本論文探討濺鍍在c面藍寶石(c-cut sapphire)基板的二氧化鈦與二氧化鉿超晶格結構與不同的週期厚度比例導致的介電係數之改變。以射頻磁控濺鍍機分別成長金紅石(rutile)(100)面二氧化鈦(TiO2)薄膜與二氧化鉿(HfO2)，以X光繞射儀(θ-2θ、rocking curve、XRR與GIXRD)分析其結構，算出濺鍍速率後，再成長TiO2/HfO2雙層交疊為一周期，總共五個週期與十個週期的超晶格薄膜。用X光繞射儀了解多層膜組成超晶格結構後的變化，之後再從穿透式電子顯微鏡觀察內部原子排列方式。成長為超晶格薄膜後TiO2與HfO2晶格都產生變化，從TEM電子繞射圖與高解析度圖(HR)顯示HfO2跟隨TiO2以金紅石結構排列，因此在XRR的模擬中能看到HfO2的密度產生很大的變化。在10週期的TiO2/HfO2超晶格樣品TEM電子繞射圖發現TiO2孿生晶體(twinned crystals)繞射點，但在五週期的TiO2/HfO2超晶格樣品因為藍寶石基板與二氧化鈦間強交互作用力作用改變二氧化鈦結構，使二氧化鈦在靠近基板時成為單晶，遠離基板則產生孿生晶體。TiO2/HfO2超晶格樣品分為A系列(十個週期)與B系列(五個週期)，A系列樣品直接在650度成長TiO2:HfO2超晶格在藍寶石基板，B系列樣品在藍寶石基板上攝氏550度環境成長一奈米二氧化鈦緩衝層，之後再於650度成長TiO2:HfO2多層膜。兩系列樣品各成長兩種周期比例，分別為1奈米TiO2與1奈米HfO2交疊為一週期(TiO2:HfO2-1:1)與3奈米二氧化鈦與1奈米二氧化鉿交疊為一週期(TiO2:HfO2-3:1)。

RF magnetron sputtering has been used to deposit thin films of TiO2/HfO2 superlattices
in alternating sequence on c-oriented sapphire substrates using titanium, or titanium
dioxide, and Hafnium dioxide targets. The thin films thus obtained have higher
dielectric constants and better insulation properties. The dielectric characteristics were
studied on samples of different numbers of cycles and thickness ratios of the two oxides.
Two series of samples, classified as series-A for [(TiO21nm/HfO21nm)10cycles and
(TiO23nm/HfO21nm)10cycles], and as series-B for [(TiO21nm/HfO21nm)5cycles and
(TiO23nm/HfO21nm)5cycles]. X-ray diffractometry (XRD) and transmission electron
microscopy (TEM) have been conducted to examine the structural properties of the
samples in relation to the dielectric properties, and lock-in amplifier used to measure
the internal impedance of the samples from 0.1 Hz to 100kHz. Change of voltage as a
function of frequency was used to calculate the values the frequency dependence of
involved capacitance and inductance.
TEM electron diffraction patterns showed that the HfO2 layers are of a few
nanometer thick and grow epitaxially on the TiO2 thin film by assuming the same
crystal structure of the underlying TiO2 layer. Traditional wisdom suggests that TiO2
thin films grown on c-sapphire should at best be twinned, if epitaxial at all. However,
in this work, the structure of the obtained TiO2 was found to be epitaxial and twin-free.
This is interpreted as associated with the overall chemical bonding forces among the Ti,
O, and Al atoms of the TiO2 (011)-plane on sapphire (0001)-plane. This led to an ideal
epitaxy with orientation relations of (TiO2)(011)//Al2O3(0001), TiO2[010]// Al2O3
[1120] and TiO2[001]// Al2O3 [1010].

