臺灣博碩士論文加值系統

本研究利用不同基板P-type silicon、N-type silicon、N-epi on P-sub silicon做PL光激發光的分析，給予不同UV光源發現在奈米結構下多孔矽結構具有顏色切換的特性；在表面特性方面，藉由不同基板的結構找出最適合做為改善表面電性的基板，利用硝酸銀與硫酸銅分別進行測試，藉由SEM與EDS觀察奈米微粒深入孔洞內的情形，並利用I-V與C-V測試表面電特性的改變。
最後在光激發光部分得知以P-type (1 0 0 )基板固定電壓15V、HF: C2H5OH 為1:6時間60min最易出現顏色切換試片；電性方面得知N-epi on P-sub 照光 HF: C2H5OH 為1:4與1:6時間60min 的條件下易使超臨界流體將金屬成功帶入深達60µm-160µm的孔洞內，相較以往電鍍、濺鍍、含浸法改善電性為佳，也發現利用超臨界流體能沉積奈米薄膜與奈米線結構，在導電特性上較未經超臨界流體處理的元件有效提高300倍，電容亦具有127.5倍的提升。

In the this study, using P-type silicon, N-type silicon, N-epi on P-sub silicon to make Photoluminescence (PL) analysis, in the nanostructure porous silicon offer different UV lights(wavelength 254nm and 365nm) that characteristic has color switch. In electrical characteristics, it was found out the most suitable porous silicon. Using AgNO3 and CuSO4 with NaBH4 was tested the best concentrations. Used scanning electron microscope(SEM), energy dispersive spectrometer (EDS) to analyze coating metal Ag and Cu by the SCF method that metal pellet are pulled into the hole and coated on the thin film of the walls. The electrical characteristics of porous silicon were analyzed by changed current-voltage curve and capacitance.
In the light excitability P type (1 0 0) silicon, voltage is 15V constant, HF: C2H5OH is 1:6, time is 60 min, has the color switch; in the electrical characteristics N-epi on P-sub HF: C2H5OH is 1:4 and 1:6, time is 60min with light can easily pull the metal in he hole until deep about 60µm-160µm as compared with electroplating, sputter, impregnation is better. Accidentally we found SCF (Super Critical Fluid) can to map the metal into the porous silicon hole to become thin film and nano-wire structure. With SCF method let electrical conductivity increase 300 times and the electrical capacitance also increase 127.5 times.

總目錄
摘要……………………………………………………………………….Ι
總目錄………………………………………………………..................ΙV
圖目錄………………………………………………………...............VIII
表目錄………………………………………………………...............XIV
第一章 前言……………………………………………………………..1
1-1多孔矽之簡介………………………………………………………..1
1-2研究動機……………………………………………………………..5
第二章 理論………………………………..……………………………7
2-1矽原子在氫氟酸之溶解過程………………………………………..7
2-2形成多孔矽之模形理論……………………………………………13
2-2.1比爾模型（Beale Model）……………………………….......13
2-2.2擴散限制模型（Diffusion-Limited Model）…………………14
2-2.3量子模型（Quantum Model）…………………………….…14
2-3超臨界二氧化碳…………………………………………………....18
2-3.1超臨界流體之簡介……………………………………….......18
2-3.2超臨界流體之定義……………………………...……………19
2-3.3超臨界流體的特性.........…………………………….…21
2-3.4超臨界流體製備微奈米粒子技術...…………………….…22
2-3.5臨界流體沈積技術……………………..………………….…24
第三章多孔矽之製備與超臨界流體的應用…..………………………28
