钛酸锶钡微晶玻璃的铈掺杂效应研究

摘要/Abstract

摘要： 通过X射线光电子能谱、紫外-可见漫反射光谱、傅里叶变换红外光谱和拉曼光谱研究了(Ba,Sr)TiO₃微晶玻璃的铈掺杂效应。玻璃体系为BaO-SrO-TiO₂-Al₂O₃-SiO₂(Ce摩尔分数为0%、1%、2%、3%)。随着Ce摩尔含量增加,Ce在(Ba,Sr)TiO₃晶格中的占位从Ce⁴⁺取代Ti⁴⁺位的形式逐渐变成了以Ce³⁺进入Ba²⁺/Sr²⁺位的形式,伴随Ce³⁺和Ce⁴⁺离子相对含量的变化。玻璃中添加CeO₂增加了网络结构的连通性。在微晶玻璃中,随着Ce摩尔分数的增加(0%到2%),禁带宽度减小,电子跃迁所需能量降低,价带电子易从价带跃迁至导带,电导率增加;相反地,Ce摩尔分数从2%增加到3%时,禁带宽度增加,电导率下降。拉曼光谱结果证实了铈离子(Ce³⁺和Ce⁴⁺)在(Ba,Sr)TiO₃晶格中的取代,并发现铈掺杂改变了该晶相的四方性。

关键词: 钛酸锶钡, 微晶玻璃, 氧化铈, 掺杂效应, 禁带宽度

Abstract: Cerium doping effect in (Ba,Sr)TiO₃ glass-ceramics has been investigated by X-ray photoelectron spectroscopy,ultraviolet-visible diffuse-reflectance spectroscopy,Fourier transform infrared spectroscopy and Raman spectroscopy.Studies were performed on specimens for BaO-SrO-TiO₂-Al₂O₃-SiO₂ glass system (with 0%,1%,2% and 3% mole fraction of cerium).With the change of relative content of Ce³⁺ and Ce⁴⁺,cerium mainly acts as Ce⁴⁺ in the Ti⁴⁺-site of (Ba,Sr)TiO₃ lattice at low content and then cerium substitution gradually occurs in the Ba²⁺/Sr²⁺-site as Ce³⁺ with increasing cerium mole content.The CeO₂ addition in the glass could effectively improve the connectivity of network structure.In (Ba,Sr)TiO₃ glass-ceramics,with the increase of cerium content (0% to 2%),the value of band gap energy decreases,electronic transition energy decreases,then electrons transit from the valence band to the conduction band easily,and the conductivity increases.In contrast,when the mole fraction of cerium increased from 2% to 3%,the value of band gap energy increases,so the conductivity decreases.The results of Raman spectra confirm that cerium ions diffuse into the (Ba,Sr)TiO₃ lattice structure and modify the tetragonality of the barium strontium titanate phase.

Key words: barium strontium titanate, glass-ceramics, ceria, doping effect, band gap

中图分类号:

TQ171

赵张媛, 梁雪薇, 张勇. 钛酸锶钡微晶玻璃的铈掺杂效应研究[J]. 硅酸盐通报, 2021, 40(1): 258-265.

ZHAO Zhangyuan, LIANG Xuewei, ZHANG Yong. Cerium Doping Effect in Barium Strontium Titanate Glass-Ceramics[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2021, 40(1): 258-265.