目錄
致謝............................................................................................................i
中文摘要...................................................................................................ii
英文摘要...................................................................................................iii
緒論............................................................................................................. 1
1-1 前言................................................................................................................ 1
1-2 材料基本介紹................................................................................................ 3
1-2-1 二氧化鈦.......................................................................................... 3
1-2-2 二氧化鉿.......................................................................................... 4
1-2-3 超晶格.............................................................................................. 5
第二章、 實驗儀器介紹以及基本原理..................................................................... 6
2-1 磁控濺鍍系統................................................................................................ 6
2-1-1 系統配置.......................................................................................... 7
2-1-2 濺鍍原理.......................................................................................... 7
2-2 X光繞射儀.................................................................................................... 9
2-2-1 布拉格繞射...................................................................................... 9
2-2-2 掃描模式介紹及原理.................................................................... 10
2-3 電子顯微鏡................................................................................................. 13
2-3-1 掃描式電子顯微鏡........................................................................ 13
2-3-2 穿透式電子顯微鏡........................................................................ 14
2-4 鎖相放大器................................................................................................. 14
第三章、 實驗設計.................................................................................................. 15
TiO2實驗參數.......................................................................................... 16
HfO2實驗參數.......................................................................................... 19
第四章、 實驗結果與分析....................................................................................... 22
4-1 樣品成長參數.............................................................................................. 22
4-2 XRD結果..................................................................................................... 23
θ-2θ............................................................................................................ 23
GIXRD...................................................................................................... 23
Rocking curve........................................................................................... 24
XRR........................................................................................................... 25
4-3 TEM和SEM結果....................................................................................... 30
SEM結果.................................................................................................. 30
