臺灣博碩士論文加值系統

本研究中以玻璃基板為主要的基材，使用磁控濺鍍法在基材上共沉積(co-sputtering) SbxTey 化合物薄膜，並且利用非平衡磁控濺鍍法(UBMS)製備碲化鉍(Sb2Te3)熱電薄膜，分別控制Sb 及Te 靶之濺射功率，以控制薄膜中Sb 和Te 成分比例，並在基材上分別通以負偏壓電源，探討基材偏壓對薄膜之微結構、組成成分與熱電性質的影響。基材偏壓提供之能量可以促使薄膜之結構更加緻密化，同時封閉式非平衡磁場，可以提高反應電漿之能量，使薄膜之結晶化結構更趨明顯。
由場發射掃描式電子顯微鏡(FE-SEM)觀察薄膜之表面形貌，可以發現具有明顯之結晶晶粒結構，而且有通以偏壓之薄膜更加緻密。本研究之成份分析，以EDS 分析薄膜之組成，得到隨著Sb 靶功率的變化，其成份成線性分佈，證實可以經由此製程方法準確的控制薄膜組成成分比。XRD 圖譜的分析中可以看出明顯的Sb2Te3(015)之結晶相，表示在低溫的製程下可獲得Sb2Te3 結晶結構，由XPS 得知薄膜Sb2Te3之鍵結形態。熱電性質部分，藉由分析薄膜之Seebeck 係數、電阻率及載子濃度，探討功率與偏壓對熱電性質之影響，由結果可獲得薄膜具有較佳之熱電性質，其Seebeck 係數約為249μV/K，功率因子PF(Power Factor)分別14.3×10-5 W/K2-m。

In this study, the power of the Antimony and tellurium targets was
controlled separately to fabricate the stoichiometric antimony telluride
(Sb2Te3) thermoelectric thin films. It was found that both the crystallinity
and thermoelectric transport properties are highly affected by the
chemical nonstoichiometry. The microstructure and chemical composition
analysis was conducted with X-ray diffraction and energy dispersive
spectrometer, and the thermoelectric properties were assessed by
measurements of Seebeck coefficient, electrical resistivity and Hall
coefficient.
The thermoelectric (TE) Sb2Te3 thin films were deposited on glass
and Si substrates using unbalanced magnetron sputtering (UBMS)
technique. The influence of bias voltage on the chemical composition,
surface morphology, crystallinity and thermoelectric properties of the
films were investigated. The ionization of both sputtering sources was
significantly enhanced by the closed field unbalanced magnetron
configuration to allow improved crystallization and thin film
microstructure.
Results showed that obvious crystallinity of Sb2Te3 with dense
texture was observed when substrate bias was applied. All of the
synthesized crystalline Sb2Te3 films were deposited at room temperature.
The Sb content of Sb2Te3 films exhibited linear dependence at fixed Te
target power. Stoichiometric Sb2Te3 film could be obtained by Sb target
power manipulation. The X-ray diffraction showed the result of Sb2Te3
(015) preferential orientation due to substrate bias with the sputtering
III
magnetron configuration. The optimized Seebeck coefficient and power
factor were 249.0 μV/K and 14.3×10-5 W/K2-m, respectively with -100V
substrate bias application

中文摘要........................................................................................................................ I
英文摘要....................................................................................................................... II
總目錄......................................................................................................................... IV
圖目錄........................................................................................................................VII
表目錄...................................................................................................................... XIV
第一章 緒論..............................................................................................................1
1-1 前言..............................................................................................................1
1-2 研究動機......................................................................................................2
1-3 研究目的......................................................................................................5
第二章 文獻回顧......................................................................................................8
2-1 熱電原理...........................................................................................................8
2-1-1 Seebeck 效應...................................................................................8
2-1-2 Peltier 效應.....................................................................................9
2-1-3 Thomson 效應...............................................................................10
2-2 熱電材料之應用與熱電效能.........................................................................12
2-2-1 熱電材料的應用.............................................................................12
2-2-2 熱電材料的種類.............................................................................15
2-2-3 熱電元件的效能.............................................................................19
2-2-4 熱電效能提昇的方法.....................................................................20
2-3 Sb2Te3 熱電薄膜製備方法.............................................................................29
2-3-1 有機金屬化學氣相沉積.................................................................29
2-3-2 共蒸鍍法.........................................................................................29
2-3-3 電化學沉積法（Electrochemical deposition） .............................30
2-3-4 分子束磊晶成長法(Molecular Beam Epitaxy，MBE) .................30
2-3-4 射頻濺鍍法.....................................................................................31
2-2-5 脈衝雷射沉積法.............................................................................31
2-2-6 非平衡磁控濺射.............................................................................31
V
