(La1-xREx)2/3Sr1/3MnO3(RE=Y,Sm,Eu,Tb;x=0.1～0.5)的晶体结构及磁性质研究

采用空气中固相反应烧结法制备了一系列钙钛矿结构的(La1-xREx)2/3Sr1/3MnO3(RE=Y,Sm,Eu,Tb;x=0.1～0.5)稀土锰氧化物多晶样品.X射线衍射(XRD)分析表明掺杂RE部分替代La以后,样品的晶体结构为正交结构,空间群为Pbmm.在室温(300K)和液氮温度(77K)下分别测试了样品的磁性质,发现磁性质的改变与RE的掺入量以及RE的离子半径有关.在掺Tb的样品中明显存在巨磁电阻效应,磁场为2 T,温度为300和77 K分别测得(La0.6Tb0.4)2/3Sr1/3MnO3和(La0.7Tb0.3)2/3Sr1/3MnO3的磁电阻(MR)为80%和85%.随着Tb掺杂量的增加,在不同的磁场下,样品电阻-温度关系曲线的峰均向高温方向移动.     

La0.7Ca0.3MnO3薄膜庞磁电阻(CMR)现象的分析

针对La0.7Ca0．3MnO3薄膜材料中磁团簇的特性及其对材料庞磁电阻(CMR)现象的影响进行了研究。根据实验数据，利用Wagner等提出的数学模型，对La0.7Ca0.3MnO3薄膜中的磁团簇随温度的变化行为特性进行了研究；通过对La0.7Ca0．3MnO3薄膜相关实验数据的拟合，发现La0．7Ca0．3MnO3薄膜的居里温度范围应当在245～250K之间，从而进一步缩小了该材料居里温度的误差范围；还通过计算MR随磁团簇总角量子数J的变化，研究了制约和影响MR值的主要因素，发现磁团簇尺寸在La0．7Ca0.3MnO3薄膜的CMR现象中扮演了重要角色。     

脉冲激光沉积制备La0.62Ca0.29K0.09MnO3外延膜及其磁热性能

采用脉冲激光沉积法在单晶SrTiO3(STO)基底上制备了La0.62Ca0.29K0.09MnO3(LCKMO)薄膜,通过调控基底温度获得了平整致密的膜层.利用二维面探X射线衍射仪和高分辨透射电子显微镜对薄膜结构进行了表征.结果表明,薄膜呈高质量取向外延生长,对应关系为{001}LCKMO||{001}STO.对薄膜的磁热性能研究表明,5 T下最大磁熵变为3.45 J/(kg·K),相对制冷效率为379.5 J/kg,磁熵半峰宽为110 K.     

IrO_2掺杂对La_(0.7)Ca_(0.2)Sr_(0.1)MnO_3室温磁电阻效应的增强

将IrO2掺杂到固相反应法制备的La0.7Ca0.2Sr0.1MnO3(LCSMO)微粉中,制备了(1-x)La0.7Ca0.2Sr0.1MnO3+xIrO2(LCSMO/IrO2)复合体系。通过X射线衍射(XRD)、振动样品磁强计(VSM)以及直流四探针法测试,对复合材料的结构及性能进行了研究。结果发现,在复合体系中,一部分Ir4+离子取代了B位的Mn4+离子,另一部分以IrO2氧化物的形式存在于颗粒的边界处。随着IrO2掺杂量的增加,样品的比饱和磁化强度(σs)快速下降,而居里温度(TC)先下降后上升,电阻率也发生显著变化。与此同时,IrO2的掺杂使样品的低场磁电阻效应(LFMR)和高场磁电阻效应(HFMR)都有所增强,在H=3 kOe,T=307 K,x=5%的样品磁电阻达到11.65%;同样对于x=5%的样品,在H=2 T,T=295 K,磁电阻达到28%,室温磁电阻得到显著增强,这可能与本征磁电阻效应的特点及材料的TC和相变温度接近室温有关,另外掺杂物本身的特性对磁电阻的增强也有一定的影响。     