A系列TEM結果..................................................................................... 31
A系列結果分析....................................................................................... 37
B系列TEM結果..................................................................................... 39
B系列結果分析....................................................................................... 47
4-4 結構分析...................................................................................................... 48
4-5 電性量測結果.............................................................................................. 51
電性量測分析........................................................................................... 52
第五章、 結論........................................................................................................... 54
參考文獻................................................................................................. 55






圖目錄
圖1-2-1(a) 介電常數與能隙表…………………………………...………..……….. 3
圖1-2-1(b) 能隙對介電常數分布圖…………………………………...………...…. 3
圖1-2-2(a)二氧化鈦的共邊八面體示意圖…………………………….…………… 4
圖1-2-2(b) rutile二氧化鈦結構…………………………………………………….. 4
圖1-2-3 二氧化鉿單斜結構……………………………………….……………….. 4
圖2-1-1 電子運動軌跡與電磁場方向……………………………….…………….. 6
圖2-1-2 磁控濺鍍系統內配置……………………………………………….…….. 7
圖2-1-3 電漿激發示意圖………………………………………………….……….. 8
圖2-1-4 電漿游離示意圖…………………………………………………………... 8
圖2-2-1 布拉格繞射圖……………………………………………………………... 9
圖2-2-1 XRD機台設置示意圖…………………………………………...……….. 10
圖2-2-2 θ-2θ掃描………………………………………………………………….. 10
圖2-2-3 掠角X光繞射…………………………………………………………… 10
圖2-2-4 X光反射率示意圖………………………………………………………... 11
圖2-2-5 多層膜影響反射位置……………………………………………………. 11
圖2-2-5 φ軸掃描…………………………………………………………………. 12
圖2-2-6 Rocking curve模式示意圖……………………………………………….. 12
圖2-3-1 掃描式電子顯微鏡………………………………………………………. 13
圖2-3-2 SEM成像示意圖……………………………………………………...….. 13
圖2-3-3 穿透式電子顯微鏡………………………………………………………. 14
圖2-3-4 TEM成像示意圖…………………………………………………………. 14
圖3-1 實驗流程……………………………………………………………………. 15
圖3-2(a) A系列樣品示意圖………………………………………………………. 16
圖3-2(b) B系列樣品示意圖………………………………………………………. 16
圖3-3 TiO2/c-sappire成長溫度變化θ-2θ 掃描………………………………….. .17
圖3-4 650oC TiO2 GIXRD…………………………………………………………. 17
圖3-5 650oCTiO2 rocking curve掃描結果………………………………………… 17
圖3-6 HfO2 θ-2θ掃描結果………………………………………………………… 19
圖3-7 HfO2 GIXRD掃描結果…………………………………………………….. 19
圖3-8 HfO2 rocking curve掃描結果………………………………………………. 19
圖3-9 電性實驗流程示意圖………………………………………………………. 21
圖3-10 電性量測線路示意圖……………………………………………………... 21
圖4-2-1 (a) TiO2:HfO2 – 1:1_θ-2θ scan………………………………...………….. 23
圖4-2-1 (b) TiO2:HfO2 – 3:1_θ-2θ scan……………………………………………. 23
圖4-2-2 (a) TiO2:HfO2 – 1:1_GIXRD……………………………………………… 23
圖4-2-2 (b) TiO2:HfO2 – 3:1_GIXRD……………………………………………… 23
圖4-2-3 (a) B series-1:1_rocking a-axis……………………………………………. 24
圖4-2-3 (b) B series-1:1_rocking m-axis………………………………………...… 24
圖4-2-4 (a) B series-3:1_rocking a-axis……………………………………………. 24
圖4-2-4 (b) B series-3:1_rocking m-axis…………………………………………... 24
圖4-2-5 (a) TiO2：HfO2 – 1：1……………………………………………………. 25
圖4-2-5 (b) TiO2：HfO2 – 3：1……………………………………………………. 25
圖4-2-6 改變週期數之XRR趨勢圖……………………………………………… 29
圖4-2-7 改變每層比例之XRR趨勢圖………………………………………...… 29
圖4-2-8 改變TiO2密度XRR趨勢圖…………………………………………….. 29
圖4-2-9 改變HfO2密度XRR趨勢圖…………………………………………….. 29
圖4-2-10 改變每層粗糙度之XRR趨勢圖………………………………………. 29
圖4-3-1 A系列T:H-1:1 倍率x5.2k…………………………………………… 30
圖4-3-2 A系列T:H-1:1 倍率x52k…………………………………………….. 30
圖4-3-3 B系列T:H-1:1 倍率x5.2k…………………………………………… 30
圖4-3-4 B系列T:H-1:1 倍率x52k…………………………………………….. 30
圖4-3-5 A系列 T:H-1:1 倍率x285k……………………………………………... 31
