层状钴基热电薄膜的制备及其激光感生热电电压效应
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摘要
本文以Bi_(2-x)Pb_xSr_2Co_2O_y(BPSCO)与Ca_3Co_4O_9(CCO)为研究对象,利用固相法制备了BPSCO与CCO多晶靶材;采用脉冲激光沉积技术在蓝宝石衬底上制备了BPSCO、CCO薄膜;测量了其LITV信号,并研究了其中可能存在的物理机理。
采用固相法成功制备了BPSCO化合物。研究表明:制备的多晶靶材具有单一的相,没有其他杂相存在;所有靶材沿c轴(001)方向择优生长。
利用脉冲激光沉积(PLD)技术分别在倾斜角度为0度、5度与10度的蓝宝石衬底上制备了BPSCO薄膜,利用XRD表征了薄膜结构,测量了其LITV信号。结果表明:在800度下制备的BPSCO薄膜沿c轴(001)方向一致取向外延生长,薄膜具有较好的结晶性。LITV信号表明:随着掺杂量的增加,峰值电压先增加后减小。在x=0.4时,薄膜的峰值电压达到最大。薄膜的LITV峰值电压随薄膜厚度增加而指数衰减。
利用固相法成功制备了CCO化合物。制备的多晶靶材具有单一的相,靶材沿c轴(001)方向择优生长。利用PLD技术在蓝宝石衬底上制备了一系列的CCO薄膜。研究了薄膜的生长条件;在倾斜衬底上制备了不同氧压,不同厚度的CCO薄膜,首次在倾斜蓝宝石衬底上制备了CCO薄膜,首次发现其激光感生热电电压(LITV)信号,讨论了原位氧压、薄膜厚度对LITV信号的影响。XRD测量结果表明:在衬底温度为800度时,CCO薄膜具有较好的结晶性,并沿c轴(001)方向生长。随着原位氧压的增加,薄膜在100Pa时外延生长,结晶性达到最佳;在200Pa时,薄膜结晶性最差,但其LITV信号灵敏度最强。LITV信号随薄膜厚度增加而减小。
In this paper,Bi_(2-x)Pb_xSr_2Co_2O_y(BPSCO)and Ca_3Co_4O_9(CCO)were investigated. BPSCO and CCO polycrystalline were papered by using solid-state reaction method. BPSCO and CCO thin films were prepared on sapphire substrates by using pulse laser deposition technology whose LITV signal were measured and related physical mechanism were discussed.
BPSCO compounds were successfully prepared by using solid state reaction method. the result show that BPSCO polycrystalline were single phase,there is no unexpected phase. all of them were preferentially oriented to(001)plane.
BPSCO thin films were prepared on vicinal-cut sapphire substrates whose titled angle is 0,5 and 10 respectively.X-ray diffraction was used to determine the micro-structure and orientation of BPSCO thin films.The results show that BPSCO thin films were preferentially oriented to(001)plane along c-axis,and exhibited good crystallinity.LITV signal show that with the increase in doping,the peak voltage increases first and then decreases,when doping is 0.4,the peak voltage reaches the highest value.The LITV peak voltage of thin films exponential decreases with the increasing of thickness of thin films.
CCO compound was successfully synthesized by using solid-state reaction method. CCO polycrystalline has single phase,and preferentially oriented alone c-axis.PLD technology was used for preparing CCO thin films on vicinal-cut sapphire substrates.The growth condition of CCO thin films was systemic investigated.CCO thin films were prepared in different partial oxygen pressure and thickness,and then LITV signal were measured,the impact of partial oxygen and thickness on thin films were discussed.The result show that when temperature of substrate was 800,CCO thin films has good crystallinity,and grow alone(001)oriented in c-axis.When the partial oxygen increased, thin films expitaxial grow alone c-axis in 100 Pa.when the partial oxygen pressure reached 100 Pa,the thin film showed the best crystallinity while the crystallinity showed the worst in 200 Pa oxygen pressure.When oxygen pressure was 200 Pa,the LITV signal reached the highest value than other oxygen pressure.LITV decrease with the increase of thickness of thin films.
