掺杂LaMnO_3系NTC材料的研究
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摘要
锰酸镧(LaMnO_3)在室温(25℃)至300℃范围内具有负阻温特性,可用于制备负温度系数热敏电阻(NTCR)。本论文通过在LaMnO_3的基础上掺杂Fe、Ni、V、Ti、Ba、Sr、Cu等进行A,B位取代,以调整材料的室温电阻率和改善材料常数B值,获得低阻值、高B值、稳定性好的新型负温度系数热敏电阻材料。并采用SEM, XRD等实验手段研究了掺杂系统组成、结构与电学性能之间的关系,深入探讨了该系列钙钛矿材料的导电机理。
首先在LaMnO_3的基础上B位掺杂Fe_2O_3 ,NiCO_3 ,V2 O5 ,TiO2,采用传统的固相合成法制备样品LaMn_(1-x)Fe_xO_3 , LaMn_(1-x)Ni_xO_3 , LaMn_(1-x)V_xO_3 ,LaMn_(1-x)Ti_xO_3 (0.1≤x≤0.4),在空气气氛下于1200℃烧结2h。通过研究它们对NTC性能的影响,发现只有Ti~(4+)高价取代Mn~(3+),能有效增大室温电阻率和B值。
然后在此基础上选出一个低阻值、高B值且烧结性能良好的配方(LaMn_(0.6)Ti_(0.4)O_3 ),继续掺杂SrCO_3、BaCO_3、CuO,制备样品La_(1-x)Sr_xMn_(0.6)Ti_(0.4)O_3,La_(1-x)Ba_xMn_(0.6)Ti_(0.4)O_3 (0.1≤x≤0.6),LaMn_(0.6)Ti_(0.4-y)Cu_yO_3(0.05≤y≤0.2)。测其在室温(25℃)至300℃范围内的电阻率随温度的变化关系(ρ-T曲线),并利用XRD和SEM对材料作物相分析和微观形貌观察。
实验结果表明,所有样品在室温(25℃)至300℃的ρ-T曲线均符合NTC特性,且可得到室温电阻率仅为180Ω·cm,而B值高达3270K且稳定性较好的新型NTC材料。并利用半导体载流子导电理论探讨了该系列材料的导电机理。
LaMnO_3 is semiconductor ceramic with negative resistance-temperature characteristic and can be used as Negative Temperature Coefficient Resistor(NTCR). In this paper, a new NTCR material have been studied through doping in LaMnO_3. To increase the resistance valueρ25℃and improve the B value as well as to get good sintering ceramic elements, introduce different elements such as Fe, Ni, V, Ti, Ba, Sr, Cu was into A and B sites. Then the relationships between structure and electrical properties are discussed by aids of XRD, SEM etc. And the conducting mechanism of the NTC material with perovskite type structure was studied .
First, Fe_2 O_3 ,NiCO_3 ,V_2O_5 and TiO_2 were doped in LaMnO_3 with different content. The systems such as LaMn_(1-x)Fe x O_3 , LaMn_(1-x)Ni_xO_3 , LaMn_(1-x)V_xO_3 ,LaMn_(1-x)Ti_xO_3 (0.1≤x 0.4) were prepared by conventional solid-state reaction at 1200℃≤for 2h in air. The NTC character of such samples was researched. And it was found thatρ25℃and the B value increase obviously when Ti~(4+) substitutes Mn~(3+).
Then the system(LaMn_(0.6)Ti_(0.4)O_3)with low resistivity, high B and good sintering way were selected to be doped with SrCO_3 , BaCO_3, CuO. The systems of La_(1-x)Srx Mn_(0.6)Ti_(0.4)O_3 ,La_(1-x)Ba x Mn_(0.6)Ti_(0.4)O_3 (0.1≤x≤0.6),LaMn_(0.6)Ti_(0.4)-yCuy O_3 (0.05≤y 0.2) were prepared by conventional solid-state reaction. The resistivity of samples changed with the temperature was measured from 25℃≤to 300℃.The X-ray diffractograms (XRD) of the samples were recorded and the microstructure was observed by scanning electron microscope (SEM). It was found that theρ-T curves of all the samples matched NTC characteristic. A new NTCR material with low resistivity(180Ω·cm ), high sensitivity to temperature change(B=3270K) and high stability can be get. And the conducting mechanism of the NTC material was studied with the semiconductor carriers mechanism.
