研究生: |
蔡昇達 SHENG - DA TSAI |
---|---|
論文名稱: |
二氧化碳雷射處理鋯鈦酸鉛鐵電厚膜於不同基材之電性研究 CO2 laser annealing of PZT thick films on different substrates |
指導教授: |
周振嘉
Chen-Chia Chou |
口試委員: |
蔡顯榮
Hsien-Lung John Tsai 潘漢昌 Han-Chang Pan |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 機械工程系 Department of Mechanical Engineering |
論文出版年: | 2007 |
畢業學年度: | 95 |
語文別: | 中文 |
論文頁數: | 86 |
中文關鍵詞: | 鋯鈦酸鉛 、鈣鈦礦結構 、CO2低溫雷射退火 |
外文關鍵詞: | PZT, perovskite structure, CO2 low laser annealing |
相關次數: | 點閱:222 下載:3 |
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本研究利用改良式溶膠-凝膠(Sol-gel)法製備鋯鈦酸鉛(PZT)鐵電厚膜,使用CO2低溫雷射退火製程,因雷射能量密度高,能快速將PZT 厚膜從非晶相結構轉換成具鐵電特性之鈣鈦礦結構。研究首先製備出500℃~650℃四種不同溫度之成相粉末,平均粒徑約150~350nm,搭配改良式Sol-gel法旋鍍於Pt/Ti/SiO2/Si(Pt/Si)及SUS 430不銹鋼二種基材上。
當元件結構為PZT(5μm~15μm)/(Pt/Si)時,以CO2低溫雷射退火條件為雷射能量密度121W/cm2,進行不同時間退火。膜厚不同,吸收雷射能量亦不相同。量測該元件鐵電特性,其殘留極化值(Pr)隨膜厚增加而上升,膜厚15μm試片之Pr值為8.49μC/cm2,其介電常數為1170,且發現漏電流高達6.42×10-6 A/cm2。因此以交叉旋鍍厚膜方式改善製程,以提升其緻密性,同樣雷射參數所測其Pr值為14.19μC/cm2,而漏電流為6.6×10-9A/cm2,符合一般元件漏電流所需求的1×10-7A/cm2以下,其介電常數則提升至1920。故此改良式製程能大幅地提升該元件之電性。
當元件結構為PZT(10μm)/(Pt/Si)試片退火條件改變雷射能量密度為69 W/cm2-90sec,藉由低能量長時間處理,使得該緻密性大幅地提升,且不破壞PZT鐵電結構,所測其Pr值為19.39μC/cm2,可獲得低漏電流2.32×10-9A/cm2。故由此可知,該製程可大幅改善其電
性。另一方面本文選用SUS 430不銹鋼基材,其使用金屬當基材可減少下電極製程,但因金屬基材於高溫時易產生元素擴散行為,進而減低電性,故本實驗先鍍製LSMO薄膜當緩衝層以抑制元素擴散。利用改良式旋鍍法製作,將PZT厚膜(5μm)旋鍍於SUS 430不銹鋼,以適當雷射能量密度為138W/cm2-46sec作熱處理,可測得最佳Pr值為4.51μC/cm2。故以之鍍製不同厚膜(5μm~30μm)於SUS 430不銹鋼,以同樣雷射能量密度138W/cm2不同時間作熱處理,厚膜約30μm所測其Pr值為24.52 μC/cm2。若選用此不銹鋼基材,將可大幅減低成本且降低製程時間而應用廣泛。
In this study, lead zirconate titanate (PZT) ferroelectric thick films are prepared by a modified sol-gel method. The microstructure of the thick film is transformed from the amorphous phase to the perovskite structure by using CO2 laser low temperature annealing. PZT powder calcined at four different temperatures (500℃~650℃), and the average grain size about 150~350nm, and to spin-coat the precursor on Pt/Ti/SiO2/Si and SUS 430 substrate.
The sandwich structures of PZT(5μm~15μm)/(Pt/Si) annealed by applying CO2 laser annealing technique. The remanent polarization, coercive field, dielectric constant and leakage current were measured, was 8.49 μC/cm2 and 1170, 6.42×10-6 A/cm2, respectively. After modifying the process to enhance the performance of pre-pressing, the Pr was 14.19 μC/cm2 and leakage current was 6.6×10-9 A/cm2, conforming the leakage current of the general devices below 1×10-7 A/cm2 , the dielectric constant can promote to 1920. So the modification not only improved the process, but also the electric property of multilayered device.
To recrystallize the melt area which laser beam irradiated, the lower laser energy density of 69 W/cm2-90 sec was applied to treat PZT(10 μm)/(Pt/Si), after that, the electric properties were highly improved as Pr and leakage current were 19.39 μC/cm2 and 2.32×10-9 A/cm2,
respectively.
In this study, the PZT coated SUS 430 substrates were use and laser annealed, but at high temperature, the elements inter-diffused between electrode and ferroelectrics. To avoid inter-diffusion phenomenon, LSMO thin films were deposited on substrates. Using the modify coating process, the PZT(5μm) coated on SUS 430 and laser annealed at 138 W/cm2-46 sec, the highest Pr value was 4.51 μC/cm2, after varied the thickness of PZT films to 30 μm, the performance of thick film device was improved,such as Pr value was 24.52 μC/cm2, respectively.
