臺灣博碩士論文加值系統

中文摘要

本論文利用脈波調變射頻功率電漿加強化學氣相沉積，在電漿功率、SiH4/N2O/H2氣體比例、沉積壓力及沉積溫度不變的條件下，以固定電漿停止工作時間(toff)，改變電漿工作時間(ton)造成電漿中氣相反應解離成份改變的製程方法，沉積出具不同矽氧比例(O/Si)的非晶氧化矽薄膜(SiOx)，探討ton控制SiOx薄膜中O/Si比例之關係。這些SiOx薄膜在氮氣環境下以1100℃退火處理30分鐘使其形成奈米結晶氧化矽薄膜(nc-SiOx)，並測量其光激發光(PL)強度，以探討薄膜的O/Si比例對PL光譜強度之影響。
腔體壓力、SiH4/N2O/H2、電漿功率、toff及沉積溫度分別固定為0.3 torr、4 /12 /80 sccm、30 W、50 ms及70℃。ton的時間由2、5、12、 25、50、100、150、200、325、450、 800、1200 ms變化至連續工作(cw)。SiOx薄膜沈積厚度固定為310 nm，其矽氧鍵結由傅立葉轉換紅外線光譜（FTIR）測量。nc-SiOx薄膜的O/Si比例、結晶結構及尺寸由能量散佈光譜(EDS)、拉曼散射光譜(Raman)、X光繞射（XRD）及高解析度穿透式電子顯微鏡(HRTEM)測量及分析。
EDS量測結果顯示，在N2O/SiH4 = 3的製程反應氣體條件下，ton由5 ms變化至800 ms的時間可有效改變電漿中反應氣體解離成份將SiOx薄膜中O/Si的比例控制在0.1到0.57倍之間。FTIR量測結果顯示，各試片具有850 cm-1 (Si-O 彎折模)、1060 cm-1 (Si-O-Si 伸縮模)及2240 cm-1(H-Si-O伸縮模)三個峰值，ton = 200 ms試片（O/Si比例：0.57）的850 cm-1及2240 cm-1峰值強度介於其他試片之間，1060 cm-1峰值強度則非常接近最大值。退火處理後，nc-SiOx試片的拉曼散射光譜的背景螢光值均較退火處理前增加約1至2個數量級，且ton = 200 ms試片有最大值92倍，此結果間接指出薄膜中形成具直接輻射發光的奈米結晶矽。而XRD結果顯示，ton = 200 ms試片在 、 、 及 處，相較其他試片有明顯的結晶訊號。nc-SiOx薄膜PL光強測量結果顯示，各試片峰值位置都約在800 nm，且強度隨著O/Si比例增加而增強，ton = 200 ms有最大的O/Si比例(0.57)其發光強度最強。上述結果顯示，O/Si比例由0.1變化至0.57可以增加nc-SiOx薄膜的PL光譜強度。由於各試片之PL發光峰值變異不大，代表矽奈米結晶尺寸變化不大，造成發光強度變化主要是由於結晶比例之變化所造成。ton = 200 ms試片的HRTEM結果顯示，薄膜中大多形成約3 nm的奈米結晶矽，由其結晶顆粒分佈之面積估計其結晶比例約為33 ﹪
調變射頻電漿工作時間可以有效控制SiOx薄膜中的矽氧原子比例。高溫退火後之nc-SiOx薄膜的PL光譜強度隨O/Si比例增加（0.1至0.57）而增強。奈米結晶矽之結晶比例是影響PL光譜強度之主要原因。