参考文献

[1] YAO Z H,SONG Z,HAO H,et al.Homogeneous/inhomogeneous-structured dielectrics and their energy-storage performances[J].Advanced Materials,2017,29(20):1601727.
[2] GORZKOWSKI E P,PAN M J,BENDER B,et al.Glass-ceramics of barium strontium titanate for high energy density capacitors[J].Journal of Electroceramics,2007,18(3/4):269-276.
[3] ZHANG Q M,WANG L,LUO J,et al.Improved energy storage density in barium strontium titanate by addition of BaO-SiO₂-B₂O₃ glass[J].Journal of the American Ceramic Society,2009,92(8):1871-1873.
[4] WANG H T,LIU J H,ZHAI J W,et al.Ultra high energy-storage density in the barium potassium niobate-based glass-ceramics for energy-storage applications[J].Journal of the American Ceramic Society,2016,99(9):2909-2912.
[5] SONG X Z,ZHANG T Y,ZHAO Z Y,et al.Relaxation processes in barium strontium titanate glass-ceramics by thermally simulated depolarization current[J].Journal of the American Ceramic Society,2019,102(3):901-906.
[6] GAUDET J A,BARKER R J,BUCHENAUER C J,et al.Research issues in developing compact pulsed power for high peak power applications on mobile platforms[J].Proceedings of the IEEE,2004,92(7):1144-1165.
[7] ALEXANDRU H V,BERBECARU C,IOACHIM A,et al.Oxides ferroelectric (Ba,Sr)TiO₃ for microwave devices[J].Materials Science and Engineering:B,2004,109(1/2/3):152-159.
[8] SU B,BUTTON T W.Microstructure and dielectric properties of Mg-doped Barium strontium titanate ceramics[J].Journal of Applied Physics,2004,95(3):1382-1385.
[9] JANA A,KUNDU T K.Microstructure and dielectric characteristics of Ni ion doped BaTiO₃ nanoparticles[J].Materials Letters,2007,61(7):1544-1548.
[10] MORRISON F D,SINCLAIR D C,WEST A R.Electrical and structural characteristics of lanthanum-doped Barium titanate ceramics[J].Journal of Applied Physics,1999,86(11):6355-6366.
[11] ZHANG Y,MA T,WANG X R,et al.Two dielectric relaxation mechanisms observed in lanthanum doped Barium strontium titanate glass ceramics[J].Journal of Applied Physics,2011,109(8):084115.
[12] SUN Q M,GU Q L,ZHU K J,et al.Crystalline structure,defect chemistry and room temperature colossal permittivity of Nd-doped barium titanate[J].Scientific Reports,2017,7:42274.
[13] KHUSHBU,KUMAR P,KUMAR V.Effect of co-substitution of Sm³⁺ and Fe³⁺ ions on structural and dielectric properties of BaTiO₃ ceramics[J].Journal of Alloys and Compounds,2018,731:760-765.
[14] GARRIDO-HERNÁNDEZ A,GARCÍA-MURILLO A,DE J CARRILLO-ROMO F,et al.Structural studies of BaTiO₃:Er³⁺ and BaTiO₃:Yb³⁺ powders synthesized by hydrothermal method[J].Journal of Rare Earths,2014,32(11):1016-1021.
[15] MITIC V V,NIKOLIC Z S,PAVLOVIC V B,et al.Influence of rare-earth dopants on barium titanate ceramics microstructure and corresponding electrical properties[J].Journal of the American Ceramic Society,2010,93(1):132-137.
[16] LU D Y,GAO X L,WANG S.Abnormal curie-temperature shift in Ho-doped BaTiO₃ ceramics with the self-compensation mode[J].Results in Physics,2019,12:585-591.
[17] LU D Y,TODA M,SUGANO M.High-permittivity double rare-earth-doped Barium titanate ceramics with diffuse phase transition[J].Journal of the American Ceramic Society,2006,89(10):3112-3123.
[18] MAKOVEC D,SAMARDÁIJA Z,KOLAR D.Solid solubility of cerium in BaTiO₃[J].Journal of Solid State Chemistry,1996,123(1):30-38.