1. 汪健民(1995),“強介電陶瓷薄膜專題緒論” ,工業材料,第107期,pp.44~48.
2. D. Damjanovic, P. Muralt, N. Seter, “Ferroelectric device”, IEEE Sensor jounral,
vol. 1, No.3, October 2001.
3. E. Defay, C. Millon, C. Malhaire, and D. Barbier, “PZT thin films integration for
the realization of a high sensitivity pressure microsensor based on a vibrating
membrane”, Sensors and Actuators A 3268 (2002) 1-4.
4. H. Kueppers, T. Leuerer, U. Schnakenberg, W. Mokwa, M. Hoffmann, T. Schneller,
U. Boettger, and R. Waser, “PZT thin films for piezoelectric microactuator
applications”, Sensors and Acturators A 97-98 (2002) 680-684.
5. Y. Miyahara, M. Deshler, T. Fujii, S. Watanabe, and H. Bleuler, “Non-contact
a tomic force microscope with a PZT cantilever used for deflection sensing , direct
oscillation and feedback actuation., Applied Surface Science 188 (2002) 450-455.
6. M. S. Chen, T.B. Wu and J. M. Wu, “Effect of Textured LaNiO3 Electrode on the
Fatigue Improvement of Pb (Zr0.53Ti0.47)O3 Thin Films”, Appl. Phys. Lett., 68[10],
1430-1432 (1996).
7. W. B. Wu, K. H. Wong, C. L. Choy and Y. H. Zhang,“Top-Interface-Controlled
Fatigue of Epitaxial Pb(Zr0.52Ti0.58)O3 Ferroelectric Thin Films on La0.5Sr0.5MnO3
Electrodes”, Appl. Phys. Lett., 77[10], 3441-3443 (2000).
8. I. Stolichnov, A. Tagantsev, N. Setter, J. S. Cross and M. Tsukad, “Top-Interface-
Controlled Switching and Fatigue Endurance of (Pb,La)(Zr,Ti)O3 Ferroelectric
capacitors”, Appl. Phys. Lett., 74[6], 3552-3554 (1999).
9. F. Wang and S. Leppavuori, “Properties of epitaxial ferroelectric PbZr0.56Ti0.44O3
heterostructures with La0.5Sr0.5CoO3 metallic qxide electrodes”, J. Appl. Phys.,
vol.82, no.3, 1293-98 (1997).
10. S. M. Yoon, E. Tokumitsu and H. Ishiwara, “Preparation of PbZrxTi1-xO3/
La1-xSrxCoO3 heterostructures using the sol-gel method and their electrical
properties”, Appl. surface science, 117, 447-52 (1997).
11. 葉劉育恩,「鈦鋯酸鉛厚膜應用二氧化碳雷射退火製程之研究」,碩士論文,
國立台灣科技大學,台北(2004)
12. T. Yamamoto, M. Saho and K. Okazaki, “Electrical Properties and Microstructure of Ca Modified PbTiO3 Ceramics”, Jpn. J. Appl. Phys., Vol. 26, pp. 57~63 (1987)
13. Franco Jona, G. Shirane, “Ferroelectric Crystals”, Dover Publications, Inc.,
p11~p14 (1993).
14. Y. H. Xu, “Ferroelectric Materials and Their Applications”, North-Holland, New
York, 102 (1991).
15. A. L. Moulson and I. M. Herbert, “Electroceramics”, Chapman and Hall, New
York, U.S.A. (1990).
16. G. H. Haertling, “Ferroelectric Ceramics: History and Technology”, J. Am. Ceram.
Soc., Vol. 82, No. 4, pp. 797-818 (1999).
17. T. Mitsw and S. Nomura, “Ferroelectrics and related substances, Springer-Verlag,
New York, p.426 (1981).
18. Masaru Oikawa and Kohji Toda, “Preparation of Pb(Zr,Ti)O3 thin film by an electron beam evaporation technique”, Appl. Phys. Lett., 28(8), pp.491~492
(1976).
19. L. Tsakalakos and T. Sands, “Epitaxial ferroelectric (Pb,La)(Zr,Ti)O3 thin film on tainless steel by excimer laser liftoff ”, Appl. Phys. Lett., 76(2), pp.227~229
(1999).
20. Q. Zou, H. E. Ruda and B. G. Yacobi,“Dielectric properties of lead zirconate titanate thin films deposited on metal foils”, Appl. Phys. Lett., 77(7),
pp.1038~1040 (2000).
21. Q. Zou,H. E. Ruda and B. G. Yacobi, “Improved dielectric properties of lead zirconate titanate thin films deposited on metal foils with LaNiO3 buffer layers”
, Appl. Phys. Lett., 78(9), pp.1282~1284 (2001).
22. Jin-Rong Cheng, Wenyi Zhu, Nan Li and L. Eric Cross,“Electrical properties of sol-gel-derived Pb(Zr0.52Ti0.48)O3 thin film on a PbTiO3-coated stainless steel
substrate”, Appl. Phys. Lett., 81(25), pp.4805~4807 (2002).