圖4-3-6 A系列T:H-1:1薄膜與基板介面D.P. …………………………………... 31
圖4-3-7 A系列 T:H-1:1 HR x590k……………………………………………….. 31
圖4-3-8 HR局部放大圖…………………………………………………………… 31
圖4-3-9 c面藍寶石基板電子繞射圖……………………………………………... 32
圖4-3-10分析區域示意圖………………………………………………………… 32
圖4-3-11(a) 區域1繞射點放大圖………………………………………………... 32
圖4-3-11(b) 區域1基板c軸方向強度分佈…………………….……………..….32
圖4-3-12(a) 區域2繞射點放大圖……………………………….……………….. 33
圖4-3-12(b) 區域2基板c軸方向強度分佈…………………….……………….. 33
圖4-3-13(a) 區域3繞射點放大圖……………………………….……………….. 33
圖4-3-13(b) 區域3基板c軸方向強度分佈…………………….……………….. 33
圖4-3-14 A系列 T:H-3:1 倍率x145k…………………………….……………… 34
圖4-3-15 A系列T:H-3:1薄膜與基板介面D.P. ………………….……………… 34
圖4-3-16 A系列 T:H-3:1 HRx400k………………………………………………. 34
圖4-3-17 HR局部放大圖………………………………………………………….. 34
圖4-3-18分析區域示意圖………………………………………………………… 35
圖4-3-19(a) 區域1繞射點放大圖…………………………………………...…… 35
圖4-3-19(b) 區域1基板c軸方向強度分佈………………………..….………… 35
圖4-3-20(a) 區域2繞射點放大圖……………………………….……………..… 36
圖4-3-20(b) 區域2基板c軸方向強度分佈…………………….…………..…… 36
圖4-3-21(a) 區域3繞射點放大圖…………………………….………..………… 36
圖4-3-21(b) 區域3黃線方向強度分佈…………………………..….…………… 36
圖4-3-22 B系列 T:H-1:1 倍率x285k……………………….…………………… 39
圖4-3-23 B系列 T:H-1:1 倍率x690k……………….…………………………… 39
圖4-3-24 B系列 T:H-1:1 HRx790k………………………………………………. 39
圖4-3-25 HR局部放大圖………………………………………………………….. 39
圖4-3-26 zone axis is m-axis……………………………………………….……… 40
圖4-3-27 zone axis is a-axis………………………………………………………... 40
圖4-3-28分析區域示意圖………………………………………………………… 41
圖4-3-29(a)區域1繞射點放大圖……………………………………………….… 41
圖4-3-29(b)區域1基板c軸方向強度分佈……………………………...……..… 41
圖4-3-30 (a)區域2繞射點放大圖………………………………………………… 42
圖4-3-30(b)區域2基板c軸方向強度分佈……………………………….……… 42
圖4-3-31(a) 區域3繞射點放大圖……………………………………….……..… 42
圖4-3-31(b) 區域3基板c軸方向強度分佈………………………………...…… 42
圖4-3-32 B系列 T:H-3:1 倍率x285k……………………………………….…… 43
圖4-3-33 B系列 T:H-3:1 倍率x450k……………………………………….…… 43
圖4-3-34 B系列 T:H-3:1 HRx450k………………………………………….…… 43
圖4-3-35 HR局部放大圖……………………………………………….……….… 43
圖4-3-36 zone axis is m-axis………………………………………….……….…… 44
圖4-3-37 zone axis is a-axis……………………………………………………...… 44
圖4-3-38處理區域示意圖………………………………………………………… 45
圖4-3-39(a)區域1繞射點放大圖…………………………………………….…… 45
圖4-3-39(b)區域1基板c軸方向強度分佈……………………………….……… 45
圖4-3-40(a)區域2繞射點放大圖……………………………………………….… 46
圖4-3-40(b)區域2基板c軸方向強度分佈………………………………….…… 46
圖4-3-41(a)區域3繞射點放大圖……………………………...……………….… 46
圖4-3-41(b)區域3基板c軸方向強度分佈…………………………………….… 46
圖5-1 TiO2/HfO2與基板磊晶關係示意圖…………………………………....…… 49
圖5-2 缺陷影響rutile二氧化鈦晶格示意圖…………………………...…...…… 50
圖4-5-1 DC量測薄膜電阻圖……………………………………………………… 51
圖4-5-2 電阻兩端電壓對頻率關係圖(實部)…………………………………...… 51
圖4-5-3電阻兩端電壓對頻率關係圖(虛部)……………………………………… 51
圖4-5-4電阻兩端電壓對頻率關係圖(總電壓)…………………………………… 51
圖4-5-5 相位角度對頻率變化圖……………………………………………….… 51
圖4-5-6 樣品內部模擬電路W…………………………………………………… 53
圖4-5-7 樣品內部模擬電路X………………………………………….………… 53
圖4-5-8 樣品內部模擬電路Y…………………………………………….……… 53
圖4-5-9 樣品內部模擬電路Z………………………………………………..…… 53
圖4-5-10 TiO2/TiOX超晶格介面磁性研究結果…………………………...……… 53




 
表目錄
表3-1 Sputter成長TiO2參數……………………………………………………… 16
表3-2 (a) TiO2成長時間30分鐘XRR模擬結果………………………………… 18
表3-3 (b) TiO2成長時間1小時XRR模擬結果…………………………………. 18
表3-4 HfO2成長時間1小時XRR模擬結果…………………………………….. 20
表4-2-1 X’pert-Reflectivity模擬模型參數………………………………………... 25
圖表4-2-2 B系列週期比例1:1樣品XRR模擬資訊……………………………. 27
圖表4-2-3 B系列週期比例1:1樣品XRR模擬資訊…………………………… 27
表4-3-1 TiO2晶格常數計算表………………………………………………….…. 40
表4-3-2 TiO2晶格常數計算表………………………………………………….…. 40
表4-3-3 TiO2晶格常數計算表…………………………………………….………. 44
表4-3-4 TiO2晶格常數計算表………………………………………………….…. 44
表5-1 體積與密度表………………………………………………………………. 49
表5-2單位晶胞內增加原子數對應密度表………………………………………. 49

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