本論文主要以同步輻射相關實驗研究硫過量摻雜於p-type矽晶產生次能隙吸收與化學態、電子結構、原子結構的相關性。實驗包含光電子能譜(XPS)、X光吸收近邊緣結構(XANES)、X光延伸吸收精細結構(EXAFS)、價電帶放射能譜(VB-PES)以及第一原理理論計算。在S 2p XPS測量，隨著S2-的濃度提高，樣品之次能隙吸收也隨著提高。樣品經過退火處理後，次能隙吸收和S2-濃度同時的減少，而(Sn2-, n> 2)則有所增加，推測次能隙吸收與 S2-濃度有關。在Si的K-edge XANES量測中我們觀察到樣品中矽導帶底端附近之已佔據(未佔據)的電子態密度增加(降低)。而VB-PES測量清楚發現，硫摻雜在能隙中產生雜質態，因此提高次能隙吸收之強度。在第一原理計算態密度泛涵理論(DFT)，預測當硫之濃度大於臨界濃度~0.46％時，造成樣品的Mott 絕緣-金屬相轉變，並且揭示出硫雜質態在價帶最大值與導帶最小值附近增加。

The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculations. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2- (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2- species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2-, n> 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in samples. In the calculations by Density Function Theory further predicted the IMT of S-doped Si at a dopant concentration of about 0.46% (~2.3x1020 cm-3) and clearly indicate that the enhancement of the Density of stats at the ECBM and EVBM.

目錄
致謝…………………………………………………………………………I
中文摘要…………………………………………………………………………II
英文摘要…………………………………………………………………………III
目錄…………………………………………………………………………IV
圖表目錄…………………………………………………………………………VI
第一章、緒論…………………………………………………………………………1
1-1. 硫過摻雜矽的起源…………………………………………………………………………1
1-2. 文獻回顧…………………………………………………………………………1
第二章、實驗技術…………………………………………………………………………6
2.1. X光吸收光譜簡介…………………………………………………………………………6
  2-1-1. 吸收邊緣與E0值…………………………………………………………………………8
2-1-2. X光吸收近邊緣結構(X-ray Absorption Near Edge)…………………………………………………………………………9
2-1-3. 延伸X光吸收精細結構(Extended X-ray Absorption Fine Structure)………………………………………………10
2-1-4. 實驗方法………………………………………………………15
2-1-5. 數據分析………………………………………………………19
2-2. X光光電子能譜簡介 ( X-ray Photoelectron Spectroscopy)…………………………………………………23
第三章、實驗數據分析與討論…………………………………………25
3-1. 樣品製備與基本量測……………………………………………25
3-2. 實驗數據分析與討論……………………………………………30
3-2-1. 掃描式電子顯微鏡 (SEM) ………………………………30
3-2-2. X光光電子能譜(XPS) ……………………………………32
3-2-3. X光吸收近邊緣結構 (XANES) …………………………43
3-2-4. 延伸X光吸收精細結構(EXAFS) ………………………47
3-2-5. 價電帶光電子能譜(VB-PES) ……………………………50
3-2-6.第一原理計算(DFT) ………………………………………55
第四章、結論……………………………………………………………60
參考文獻…………………………………………………………………61

圖表目錄
圖1-1 硫過摻雜於矽樣品光捕捉示意圖 …………………………………4
圖1-2硫過摻雜於矽樣品文獻之SEM表面幾何結構……………………4
圖1-3 硫過摻雜於矽樣品文獻XES之圖譜………………………………5
圖2-1 光子能量與銅吸收截面關係圖 ……………………………………7
圖2-2 XANES與EXAFS分界圖	…………………………………………12
圖2-3 光電子平均自由路徑與能量關係圖………………………………12
圖2-4 單一散射與多重散射之圖像
      (a)為單一散射路程示意圖…………………………………………13
      (b)為多重散射路程示意圖…………………………………………13
圖2-5 射出電子受鄰近原子的背向散射，而產生干涉現象
(a)建設性干涉  (b)破壞性干涉……………………………………14
圖2-6 X光吸收光譜實驗示意圖…………………………………………16
圖2-7 三種光譜量測方法…………………………………………………18
圖2-8 X光吸收光譜之數據分析流程……………………………………19
圖2-9 XPS能量分布曲線圖………………………………………………24
圖3-1 樣品製作過程示意圖………………………………………………27
圖3-2 紫外光-可見光-近紅外光吸收光譜………………………………28
圖3-3 XPS全譜掃描譜圖…………………………………………………29
圖3-4樣品表面SEM影像…………………………………………………31
圖3-5樣品與硫粉XPS S 2p解析圖………………………………………37
表3-1 XPS S 2p各硫化物分析計算結果…………………………………38
圖3-6 平均次能隙吸收強度與硫化物濃度的關係圖……………………39
表3-2 XPS全譜解析結果…………………………………………………39
圖3-7 各樣品硫化物比例關係圖…………………………………………40
圖3-8樣品與矽晶 (100) XPS Si 2p解析圖………………………………40
圖3-9樣品與矽晶(100)之拉曼圖譜………………………………………42
圖3-10樣品與硫粉S K-edge XANES圖譜………………………………46
圖3-11樣品與矽晶 (100) Si K-edge XANES圖譜………………………46
圖3-12樣品與矽晶 (100) Si K-edge 傅立葉轉換圖 ……………………49
圖3-13樣品與矽晶(100)之VB-PES………………………………………53
圖3-14 在矽能隙中之硫雜質態模擬圖 …………………………………54
圖3-15(a)多種硫濃度的總態密度圖譜……………………………………57
圖3-15(b)1.56%硫濃度的能帶結構圖……………………………………57
圖3-15(c) 0.46%硫濃度的能帶結構圖……………………………………58
圖3-15(d) 對齊EVBM之態密度圖譜………………………………………58
圖3-16 以PBE算出之總態密度和部分態密度圖譜……………………59
圖3-17 以HSE06算出之總態密和部分態密度圖譜……………………59

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