铜含量对La2/3Sr1/3MnO3的电输运及磁电阻的影响

先用溶胶-凝胶法制备出La2/3Sr1/3MnO3的颗粒系统, 然后用化学的方法将Cu材料引入到La2/3Sr1/3MnO3的颗粒表面, 形成(1-x)La2/3Sr1/3MnO3/xCu (x≤0.05)的复合样品. 实验表明 Cu含量较低(x＜0.02)时, 复合样品电阻率较大, 仅在低温区表现出大的磁电阻效应, Cu含量较高(x＞0.025)时, 复合样品的电阻率较小(～10-2 Ω·cm), 在室温附近(270～300 K)、 3 T的磁场下, 表现出较大的不随温度变化的磁电阻效应～10%.     

微观结构对溶胶-凝胶法合成的La0.67Sr0.33MnO3电磁性能影响

采用溶胶-凝胶法制备了不同烧结温度的钙钛矿类锰氧化物La0.67Sr0.33MnO3样品。实验结果表明,在1573 K以上烧结的样品,晶粒出现异常长大,晶界效应明显。随着烧结温度的提高,磁化强度逐渐增大,但样品的居里温度基本不变。此外,在1173和1573 K温度下烧结的样品,均出现了低于居里温度的金属-半导体导电行为转变。在合适的烧结条件下,可以观察到隧道磁电阻(TMR)和超大磁电阻(CMR)2种磁电阻效应。实验表明,自旋电子的输运,不仅与样品平均粒径的大小和密度有关,而且与晶界的微观结构有密切关系。     

钙钛矿锰氧化物(La_(1-x)Gd_x)_(0.5)Sr_(0.5)MnO_3的磁电阻效应

采用传统的高温固相法制备了多晶样品(La1-xGdx)0.5Sr0.5MnO3(x=0,0.1,0.2,0.3,0.4),利用X射线衍射仪(XRD)、超导量子磁强计(SQUID)、标准四端引线法分别对样品结构、磁性、电性以及磁电阻效应进行了研究。研究表明:Gd的少量替代并没有引起结构变化;随着Gd含量的增加,所有样品的居里温度TC和金属-绝缘体转变温度Tp都降低了;在TC附近发现了磁电阻效应,同时在低温下发现了更大的磁电阻;并且Gd的少量替代可使磁电阻MR增大。     

稀土(Sm,Gd,Dy)代换镧对La0.7Sr0.3MnO3磁电性质的影响及室温CMR的增强

用固相反应法制备了La0.7-xSm,Sr0.3MnO3,La0.7-x,GdxSr0.3MnO3和La0.7-xDyxSr0.3MnO3(x=0.00,0.10,0.20,0.30)系列样品.通过M-T'曲线,ρ-T曲线,研究了用稀土离子代换La对La0.7Sr0.3MnO3磁电性质和磁电阻的影响.结果表明:稀土离子代换La引起的晶格畸变和稀土离子的额外磁性对钙钛矿锰氧化物的磁电性质影响很大;稀土离子代换La是改变钙钛矿锰氧化物居里温度和增强MR的有效途径;适量稀土离子代换La可以在室温附近产生大的磁电阻.     

Dy_3NiSi_2合金磁相变与磁热性能研究

通过对Dy_3NiSi_2合金样品的X射线粉末衍射谱、等温变磁磁化曲线、等磁场变温磁化曲线分析,主要研究了合金的相结构和晶格参数、磁相变属性和磁热性能。X射线衍射谱表明Dy_3NiSi_2样品几乎为Gd_3NiSi_2型正交结构(空间群:Pnma, No.62)的单相合金,其晶格常数分别为a=1.1242(3) nm,b=0.41073(3) nm,c=1.1223(9) nm。在45～300 K温度范围内, Dy_3NiSi_2合金仅展现出铁磁-顺磁相变, 0.01 T磁场下的dM/dT和0～2 T磁场下的Arrott图表明, Dy_3NiSi_2合金的磁相变为居里温度T_c=54 K的铁磁-顺磁二级磁相变。在0～2 T磁场范围内, Dy_3NiSi_2合金居里温度处的最大磁熵变为3.65 J·(kg·K)~(-1),相对制冷量为167.9 J·kg~(-1)。     

