臺灣博碩士論文加值系統

本實驗利用射頻磁控濺鍍(RF Magnetron Sputtering )系統成長鈮酸鋰薄膜於矽基板及單晶氧化鋁基板上。固定濺射功率以及靶材與基板之間距，改變氧氣與Ar混合比例、成長溫度，探討製程參數對於鈮酸鋰薄膜成長之影響。以X-ray、SEM、TEM等儀器分析沉積薄膜之結構以及表面型態，並觀察經由不同氣氛下退火之結晶結構與表面型態之差異。
實驗結果顯示，矽基板成長鈮酸鋰薄膜在溫度500℃、混合Ar/O2為 8/2時，可得到最佳優選方向之結晶結構。在單晶氧化鋁基板上沉積在450℃以上、混合氣氛8/2及6/4皆可得到有優選方向之鈮酸鋰薄膜結構，經過氧氣氛中500℃持溫2小時之熱處理條件，強化(006)面之優選方向，且穿透率可由56%提升至68%；在矽基板上成長之薄膜無法在熱處理之後保有鈮酸鋰結構，而轉為缺鋰相存在。
由電滯曲線量測確認薄膜的確具有鐵電現象，且在氧氣氛分壓為20%、500℃下成長之鈮酸鋰薄膜，因其結構異向性及結晶性質較佳而呈現較強之鐵電相電滯曲線。

LiNbO3 thin films were deposition on Si and Sapphire substrate by RF Sputtering deposition technique. The growth temperature and Ar/O2 gas ratio were varied during the deposition of LiNbO3. The power was 150W and the distance between target and substrate was 45mm. The microstructuce and surface morphology were examined by using α–step, Scanning electron microscopy, transmission electron microscopy and X-ray diffractionmetry.

The LiNbO3 thin film on Si substrate growth at 500℃, Ar/O2 ratio was 8/2, would be better preferred orientation at C-axis. On sapphire substrate, when the growth temperature was above 450℃, it would be easy to get preferred orientation at Ar/O2 ratio of 8/2 and 6/4. Post annealing at 500℃、2 hours in O2 atmosphere would increased the LiNbO3 preferred orientation. But the LiNbO3 on Si substrate transform to Li deficiencies phase. The ferroelectric property was measured by P-E Curve, film growth at 500℃, gas ratio Ar/O2 = 8/2, have better polarization and hysetersis.

中文摘要.............................................................................................. I
英文摘要............................................................................................. II
目錄..................................................................................................... III
圖目錄.................................................................................................. VI
表目錄................................................................................................... X
第一章 前言...................................................................................... 1
1-1 簡介............................................................................................... 1
1-2 研究動機及目的........................................................................... 1
第二章 理論基礎與文獻回顧.......................................................... 3
2-1 LiNbO3基本性質.......................................................................... 3
2-1-1 晶體結構及性質.................................................................... 3
2-1-2 偏離計量比之影響與光學應用限制.……............................ 5
2-2 射頻磁控濺鍍理論....................................................................... 9
2-2-1 電漿濺鍍的基本理論............................................................. 9
2-2-2 直流電漿(DC plasma) ........................................................... 13
2-2-3 射頻放電(Radio Frequency Gas Discharge) ......................... 15
2-2-4 磁控濺鍍................................................................................ 16
2-3 薄膜成長....................................................................................... 17
2-3-1 薄膜成長力學........................................................................ 17
2-3-2 薄膜之微結構........................................................................ 19
2-3-3 薄膜成份控制........................................................................ 22
2-4 電光效應....................................................................................... 25
第三章 實驗步驟與方法................................................................... 27
3-1實驗流程…................................................................................... 27
3-2 靶材製作…............................................................…......…........ 28
3-3 基板準備….................................................................................. 28
3-3-1 基板清洗…........................................................................... 28
3-4 薄膜濺鍍過程.............................................................................. 30
3-4-1 濺鍍步驟............................................................................... 30
3-4-2 薄膜成長條件....................................................................... 29
3-5 熱處理.......................................................................................... 32
3-5-1 空氣中退火........................................................................... 32
3-5-2 氧氣氛下退火....................................................................... 32
3-6 薄膜基本性質量測...................................................................... 34
3-6-1 X-Ray結晶結構分析........................................................... 34
3-6-2 膜厚測定............................................................................... 34
3-6-2a 橢圓偏光儀之膜厚測定....................................................... 34
3-6-2b α-step膜厚量測.................................................................... 35
3-7 顯微結構分析............................................................................. 35
3-7-1 掃描式電子顯微鏡(SEM)分析............................................ 35
3-7-2 穿透式電子顯微鏡(TEM)分析............................................ 37
3-8 P-E特性分析............................................................................... 37
3-9穿透率量測.................................................................................. 37
第四章 結果與討論........................................................................... 39
4-1 靶材製備...................................................................................... 39
4-2 在Si基板上成長LiNbO3薄膜................................................... 40
4-2-1 不同成長氣氛........................................................................ 40
4-2-2 不同比例超額鋰靶材............................................................ 42
4-2-3 SEM顯微觀察....................................................................... 42
4-2-4 TEM繞射圖形及BF觀察.................................................... 43
4-3 在Sapphire基板上沉積LiNbO3................................................ 44
4-4 不同氣氛下退火.......................................................................... 46
4-4-1 XRD分析............................................................................... 46
4-4-1 SEM顯微結構觀察................................................................ 47
4-5 P-E Curve量測........................................................................... 49
4-6 穿透率量測................................................................................. 50
第五章 結論........................................................................................ 81
參考文獻.............................................................................................. 82

