镍掺杂BST薄膜的制备及性能研究
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摘要
钛酸锶钡是钛酸钡(BaTiO3)和钛酸锶(SrTiO3)的连续固溶体,属于ABO3型钙钛矿结构,其具有高介电常数、低介电损耗、低漏电流密度、居里温度可调,以及显著的热释电效应和较低的消光系数等特点,在动态随机存储器、热释电红外探测器、微波调谐器、移相器、滤波器等方面有着广泛的应用。随着大规模集成电路的快速发展,薄膜材料成为人们研究的热点,如何制备出结晶度良好,电学及光学性能优越的钛酸锶钡薄膜材料,也成为热点之一。
本文采用溶胶-凝胶法,制备纯相Ba0.6Sr0.4Ti03(BST)薄膜,并进行不同含量镍掺杂,研究镍掺杂对BST薄膜各种性能的影响,具体研究成果如下：
(1)通过多次实验,分别在LNO衬底、Si衬底和石英衬底上成功生长出了质量优良的纯BST及不同含量镍掺杂的BST薄膜。
(2)使用X射线衍射(XRD),分别研究了不同衬底上、不同乙酰丙酮加入量,以及不同含量镍掺杂BST薄膜的微结构；使用扫描电子显微镜(SEM)研究了LNO衬底上BST薄膜的表面形貌和截面情况；使用原子力显微镜(AFM)研究了LNO衬底上,镍掺杂对BST薄膜的三维表面形貌的影响。结果表明,LNO衬底上,10%镍掺杂的BST薄膜的结晶质量最好,表面平整,晶粒略有增大。
(3)使用电学测试仪器,研究了镍掺杂对BST薄膜铁电及介电性能的影响。结果显示,镍的掺入能有效改善BST薄膜的铁电性能,当掺镍量为10%时,电滞回线曲度明显且出现饱和,外加电压为20V时,剩余极化强度约为2.8μC/cm2,矫顽电场约为16kV/cm;镍的掺入使介电常数增大,介电损耗减小,有效改善了BST薄膜的介电性能。
(4)进行拉曼光谱测试,进一步表明镍的掺入对BST薄膜的微观结构产生了一定程度的优化影响。椭圆偏振光谱测试结果表明,镍的掺入会减小BST薄膜的折射率。透射光谱显示,薄膜的透明度很高,数据处理得到各BST薄膜的禁带宽度在4eV附近。
Barium strontium titanate is the complete solid solution of BaTiO3and SrTiO3, and it is ABO3perovskite structure. It is widely applied in the various fields such as dynamic random access memories, Pyroelectric infrared detectors, tunable microwave devices and phase shifters, due to its high dielectric constant, low dielectric loss, high breakdown electric field, low leakage current, excellent pyroelectric property, and low extinction coefficient. In recent years, as the rapid development of VLSI process, BST thin films applied in integrated devices has attracted great interest. It is a key problem that how to prepare the barium strontium titanate thin films with high crystalline and superior electric and optical properties.
In this dissertation, Ba0.6Sr0.4TiO3(BST)films were synthesized by sol-gel method, and different amount of Ni was doped. Then the influence of the doping to the crystalline quality and the photoelectric property of the BST thin film crystal was systemic researched. The main results and conclusions can be summarized as following:
(1). The pure BST precursor and those with different concentration of Ni doping were successfully made after many times experiments. The thin films of pure BST and the ones with different amount of Ni doped were deposited on LNO, Si, and quartz substrates, respectively.
(2). The X-Ray Diffraction (XRD) was used to study the microstructure of the BST thin films with different addition of acetylacetone and Ni doped, and on different substrates. The Scanning Electron Microscope (SEM) was used to study the surface and section of BST thin films on LNO substrates. The influence of Ni doped on the3D surface of BST films was researched by using Atomic Force Microscope on LNO substrates. The results illustrated that the BST film on LNO substrates with10percent Ni doped performes the best quality of crystal and has more flat surface and weak larger grain size.