La—Sm—Ca—Mn—O的晶格效应

在La0.67Ca0.33MnO3氧化物中进行了掺Sm研究,结果发现,随着Sm掺入量的增加,材料的金属-绝缘体相变温度逐渐降低,对应的峰值电阻急剧增大,居里温度逐渐下降,材料的磁电阻比迅速增加。对Sm掺杂的作用可以用晶格效应来解释。     

Enhanced ferromagnetic transition and magnetoresistance in granular Ag-added La0.7Ca0.3MnO3

Granular Ag-added La_0.7Ca_0.3MnO₃ (LCMO) samples were prepared by a sol-gel chemical route. Significant enhancements in Curie temperature (T_C), metal−insulator transition (T_p) and magnetoresistance (MR) effects near room temperature are observed in as-obtained samples. 10 wt% addition of Ag in LCMO causes T_C shift from 272 to 290 K, T_p boost up for more than 100 K and resistivity decrease by more than 3 orders of magnitude. X-ray diffraction patterns, thermal analysis and energy dispersive analysis of X-rays evidently show the existence of metal silver in LCMO matrices. High-resolution electron microscopy illustrates a well crystallization for LCMO grains in existence of Ag. It is argued that improved grain boundary effect and better crystallization caused by Ag addition are responsible for the enhancements.     

Structural and magnetic anomalies among the spin-chain compounds, Ca3Co1+xIr1?xO6

The results of X-ray diffraction, andac anddc magnetisation as a function of temperature are reported for a new class of spin-chain oxides, Ca₃Co_1+x Ir_1−x O₆. While thex = 0.0, 0.3, 0.5 and 1.0 are found to form in the K₄CdCl₆-derived rhombhohedral (space group ) structure, thex = 0.7 composition is found to undergo a monoclinic distortion in contrast to a literature report. Apparently, the change in the crystal symmetry withx manifests itself as a change in the sign of paramagnetic Curie temperature for this composition as though magnetic coupling sensitively depends on such crystallographic distortions. All the compositions exhibit spin-glass anomalies with an unusuallylarge frequency dependence of the peak temperature inac susceptibility in a temperature range below 50 K, interestingly obeying Vogel-Fulcher relationship even for the stoichiometric compounds. Dedicated to Professor C N R Rao on his 70th birthday     

Synthesis and Properties of Highly Conductive Thin Films as Buffer Layer from Sol-Gel Process

We prepared epitaxial growth SrRuO₃ thin film on LaAlO₃ (001) (LAO) single crystal substrate and highly oriented BaTiO₃ ferroelectric thin film on the epitaxial SrRuO₃ thin film. A homogeneous precursor solution for preparing SrRuO₃ thin film was prepared with Sr(O—i—C₃H₇)₂ and Ru(NO)(NO₃)₃ as starting materials, and 2-methoxy ethanol as solvents. The as-coated thin films were heat treated at temperatures from 723 to 1273 K for 1 h in air. SrRuO₃ grew epitaxially on LAO(001) substrate, which were confirmed by XRD theta-2theta method and XRD pole figure analysis. The crystallographic relationship of the film and substrate was SrRuO₃(001) parallel to LAO(001) and SrRuO₃[110] parallel to LAO[100]. A homogeneous precursor solution for preparing BaTiO₃ thin film was prepared with Ti[O—n—(CH₂)₃CH₃]₄ and Ba(OCOCH₃)₂ as starting materials, and acetic acid, 2-methoxy ethanol. SrRuO₃ coated LAO substrates were coated by spin-coating method with the coating solution. The as-coated thin films were heat treated at temperatures from 973 to 1173 K in air. It was confirmed that the thin films were growing orientated for c-axis by measurement of XRD theta-2theta method.     