[19] ZHAO Z Y,LIANG X W,ZHANG T Y,et al.Effects of cerium doping on dielectric properties and defect mechanism of barium strontium titanate glass-ceramics[J].Journal of the European Ceramic Society,2020,40(3):712-719.
[20] NICOLINI V,GAMBUZZI E,MALAVASI G,et al.Evidence of catalase mimetic activity in Ce³⁺/Ce⁴⁺ doped bioactive glasses[J].The Journal of Physical Chemistry B,2015,119(10):4009-4019.
[21] TAUC J,GRIGOROVICI R,VANCU A.Optical properties and electronic structure of amorphous germanium[J].Physica Status Solidi (b),1966,15(2):627-637.
[22] DAVIS E A,MOTT N F.Conduction in non-crystalline systems V.Conductivity,optical absorption and photoconductivity in amorphous semiconductors[J].The Philosophical Magazine:A Journal of Theoretical Experimental and Applied Physics,1970,22(179):903-922.
[23] FOX M.Optical properties of solids[M].Oxford University Press,2010.
[24] LIN S L,HWANG C S.Structures of CeO₂-Al₂O₃-SiO₂ glasses[J].Journal of Non-Crystalline Solids,1996,202(1/2):61-67.
[25] YOUSEF E S,EL-ADAWY A,EL KOSHKHANY N,et al.Optical and acoustic properties of TeO₂/WO₃ glasses with small amount of additive ZrO₂[J].Journal of Physics and Chemistry of Solids,2006,67(8):1649-1655.
[26] AGUIAR H,SERRA J,GONZZLEZ P,et al.Structural study of sol-gel silicate glasses by IR and Raman spectroscopies[J].Journal of Non-Crystalline Solids,2009,355(8):475-480.
[27] BELL R J,BIRD N F,DEAN P.The vibrational spectra of vitreous silica,germania and beryllium fluoride[J].Journal of Physics C:Solid State Physics,1968,1(2):299-303.
[28] ZHU M K,WANG B,LIU P,et al.Preparation and properties of BaTiSi₂O₇ glass-ceramics[J].Optical Materials,2003,23(1/2):323-326.
[29] DAI W K,ZHU M K,HOU Y D,et al.Preparation and characterization of Ba₂TiSi₂O₈ ferroelectric films produced by sol-gel method[J].Materials Letters,2004,58(22/23):2927-2931.
[30] LEE H K,LEE Y S,BHALLA A S,et al.The effect of K₂O in the glass-ceramics based on the BaO-TiO₂-SiO₂ glasses[J].Materials Letters,2006,60(20):2457-2460.
[31] WANG X R,ZHANG Y,ZHU J,et al.Lanthanum doping effect in barium strontium titanate glass ceramics[J].Ceramics International,2014,40(10):16557-16562.
[32] DIDOMENICO M,WEMPLE S H,PORTO S P S,et al.Raman spectrum of single-domain BaTiO₃[J].Physical Review,1968,174(2):522.
[33] PARIDA S,ROUT S K,SUBRAMANIAN V,et al.Structural,microwave dielectric properties and dielectric resonator antenna studies of Sr(Zr_xTi_1-x)O₃ ceramics[J].Journal of Alloys and Compounds,2012,528:126-134.
[34] DOBAL P S,DIXIT A,KATIYAR R S.Effect of lanthanum substitution on the Raman spectra of barium titanate thin films[J].Journal of Raman Spectroscopy,2007,38(2):142-146.
[35] WANG G F,MU Q Y,CHEN T,et al.Synthesis,characterization and photoluminescence of CeO₂ nanoparticles by a facile method at room temperature[J].Journal of Alloys and Compounds,2010,493(1/2):202-207.
[36] KOSACKI I,SUZUKI T,ANDERSON H U,et al.Raman scattering and lattice defects in nanocrystalline CeO₂ thin films[J].Solid State Ionics,2002,149(1/2):99-105.
[37] PHOKA S,LAOKUL P,SWATSITANG E,et al.Synthesis,structural and optical properties of CeO₂ nanoparticles synthesized by a simple polyvinyl pyrrolidone (PVP) solution route[J].Materials Chemistry and Physics,2009,115(1):423-428.