(3) The ferroelectric and dielectric properties of Ni doped BST thin films were studied. The results show that Ni-doped can increase the dielectric constant, and decrease dielectric loss. Ferroelectric property of10mol%Ni-doped BST thin film is the best, and Pr is about2.8μC/cm2. In a word, Ni doping can effectively improve the ferroelectric and dielectric properties of BST thin films.
(4)The Raman spectroscopy implys that Ni-doped can affect the microstructure of the BST thin films. Spectroscopic ellipsometry shows that Ni-doped can decrease the refractive index of BST thin films. By transmittance spectra, we the optical band gap was obtained, about4eV.
本文采用溶胶-凝胶法,制备纯相Ba0.6Sr0.4Ti03(BST)薄膜,并进行不同含量镍掺杂,研究镍掺杂对BST薄膜各种性能的影响,具体研究成果如下：
(1)通过多次实验,分别在LNO衬底、Si衬底和石英衬底上成功生长出了质量优良的纯BST及不同含量镍掺杂的BST薄膜。
(2)使用X射线衍射(XRD),分别研究了不同衬底上、不同乙酰丙酮加入量,以及不同含量镍掺杂BST薄膜的微结构；使用扫描电子显微镜(SEM)研究了LNO衬底上BST薄膜的表面形貌和截面情况；使用原子力显微镜(AFM)研究了LNO衬底上,镍掺杂对BST薄膜的三维表面形貌的影响。结果表明,LNO衬底上,10%镍掺杂的BST薄膜的结晶质量最好,表面平整,晶粒略有增大。
(3)使用电学测试仪器,研究了镍掺杂对BST薄膜铁电及介电性能的影响。结果显示,镍的掺入能有效改善BST薄膜的铁电性能,当掺镍量为10%时,电滞回线曲度明显且出现饱和,外加电压为20V时,剩余极化强度约为2.8μC/cm2,矫顽电场约为16kV/cm;镍的掺入使介电常数增大,介电损耗减小,有效改善了BST薄膜的介电性能。
(4)进行拉曼光谱测试,进一步表明镍的掺入对BST薄膜的微观结构产生了一定程度的优化影响。椭圆偏振光谱测试结果表明,镍的掺入会减小BST薄膜的折射率。透射光谱显示,薄膜的透明度很高,数据处理得到各BST薄膜的禁带宽度在4eV附近。
Barium strontium titanate is the complete solid solution of BaTiO3and SrTiO3, and it is ABO3perovskite structure. It is widely applied in the various fields such as dynamic random access memories, Pyroelectric infrared detectors, tunable microwave devices and phase shifters, due to its high dielectric constant, low dielectric loss, high breakdown electric field, low leakage current, excellent pyroelectric property, and low extinction coefficient. In recent years, as the rapid development of VLSI process, BST thin films applied in integrated devices has attracted great interest. It is a key problem that how to prepare the barium strontium titanate thin films with high crystalline and superior electric and optical properties.
In this dissertation, Ba0.6Sr0.4TiO3(BST)films were synthesized by sol-gel method, and different amount of Ni was doped. Then the influence of the doping to the crystalline quality and the photoelectric property of the BST thin film crystal was systemic researched. The main results and conclusions can be summarized as following:
(1). The pure BST precursor and those with different concentration of Ni doping were successfully made after many times experiments. The thin films of pure BST and the ones with different amount of Ni doped were deposited on LNO, Si, and quartz substrates, respectively.
(2). The X-Ray Diffraction (XRD) was used to study the microstructure of the BST thin films with different addition of acetylacetone and Ni doped, and on different substrates. The Scanning Electron Microscope (SEM) was used to study the surface and section of BST thin films on LNO substrates. The influence of Ni doped on the3D surface of BST films was researched by using Atomic Force Microscope on LNO substrates. The results illustrated that the BST film on LNO substrates with10percent Ni doped performes the best quality of crystal and has more flat surface and weak larger grain size.