Abstract

In this thesis, the amorphous silicon oxide (SiOx) films with various O/Si ratios were deposited by plasma-enhanced chemical vapor deposition with the pulse-modulated RF power. The influence of the pulse-on time (ton) on the O/Si ratio of the SiOx films was elucidated. These amorphous SiOx films were then annealed in N2 atmosphere at 1100℃ for 30 min to be converted into nc-SiOx films. The intensities and the peak positions of the photoluminescence (PL) of these nc-SiOx films were measured to explore how the O/Si ratio of the as-deposited amorphous SiOx films affects the PL signals of the obtained nc-SiOx films after annealing.
The chamber pressure, SiH4/N2O/H2, the plasma power, the pulse-off time (toff), and the substrate temperature were fixed at 0.3 torr, 4/12/80 sccm, 30 W, 50 ms, and 70 ℃, respectively. The ton was varied from 2, 5, 12, 25, 50, 100, 150, 200, 325, 450, 800, 1200 ms, to continuous wave (cw). The thickness of all SiOx thin films was fixed at 310 nm, and the Si-O bonding modes of the SiOx films were measured by Fourier transform infrared spectrometer (FTIR). Energy dispersive spectrometer (EDS), Raman scattering spectrometer, x-ray diffraction (XRD), and high resolution transmission electron microscope (HRTEM) were used to measure and analyze the O/Si ratio and the crystalline structures and sizes of the nc-SiOx films.
EDS results show that, the O/Si ratio of the SiOx films can be controlled between 0.1 and 0.57 for ton changed from 5 to 800 ms in the condition of N2O/SiH4 = 3. FTIR measurements display that there are three peaks of 850 cm-1 (Si-O bending mode), 1060 cm-1 (Si-O-Si stretching mode), and 2240 cm-1 (H-Si-O stretching mode) in each samples. For the ton = 200 ms sample, which the O/Si ratio is 0.57, the intensities of the 850 cm-1 and 2240 cm-1 peaks are in between those of the other samples, and the intensity of the 1060 cm-1 peak is close to the maximum value of all samples. The background fluorescence intensities of the Raman scattering of the nc-SiOx films obtained after annealing is lager than those of as-deposited amorphous SiOx films about 1 to 2 orders. Especially, the ton = 200 ms sample has the maximum value about 92 times. The results indicate that the increasing of the background fluorescence of Raman scattering is due to light scattering from the nanocrystalline silicon (nc-Si) existed in the nc-SiOx films. XRD results present that there are four distinct crystalline signals at , , , and in the ton = 200 ms sample. The peak positions of the PL signals of all nc-SiOx films are located at about 800 nm. The PL intensity of the nc-SiOx film is increased as the O/Si ratio increases from 0.1 to 0.57. The ton = 200 ms sample exhibiting maximum O/Si ratio (0.57) has the strongest PL intensity. Notely, the small variation of peak positions of all samples implies that there is little change in the size of nc-Si in all samples. The variation of PL intensity is mainly influenced by the fraction of nc-Si in nc-SiOx films. The HRTEM data of ton = 200 ms sample shows that the size of the nc-Si is about 3 nm. The fraction of nc-Si in nc-SiOx film is about 33 %, which is estimated from the area ratio of the nc-Si in nc-SiOx film.
The O/Si ratio of the SiOx thin films can be effectively controlled by modulating ton of the pulse-modulated RF power. The PL intensity of the nc-SiOx thin films increases as the O/Si ratio increases from 0.1 to 0.57. The PL intensity of the nc-SiOx films is mainly affected by the fraction of nc-Si in nc-SiOx films.

目錄
第1章 前言
1.1 研究背景和動機 ………………………………………………1
1.2 文獻探討 ………………………………………………………3
1.3 研究目的 ………………………………………………………9
1.4 論文架構 ………………………….……………………….…10
第2章 實驗方法
2.1 製程設備 ………………………………………………….…11
2.1.1 PECVD系統架構 …………..………………………...11
2.1.2 高溫石英爐管………………...………………………. 15
2.2 試片清洗
2.2.1 四吋矽晶圓(silicon wafer)基板清洗 …………….....16
2.2.2 四吋石英晶圓(quartz wafer)基板清洗 ….…….……..17
2.3 量測儀器及分析理論
2.3.1 薄膜測厚儀(α-step) ……….……………………….18
2.3.2 光激發光光譜儀(Photoluminescence spectrometer) …18
2.3.3 傅立葉轉換紅外線光譜儀（FTIR）及分析理論 …..19
2.3.4 拉曼散射光譜儀(Raman scattering) 及分析理論 …..20
2.3.5 能量散佈光譜儀 ( EDS ) ……………………………..22
2.3.6 X光薄膜繞射儀（XRD）…………….....….……….23
2.3.7 高解析度穿透式電子顯微鏡(HRTEM) …..….…..…...23
2.4 奈米結晶氧化矽薄膜試片之製作
2.4.1 以PECVD沉積a-SiOx薄膜 …………….…………….24
2.4.2 a-SiOx薄膜膜厚量測………..………………………..26
2.4.3 以高溫石英爐管退火處理製作nc-SiOx薄膜………….27
第3章 結果與討論
3.1 a-SiOx薄膜之沉積速率…………….…………..…………….. 28
3.2 a-SiOx薄膜之EDS量測………..…..………..………………..30
3.3 a-SiOx薄膜之FTIR量測…………...…………………………32
3.4 nc-SiOx薄膜之拉曼光譜量測…...….………………….….…..35
3.5 nc-SiOx薄膜之XRD量測…………………………..…….….. 36
3.6 nc-SiOx薄膜之光激發光光譜量測………………..……...…..34
3.7 nc-SiOx薄膜之HRTEM量測....…………..………….….……37
第4章 結論 ………………………………………………………39
第5章 未來工作………………………………………………………40

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