采用固相法成功制备了BPSCO化合物。研究表明:制备的多晶靶材具有单一的相,没有其他杂相存在;所有靶材沿c轴(001)方向择优生长。
利用脉冲激光沉积(PLD)技术分别在倾斜角度为0度、5度与10度的蓝宝石衬底上制备了BPSCO薄膜,利用XRD表征了薄膜结构,测量了其LITV信号。结果表明:在800度下制备的BPSCO薄膜沿c轴(001)方向一致取向外延生长,薄膜具有较好的结晶性。LITV信号表明:随着掺杂量的增加,峰值电压先增加后减小。在x=0.4时,薄膜的峰值电压达到最大。薄膜的LITV峰值电压随薄膜厚度增加而指数衰减。
利用固相法成功制备了CCO化合物。制备的多晶靶材具有单一的相,靶材沿c轴(001)方向择优生长。利用PLD技术在蓝宝石衬底上制备了一系列的CCO薄膜。研究了薄膜的生长条件;在倾斜衬底上制备了不同氧压,不同厚度的CCO薄膜,首次在倾斜蓝宝石衬底上制备了CCO薄膜,首次发现其激光感生热电电压(LITV)信号,讨论了原位氧压、薄膜厚度对LITV信号的影响。XRD测量结果表明:在衬底温度为800度时,CCO薄膜具有较好的结晶性,并沿c轴(001)方向生长。随着原位氧压的增加,薄膜在100Pa时外延生长,结晶性达到最佳;在200Pa时,薄膜结晶性最差,但其LITV信号灵敏度最强。LITV信号随薄膜厚度增加而减小。
In this paper,Bi_(2-x)Pb_xSr_2Co_2O_y(BPSCO)and Ca_3Co_4O_9(CCO)were investigated. BPSCO and CCO polycrystalline were papered by using solid-state reaction method. BPSCO and CCO thin films were prepared on sapphire substrates by using pulse laser deposition technology whose LITV signal were measured and related physical mechanism were discussed.
BPSCO compounds were successfully prepared by using solid state reaction method. the result show that BPSCO polycrystalline were single phase,there is no unexpected phase. all of them were preferentially oriented to(001)plane.
BPSCO thin films were prepared on vicinal-cut sapphire substrates whose titled angle is 0,5 and 10 respectively.X-ray diffraction was used to determine the micro-structure and orientation of BPSCO thin films.The results show that BPSCO thin films were preferentially oriented to(001)plane along c-axis,and exhibited good crystallinity.LITV signal show that with the increase in doping,the peak voltage increases first and then decreases,when doping is 0.4,the peak voltage reaches the highest value.The LITV peak voltage of thin films exponential decreases with the increasing of thickness of thin films.
CCO compound was successfully synthesized by using solid-state reaction method. CCO polycrystalline has single phase,and preferentially oriented alone c-axis.PLD technology was used for preparing CCO thin films on vicinal-cut sapphire substrates.The growth condition of CCO thin films was systemic investigated.CCO thin films were prepared in different partial oxygen pressure and thickness,and then LITV signal were measured,the impact of partial oxygen and thickness on thin films were discussed.The result show that when temperature of substrate was 800,CCO thin films has good crystallinity,and grow alone(001)oriented in c-axis.When the partial oxygen increased, thin films expitaxial grow alone c-axis in 100 Pa.when the partial oxygen pressure reached 100 Pa,the thin film showed the best crystallinity while the crystallinity showed the worst in 200 Pa oxygen pressure.When oxygen pressure was 200 Pa,the LITV signal reached the highest value than other oxygen pressure.LITV decrease with the increase of thickness of thin films.
引文
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[2]F.J.Disalvo.Thermoelectric and Power Generation.Science;1999,285:703-706
[3]Y.Gene,S.Heike,D.C.Johnson.Caorimetric study of the nucleation of La_xCo_4Sb_(12)prepared from modulated elemental reactants.Thermochemica Acta B,2002,933:1-8
[4]朱铁军,赵新兵,β-FeSi_2热电材料的性能优化及测试方法,材料科学与工程,1999,17(12):55-59
[5]M.Partik,H.D.Lutz.Semiempirical Band Structure Caculations on Skutterudite Type Compounds.Physic and Chemical Material,1999,27:41-46
[6]X.C.Xu.On the optimal design of multistage thermoelectric coolers.Semiconductor Science and Technology,2002,17:625-629
[7]C.Wood.Materials for thermoelectric energy conversion.Rep.Prog.Phys..1988,51:459-539
[8]S.M.EI-Genk,H.Hamed,T.Caillat.Efficient segmented thermoelectric uncouples for space power applications.Energy Conversion Management,2003,14(11):1755-1772
[9]H.Kandyel,S.Elsayed.Synthesis,structure and physical properties of new Terbium containing Tb-Hg-Sr-Ca-Cu-O superconducting system.Journal of Physics and Chemistry of Solids,2003,64(5):731-739
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[11]沈强,涂溶,张联盟,热电材料的研究进展,硅酸盐学报,1998,(4):23-27
[12]Terasaki I,Uchinokura K Y.Large thermopower in a layered oxides NaCo_2O_4.17~(th)International Conference on Thermoelectric.Negoya:IEEE,1998,567-569
