La,V共掺杂的Bi_4Ti_3O_(12)铁电薄膜的溶胶-凝胶法制备及性能测试

采用溶胶-凝胶(sol-gel)工艺在Pt/TiO2/SiO2/p-Si(100)衬底上制备出Bi4Ti3O12(BIT)和Bi3.25La0.75Ti2.97V0.03O12(BLTV)铁电薄膜,研究了La,V共掺杂对BIT薄膜的晶体结构和电学性能的影响.BIT薄膜为c轴择优取向,BLTV薄膜为随机取向,拉曼光谱分析表明V掺杂降低了TiO6(或VO6)八面体的对称性,也增强了Ti—O键(或V—O键)杂化.BLTV薄膜的剩余极化Pr为25.4μC/cm2,远大于BIT薄膜的9.2μC/cm2,表现出良好的铁电性能.疲劳、漏电流测试显示BLTV薄膜具有优良的抗疲劳特性和漏电流特性,表明La,V共掺杂能有效地降低薄膜中的氧空位.     

Effect of Terraces at the Interface on the Structural and Physical Properties of La_(0.8)Sr_(0.2)MnO_3 Thin Films

Employing atomic force microscopy,transmission electron microscopy and the second harmonic generation technique,we carefully explore the structural properties of 6-unit-cell-thick La_(0.8)Sr_(0.2)MnO_3 films grown on SrTiO_3 with atomically flat TiO_2-terminated terraces on the surface.The results clearly demonstrate that the terraces on the surface of TiO_2-terminated SrTiO_3 can improve the layer-by-layer epitaxial growth of the manganite films,which results in uniform film coverage at the beginning of growth and thus reduces the substrate-induced disorder at or near the interface.Comparing the magnetic and transport properties of La_(0.8)Sr_(0.2)MnO_3 films with the thicknesses varying from 6 unit cells to 80 unit cells grown respectively on as-received SrTiO_3 and TiO_2-terminated SrTiO_3,it is found that these atomically flat terraces on the surface of TiO_2-terminated SrTiO_3 can greatly enhance the Curie temperature and conductivities of the ultrathin La_(0.8)Sr_(0.2)MnO_3 films with thickness less than 50 unit cells,while no obvious difference is detected in the magnetic and transport properties of the 80unit-cell thick films.     

二氧化钛多孔膜的UV-Vis光谱与光催化性能研究

以钛酸四丁酯(Ti(OBu)4)、乙醇胺(MEA)、聚乙二醇(PEG)和无水乙醇为反应体系,采用溶胶-凝胶法制备了TiO2溶胶并通过浸渍提拉法制得了TiO2多孔膜,用UV-Vis,XRD和AFM对制得的多孔膜进行了表征,讨论了薄膜的紫外-可见透过光谱随着薄膜层数的变化规律以及其与膜厚的关系,结果表明在本实验条件下薄膜转移得很均匀,每层膜厚度约为60nm。多孔膜的光催化测试结果表明,随着薄膜层数的增加,光催化活性也逐渐增强,10层多孔膜的光催化活性最高。     

Observation of Tunneling Gap in Epitaxial Ultrathin Films of Pyrite-Type Copper Disulfide

We report scanning tunneling microscopy investigation on epitaxial ultrathin films of pyrite-type copper disulfide.Layer-by-layer growth of CuS_(2 )films with a preferential orientation of(111)on SrTiO_3(001)and Bi_2Sr_2Ca Cu_2O_(8+)substrates is achieved by molecular beam epitaxy growth.For ultrathin films on both kinds of substrates,we observe symmetric tunneling gap around the Fermi level that persists up to~15 K.The tunneling gap degrades with either increasing temperature or increasing thickness,suggesting new matter states at the extreme twodimensional limit.     

Bi4-xLaxTi3O12-SrBi4Ti4O15,共生结构铁电材料拉曼光谱研究

在常温下，对La掺杂共生结构铁电陶瓷Bi_4-xLa_xTi_3O_12-SrBi_4-yLayTi_4O_15［BLT-SBLT(x+y),x+y= 0.00, 0.25,0.50,0.75,1.00,1.25,1.50］进行了拉曼光谱研究.结果表明，在掺杂量低于0.50时，La只取代类钙钛矿层中的Bi，当掺杂 量高于0.50后，部分La开始进入(Bi_2O_2)^2+层. La取代(Bi_2O_2)^2+层中的部分Bi以后，(Bi_2O_2)^2+层结构发生变化 ，原有的绝缘层和空间电荷库的作用减弱，导致材料剩余极化下降. La掺杂量增至1.50时，样品出现弛豫铁电性，这与30cm^-1以下模的软化相对应，说明La掺杂可引起材料 的结构相变. 关键词： Bi4-xLaxTi3O12-SrBi4Ti4O15 La掺杂 声子模 拉曼频移     

Electrical analysis of inter-growth structured Bi_4Ti_3O_(12)-Na_(0.5)Bi_(4.5)Ti_4O_(15) ceramics

Inter-growth bismuth layer-structured ferroelectrics(BLSFs), Bi_4Ti_3O_(12)-Na_(0.5)Bi_(4.5)Ti_4O_(15)(BIT-NBT), were successfully synthesized using the traditional solid-state reaction method. X-ray diffraction(XRD) Rietveld refinements were conducted using GSAS software. Good agreement and low residual are obtained. The XRD diffraction peaks can be well indexed into I2 cm space group. The inter-growth structure was further observed in the high-resolution TEM image. Dielectric and impedance properties were measured and systematically analyzed. At the temperature range 763-923 K(below T_c), doubly ionized oxygen vacancies(OVs) are localized and the short-range hopping leads to the relaxation processes with an activation energy of 0.79-1.01 eV. Above T_c, the doubly charged OVs are delocalized and become free ones, which contribute to the long-range dc conduction. The reduction in relaxation species gives rise to a higher relaxation activation energy ~ 1.6 eV.     