(3) The ferroelectric and dielectric properties of Ni doped BST thin films were studied. The results show that Ni-doped can increase the dielectric constant, and decrease dielectric loss. Ferroelectric property of10mol%Ni-doped BST thin film is the best, and Pr is about2.8μC/cm2. In a word, Ni doping can effectively improve the ferroelectric and dielectric properties of BST thin films.
(4)The Raman spectroscopy implys that Ni-doped can affect the microstructure of the BST thin films. Spectroscopic ellipsometry shows that Ni-doped can decrease the refractive index of BST thin films. By transmittance spectra, we the optical band gap was obtained, about4eV.
引文
[1]符春林.《铁电薄膜材料及其应用》[M],北京：科学出版社,2009
[2]曾龙,华东师范大学硕士学位论文,2010
[3]刘梅冬,许毓春.压电铁电材料与器材[M],武汉,华中理工大学出版社,1990
[4]肖定全.集成铁电学与铁电集成薄膜[J].物理,1994,23
[5]刘志鹏,华东师范大学硕士论文,2010
[6]方瑜.溶胶凝胶技术制备钛酸锶钡系列铁电薄膜及其性能研究.四川大学硕士学位论文.2005.
[7]符春林,杨传仁等,钛酸锶钡(BST)薄膜的组成、结构与性能研究进展[J],真空科学与技术,2003,23(4)：255-263
[8]沈志刚,陈建锋,刘方涛等.功能材料.2003年第五期(34)卷
[9]符春林,杨传仁等,钛酸锶钡(BST)薄膜的制备与应用研究进展,电子元件与材料,Vol.22, No.5 May 2003
[10]丁历,廖恒成,姜云峰,BST铁电薄膜的制备、应用及其研究进展,Chemical lndu try Time,2005,19(5)
[11]方瑜,肖定全.钛酸锶钡薄膜掺杂改性研究进展.材料导报.2005.19(12)
[12]王根水,赖珍荃等.化学溶液法制备的Ba0.9Sr0.1TiO3薄膜的结构及光学特性研究[J].红外与毫米波学报.2002.21(1)
[13]苗鸿雁等.BST铁电薄膜材料的研究现状及其进展[J].材料导报.2005.12
[14]汪竞阳,屈少华等,Nd掺杂BST薄膜的微结构与光学特性研究,湖北大学学报(自然科学版)Vol.32. No.2 Jun.2010
[15]Y. Y. Zhang, G. S. Wang, et al. Effect of Donor, Acceptor, and Donor-Acceptor Codoping on the Electrical Properties of Bao.6Sro.4Ti03 Thin Films for Tunable Device Applications. J. Am. Ceram. Soc.,92(11)2759-2761(2009)
[16]K.-T. Kim, C.-I. Kim/Microelectronic Engineering 66 (2003) 835-841
[17]Z. Yuan, Y. Lin, J. Weaver, et al. Large Dielectric Tunability and Microwave Properties of Mn-Doped (Ba,Sr)TiO3 Thin Films, Appl. Phys. Lett.,87, 152901-3(2005).
[18]K.Imai, S.Takeno, and K. Nakamura, Effect of Fe Doping of Thin (Ba,Sr)TiO3 Films on Increase in Dielectric Constant, Jpn. J. Appl. Phys.,41,6060-4 (2002).
[19]W. Y. Park, C. S. Hwang, J. D. Baniecki, et al. Unusual Thickness Dependence of Permittivity and Elastic Strain in Sc Modified Epitaxial (Ba,Sr)TiO3 Thin Films, Appl. Phys. Lett.,92,102902(2008)
[1]刘志鹏.华东师范大学硕士学位论文,2010
[2]张勤勇,蒋书文,李言荣.快速热处理对(Ba,Sr)TiO3薄膜晶化行为的影响[J].材料导报,2006,20(11).