23. Han-Chang Pan, Chen-Chia Chou and Hsien-Lung Tsai, “Low temperature processing of sol-gel derived La0.5Sr0.5MnO3 buffer electrode and PbZr0.52Ti0.48O3 films using CO2 laser annelaing”, Applied Physics Letters, Vol.83, No.15, (2003).
24. 劉柏亨, “CO2雷射低溫熱處理鋯鈦酸鉛鐵電薄膜於不同基材之電性研究”,
國立台灣科技大學碩士論文, 民國95年7月
25. C. Xiong, Y. Tang, J. Gao, H. Zhu, L. Pi, K. Li, J. Zhu and Y. Zhang, “Magnetoresistivity effect in La0.67Sr0.33MnO3/Pr0.7Sr0.33MnO3/ La0.67Sr0.33MnO3 trilayered films”, American Phys. Soc., vol.59, no.14, 9437-41 (1999).
26. T. Namikawa, K. Kaneta, N. Matsushita, S. Nakagawa and M. Naoe, “Annealing effect on magnetic characteristics on (La,Sr)MnO3 sputter films”, IEEE
Transactions on magnetics, vol.35, no.5, 2850-52 (1999).
27. N. Soyama, K. Maki, S. Mori and K. Ogi, “Preparation of PZT thin films for low
voltage application by sol-gel method”, IEEE, 611-14 (2001).
28. Chia-Fong Chou, Han-Chang Pan and Chen-Chia Chou “Electrical Properties and Microstructures of PbZrTiO3 Thin Films Prepared By Laser Annealing Techniques”, Jpn. J. Appl. Phys. Vol.41, No.11B, part 1, pp.6679~6681 (2002).
29. C. J. Brinker, A. J. Hurd, P. R. Schunk, G. C. Frye, and C. S. Ashley, 「Review of Sol-Gel Thin Film Formation」, J. Non-Cryst. Solids., 147&148, 424-436 (1992).
30. B. A. Tuttle, and R. W. Schwartz, 「Solution Deposition of Ferroelectric Thin
Films」, Mater. Res. Soc., 49-54 (1996).
31. J. A. Fernie,「Sol-Gel:Principles and Applications」, Cera. Indust. Inter.,
17-19(1992).
32. R. A. Lipeles, D. J. Coleman, and M. S. Leung,「Metallorganic Solution Deposition of Ferroelectric PZT Films」, IEEE Trans. Ultrason., Ferroelectr.
Frequency Control, 38, 684-689 (1991).
33. C. Sanchez, and M. In,「Molecular Design of Alkoxide Precursors for the Synthesis of Hybrid Organic-Inorganic Gels」, J. Non-Cryst. Solids., 147&148,
1-12(1992).
34. D. R. Uhlmann, G. Teowee, J. M. Boulton, S. Motakef, and S. C. Lee,「Electrical and Optical Properties of Chemically Derived Ferroelectric Films」, J. Non-Cryst.
Solids., 147-148, 409-423 (1992).
35. D. L. Corker, Q. Zhang, R. W. Whatmore, and C. Perrin, “PZT ‘composite’ ferroelectric thick films, ” Journal of the European Ceramic Society, Vol. 22, pp.
383-390 (2002).
36. J. H. Ma, X. J. Meng, J. L. Sun, T. Lin, F. W. Shi, and J. H. Chu, “Effect of annealing ambient on structure and ferroelectric properties of Pb(Zr0.4Ti0.6)O3 thin films on LaNiO3 coated Si substrates, ” Materials Research Bulletin, Vol. 40, pp.
221-228 (2005).
37. 黃敏儀,“添加微粉於有機金屬塩溶液中製備PZT鐵電厚膜之研究”,國立清
華大學碩士論文,民國87年
38. D.L.Corker,Q.Zhang,R.W.Whatmore,C.Perrin“PZT composite ferroelectric thick films”,Journal of the European Ceramic Society 22, pp.383-390 (2002).
39. B.Matthes, G.Tomandl and G.Werner “Characterization of PZT Thin Film Prepared by a Modified Sol-Gel Method”Journal of the European Ceramic Society
19,pp.1387-1389(1999)
40. D.Xia,M.Liu,Y.Zeng,C.Li“Fabrication and electrical properties of lead zirconate titanate thick films by the new sol-gel method”Materials Science and Engineering
B87, pp.160-163(2001).
41. S. H. Hu, X. J. Meng, G. S. Wang, J. L. Sun, D. X. Li “Preparation and characterization of multi-coating PZT thick films by sol-gel process”Journal of
Crystal Growth,Vol264,pp.307-311(2004).
42. 涂文香, “二氧化碳雷射退火製備鋯鈦酸鉛鐵電厚膜特性研究”, 國立台灣科
技大學碩士論文, 民國95年7月
43. Q.F.Zhou, H.L.W.Chan and C.L.Choy “Nanocrystalline powder and fibres of lead zirconate titanate prepared by the sol-gel process,”Journal of Materials Processing Technology 63,pp.281-285 (1997)