首先在LaMnO_3的基础上B位掺杂Fe_2O_3 ,NiCO_3 ,V2 O5 ,TiO2,采用传统的固相合成法制备样品LaMn_(1-x)Fe_xO_3 , LaMn_(1-x)Ni_xO_3 , LaMn_(1-x)V_xO_3 ,LaMn_(1-x)Ti_xO_3 (0.1≤x≤0.4),在空气气氛下于1200℃烧结2h。通过研究它们对NTC性能的影响,发现只有Ti~(4+)高价取代Mn~(3+),能有效增大室温电阻率和B值。
然后在此基础上选出一个低阻值、高B值且烧结性能良好的配方(LaMn_(0.6)Ti_(0.4)O_3 ),继续掺杂SrCO_3、BaCO_3、CuO,制备样品La_(1-x)Sr_xMn_(0.6)Ti_(0.4)O_3,La_(1-x)Ba_xMn_(0.6)Ti_(0.4)O_3 (0.1≤x≤0.6),LaMn_(0.6)Ti_(0.4-y)Cu_yO_3(0.05≤y≤0.2)。测其在室温(25℃)至300℃范围内的电阻率随温度的变化关系(ρ-T曲线),并利用XRD和SEM对材料作物相分析和微观形貌观察。
实验结果表明,所有样品在室温(25℃)至300℃的ρ-T曲线均符合NTC特性,且可得到室温电阻率仅为180Ω·cm,而B值高达3270K且稳定性较好的新型NTC材料。并利用半导体载流子导电理论探讨了该系列材料的导电机理。
LaMnO_3 is semiconductor ceramic with negative resistance-temperature characteristic and can be used as Negative Temperature Coefficient Resistor(NTCR). In this paper, a new NTCR material have been studied through doping in LaMnO_3. To increase the resistance valueρ25℃and improve the B value as well as to get good sintering ceramic elements, introduce different elements such as Fe, Ni, V, Ti, Ba, Sr, Cu was into A and B sites. Then the relationships between structure and electrical properties are discussed by aids of XRD, SEM etc. And the conducting mechanism of the NTC material with perovskite type structure was studied .
First, Fe_2 O_3 ,NiCO_3 ,V_2O_5 and TiO_2 were doped in LaMnO_3 with different content. The systems such as LaMn_(1-x)Fe x O_3 , LaMn_(1-x)Ni_xO_3 , LaMn_(1-x)V_xO_3 ,LaMn_(1-x)Ti_xO_3 (0.1≤x 0.4) were prepared by conventional solid-state reaction at 1200℃≤for 2h in air. The NTC character of such samples was researched. And it was found thatρ25℃and the B value increase obviously when Ti~(4+) substitutes Mn~(3+).
Then the system(LaMn_(0.6)Ti_(0.4)O_3)with low resistivity, high B and good sintering way were selected to be doped with SrCO_3 , BaCO_3, CuO. The systems of La_(1-x)Srx Mn_(0.6)Ti_(0.4)O_3 ,La_(1-x)Ba x Mn_(0.6)Ti_(0.4)O_3 (0.1≤x≤0.6),LaMn_(0.6)Ti_(0.4)-yCuy O_3 (0.05≤y 0.2) were prepared by conventional solid-state reaction. The resistivity of samples changed with the temperature was measured from 25℃≤to 300℃.The X-ray diffractograms (XRD) of the samples were recorded and the microstructure was observed by scanning electron microscope (SEM). It was found that theρ-T curves of all the samples matched NTC characteristic. A new NTCR material with low resistivity(180Ω·cm ), high sensitivity to temperature change(B=3270K) and high stability can be get. And the conducting mechanism of the NTC material was studied with the semiconductor carriers mechanism.
引文
[1] 王卫民,赵 鸣,张慧君,NTC 热敏电阻材料组成及制备工艺研究进展,材料科学与工程学报,2005,23(2):286-289
[2]肖学华,NTC 热敏电阻温度传感器,通用元器件,1997,12:53-55
[3] 李言荣,恽正中,电子材料导论[M],北京:清华大学出版社,2001:384-388.
[4]Jin S, Tiefel T H., Thousandfold Change in Resistivity in Magneto resistive La-Ca-Mn-O Films. Science, 1994, 264 (15) ∶413- 415
[5]高濂,严东生,固体氧化物燃料电池,无机材料学报,1991,6(2):130-104
[6]HAMADA H., Electronic Bond Structure of La1- xBa x MnO3,J. Phys Chem Solids, 1995, 56(12) ∶1719- 1720
[7]王恩信,王鹏程,NTC热敏电阻器的现状与发展趋势,电子元件与材料,1997,16(4):1-9
[8] Juu Kamiyma, High thermistors resist high temprerature, JEE., 1990, 9: 90-92
[9]Yoshiharu Tanaka, Temperature sensors ploy Important roles in industry & society.JEE., 1990 , 8:60-63
[10]徐汇尼,广泛应用的负温度系数热敏电阻,传感器,2001,1:73
[11]Tetsu Miura , Thermistor’s sensitivity makes them desirable in many applications.JEE,1990,8:86～89
[12]曲远方等,功能陶瓷及应用,北京:化学工业出版社,2003,359-399
[13]黄昆,韩汝琦,《半导体物理基础》新华出版社,1979,1-2,60
[14]周东祥,刘树英等,NTC热敏陶瓷材料设计原理,电子元件与材料,1997,4(16):56-57
[15]Akinori Nakayama, Application of Lanthanum Cobaltite to Component for Excessive Inrush Current Suppression, IEEE,TC1-4, 338
[16]孙小龙,(Ba,Sr,Pb) Ti03-BaPbO3系统复合陶瓷的研究,[硕士学位论文],天津,天津大学,2002
[17]Jahn H A, Tell E.,Stability of Polyatomic Molecules in Degenerate Electronic States Orbital Degeneracy, Proc. Roy. Soc.A , 1937,161: 220-224.
[18]J. B. Goodenough, J. M. Lango., Crystallographic and magnetic properties of perovskite and perovskite–related compounds, News series VolⅢ/4a Springer, Berlin( 1970) .
[19]Minh N Q, Takahashi T., Science and Technology of Ceramic Fuel Cells. California, USA, 1995
[20]W. E. Pickett, D. J. Singh. Electronic structure and half-metalic transport in the La1-xCaxMn0 3 system,Phys. Rev. B, 1996, 53:1146-1160.
[21]A .Fujimori, Doping-induced changes in the electronic structure of La x Sr1-xTiO3: Limitation of the one-electron rigid-band model and the Hubbard model[J], Phys. Rev. B,1996,46:9841-9844.
[22] H. L. Yakel, On the structures of some compounds of the perovskite type, Acta Cryst,1955,8: 394-398.
[23]Jonker G.H. Van Santen J.H. Ferromagnetic compound of manganese with perovskite structure, Physica, 1950, 16:337-369.
[24]Zener C. Interaction between the d-shells in the transition metals [J]. Phys Rev, 1951, 8l: 403-405.
[25]Millis A.J, Littlewood P.B, Shraiman B.Double exchange alone does not explain the resistivity of La1-xSr xMnO, Phys Rev Lett, 1995, 74(25): 5144-5147
[26]Millis A.J, Shraiman B, Mueller R. Dynamic Jahn-Teller effect and colossal magnetoresistance in La1-xSrxMnO, Phys Rev Lett, 1996, 77(1): 1990-1992
[27]Roler H, Zamg J, Bishop A.P., Lattice effect in the colossal magnetoresistance manganites, Phys Rev Lett, 1996, 76: 1356-1359
[28]Alexandrov A.S., Bratkovsky A.M., Carrier density collapse and colossal mangnetoresietance in dope manganites, Phys Rev Lett, 1999, 82 (1): 141-144.
[29]Anderson P.W, Hasegawa H., Considerations on Double Exchange., Phys Rev, 1955,l00 (2): 675-681.
[30]DeGennes P.G., Effect of Double Exchange in Magnetic Crystals, Phys Rev, 1960, l18 (1): 141-154.
[31]Zhao G.M, Conder K, Keller H, Muller K.A. Giant oxygen isotope shift in the magnetoresistive perovskite La1-xCa x MnO3 , Nature, 1996, 381: 676-678.
[32]Radaelli P.G., Cox D.E,Marezio M,et al. Simultaneous structura1, magnetic and electronic transition in La1-xCaxMnO3 with x=0.25 and 0.50, Phys Rev. Lett. 1995 , 75 (24):4488-4491.
[33]Dai P,Zhang J,Mook H A,Experimental evidence for the dynamic Jahn- Teller effect in La 1-x Ca x MnO3 [J]. Phys Rev B, 1996, 54 (6):3694-3697.
[34]Kaplan S.G.,Quijada M,Drew H.D.,Optical evidence for the dynamicJahn-Teller effect in Nd1-xSr x MnO3 , Phys. Rev Lett.1996, 77 (10):2081-2084
[35]Jaime M,Salamon M B,Rubinstein,High-temperature thermopower in La1-xCaxMnO3 films:Evidence for polaron transport, Phys Rev B,l996,54 (I7): 11914-11917
[36]Jaime M, Hardner H.T. , Salamon M.B., Hall-effect sign anomaly and mall-polaron conduction in (La,Gd)1-xCa x MnO3[J]. Phys. Rev Lett., 1997,78 (5): 951-954
[37]Jaime M,Lin P.,Chun S.H., Coexistence of localized and itinerant carriers near TC in calcium-doped manganites[J] Phys Rev B,1999,60 (2):1028-1032.
[38]Kobayashi Y.,Murata S.,Tranquada J. M.,Magnetic and transport properties of LaCo1-xNi x O3 , comparison with La1-xSrxCoO3, J. Phys. Soc. Japan, 1999,68:1011-1017
[39]夏正材、唐超群,La1-xSrx MnO3阴及材料的导电机理,物理学报,1999,48:1591-1520
[40] 任清褒 LaMnO3不同晶位掺杂的磁电阻效应,西安交通大学学报,2004,38(6):645-649
[41]何泽明,PTC 陶瓷材料及金属/PTC 陶瓷复合材料研究,[硕士学位论文],天津;天津大学,1997
[42]Ahn K. H. , WU X. W., LIU K., Magnetic properties and colossal magnetoresistance of La(Ca)MnO3 materials doped with Fe, J. Phys. Rev(B),1996,54(21):15299-15302
[43]李宝河 钙钛矿型稀土锰氧化物La0.7Sr0.3Fe x Mn1-xO3的磁性和巨磁阻效应,中国稀土学报,2001,19(2):175-178
[44]Zbigniew T.a, Marta W., Janusz C., Magnetic and transport properties of Fe-substituted manganites La0.67Ca0.33Mn1-xFe x O3, J. Phys. B ,2003, 329: 721–722
[45]L.Seetha Lakshmi, V.Sridharan, D.V. Natarajan, e Double metal-insulator transitions and MR in La 0.67Ca0.33Mn1-xRux O3 (x≤0.10): a qualitative understanding in light of possible magnetic phase separation , Journal of Magnetism and Magnetic Materials, 2004, 279: 41–50
[46]A.N. Ulyanov, Seong-Cho Yu, Dong-Seok Yang, Mn-site-substituted lanthanum manganites: destruction of electron pathway and local structure effects on Curie temperature Journal of Magnetism and Magnetic Materials, 2004, 282: 303–306
[47]M.M. Xavier Jr., F.A.O. Cabral, J.H. de Araújo, Elect of Fe doping inpolycrystalline La0.7Sr0.3MnO3 on transport and magnetic properties Journal of Magnetism and Magnetic Materials, 2001, 226: 826-828
[48]Anthony Petric ,, Peng Huang, Frank Tietz, Evaluation of La–Sr–Co– Fe–O perovskites for solid oxide fuel cells and gas separation membranes, Solid State Ionics, 2000, 135: 719–725
[49]A. Fossdal, M.-A. Einarsrud, T. Grande, Mechanical properties of LaFeO3 ceramics, Journal of the European Ceramic Society, 2005, 25: 927–933
[50]D.P. Fagg , V.V. Khartona, J.R. Frade , Stability and mixed ionic– electronic conductivity of (Sr,La)(Ti,Fe)O3- δ perovskites, Solid State Ionics 2003, 156: 45– 57.
[51]R. Chiba , F. Yoshimura, Y. Sakurai, Properties of La1-ySr y Ni1-xFe x O3 as a cathode material for a low-temperature operating SOFC, Solid State Ionics, 2002, 152: 575– 582
[52]胡季帆,秦宏伟,王勇,大磁电阻材料La0.67Ca 0.33Mn1-xNixO3的研究,功能材料,2001,32(2):234-235
[53] A.E. Teplykh, A.N. Pirogov, A.Z. Menshikov, The crystal and magnetic structure of LaMn1-xVx O3 , Physica B 2000,276:574-575
[54] V.S. Kolat, H. Gencer, S. Atalay,Magnetic and electrical properties of La0.67Ca0.33Mn0.9V0.1O3 two-phase composite,Physica B, 2006,371: 199-204
[55]E.V. Tsipis , M.V. Patrakeev, V.V. Kharton, Transport properties and thermal expansion of Ti-substituted La1 ?x SrxFeO3 ?δ (x=0.5–0.7) , Solid State Sciences, 2005,7: 355–365.
[56]Hideki Taguchi, Masanori Sonoda, and Mahiko Nagao, Role of T etravalent Ion in Metal–Insulator Transition in (La0.1Ca0.9)(Mn1-xTix )O3, J. Solid State Chemistry, 1996, 126: 235–241.
[57]G. Nalini, M. Sahana, M.S. Hegde, Structure of the mixed oxides La0.6Pb0.4Mn1-yTiyO3 ± z(0 [58]Migaku Kobayashi , Ryouko Katsuraya , Syou Kurita , Synthesis and crystal structure of (Ca, R)(Mn, Ti)O3 (R, rare earth),J. Alloys and Compounds,2006, 408: 1173–1176.
[59]K.Y. Wang, J. Arcas, D.X. Chen, Formation of perovskite-type compounds La0.5Ca0.5 Mn1-xTixO3 (0 ≤ x≤0.5), Journal of Alloys and Compounds,1997, 252:126–128.
[60]Maignan A,Martin C,Ravean B., Substitution of manganese by rivalent and tetravalent elements in the CMR perovskites Pr1-x(Ca, Sr)x MnO3 ,J. Phys B,1997,102:19-24.
[61]Awana V P S,Schmitt E,Gmelin E,Effect of Zn substitution on para- to ferromagnetic transition temperature, J Appl. Phys,2000,87(9):5034-5036.
[62] N. Kallel, G. Dezanneau, J. Dhahri, Structure, magnetic and electrical behaviour of La 0.7Sr0.3Mn1-xTix O3 with 0 ≤ x≤0.3 Journal of Magnetism and Magnetic Materials, 2003,261: 56–65.
[63]Tetsuo Shimura, Toshimasa Hayashi, Yoshiyuki Inaguma, Magnetic and Electrical Properties of La1-xAx MnO3 (A= Na, K, Rb, and Sr) with Perovskite-Type Structure, J. Solid State Chemistry, 1996, 124: 250–263
[64]高湉,曹世勋,李文娟,Cu掺杂LaMn1-xCuxO3体系的磁转变和导电行为研究,物理学报,2006,55(7): 3692-3697
[65]刘兴民,唐贵德,刘力虎,La0.67Sr0.33-xCuxMnO3的室温磁电阻效应,材料科学与工程学报,2004, 22(1) :101-103
[66]Nguyen Chau, Pham Quang Niem, Hoang Nam Nhat, et al., Influence of Cu substitution for Mn on the structure, magnetic, magnetocaloric and magnetoresistance properties of La0.7Sr0.3MnO3 perovskites, Physica B, 2003, 327: 214–217
[67]Chahara K, Ohno T, Kasai M , et al. Magnetoresistanec effect of La0.75Ca0.25MnOx /YBa 2 Cu 3 O7 /La0.72Ca0.25MnOz trilayered films, J. Appl Phys Lett,1993,62:780.
[68] Prieto P,Vivas P,Campillo G,et a1.Magnetism and superconductivity in La0.7Ca0.3MnO3 /YBa 2 Cu 3 O7-delta superlattices, J. Appl Phys,2001,89:8026.
[2]肖学华,NTC 热敏电阻温度传感器,通用元器件,1997,12:53-55
[3] 李言荣,恽正中,电子材料导论[M],北京:清华大学出版社,2001:384-388.
[4]Jin S, Tiefel T H., Thousandfold Change in Resistivity in Magneto resistive La-Ca-Mn-O Films. Science, 1994, 264 (15) ∶413- 415
[5]高濂,严东生,固体氧化物燃料电池,无机材料学报,1991,6(2):130-104
[6]HAMADA H., Electronic Bond Structure of La1- xBa x MnO3,J. Phys Chem Solids, 1995, 56(12) ∶1719- 1720
[7]王恩信,王鹏程,NTC热敏电阻器的现状与发展趋势,电子元件与材料,1997,16(4):1-9
[8] Juu Kamiyma, High thermistors resist high temprerature, JEE., 1990, 9: 90-92
[9]Yoshiharu Tanaka, Temperature sensors ploy Important roles in industry & society.JEE., 1990 , 8:60-63
[10]徐汇尼,广泛应用的负温度系数热敏电阻,传感器,2001,1:73
[11]Tetsu Miura , Thermistor’s sensitivity makes them desirable in many applications.JEE,1990,8:86～89
[12]曲远方等,功能陶瓷及应用,北京:化学工业出版社,2003,359-399
[13]黄昆,韩汝琦,《半导体物理基础》新华出版社,1979,1-2,60
[14]周东祥,刘树英等,NTC热敏陶瓷材料设计原理,电子元件与材料,1997,4(16):56-57
[15]Akinori Nakayama, Application of Lanthanum Cobaltite to Component for Excessive Inrush Current Suppression, IEEE,TC1-4, 338
[16]孙小龙,(Ba,Sr,Pb) Ti03-BaPbO3系统复合陶瓷的研究,[硕士学位论文],天津,天津大学,2002
[17]Jahn H A, Tell E.,Stability of Polyatomic Molecules in Degenerate Electronic States Orbital Degeneracy, Proc. Roy. Soc.A , 1937,161: 220-224.
[18]J. B. Goodenough, J. M. Lango., Crystallographic and magnetic properties of perovskite and perovskite–related compounds, News series VolⅢ/4a Springer, Berlin( 1970) .
[19]Minh N Q, Takahashi T., Science and Technology of Ceramic Fuel Cells. California, USA, 1995
[20]W. E. Pickett, D. J. Singh. Electronic structure and half-metalic transport in the La1-xCaxMn0 3 system,Phys. Rev. B, 1996, 53:1146-1160.
[21]A .Fujimori, Doping-induced changes in the electronic structure of La x Sr1-xTiO3: Limitation of the one-electron rigid-band model and the Hubbard model[J], Phys. Rev. B,1996,46:9841-9844.
[22] H. L. Yakel, On the structures of some compounds of the perovskite type, Acta Cryst,1955,8: 394-398.
[23]Jonker G.H. Van Santen J.H. Ferromagnetic compound of manganese with perovskite structure, Physica, 1950, 16:337-369.
[24]Zener C. Interaction between the d-shells in the transition metals [J]. Phys Rev, 1951, 8l: 403-405.
[25]Millis A.J, Littlewood P.B, Shraiman B.Double exchange alone does not explain the resistivity of La1-xSr xMnO, Phys Rev Lett, 1995, 74(25): 5144-5147
[26]Millis A.J, Shraiman B, Mueller R. Dynamic Jahn-Teller effect and colossal magnetoresistance in La1-xSrxMnO, Phys Rev Lett, 1996, 77(1): 1990-1992
[27]Roler H, Zamg J, Bishop A.P., Lattice effect in the colossal magnetoresistance manganites, Phys Rev Lett, 1996, 76: 1356-1359
[28]Alexandrov A.S., Bratkovsky A.M., Carrier density collapse and colossal mangnetoresietance in dope manganites, Phys Rev Lett, 1999, 82 (1): 141-144.
[29]Anderson P.W, Hasegawa H., Considerations on Double Exchange., Phys Rev, 1955,l00 (2): 675-681.
[30]DeGennes P.G., Effect of Double Exchange in Magnetic Crystals, Phys Rev, 1960, l18 (1): 141-154.
[31]Zhao G.M, Conder K, Keller H, Muller K.A. Giant oxygen isotope shift in the magnetoresistive perovskite La1-xCa x MnO3 , Nature, 1996, 381: 676-678.
[32]Radaelli P.G., Cox D.E,Marezio M,et al. Simultaneous structura1, magnetic and electronic transition in La1-xCaxMnO3 with x=0.25 and 0.50, Phys Rev. Lett. 1995 , 75 (24):4488-4491.
[33]Dai P,Zhang J,Mook H A,Experimental evidence for the dynamic Jahn- Teller effect in La 1-x Ca x MnO3 [J]. Phys Rev B, 1996, 54 (6):3694-3697.
[34]Kaplan S.G.,Quijada M,Drew H.D.,Optical evidence for the dynamicJahn-Teller effect in Nd1-xSr x MnO3 , Phys. Rev Lett.1996, 77 (10):2081-2084
[35]Jaime M,Salamon M B,Rubinstein,High-temperature thermopower in La1-xCaxMnO3 films:Evidence for polaron transport, Phys Rev B,l996,54 (I7): 11914-11917
[36]Jaime M, Hardner H.T. , Salamon M.B., Hall-effect sign anomaly and mall-polaron conduction in (La,Gd)1-xCa x MnO3[J]. Phys. Rev Lett., 1997,78 (5): 951-954
[37]Jaime M,Lin P.,Chun S.H., Coexistence of localized and itinerant carriers near TC in calcium-doped manganites[J] Phys Rev B,1999,60 (2):1028-1032.
[38]Kobayashi Y.,Murata S.,Tranquada J. M.,Magnetic and transport properties of LaCo1-xNi x O3 , comparison with La1-xSrxCoO3, J. Phys. Soc. Japan, 1999,68:1011-1017
[39]夏正材、唐超群,La1-xSrx MnO3阴及材料的导电机理,物理学报,1999,48:1591-1520
[40] 任清褒 LaMnO3不同晶位掺杂的磁电阻效应,西安交通大学学报,2004,38(6):645-649
[41]何泽明,PTC 陶瓷材料及金属/PTC 陶瓷复合材料研究,[硕士学位论文],天津;天津大学,1997
[42]Ahn K. H. , WU X. W., LIU K., Magnetic properties and colossal magnetoresistance of La(Ca)MnO3 materials doped with Fe, J. Phys. Rev(B),1996,54(21):15299-15302
[43]李宝河 钙钛矿型稀土锰氧化物La0.7Sr0.3Fe x Mn1-xO3的磁性和巨磁阻效应,中国稀土学报,2001,19(2):175-178
[44]Zbigniew T.a, Marta W., Janusz C., Magnetic and transport properties of Fe-substituted manganites La0.67Ca0.33Mn1-xFe x O3, J. Phys. B ,2003, 329: 721–722
[45]L.Seetha Lakshmi, V.Sridharan, D.V. Natarajan, e Double metal-insulator transitions and MR in La 0.67Ca0.33Mn1-xRux O3 (x≤0.10): a qualitative understanding in light of possible magnetic phase separation , Journal of Magnetism and Magnetic Materials, 2004, 279: 41–50
[46]A.N. Ulyanov, Seong-Cho Yu, Dong-Seok Yang, Mn-site-substituted lanthanum manganites: destruction of electron pathway and local structure effects on Curie temperature Journal of Magnetism and Magnetic Materials, 2004, 282: 303–306
[47]M.M. Xavier Jr., F.A.O. Cabral, J.H. de Araújo, Elect of Fe doping inpolycrystalline La0.7Sr0.3MnO3 on transport and magnetic properties Journal of Magnetism and Magnetic Materials, 2001, 226: 826-828
[48]Anthony Petric ,, Peng Huang, Frank Tietz, Evaluation of La–Sr–Co– Fe–O perovskites for solid oxide fuel cells and gas separation membranes, Solid State Ionics, 2000, 135: 719–725
[49]A. Fossdal, M.-A. Einarsrud, T. Grande, Mechanical properties of LaFeO3 ceramics, Journal of the European Ceramic Society, 2005, 25: 927–933
[50]D.P. Fagg , V.V. Khartona, J.R. Frade , Stability and mixed ionic– electronic conductivity of (Sr,La)(Ti,Fe)O3- δ perovskites, Solid State Ionics 2003, 156: 45– 57.
[51]R. Chiba , F. Yoshimura, Y. Sakurai, Properties of La1-ySr y Ni1-xFe x O3 as a cathode material for a low-temperature operating SOFC, Solid State Ionics, 2002, 152: 575– 582
[52]胡季帆,秦宏伟,王勇,大磁电阻材料La0.67Ca 0.33Mn1-xNixO3的研究,功能材料,2001,32(2):234-235
[53] A.E. Teplykh, A.N. Pirogov, A.Z. Menshikov, The crystal and magnetic structure of LaMn1-xVx O3 , Physica B 2000,276:574-575
[54] V.S. Kolat, H. Gencer, S. Atalay,Magnetic and electrical properties of La0.67Ca0.33Mn0.9V0.1O3 two-phase composite,Physica B, 2006,371: 199-204
[55]E.V. Tsipis , M.V. Patrakeev, V.V. Kharton, Transport properties and thermal expansion of Ti-substituted La1 ?x SrxFeO3 ?δ (x=0.5–0.7) , Solid State Sciences, 2005,7: 355–365.
[56]Hideki Taguchi, Masanori Sonoda, and Mahiko Nagao, Role of T etravalent Ion in Metal–Insulator Transition in (La0.1Ca0.9)(Mn1-xTix )O3, J. Solid State Chemistry, 1996, 126: 235–241.
[57]G. Nalini, M. Sahana, M.S. Hegde, Structure of the mixed oxides La0.6Pb0.4Mn1-yTiyO3 ± z(0
[59]K.Y. Wang, J. Arcas, D.X. Chen, Formation of perovskite-type compounds La0.5Ca0.5 Mn1-xTixO3 (0 ≤ x≤0.5), Journal of Alloys and Compounds,1997, 252:126–128.
[60]Maignan A,Martin C,Ravean B., Substitution of manganese by rivalent and tetravalent elements in the CMR perovskites Pr1-x(Ca, Sr)x MnO3 ,J. Phys B,1997,102:19-24.
[61]Awana V P S,Schmitt E,Gmelin E,Effect of Zn substitution on para- to ferromagnetic transition temperature, J Appl. Phys,2000,87(9):5034-5036.
[62] N. Kallel, G. Dezanneau, J. Dhahri, Structure, magnetic and electrical behaviour of La 0.7Sr0.3Mn1-xTix O3 with 0 ≤ x≤0.3 Journal of Magnetism and Magnetic Materials, 2003,261: 56–65.
[63]Tetsuo Shimura, Toshimasa Hayashi, Yoshiyuki Inaguma, Magnetic and Electrical Properties of La1-xAx MnO3 (A= Na, K, Rb, and Sr) with Perovskite-Type Structure, J. Solid State Chemistry, 1996, 124: 250–263
[64]高湉,曹世勋,李文娟,Cu掺杂LaMn1-xCuxO3体系的磁转变和导电行为研究,物理学报,2006,55(7): 3692-3697
[65]刘兴民,唐贵德,刘力虎,La0.67Sr0.33-xCuxMnO3的室温磁电阻效应,材料科学与工程学报,2004, 22(1) :101-103
[66]Nguyen Chau, Pham Quang Niem, Hoang Nam Nhat, et al., Influence of Cu substitution for Mn on the structure, magnetic, magnetocaloric and magnetoresistance properties of La0.7Sr0.3MnO3 perovskites, Physica B, 2003, 327: 214–217
[67]Chahara K, Ohno T, Kasai M , et al. Magnetoresistanec effect of La0.75Ca0.25MnOx /YBa 2 Cu 3 O7 /La0.72Ca0.25MnOz trilayered films, J. Appl Phys Lett,1993,62:780.
[68] Prieto P,Vivas P,Campillo G,et a1.Magnetism and superconductivity in La0.7Ca0.3MnO3 /YBa 2 Cu 3 O7-delta superlattices, J. Appl Phys,2001,89:8026.