[3]黄东骥.华东师范大学硕士学位论文,2011
[4]百度文库：化学元素的离子半径及共价半径
[5]王根水,赖珍荃等.化学溶液法制备的Ba0.9Sr0.1TiO3薄膜的结构及光学特性研究[J].红外与毫米波学报.2002.21(1)
[6]J.G.Cheng, X.J.Men, et al. Ferroelectricity in sol-gel derived Ba0.8Sr0.2TiO3 thin films using a highly diluted precursor so lution. Appl. Phys. Lett.1999,75: 2132
[1]Anthony C.T. North, X-Ray Crystallography of Macromolecules, Theory and Methods [J]. Encyc. Spec. Spec. (2009) 2968-2975
[2]黄东骥,华东师范大学硕士学位论文,2011
[3]翁丽敏,华东师范大学硕士学位论文,1999
[4]周宗辉,刘敬,基底材料对溶胶_凝胶法制备BST薄膜的影响,人工晶体学报,2009年8月,第38卷
[5]Lange F F. Chemical Solution Routes to Single2crystal Thin Films[J]. Science, 1996,273:9032909
[6]Hongwei Chen, Chuanren Yang, Jihua Zhang, et al. Two critical grain sizes of Ba0.6Sr0.4Ti03 thin films. J Mater Sci:Mater Electron (2010)21:236-240
[7]张佳,廖家轩等,PVP添加剂改善溶胶-凝胶法制备BST薄膜表面结构及介电性能,硅酸盐通报,2009年8月,第28卷
[8]张训栋,杨晓静等,镍掺杂对钛酸锶钡铁电薄膜性能的影响,压电与声光,Vol.27 No.4, Aug.2005
[1]曾龙,华东师范大学硕士学位论文,2010
[2]黄东骥,华东师范大学硕士学位论文,2011
[3]刘志鹏,华东师范大学硕士学位论文,2010
[4]彭程,华东师范大学学士论文,2009
[5]钟维烈,《铁电体物理学》,科学出版社,2000
[6]Hongwei Chen, Chuanren Yang, Jihua Zhang, et al. Two critical grain sizes of Ba0.6Sr0.4Ti03 thin films. J Mater Sci:Mater Electron (2010) 21:236-240
[7]刘敬,周宗辉.浓度对Sol-Gel法制备BST薄膜结晶及介电性能的影响,红外,Vol.30, No.2, FEB 2009
[8]符春林著,《铁电薄膜材料及其应用》,北京：科学出版社,2009
[9]章天金等,溶胶-凝胶法制备外延Ba1-xSrxTiO3薄膜及其结构与性能研究,红外与毫米波学报,Vol.21,No.5, October,2002
[10]Hongri Liu, Zuli Liu, Qing Liu, Kailun Yao, Ferroelectric properties of BiFeO3 films grown by sol-gel process, Thin Solid Films 500 (2006) 105-109
[11]赵建玲,王晓慧,李龙土,溶胶凝胶法制备<100>择优取向钛酸锶钡薄膜,稀有金属材料与工程,Vol.34, Suppl.1 June 2005
[12]方瑜.溶胶凝胶技术制备钛酸锶钡系列铁电薄膜及其性能研究.四川大学硕士学位论文.2005.
[1]汪竞阳,屈少华等,Nd掺杂BST薄膜的微结构与光学特性研究,湖北大学学报(自然科学版)Vol.32 No.2 Jun.2010
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[12]王根水,赖珍荃等.化学溶液法制备的Ba0.9Sr0.1TiO3薄膜的结构及光学特性研究[J].红外与毫米波学报.2002.21(1)
[2]曾龙,华东师范大学硕士学位论文,2010
[3]刘梅冬,许毓春.压电铁电材料与器材[M],武汉,华中理工大学出版社,1990
[4]肖定全.集成铁电学与铁电集成薄膜[J].物理,1994,23
[5]刘志鹏,华东师范大学硕士论文,2010
[6]方瑜.溶胶凝胶技术制备钛酸锶钡系列铁电薄膜及其性能研究.四川大学硕士学位论文.2005.