[13]Yakabe H,Kikuchi K,Terasaki I,et al.Thermoelectric properties of transition-metal oxide NaxCoO4 system[A].Proceeding of 16~(th)International Conference on Thermoelectric.Dresden:IEEE,1997,523-527
[14]Shin T, Toshihiko T, Shinya I, et al .Thermoelectric properties of highly textured NaCo2O4 ceramics processed by the reactive templated grain growth method. Materials Science and Engineering,2001,B86(5):20-25
[15]Zandbergen, H.W.,Foo,M., et al. Sodium ion ordering in NaxCoO2.Electron diffraction study, Physic Review B, 2004(70):024101-024108
[16]Terasaki I. Transport properties and electronics states of the thermoelectric oxide NaCO2O4.Physics,2003,B328(7):63-67
[17]Yasuhiro O, Ryuji I, Yuzuru M, et al. Crystal structure, electric and magnetic properties of layered cobaltite B-NaxCoO2.Journal of Solid State Chemistry 2002,166(4): 177-181
[18]Masset A C, Michel C, Maignan A, et al. Misfit-layered cobaltite with an anisotropic giant magnetoresistance: Ca3Co4O9 .Physics Review B,2000,62(1): 166-175
[19]R.Funahashi, I. Matsubara et al. Thermoelectric properties of Bi2Sr2Co2Ox polycrystalline materials. Applied Physics Letter,2000,76:2385-2388
[20]T.Ito, I.Terasaki et al. Journal of Japan Applied physics,2000,39:6658-6661
[21]Takenori Fuji, Ichiro Terasaki, Takao Watanabe, et al., Large In-plane Anisotropy Resistivity and Thermopower in The Misfit Layered Oxide B1-xPbxSr2Co2Oy. Applied Physics Letter, Journal of Japanese Applied Physics;2002,41:783-786
[22]S.W.Li, R.Funahashi, I.Matsubara. Synthesis and thermoelectric properties of the new oxide materials Ca3-xBixCo4O9.Chemistry Materials, 2000,12:2424-2427
[23]G.J.Xu, R.Funahashi, M.Shikano. High temperature transport properties of Ca3-xNaxCo4O9 system. Solid State Communications, 2002,124:73-76
[24J.Nan, J.B.Wu, Y.Deng. Synthesis and thermoelectric properties of (NaxCa1-x)Co4O9 ceramics. Journal of European Ceramics,2003,23(6)859-863
[25]E.Guilmeau, M.Pollet, D.Grebille, D.Chateigner, et al. Neutron diffraction texture analysis and thermoelectric properties of BiCaCoO misfit compounds.Materials Research Bulletin;2008,43(2):394-400
[26]Chang C.L.,Kleinhammes A, Moulton W.G.,Testardi L.R. Symmetry-forbidden laser-induced voltages in YBa2Cu3O7 .Physics Review B 1990,41:11564-11567
[27]Kwok H.S.,Zheng J.P.,Ying Q.Y.et al.Nonthermal optical response of Y-Ba-Cu-O thin films.Applied Physics Letter,1989,54,2473-2478
[28]C.L.Chang,A.Kleinhammes,W.G.moulton,et al.Symmetry-forbidden thermoelectric voltage in YBa2Cu3O7.Physics Review B,1990,40:11564-11567
[29]Tate K.L.Johnson R.D.,Chang C.L.,et al.Transient laser-induced voltages in room-temperature films of YBa2Cu3O7.Applied Physic Letter,1990,67:4375-4380
[30]H.S.Kwok,J.P.Zheng.Laser-induced voltages in Unbiased YBCO-Dependence on Crystalline Anisotropy.Physics Review B,1991,27(2):1288-1290
[31]T.L.Aselage,D.Emin,S.S.Mcready.et al.Large Enhancement of Boron Carbides'Seebeck Coefficients through Vibrational Softening.Physics Review Letter,1998,81:2316-2319
[32]Lengfellner H,Kremb G,Schnellbogl A,et al.Giant Voltages upon Surface Heating in Normal YBa2Cu3O7-d Films Suggesting an Atomic Layer Thermopile.Applied Physics Letter,1992,60:501-503
[33]RX.Zhang,W.K.Lee,GY.Zhang.Time dependence of laser-induced thermoelectric voltages in La_(1-x)Ca_xMnO_3 and YBa_2Cu_3O_(7-δ)thin films.Applied Physics Letter,2002,81:4026-4030
[34]Zhang GY.,Zhang P.X.Zhang H.Figure Merit of Detectors Based on Laser-induced Thermoelectric Voltages in La_(1-x)Ca_xMnO_3 and YBa_2Cu_3O_(7-δ)thin films.China Physics Letter,2005,22:2379-2381
[35]P.X.Zhang,U.Sticher,B.Leibold et al.Thickness dependence of the thermoelectric voltages in YBaCuO_(7-d)thin films on tilted substrate of SrTiO_3.Physical C,1997,4:2551-2552
[36]张国勇.LCMO及YBCO薄膜的时变感生电压:[硕士学位论文].昆明:昆明理工大学,2002
[37]Lengfellner H,Kremb G,Schnellbogl A,et al.Giant Voltages upon Surface Heating in Normal YBa2Cu3O7-d Films Suggesting an Atomic Layer Thermopile.Applied Physics Letter,1992,60:501-503
[38]Anisimov S.I..Vaporiazation of Metal Absorbing Laser Radiation.1988,Soviet.Physics 27:182-185
[38]朱绍将,刘翔,彭巨擘等,氧气氛后退火对La0.67Ca0.33MNO3-Ag薄膜性能的影响,贵金属,2003,24(4):49-52
[40]舒启清,电子隧穿原理.北京:科学出版社,1998
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