低温合成超导体Ba1-xKxBiO3

先以BaCO₃和Bi₂O₃为原料由传统的固相反应制备纯BaBiO₃,然后在低温下将用KOH-KF熔盐处理这样的拓扑反应合成了Ba_1-xK_xBiO₃超导体. 所有样品均进行了粉末X射线衍射（XRD）和磁性表征. XRD结果表明,所得Ba_1-xK_xBiO₃样品均为纯相,且均可用赝立方晶胞指标化. 磁性测量表明所有样品具有超导电性,最高超导转变温度（T_c）为30.6 K. 讨论了反应时间、前驱体与熔盐质量比对超导转变温度的影响. 最佳的反应条件为：反应温度450 ℃,反应时间4 h,BaBiO₃：KOH：KF质量比1：5：2.5.     

Epitaxial Growth of Sr x Ba1 − x Nb2O6 Thin Films Prepared from Sol-Gel Process

In this study, we prepared Sr _x Ba_{1 – x} Nb₂O₆ (x = 0.3, 0.5 and 0.7) thin film on 0.75 wt% La doped SrTiO₃ (100) and (110) single crystal substrates. A homogeneous coating solution was prepared with Sr and Ba acetates and Nb(OEt)₅ as raw materials, and acetic acid and diethlene glycol monomethyl ether as solvents. The substrates were coated with the solution by spin coating method. As-coated thin films were heated from 973 to 1273 K in air. The grains of the thin film on La doped SrTiO₃ (100) were pillar shaped and arranged in right angle to each other. On the other hand, the grains of these thin films on La doped SrTiO₃ were pillar shape and arranged in one direction. The crystallographic relationship of the thin film between Sr _x Ba_{1 – x} Nb₂O₆ and substrate that the 130 and 310 direction of the thin film on the substrate were oriented with c-axis in parallel to the substrate surface. On the other hand, (hk0) phase diffractions of Sr _x Ba_{1 – x} Nb₂O₆ thin film on the substrate (110) were investigated in the XRD theta-2theta measurement. It is expected that the Sr _x Ba_{1 – x} Nb₂O₆ (x = 0.3, 0.5 and 0.7) were highly oriented or epitaxial growing on La doped SrTiO₃ (110) single crystal substrate.     

高色纯度高热稳定性红色荧光粉Sr3La2Ge3O12:Sm^3+的合成及其性能

通过高温固相法合成了一系列Sr3La2-xGe3O12:xSm^3+(0≤x≤0.04)红色荧光粉,并对样品的形貌、元素组成、晶体结构、发光性能及热稳定性进行了探究。结果表明:样品Sr3La2Ge3O12:xSm^3+为较宽尺寸分布的颗粒,且结构中仅含有Sr、La、Ge、O、Sm等元素。样品Sr3La1.97Ge3O12:0.03Sm^3+的Rietveld结构精修图与实测XRD图完全吻合,具有六方晶系结构。漫反射测试结果显示基质Sr3La2Ge3O12的带宽为5.54 eV,属于宽带隙材料。在404 nm激发下,样品Sr3La2-xGe3O12:xSm^3+(0≤x≤0.04)的最大发射峰位于601nm处,属于Sm^3+的6H5/2→4L13/2能级跃迁。此外,样品Sr3La1.97Ge3O12:0.03Sm^3+的发光性能最佳,其CIE色坐标为(0.5321,0.4601),色纯度高达94.2%,在298-473 K范围内具有较好的热稳定性,测试温度达到423 K时发射强度仍为室温时的81.6%。     