2-4 鍍膜成長機制..............................................................................................34
2-4-1 氣體分壓與沉積溫度.....................................................................34
2-4-2 基材偏壓.........................................................................................37
第三章 實驗步驟....................................................................................................39
3-1 鍍膜系統....................................................................................................39
3-2 實驗參數設計與流程................................................................................41
3-3 實驗參數......................................................................................................44
3-4 薄膜分析與檢測方法..................................................................................46
3-4-1 場發射掃描式電子顯微鏡(FE-SEM) ............................................46
3-4-2 能量散佈光譜儀(EDS)...................................................................48
3-4-3 X 光繞射分析儀(XRD)..................................................................50
3-4-4 X 射線光電子能譜儀(XPS) ...........................................................52
3-4-5 電阻率量測.....................................................................................53
3-4-6 Seebeck 量測...................................................................................55
3-4-7 載子濃度量測.................................................................................56
第四章 結果與討論................................................................................................59
4-1 薄膜微結構分析.............................................................................................59
4-1-1 表面形貌分析..............................................................................60
4-2-2 斷面膜厚量測..............................................................................63
4-2 化學成分分析..............................................................................................68
4-2-1 XPS 分析....................................................................................76
4-3 微結構與相鍵定..........................................................................................82
4-4 電阻率量測分析..........................................................................................86
4-5 Seebeck 係數量測分析................................................................................87
4-6 Hall effect 量測分析....................................................................................91
第五章 結論............................................................................................................97
參考文獻....................................................................................................................100
VI
圖目錄
Fig.1-1 典型熱電元件示意圖................................................................................. 1
Fig.1-2 (a)應用於人體體溫熱之手錶(b)熱電材料應用於航太產業(c)
熱電材料制冷元件用於光通訊放大器之冷卻與溫控............................. 4
Fig.2-1 Seebeck 效應示意圖................................................................................. 9
Fig.2-2 Peltier 效應示意圖......................................................................... 9
Fig.2-3 Thomson 效應.................................................................................. 10
Fig.2-4 將p 型及n 型熱電材料接成一迴路個體，若在迴路中通入電
流，即可作為一簡單的熱電元件........................................................... 12
Fig.2-5 以串聯的方式連接多個n 型半導體組成之熱電元件........................... 13
Fig.2-6 (a)熱電制冷器(TEC) (b)熱電發電器(TEG)............................................ 13
Fig.2-7 Bi2Te3 晶體結構示意圖............................................................................ 16
Fig.2-8 Sb2Te3 與Bi2Te3 結構示意圖................................................................... 17
Fig.2-9 Sb2Te3 結構示意圖................................................................................... 18
Fig.2-10 熱電效能Power factor 與Seebeck coefficient (S)、electrical
conductivity (σ)、thermal conductivity (κ)值間之關係.......................... 22
Fig.2-11 聲子散射示意圖....................................................................................... 23
Fig.2-12 點缺陷和合金(alloy)散射示意圖............................................................ 24
Fig.2-13 熱電材料性能發展示意圖....................................................................... 25
Fig.2-14 理論計算碲化鉍熱電材料ZT 值隨材料尺度減少而大幅增加
................................................................................................................... 26
Fig.2-15 (a) 多孔隙材料 (b)奈米熱電材料量子線陣列..................................... 27
Fig.2-16 Bi2Te3/Sb2Te3 超晶格薄膜ZT 值達到2 以上......................................... 28
Fig.2-17 磁控濺射示意圖....................................................................................... 32
Fig.2-18 磁場磁控濺射示意圖(左)封閉式磁場(右)鏡向式磁場......................... 33
Fig.2-19 Thronton 的Zone 結構圖........................................................................ 36
Fig.2-20 偏壓對沉積率的影響............................................................................... 38
Fig.3-1 實驗系統架構示意圖............................................................................... 39
VII
Fig.3-2 非平衡磁控濺射封閉式磁場................................................................... 40