3-1試片的準備…………………………………………………………28
3-2矽晶片蝕刻…………………………………………………………29
3-3多孔矽之蝕刻參數…………………………………………………31
3-3.1多孔矽的孔隙率……………………………………………..32
3-3.2多孔隙的蝕刻速率（Etching Rate）…….…………………….35
3-3.3基材矽的摻雜濃度、型態與蝕刻參數間的關係…..………36
3-4超臨界流體製程……………………………………………………39
3-5正面電極之製作……………………………………………………41
第四章 實驗結果討論…………………………………………………44
4-1實驗參數比較………….………...…………………………………44
4-1.1不同參數下蝕刻P-type、 N-type、P-N junction矽基板比
較………………..……………………………………………44
4-1.2P 型(1 0 0)試片濃度的影響…….……………..….....………..47
4-1.3P型(1 0 0)試片電流密度的影響…...………………………..51
4-1.4N型(1 0 0)試片濃度的影響………....……………………….54
4-1.5N型(1 0 0)試片電流密度的影響………....………………….54
4-1.6N-epi and P-sub型試片濃度的影響………....………………60
4-1.7 N-epi and P-sub型試片電流密度的影響………...…………62
4-2多孔矽的光激發光…………………………………………………68
4-2.1不同基板的光激發光………………………………..………68
4-2.2 P (1 0 0) type基板的光激發光……………………………....72
a.固定電壓下的濃度變化……………………...……….......72
b.固定電流的濃度變化………………………...…………...82
c.改變電流密度………………………………….………….89
4-2.3 N型基板的光激發光……………………………….……….93
a. 固定電流下改變濃度……………….…………...….…….93
b. 固定濃度改變電流密度………….…………….…….....99
4-2.4 N-epi on P-sub型基板的光激發光….…………….……….103
a. 固定電流下改變濃度………….……………...…….…...103
b. 固定濃度改變電流密度………….…………….……...109
4-3奈米金屬微粒填入多孔矽之情況…………..…………….……...112
4-3.1超臨界流體下濃度的影響….………………..…….……….114
a. 10% AgNO3…….………………………………...….…...114
b. 10% AgNO3……………………….…………….……...114
4-3.2 N-type 超臨界流體下銅、銀金屬的沉積情形…....……….119
4-3.3N-type 與N-epi on P-sub 超臨界流體1%AgNO3沉積 比
較 ………………………………………………………….121
4-3.4照光型N-type /N-epi on P-sub超臨界流體1%AgNO3沉積比
較………………………………………………………...…123
4-3.5照光型N-epi on P-sub在超臨界流體成長奈米線結構…...127
4-4 填入金屬多孔矽之電性探討…….………………………………129
4-4.1 不同多孔矽型態的電性.…..……………………………...130
4-4.2濃度上對導電性的影響…………………………………..132
4-4.3不同奈米金屬之導電性………………………………......134
4-4.4照光型的基板的導電性………………...………………….135
4-4.5不同佈植方式的電性比較……………...………………….137
4-4.6 N-epi on P-sub 奈米薄膜與奈米線比較…………………..142
4-4.7 N-epi on P-sub內部型態的電容分析………………..143
第五章 結論…………………………………………………………..145
參考文獻………………………………………………………………147
















圖目錄
圖1-1陽極氧化參數與p型矽基板之關係圖………………………….4
圖1-2陽極氧化參數與n型矽基板之關係圖………………………….4
圖1-3超臨界流體沉積技術處理多孔矽前後示意圖…...……………...6
圖2-1多孔矽電化學蝕刻機制之圖解…………………………………..9
圖2-2 HF濃度與電流密度之反應關係示意圖.………………………10
圖2-3多孔矽電化學蝕刻化學反應示意圖…………………...……….12
圖2-4多孔矽陽極氧化時周圍電力線分佈圖…………………………16
圖2-5量子模型…………………………………………………………17
圖2-6一般純物質之三相圖…...……………………………………….20
圖2-7 二氧化碳在不同溫度下黏度對壓力變化情形………………..20
圖2-8 RESS 製程流程圖………………………………………………27
圖2-9 GAS/GAS 製程流程圖…………………….…………………27
圖3-1多孔矽蝕刻設備示意圖…………………………………………31
圖3-2多孔矽蝕刻參數量子模型(a)HF濃度(b)照光(c)電流密度……33
圖3-3不同摻雜濃度基板的電洞蝕刻路徑圖…………………………38
圖3-4 超臨界流體設備示意圖………………………………………..40
圖3-5傳統多孔矽元件之結構圖………………………………………42
圖3-6改良多孔矽元件之結構圖………………………………………43
圖3-7 經過SCF之改良多孔矽元件示意圖…………………………..43
圖4-1不同矽基板蝕刻示意圖…………………………………………46
圖4-2蝕刻液濃度對P型(1 0 0)之多孔矽之SEM 上視圖............….49
圖4-3蝕刻液濃度對P型(1 0 0)之多孔矽之SEM 側拍圖………….50
圖4-4電流密度P型(1 0 0)之多孔矽之SEM 上視圖………………...52
圖4-5電流密度P型(1 0 0)之多孔矽之SEM 側拍圖………………...53
圖4-6蝕刻液濃度對N型之多孔矽之SEM 上視圖………………….55
圖4-7蝕刻液濃度對N型之多孔矽之SEM 側拍圖……………….…56
圖4-8電流密度N型之多孔矽之SEM 上視圖…………………….…58
圖4-9電流密度N型之多孔矽之SEM 側拍圖…………………….…59
圖4-10蝕刻液濃度N-epi and P-sub型之多孔矽之SEM 上視圖……62
圖4-11蝕刻液濃度N-epi and P-sub型之多孔矽之SEM 側拍圖…....63
圖4-12電流密度N-epi and P-sub型之多孔矽之SEM 側拍圖…........66
圖4-13電流密度N-epi and P-sub型之多孔矽之SEM 上視圖…........67
圖4-14 不同矽基板蝕刻加予照光……………………………………69
圖4-15 不同矽基板蝕刻加予UV 365nm………………..……………70
圖4-16不同基板的PL圖………..…………………………………..…71
圖4-17 HF:乙醇=1:2 15V 時間60 min P型…………………………76
圖4-18: HF:乙醇=1:4 15V 時間60 min P型………………………….77
圖4-19 HF:乙醇 =1:6 15V 時間60 min P型…………………………78
圖4-20顏色切換P型 (a)-(d)正視(e)-(h)SEM側拍圖……………...…79
圖4-21 P型顏色切換試片烘乾前可見光示意圖...................................80
圖4-22 P型顏色切換試片烘乾後可見光示意圖...................................80
圖4-23 可見光光譜................................................................................81
圖4-24不同濃度固定電壓的P型PL圖…………………………….....81
圖4-25 HF:乙醇=1:4 40mA/cm2 時間60 min P型…………...............84
圖4-26固定電流P型 (a)-(d)正視(e)-(h)SEM側拍...............................85
圖4-27 HF:乙醇=1:6 40mA/cm2 時間60 min P型...............................86
圖4-28固定電流P型 (a)-(d)正視(e)-(h)SEM側拍...............................87
圖4-29固定電流比固定電壓P型1:4與1:6 PL圖…………………...88
圖4-30 HF :乙醇=1:4 20mA/cm2 時間60 min P型…………………...90
圖4-31 HF:乙醇=1:4 60mA/cm2 時間60 min P型………………...….91
圖4-32 固定濃度改變電流密度P型PL圖…………………...…...….92
圖4-33 HF:乙醇=1:2 40mA/cm2 時間60 min 照光N型…...…......….95
圖4-34 HF:乙醇=1:4 40mA/cm2 時間60 min 照光N型…...…..…….96圖4-35 HF:乙醇=1:6 40mA/cm2 時間60 min 照光N型…...…...……97
圖4-36同電流密度改變濃度的N型PL圖…...………………..……98
圖4-37 HF:乙醇=1:4 20mA/cm2時間60min照光N 型……………100
圖4-38乙醇:HF=1:4 60mA/cm2時間60min照光N 型……...………101
圖4-39 不同電流密度固定濃度的N 型PL圖………………...……102
圖4-40 HF:乙醇=1:2 40mA/cm2 時間60min N-epi and P-sub照光105
圖4-41 HF:乙醇=1:4 40mA/cm2 時間60min N-epi and P-sub照光106
圖4-42 HF:乙醇=1:6 40mA/cm2 時間60min N-epi and P-sub照光107
圖4-43同電流密度改變濃度的N-epi and P-sub型PL圖…………108
圖4-44 HF:乙醇=1:4 20mA/cm2 時間60min N-epi and P-sub照光 110
圖4-45 HF:乙醇=1:4 60mA/cm2 時間60min N-epi and P-sub 照光111
圖4-46同濃度電流密度改變的N-epi and P-sub型PL圖…………...112
圖4-47 超臨界流體於10% Ag 之SEM圖………………………......114
圖4-48 超臨界流體10%AgNO3 在N-type SEM圖………................117
圖4-49 N型10%AgNO3正面EDS…....................................................117
圖4-50 N型10%AgNO3側面EDS…....................................................117
圖4-51 超臨界流體1%AgNO3 在N-type SEM圖………................118
圖4-52 N型1%AgNO3正面EDS…......................................................118