钙钛矿型稀土锰氧化物La0.7Sr0.3FexMn1—xO3的磁性和巨磁电阻效应

采用溶胶-凝胶工艺制备了La     

低浓度甲烷甲醇深度氧化Ag/La0.6Sr0.4MnO3催化剂

Ag-modified La0.6Sr0.4MnO3 catalysts were prepared and their catalytic performance for deep oxidation of CH4 and CH3OH at low concentrations were investigated. The results showed that the La0.6Sr0.4MnO3 host catalyst with the perovskite-type nano-crystallite structure displayed considerably high catalytic activity for deep oxidation of CH4 and CH3OH at low concentrations. Ag modification to the La0.6Sr0.4MnO3 host catalyst resulted in significant enhancement of the catalyst activity, making the T95 (the reaction temperature needed for conversion of 95%of CH4 or CH3OH) lowered down to 735K (for CH4) and 421K (for CH3OH) from 813 and 465 K over the Ag-free system under the reaction conditions:0.1MPa,CH4/O2/N2=2/12/86(molar ratio),GHSV=45000 h-1 and CH3OH/O2/N2= 0.2/1.0/98.8 (molar ratio),GHSV=58000 h-1,respectively.The carbon containing product was almost CO2 and the contents of HCHO and CO in the reaction exit gas were both under GC detectable limit in both cases.
The results of spectroscopic characterization indicated that modification by proper amount of Ag-dopant did not change the perovskite structure of the La0.6Sr0.4MnO3 host catalyst as a whole. Interaction of Ag-dopant with the surface of the host catalyst,La0.6Sr0.4MnO3,was in favor of high dispersion of the Ag component at the catalyst surface and led to the oxidation of part of the Mn3+species to Mn4+,resulting in an increase of amounts of the reducible Mnn+ species and a decrease of their reduction temperature. On the other hand, this interaction led also to enhancement of adsorption ability of the catalyst toward O2 at relatively low temperature. High activity of the Ag modified La0.6Sr0.4MnO3 catalyst for CH4 and CH3OH complete oxidation was closely related to high redox-activity of the catalyst and its prominent adsorption-activation ability to O2 at relatively low temperatures.     

均匀共沉淀法制备BaTiO3 -Nix Zn1-x Fe2 O4 核-壳粒子及其性能

以尿素为沉淀剂, 在无后续热处理的情况下, 采用均匀共沉淀法制备了BaTiO3-NixZn1-xFe2O4核-壳粒子. 采用透射电子显微镜(TEM)、 X射线衍射仪(XRD)、 能谱仪(EDS)及振动样品磁强计(VSM)对BaTiO3-NixZn1-xFe2O4核-壳粒子的形貌、 结构、 成分和磁性能进行了表征. 结果表明, 制备的核-壳结构粒子中NixZn1-xFe2O4壳层在BaTiO3颗粒的表面包覆完整. 通过控制共沉淀中NiCl2·6H2O与ZnCl2的摩尔比可以调控BaTiO3-NixZn1-xFe2O4核-壳粒子的磁性; 加入的NiCl2·6H2O与ZnCl2摩尔比为7∶3时制得的核-壳粒子具有较好的磁性能, 其饱和磁化强度和矫顽力分别为26.999 A·m2/kg和902.787 A/m.     

Synthesis and characterization of metal substituted AlxCr1−x(acetylacetonate)3 single-source precursors for their application to MOCVD of thin films

A detailed study, involving the synthesis of a single-source precursor containing two metal ions sharing the same crystallographic site, has been undertaken to elucidate the use of such a single-source precursor in a CVD process for growing thin films of oxides comprising these two metals, ensuring a uniform composition and distribution of metal ions. The substituted complexes Cr_1−xAl_x(acac)₃, where acac = acetylacetonate, have been prepared by a co-synthesis method, and characterized using UV–Vis spectroscopy, TGA/DTA measurements, and single crystal X-ray diffraction at low temperature. All the studied compositions crystallize in the monoclinic space group P2₁/c with Z = 4 in the unit cell. It was observed that the ratio (Al:Cr) of the site occupancy for the metal ions, obtained from single crystal refinement, is in agreement with the results obtained from complexometric titrations. All the solid state structures have the metal in an octahedral environment forming six-membered chelate rings. M–O acac bond lengths and disorder in the terminal carbon have been studied in detail for these substituted metal–organic complexes. One composition among these was chosen to evaluate their suitability as a single-source precursor in a LPMOCVD process (low-pressure metal–organic chemical vapour deposition) for the deposition of a substituted binary metal oxide thin film. The resulting thin films were characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy.