La0.60Sr0.40-xNaxMnO3钙钛矿材料在室温附近磁电阻的温度稳定性

采用溶胶-凝胶法(sol-gel)制备了名义组分为La0.60Sr0.40-xNaxMnO3(x=0.00,0.10,0.15,0.20,0.30,0.33,0.35)的类钙钛矿型稀土锰氧化物多晶样品。发现用Na+替代部分Sr+2后,可使样品的居里温度降至室温附近,并且使样品的室温磁电阻比替代前明显增大。在1.8T的磁场作用下,样品La0.60Sr0.07Na0.33MnO3在292K时磁电阻为24.4%,比不含Na的La0.60Sr0.40MnO3增大了2.8倍;样品La0.60Sr0.25Na0.15MnO3在285K～345K温区内磁电阻保持在3.9%(±0.2%)左右,受温度影响不大,因此显著提高了样品的室温磁电阻和其温度稳定性。迄今为止还未见这类材料在室温附近具有如此宽范围和高温度上限的MR温度稳定性报道。这对于该类磁电阻材料的应用有很大意义。     

Nb5+的掺杂对La0.67Sr0.33MnO3磁性和传输性的影响

将用溶胶-凝胶法制备的La0.67Sr0.33MnO3(LSMO)微粉与(Nb2O5)x/2粉在1100℃下混合烧结,形成了具有钙钛矿结构的锰氧化物与LaNbO4的复合体系,x是掺入的Nb5 离子与母体材料的摩尔比.在x=0.07的样品中得到最大电阻率为23.74 Ω·cm,比LSMO 高三个数量级.Nb5 离子的掺杂使样品的低场磁电阻(LFMR)和高场磁电阻(HFMR)效应都有所增强.77 K下,0.1 T和1 T磁场下在x=0.07 样品中分别得到24 % 和33.8 %的磁电阻效应,是LSMO样品的2倍和1.7倍.室温下x=0.05样品的磁电阻最大,为9 %.其中,LFMR来源于颗粒晶界处电子的自旋相关隧穿及散射作用,而HFMR来源于表面层的自旋非共线结构.     

La0.67Sr0.33-xAgxMnO3的室温磁电阻效应

采用溶胶-凝胶(sol-gel)法制备了名义组分为La0.67Sr0.33-xAgrMnO3(x=0.15、0．20)的多晶样品,发现用Ag部分替代Sr后样品的室温磁电阻比替代前明显增大。在1．8T下,La0．67Sr0.18Ag0.15MnO3样品的磁电阻在330K出现峰值,其峰值为35％;对于La0．67Sr0.13Ag0.2 MnO3样品,磁电阻峰值为26％．且峰的宽度较大,在290～315K之间的磁电阻随着温度变化不大．因此显著提高了室温时样品的磁电阻和磁电阻的温度稳定性,另外．还提高了样品的磁场灵敏度。这对磁电阻的应用有很大意义。     

Nb5+的掺杂引起La0.67Sr0.33MnO3增强的磁电阻效应

将Nb2O5掺杂到用溶胶-凝胶法制备的La0.67Sr0.33MnO3(LSMO)微粉中,XRD测量结果表明所有样品均为单相菱面结构.随着Nb5 掺杂量的增加,材料电阻率发生显著变化.在x=0.06的掺杂样品中得到最高为1110Ω·cm电阻率(x是掺入的Nb离子与母体材料的摩尔比),比LSMO高5个数量级,这是由于晶界处以及颗粒内部增加的自旋相关的散射和隧穿效应所致.Nb5 离子的掺杂使样品的低场磁电阻(LFMR)和高场磁电阻(HFMR)效应都有所增强.77K下,0.1和1T磁场下在x=0.07样品中分别得到25%和42%的磁电阻效应,分别是LSMO样品的2倍和1.7倍.室温下x=0.03样品的磁电阻最大,为7%.其中,LFMR来源于颗粒晶界处电子的自旋相关隧穿及散射作用,而HFMR来源于表面层的自旋非共线结构.     

La0.67Ba0.33MnO3中Ag的掺杂效应

在溶胶-凝胶法制备的La0.67 Ba0.33 MnO3(LBMO)微粉中掺入Ag2O粉,制成一系列(LBMO)／(Ag2O)x／2(x=0～0．35,为摩尔比)掺杂材料,实验结果发现Ag掺杂可明显降低材料的电阻率。当掺Ag量为x=0．25时,样品的电阻率达到最低值。同时在居里点附近,样品的峰值磁电阻得到显著增强。微量的Ag掺杂有助于提高样品的自旋相关隧穿磁电阻,使低场磁电阻得到显著增强。     

La0.67Sr0.33MnO3中Bi的掺杂效应

将Bi2O3掺杂到用溶胶—凝胶法制备的La0.6Sr0．33MnO3(LSMO)微粉中,XRD测量结果证实有过量的Bi析出。随着Bi掺杂量的增加,LSMO／(Bi2O3)x/2材料电阻率发生明显变化,在x=(0—0．10)摩尔比的掺杂范围内,电阻率先上升后突然下降。当X=0．1时,电阻率比未掺杂样品下降了一个数量级。Bi掺杂对低温和室温磁电阻有着完全不同的影响。低温下,随掺杂量增加,磁电阻下降;室温下Bi的微量掺杂可以使磁电阻增大,掺入x=0.03Bi使室温磁电阻由-4.4％提高到-5．6％。     

La_(0.60)Sr_(0.40-x)K_xMnO_3系列材料的磁电阻效应

利用溶胶-凝胶法(sol-gel)制备了多晶类钙钛矿型稀土锰氧化物La0.60Sr0.40-xKxMnO3(x=0.00,0.15,0.20,0.30)。发现K+取代部分Sr2+后,可使样品的居里温度降至室温附近,并且使样品的室温磁电阻比替代前明显增大。在1.8T的磁场下,x=0.30的样品磁电阻峰值为21%,相应的峰值温度为304K。而母体La0.60Sr0.40MnO3的磁电阻峰值仅为6.4%,峰值温度为373K。可见K+离子替代使室温附近样品的庞磁电阻效应有了明显的改善。     

Ti掺杂对La0.67Ba0.33MnO3磁性和磁电阻影响

系统地研究了Ti掺杂对La0.67Ba0．33MnO3颗粒材料磁性、电性和磁电阻效应的影响，随着Ti含量的增加，材料的磁化强度和居里温度快速下降，电阻率急剧增大，电阻率的峰值逐渐向低温移动。Ti的掺杂对材料低温下低场磁电阻影响不大，主要是显著提高了材料的本征磁电阻。1％的Ti掺杂使材料的室温磁电阻得到显著增强，1T磁场下，室温磁电阻达到-8．4％，比未掺杂的La0.67Ba0．33MnO3材料增强了50％。     

LaMnO3的A位二元掺杂对磁电阻效应的调制和提高

基于探讨钙钛矿型锰氧化物磁电阻效应的目的,样品采用固相反应法制备,主要就LaMnO3的A位二元掺杂对磁电阻效应的影响作比较研究,发现(La1-xRx)0.67T0.33MnO3(T为Ca,Sr;R为Sm,Gd,Tb,Y)随x的增加,Tp和Tc逐渐降低,ρm和磁电阻值迅速增加,均可用晶格效应来解释;La0.67Sr0.33-xCuxMnO3(0≤x≤O.33)的Tp随x的增加而下降,室温磁电阻值明显增大还提高了其温度稳定性,是因A位平均离子半径和A位离子的失配度起主要作用;La0.67(Ba1-xCax)0.33MnO3(x=0,0.40,0.45,0.55,0.60,1.00)的ρ-T变化呈现双峰特性,在O.4 T的磁场下,在77 K～230 K的温区内,磁电阻随T的升高而单调下降,可用晶界效应来解释,在Tc附近出现峰值磁电阻,这种高温磁电阻变化行为可用DE模型及非磁无序来说明;La0.5Ca0.5-xBaxMnO3(0≤x≤0.50)系列样品,当x≥0.14时随x的增加Tp升高,Tp处的峰值电阻逐渐减小,在5 T的磁场下,x≤0.20时磁电阻随T的降低先增大后减小再增大,峰值在Tp附近,x≥0.20时磁电阻随T降低而线性增加,其原因是相邻Mn离子间存在铁磁性和反铁磁性两种效应相互竞争.     

La0.6Sr0.15Na0.1□0.15MnO3+xAgNO3复合体系的结构、磁性及磁电阻的温度稳定性研究

采用固相反应法制备了La0.6Sr0.15Na0.1□0.15MnO3+xAgNO3(x=0.08、0.16、1.00,x为物质的量比,□代表空位)系列复合材料样品,对复合样品的相结构、磁性质及其磁电阻效应进行了研究。通过相结构的研究发现:复合样品近似呈现La0.6Sr0.15Na0.1□0.15MnO3/Ag/Mn3O4的特殊复合结构。通过对磁电阻的研究发现:复合样品不同程度地提高了母体样品的MR峰值,降低了峰值温度,使其更接近室温。在204～280K的温度范围内和1.8T外磁场作用下,当x=0.08时,MR保持在(4.70±0.25)%;x=0.16时,MR保持在(7.20±0.28)%。所以,复合样品较之母体样品,磁电阻的温度稳定性有了很大提高。     

The Tb Doping Effect on the Room Temperature Magnetoresistance in (La1-xTbx)0.67Sr0.33MnO3 (x≤ 0.4)

by Tb in (La1-xTbx)0.67Sr0.33MnO3, the room temperature magnetoresistance △R/R0 drops at first, then undergoes an increase near x≈0.1, and finally drops again. The value of room temperature magnetoresistance at a field H=12 kOe for (La1-xTbx)0.67Sr0.33MnO3 is -3.56%. The enhancement of the room temperature magnetoresistance induced by an appropriate Tb substitution in (La1-xTbx)0.67Sr0.33MnO3 is correlated with the shifts of the Curie temperature and metal-insulator temperature to near room temperature. The drop of the room temperature magnetoresistance at large Tb doping-contents may be due to its lower TC and TMI far from the room temperature.     

Research on a New Process of Preparation for Nano-SiO2 with High Activity and Mesopores

Nano-SiO_2 with high activity and mesopores was prepared through sol-gel synthesis followed by low-temperatureheat treatment and ball milling firstly in our experiments. TEM was performed to measure particle sizes. Nitrogenadsorption experiments were carried out to estimate specific surface area, porous distribution and porous ratio by BETand BJH methods. The content of Si-OH in SiO_2 surface was calculated by analysis of the results of hydrogen-oxygencontent mensuration (HOCM). As a result, appropriate heat treatment system and ball milling time are important topreparation for nano-SiO_2 with high activity and mesopores, which are 5～50 nm particles, 5～6 nm average aperture,85%～93% porous ratio, and 51%～55% Si-OH content in surface. Nano-SiO_2 with that structure has high surfaceenergy and activity. This process, which has simple facilities and operation rules, is a new way of preparation fornano-SiO_2 with high activity and mesopores.     

Ag／La0.67Sr0.33MnO3/Pt异质结构的电阻开关特性

采用脉冲激光沉积技术在Pt／Ti／SiO2／Si（100）衬底上制备出多晶La0.67Sr0.33MnO3（LSMO）薄膜,对其电脉冲致非挥发可逆电阻开关特性进行研究．结果表明,Ag/LSMO／Pt结构具有明显的室温电脉冲诱发电阻开关特性,且在宽电压脉冲作用下表现出较低的开关电压和较快的变阻饱和速度．由此可见,总脉冲能量或电荷（电流作用）为该结构的电阻开关效应提供驱动力．对Ag／LsMO／Pt结构进行了耐久性测试,表明该结构具有良好的疲劳特性与保持特性,可应用于新型不挥发存储器、传感器及可变电阻等电子元器件的研制     

Piezoresistivity in films of nanocrystalline manganites

Rare earth manganites having perovskite structure are susceptible to lattice strain. So far most investigations have been done with hydrostatic pressure or biaxial strain. We have observed that hole doped rare-earth manganites, which are known to display colossal magnetoresistance (CMR) also show change in its resistance under the influence of uniaxial strain. We report the direct measurement of piezoresistive response of La0.67Ca0.33MnO3 (LCMO) and La0.67Sr0.33MnO3 (LSMO) of this manganite family. The measurements were carried out on nanostructured polycrystalline films of LCMO and LSMO grown on oxidized Si(100) substrates. The piezoresistance was measured by bending the Si cantilevers (on which the film is grown) in flexural mode both with compressive and tensile strain. At room temperature the gauge factor approximately 10-20 and it increases to a large value near metal-insulator transition temperature (Tp) where the resistivity shows a peak.     

La0.67Sr0.33-xCuxMnO3的室温磁电阻效应

采用溶胶一凝胶(sol-gel)法制备了名义组分为La0.67Sr0.33-XCuXMnO3(x=0～0.33)的多晶样品,发现用Cu替代少部分Sr后样品的室温磁电阻比替代前的明显增大.在1.8T磁场作用下,当x＝0.15时,磁电阻峰值为27.7%,峰值温度为306K,当温度低于306K时磁电阻值随温度的升高而增大,当温度高于306K时磁电阻值随温度的升高而减小;当x＝0.1时,在295K-310K温度之间磁电阻值达19%左右,受温度影响很小;因此在提高了室温磁电阻值的同时,又提高了磁电阻的温度稳定性.这对于该类磁电阻材料的应用具有很大意义.     

Microwave assisted hydrothermal synthesis and magnetocaloric properties of La0.67Sr0.33MnO3 manganite

We report microwave assisted hydrothermal synthesis and magnetocaloric properties of La0.67Sr0.33MnO3 manganite. The synthesized La0.67Sr0.33MnO3 nanoparticles was characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS) and magnetization measurements. The XRD results indicated that La0.67Sr0.33MnO3 nanoparticles have polycrystalline nature with monoclinic structure. FE-SEM results suggested that La0.67Sr0.33MnO3 nanoparticles are assembled into rod like morphology. Magnetization measurements show that La0.67Sr0.33MnO3 nanoparticles exhibit transition temperature (Tc) above room temperature. The maximum magnetic entropy change (deltaS(M))max was found to be 0.52 J/kg K near Tc approximately 325 K at applied magnetc field of 20 kOe. This compound may considered as potential material for magnetic refrigeration near room temperature.     

异质结构掺锰氧化物（La0.60Sr0．4-xNaxMnO3）的磁电阻研究术

利用掺杂锰氧化物La0.60Sr0.05Na0.05MnO3和La0.60Sr0.15Na0.25MnO3两种块体材料串联焊接成异质结构样品,其磁电阻在不同温度出现两个峰值。得到启示：选取一系列磁电阻峰值在不同温度的材料,制成异质结构样品多层膜,适当调整各层膜厚度的比例,可以使多层膜的磁电阻在一个较宽的温度区间内保持基本稳定,并且有较好的磁场灵敏度,从而成为较好的磁电阻磁场传感器。     

La0.67 Ca0.33 MnO3和La0.67 Ba0.33 MnO3中Dy的置换作用

在La0.67Ca0.33MnO3和La0.67Ba0.33MnO3中用Dy对La进行了置换研究。结果发现，随掺Dy量的增加，两类材料的居里温度和金属-绝缘体相变温度单调下降，峰值电阻率单调增加。在Ca系样品中，掺入13％的Dy后，在5T的磁场下，最大磁电阻比达到7900％。在Ba系样品中．掺Dy对磁电阻的影响要小得多。掺Dy对材料性质的影响可以用晶格效应来解释，但晶格效应产生的作用与碱土离子的品种有明显关系。