1.W. H. Zachariasen, Skr. Norske Vid-Ada, Oslo, Mat. Naturv. No.4 (1928)
2.A. A. Ballman, J. American Ceram.Soc.48, (1965) p112.
3.A. Yeh, and P. Yeh, “Optical waves in crystals”, Wiley, New York (1984)
4.M. Haruna, J. Tsutumi, Y. Segawa, H. Nishhara, SPIE 2045, (1994) p133.
5.B. T. Matthias and J. P. Remeika, Ferroelectricity in the materials by the Czochralski technique, J. American Cream. Soc.48, (1965) p112.
6.P. Lener, C. Legras et J. P. Duman, Stoechiometric des monocristanx de metaniobate delithium, J. Crystal Growth 3/4 (1968) p231.
7.S. C. Abrahams, J. M. Reddy and J. L. Bernstein, Ferroelectric lithium niobate. 3. Single crystal X-ray diffraction study at 24℃, J. Phys. Chem. Solids 27, (1966) p997.
8.S. C. Abrahams, W. C. Hamilton and J.M. Reddy, Ferroelectric lithium nibate. 4. Single crystal X-ray diffraction study at 24℃ and 1200℃, J. Phys. Chem. Solids 27, (1966) p1019.
9.S. C. Abrahams, H. J. Levinstein and J. M. Reddy, Ferroelectric lithium niobate. 5. Single crystal X-ray diffraction study between 24℃ and 1200℃, J. Phys. Chem. Solids 27, (1966) p1019.
10.S. C. Abrahams and P. Marsh, Defect structure dependence on composition in lithium niobate, Acta Cryst. B42, (1986) p61.
11.K. Nassauand M. E. Lines, Stacking fault model for Stoichiometry deviation in LiNbO3 and LiTaO3 and the effect on the Curie temperature, J. Appl. Phys. 41, (1970) p533.
12.M. V. Hobden and J. Warner, The temperature Dependence of the refractive indices of pure lithium niobate, Phys. Lett.22, (1966) p243.
13.J. D. Zook, D. chen and G. N. Otto, Temperature depencence and modal of the electrio-optic effect in LiNbO3, Appl. Phys. Lett.11, (1967) p159.
14.M. M. Choy and R. L. Byer, Accurate second–order Susceptibility measurements of visible and infrared nonlinear crystals, Phys. Rev. B14 (1976) p1693.
15.C. J. G. Kirby, in Properties of LiNbO3, EMI Datareview Series No.5, INSPEC, London (1989)
16.A. Garcia-Cabanes, J. A. Sanz-Garcia, J. M. Cabrera, F. Agullo-Lopez, C. Zaldo, R. Parja, K. Polgar, K. Rakanyi and I. Foldvari, Phys. Rev. B37, (1988) p6085.
17.I. Foldvari, K. Polgar, and A. Meceski, Acta Phys. Hung. 55, (1984) p321.
18.J. G.. Bergman, A. Ashin, A. A. Ballman, J. M. Dziedzic, H. J. Levinstein and R. G. Smith, Appl. Phys. Letter 12, (1968) p92.
19.N. V. Kukhtarev, Kinetic of hdogram recording and erasure in electro optic crystal, Sov. Tech. Phys. Lett. 2, (1976) p438.
20.B. Gross, B. Grycz and K. Miklossy, “Plasma Technology”, American Elsevier Publishing, (1969) p354.
21.S. H. Rossnagel, J. Vac. Sci. Technol., A6, (1988)p19.
22.J. L. Vossen and K. Werner, “Thin film Process”, Academic press, (1978) p23.
23.D. W. Hoffman, J. Vac. Sci. Technol., A3, (1985) p561.
24.楊錦張, 基礎濺鍍電漿, 電子發展月刊 Vol.68, (1983) p31.
25.W. kiyotaka and H. Shieru, “Handbook of sputter deposition technology”, Noyes Publishing, (1991) p10.
26.J. A. Thornton, J. Vac. Sci. Technol., Vol. 11, No.4, (1974) p666.
27.D. Henderson, M. H. Brosdky and P. Chaudhari, Appl. Phys. Lett., Vol.25, (1974) p641.
28.A. G. Dirks and H. J. Leamy, Thin Solid Films, Vol.47, (1977) p219
29.R. Messier, A. P. Giri and R. A. Roy, J. Vac. Sci. Technol., A2(2), (1984) p500.
30.O. Auciello and J. Engemann(eds), “Miltilayered Thin Film for Advanced Microtechnologies ”, Kluwer Academic Publish ing, (1993) p129.
31.S. M. Rossnagel, J. J. Cuomo, AVS. Soc. Symp. Proc., Vol.165, (1988) p106.
32.D. Theirich and J. Engemann, Nucl. Inst. and Meth. B, 59/60, (1991) p336.
33.A. Yariv, P. Yeh, Optical Wave in Crystals, Wiley, New York (1984) p220.
34.C. J. Kirkly, Ferroelectrics, 37, (1981) p567.
35.李金宏,橢圓偏光儀簡介,量測資訊,第66期, (1999.3) p38.
36.B. D. Cullity,”Diffraction I: Direction of Diffraction Beams” Element of X-Ray Diffraction, Second edition (1978).
37.C. V. Thompson and R. Carel, Materials Science and Engineering, B32, (1995) p211.
38.胡榮章, ”MgO-LiNbO3單晶成長及其特性研究”, 成功大學博士論文, (1991) p161.
39.F. Agullo-Lopez, J. M. Carbrera, F. Agullo-Rueda,”Electrooptics: phenomena, materials and applications”, Academic press, London (1994) p35.
40.F. Agullo-Lopez, J. M. Carbrera, F. Agullo-Rueda,”Electrooptics: phenomena, materials and applications”, Academic press, London (1994) p286.