圖4-53 N型1%AgNO3側面EDS…......................................................118
圖4-54 超臨界流體1% CuSO4 在N-type SEM圖.............................120
圖4-55 N 型1% CuSO4正面EDS…....................................................120
圖4-56 N 型1% CuSO4側面EDS…....................................................120
圖4-57 超臨界流體1% AgNO3 在N-epi on P-sub SEM圖…………122
圖4-58 N/P型1% AgNO3正面EDS…..................................................122
圖4-59 N/P 型1% AgNO3側面EDS…................................................122
圖4-60 超臨界流體1% AgNO3 在N-type 照光 SEM圖..................125
圖4-61 N 照光1%AgNO3正面EDS....................................................125
圖4-62 N照光 1%AgNO3側面EDS....................................................125
圖4-63 超臨界流體1% AgNO3 在N-epi on P-sub 照光 SEM圖….126
圖4-64 N/P照光1%AgNO3正面EDS………………………………126
圖4-65 N/P照光1%AgNO3正面EDS………………………………126
圖4-66 超臨界流體2.5% AgNO3 在N-epi on P-sub 照光 SEM圖128
圖4-67 N/P照光2.5%AgNO3正面EDS……………...………………128
圖4-68 N/P照光2.5%AgNO3側面EDS…………………………...…128
圖4-69不同基板SCF10%Ag的I-V圖…………………………...…..131
圖4-70不同基板下SCF10%Cu的I-V圖…………………….......…..131
圖4-71 N-epi on P-sub未照光SCF Cu之I-V………………………133
圖4-72 N-epi on P-sub未照光SCF Ag之I-V…………………...……133
圖4-73 N-epi on P-sub未照光SCF Ag與Cu之I-V……………...…134
圖4-74 N-epi on P-sub未照光與照光基板之SCF I-V……………...136
圖4-75 N-epi on P-sub不同塗佈方式的比較 I-V…………………...138
圖4-76 N-epi on P-sub不同塗佈方式SEM與示意圖………………139
圖4-77 殘餘矽柱尺寸與能隙寬(Eg)之關係圖……………………....140
圖4-78 N-epi on P-sub中奈米線與薄膜的 I-V………………….......141
圖4-79 N-epi on P-sub 內部型態的電容…………….………………142
圖4-80 SCF 10% Ag 不同基板電容的比較…………………………143
圖4-81 SCF 10% Cu 不同基板電容的比較…………………………143
圖4-81 N-epi on P-sub照光與未照光與不同濃度電容圖…………...144















表目錄
表2-1氣體、超臨界流體與液體的一般物理性質……….……………..21
表2-2各種化合物的超臨界性質………………………...…………....23
表4-1 P型濃度變化下的PL強度與波長對照表…………................73
表4-2 N型濃度變化下的PL強度與波長對照表…………................94
表4-3 10%AgNO3正面成分分析……………………………...............117
表4-4 10%AgNO3側面成分分析……………………………..............117
表4-5 1% CuSO4正面成分分析……………………………................120
表4-6 1% CuSO4側面成分分析……………………………................120
表4-7 N/P型1% AgNO3正面成分分析…………................................122
表4-8 N/P型1% AgNO3側面成分分析…………................................122
表4-9 N 照光 1%AgNO3正面成分分析.............................................125
表4-10 N 照光1%AgNO3側面成分分析............................................125
表4-11 N/P照光1%AgNO3正面成分分析...........................................126
表4-11 N/P照光1%AgNO3正面成分分析...........................................126
表4-12 N/P照光2.5%AgNO3正面成分分析.......................................128
表4-13 N/P照光2.5%AgNO3側面成分分析.......................................128

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