Fig.3-3 實驗與分析流程圖................................................................................... 41
Fig.3-4 入射電子束與試片交互作用結果示意圖............................................... 47
Fig.3-5 高解析熱場發射掃描式電子顯微鏡（HR FESEM） ........................... 47
Fig.3-6 X-ray 濺射性干涉示意圖........................................................................ 50
Fig.3-7 X 光粉末繞射分析儀............................................................................... 51
Fig.3-8 四點探針量測示意圖............................................................................... 54
Fig.3-9 Seebeck 係數分析.................................................................................... 55
Fig.3-10 電子傳導示意圖....................................................................................... 56
Fig.3-11 電場對傳導電子示意圖........................................................................... 57
Fig.3-12 電場對傳導電子移動示意圖................................................................... 58
Fig.4-1 表面形貌觀察Te 功率25w、Sb 功率(a)55w(b)60w(c)65w
Bias 0v 與Bias 100v 之10 萬倍率........................................................ 61
Fig.4-2 表面形貌觀察Te 功率50W、Sb 功率(a)75W(b)85W(c)100W
Bias 0V 與Bias -100v 之10 萬倍率。.................................................. 62
Fig.4-3 斷面形貌觀察Te 功率25w、Sb 功率(a)55W(b)60W(c)65W
Bias 0V 與Bias -100V 之5 萬倍率....................................................... 66
Fig.4-4 斷面形貌觀察Te 功率25W、Sb 功率(a)75W(b)85W(c)90W
Bias 0V 與Bias -100V。......................................................................... 67
Fig.4-5 Sb 成分隨Sb 功率之線性分佈變化....................................................... 68
Fig.4-6 (a)Sb 功率100(w) 30min.(b)Te 功率75(w)沉積30min......................... 69
Fig.4-7 Te、Sb、O 的含量變化 Te 25W Bias 0V。.......................................... 71
Fig.4-8 Te、Sb、O 的含量變化 Te 25W Bias 100V。...................................... 72
Fig.4-9 Te、Sb、O 的含量變化 Te 50W Bias 0V。.......................................... 73
Fig.4-9 Te、Sb、O 的含量變化 Te 50W Bias 100V。...................................... 74
Fig.4-11 Te 功率50W、Sb 功率75W Bias 0v EDS 分析.................................... 75
Fig.4-12 Te 功率50W、Sb 功率70WBias-100v EDS 分析................................. 75
Fig.4-13 固定Te50W 改變Sb 功率未施加偏壓系列之全能譜圖....................... 78
Fig.4-14 固定Te50W 改變Sb 功率施加偏壓-100V 系列之全能譜圖............... 78
VIII
Fig.4-15 固定Te50W 改變Sb 功率未施加偏壓之Te 細部能譜圖..................... 79
Fig.4-16 施加偏壓100V 之Te 分析能譜圖.......................................................... 79
Fig.4-17 固定Te50W 改變Sb 功率未施加偏壓之Sb 細部能譜圖.................... 80
Fig.4-18 固定Te50W 改變Sb 功率施加偏壓-100V 之Sb 細部能譜圖............. 80
Fig.4-19 Te 50W、Sb 90W 未施加偏壓之Sb 細部能譜圖.................................. 81
Fig.4-20 Te 50W、Sb 90W 施加偏壓-100V 之Sb 細部能譜圖.......................... 81
Fig.4-21 固定Te 功率25W、Sb 55-65W 未施加偏壓之X 光繞射圖................ 84
Fig.4-22 固定Te 功率25W、Sb 55-65W 施加偏壓-100V X 光繞射圖............. 84
Fig.4-23 Te 功率50w、Sb75、85、90w 未施加偏壓之X 光繞射圖譜
................................................................................................................... 85
Fig.4-24 Te 功率50w Sb(55~100)之施加偏壓100v 之X 光繞射圖譜............... 85
Fig.4-25 未施加偏壓0 V 與施加偏壓-100 V 之電阻率....................................... 86
Fig.4-26 Seebeck 量測法........................................................................................ 87
Fig.4-27 不同偏壓之Seebeck 表現圖(a)Te 功率25bias 0V(b) Te 功率
25W bias 100V (c) Te 功率25W bias 0V (d) Te 功率25W bias
100V.......................................................................................................... 90
Fig.4-28 S，σ 和S2σ 作為功能載子濃度示意圖................................................. 91
Fig.4-29 固定Te 功率25W 改變Sb 功率 Bias 0V 時Te 含量對S，ρ 和PF 值之
變化………………..……………………………………………………..93
Fig.4-30 固定Te 功率25W 改變Sb 功率 Bias -100V 時Te 含量對S，ρ 和PF 值
之變化…………………………………………………………………....93
Fig.4-31 固定Te 功率50W 改變Sb 功率 Bias 0V 時Te 含量對S，ρ
和PF 值之變化........................................................................................ 95
Fig.4-32 固定Te 功率50W 改變Sb 功率 Bias -100V 時Te 含量對S，
ρ 和PF 值之變化..................................................................................... 95
IX
表目錄
Table.3-1 實驗參數表............................................................................................. 45
Table.3-2 Experimental paramenters of sputtered SbxTey films for
multi-gun deposition ............................................................................... 46
Table.3-3 本實驗製程之實驗參數......................................................................... 37
Table.4-1 固定Te 功率25(w)各個不同功率下的SEM 膜厚............................... 65
Table.4-2 固定Te 功率50 (w)各個不同功率下的SEM 膜厚.............................. 65
Table.4-3 Te、Sb、O 的含量變化 Te 25w Bias 0V.............................................. 71
Table.4-4 Te、Sb、O 的含量變化 Te 25w Bias100V........................................... 72
Table.4-5 Te、Sb、O 的含量變化 Te 50w Bias 0V.............................................. 73
Table.4-6 Te、Sb、O 的含量變化 Bias 100V ...................................................... 74
Table.4-7 Te 25w 之Sb2Te3 熱電性質.................................................................... 92
Table.4-8 Te 50w 之Sb2Te3 熱電性質.................................................................... 94

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