 4.1 INTRODUCTION 51 4.2 GROWTH PROCEDURE OF NANODIAMOND THIN FILMS 52 4.2.1 CHOICE AND STANDARD CLEAN PROCESS FOR THE SUBSTRATES 52 4.2.2 STANDARD DIAMOND SEEDING PROCESS 54 4.2.3 STANDARD DEPOSITING PROCESS OF NANODIAMOND THIN FILMS 56 4.3 NANODIAMOND BASED RESISTIVE RANDOM ACCESS MEMORY PROCEDURE 60 4.3.1 DEMONSTRATING PROCESS OF THE RESISTIVE RANDOM ACCESS MEMORY DEVICES 60 4.3.2 PROCESS OF THE BOTTOM ELECTRODE 62 4.3.3 PROCESS OF THE NANODIAMOND THIN FILMS AS THE DIELECTRIC THIN FILMS 64 4.3.4 PROCESS OF THE TOP ELECTRODES 66 CHAPTER 5 RESULTS AND DISCUSSIONS 68 5.1 PROMOTION OF NUCLEATION DENSITY 68 5.2 PHYSICAL ANALYSIS OF NANODIAMOND THIN FILMS 71 5.2.1 ANALYZING TO NANODIAMOND THIN FILMS DEPOSITED FOR DIFFERENT TIME 72 5.3 RESISTIVE SWITCHING CHARACTERISTICS OF NANODIAMOND BASED RRAM. 87 5.3.1 ELECTRICAL PROPERTY OF NANODIAMOND BASED RRAM 88 5.3.2 RETENTION CHARACTERISTICS AT HIGH TEMPERATURE 92 5.3.3 SWITCHING AND CONDUCTION MECHANISMS OF NANODIAMOND-RRAM 97 5.4 NANODIAMOND-RRAM WITH FINGER ELECTRODES 103 CHAPTER 6 CONCLUSIONS AND FUTURE WORK 108 6.1 CONCLUSIONS 108 6.2 FUTURE WORK 109 REFERENCE 110

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