[7]符春林,杨传仁等,钛酸锶钡(BST)薄膜的组成、结构与性能研究进展[J],真空科学与技术,2003,23(4)：255-263
[8]沈志刚,陈建锋,刘方涛等.功能材料.2003年第五期(34)卷
[9]符春林,杨传仁等,钛酸锶钡(BST)薄膜的制备与应用研究进展,电子元件与材料,Vol.22, No.5 May 2003
[10]丁历,廖恒成,姜云峰,BST铁电薄膜的制备、应用及其研究进展,Chemical lndu try Time,2005,19(5)
[11]方瑜,肖定全.钛酸锶钡薄膜掺杂改性研究进展.材料导报.2005.19(12)
[12]王根水,赖珍荃等.化学溶液法制备的Ba0.9Sr0.1TiO3薄膜的结构及光学特性研究[J].红外与毫米波学报.2002.21(1)
[13]苗鸿雁等.BST铁电薄膜材料的研究现状及其进展[J].材料导报.2005.12
[14]汪竞阳,屈少华等,Nd掺杂BST薄膜的微结构与光学特性研究,湖北大学学报(自然科学版)Vol.32. No.2 Jun.2010
[15]Y. Y. Zhang, G. S. Wang, et al. Effect of Donor, Acceptor, and Donor-Acceptor Codoping on the Electrical Properties of Bao.6Sro.4Ti03 Thin Films for Tunable Device Applications. J. Am. Ceram. Soc.,92(11)2759-2761(2009)
[16]K.-T. Kim, C.-I. Kim/Microelectronic Engineering 66 (2003) 835-841
[17]Z. Yuan, Y. Lin, J. Weaver, et al. Large Dielectric Tunability and Microwave Properties of Mn-Doped (Ba,Sr)TiO3 Thin Films, Appl. Phys. Lett.,87, 152901-3(2005).
[18]K.Imai, S.Takeno, and K. Nakamura, Effect of Fe Doping of Thin (Ba,Sr)TiO3 Films on Increase in Dielectric Constant, Jpn. J. Appl. Phys.,41,6060-4 (2002).
[19]W. Y. Park, C. S. Hwang, J. D. Baniecki, et al. Unusual Thickness Dependence of Permittivity and Elastic Strain in Sc Modified Epitaxial (Ba,Sr)TiO3 Thin Films, Appl. Phys. Lett.,92,102902(2008)
[1]刘志鹏.华东师范大学硕士学位论文,2010
[2]张勤勇,蒋书文,李言荣.快速热处理对(Ba,Sr)TiO3薄膜晶化行为的影响[J].材料导报,2006,20(11).
[3]黄东骥.华东师范大学硕士学位论文,2011
[4]百度文库：化学元素的离子半径及共价半径
[5]王根水,赖珍荃等.化学溶液法制备的Ba0.9Sr0.1TiO3薄膜的结构及光学特性研究[J].红外与毫米波学报.2002.21(1)
[6]J.G.Cheng, X.J.Men, et al. Ferroelectricity in sol-gel derived Ba0.8Sr0.2TiO3 thin films using a highly diluted precursor so lution. Appl. Phys. Lett.1999,75: 2132
[1]Anthony C.T. North, X-Ray Crystallography of Macromolecules, Theory and Methods [J]. Encyc. Spec. Spec. (2009) 2968-2975
[2]黄东骥,华东师范大学硕士学位论文,2011
[3]翁丽敏,华东师范大学硕士学位论文,1999
[4]周宗辉,刘敬,基底材料对溶胶_凝胶法制备BST薄膜的影响,人工晶体学报,2009年8月,第38卷
[5]Lange F F. Chemical Solution Routes to Single2crystal Thin Films[J]. Science, 1996,273:9032909
[6]Hongwei Chen, Chuanren Yang, Jihua Zhang, et al. Two critical grain sizes of Ba0.6Sr0.4Ti03 thin films. J Mater Sci:Mater Electron (2010)21:236-240
[7]张佳,廖家轩等,PVP添加剂改善溶胶-凝胶法制备BST薄膜表面结构及介电性能,硅酸盐通报,2009年8月,第28卷
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