Remanence Enhancement Effect in Ni_(0.7)Zn_(0.3)Fe_2O_4/Co_(0.8)Fe_(2.2)O_4 Ferrite Multilayer Film

Ni_(0.7)Zn_(0.3)Fe_2O_4/Co_(0.8)Fe_(2.2)O_4(NZFO/CFO) multilayer films are fabricated on Si(100) substrates by the chemical solution deposition method.The microstructure and magnetic properties are systematically investigated.The results of field-emission scanning electronic microscopy show that the grain size of the NZFO/CFO multilayer film is quite uniform and the thickness is about 300 nm.The remanence enhancement effect of the NZFO/CFO multilayer film can be mainly attributed to the exchange coupling interaction between NZFO and CFO ferrite films,which is in favor of the design and fabrication of modern electronic devices.     

高氧压下氧化物薄膜同质和异质外延的RHEED实时监测

我们自行研制了具有三级差分气路可以在高气压下工作的RHEED系统(High-pressure RHEED),并利用本系统实时监测了(001)SrTiO3基片上SrTiO3:Nb、Ba0.5Sr0.5TiO3、YBa2Cu3O7单层薄膜,及Ba0.5Sr0.5TiO3/SrTiO3:Nb双层膜的生长过程.研究结果表明当镀膜室氧压高达21Pa时该系统仍然可以正常工作,并且能够获取较清晰的衍射图样.通过分析衍射图样我们发现,所有这些薄膜都是外延生长且晶体质量良好,但薄膜生长模式及表面平整度受沉积条件影响较大.在真空下薄膜基本上以层状模式生长,具备纳米级光滑的表面,且其表面平整度并不因膜厚的改变而变化;而在10Pa量级氧压下薄膜更倾向于以岛状模式生长,膜表面平整度较差,并且随膜厚的增加粗糙度上升.此外对多层薄膜而言,底层薄膜的表面和结构直接影响到顶层薄膜的质量和品质.     

Bipolar Resistive Switching in Epitaxial Mn_3O_4 Thin Films on Nb-Doped SrTiO_3 Substrates

Spinel(001)-orientated Mn_3O_4 thin films on Nb-doped SrTiO_3(001) substrates are fabricated via the pulsed laser deposition method.X-ray diffraction and high-resolution transmission electron microscopy indicate that the as-prepared epitaxial film is well crystallized.In the film plane the orientation relationship between the film and the substrate is[100]Mn_3O_4\\[110]Nb-doped SrTiO_3.After an electroforming process,the film shows bipolar nonvolatile resistance switching behavior.The positive voltage bias drives the sample into a low resistance state,while the negative voltage switches it back to a high resistance state.The switching polarity is different from the previous studies.The complex impedance measurement suggests that the resistance switching behavior is of filament type.Due to the performance reproducibility and state stability,Mn_3O_4 might be a promising candidate for the resistive random access memory devices.     

厚度与应变效应对La0.67Ca0.33MnO3薄膜电输运与居里温度的影响

在厚度为25—400nm范围内，系统地研究了 (001)SrTiO_3(STO), (001)LaAlO_3(LAO)衬底上La_0.67Ca_0.33Mn_O.3 (LCMO)薄膜的电输运与居里温度T_C随薄膜厚度及衬底的变化. 结果表明，随薄膜变薄，电阻率ρ增加，T_C降低. 对于同一薄膜厚度，LCMO/STO薄膜的ρ大于LCMO/LAO基上的薄膜的ρ. T_C衬底的依赖关系则与ρ相反. 分析表明，LCMO薄膜的低温区电阻温度(ρ-T) 符合关系式ρ=ρ_0+Bω_s/sin h^2(ω_s/2/k_BT)+CT^n， 其中ρ_0为剩余电阻；等号右端第二项反映软光学模声子对电子散射的贡献；第三项包括其余可能散射机 理在电输运过程中所起的作用；B，ωs（软光学模声子的平均频率）与C都为拟合系数. 高温区的电输运则由小极化子跃迁模型ρ=DT×exp（E_a/k_BT）描述（E_a为极化子激 发能）. 根据ρ_0，ωs，E_a以及T_Ｃ变化，初步讨论了薄膜中的厚度与应变效应. 进一步 研究发现ωs，E_a的变化与T_C相关，从而说明极化子效应为影响T_C变化的主要因素. 关键词： 锰氧化物薄膜 电输运 居里温度 极化子     

Morphology and microstructure of all-epitaxial ferroelectric tri-layered (Bi,La)4Ti3O12/Pb(Zr0.4Ti0.6)O3/ (Bi,La)4Ti3O12 thin films on SrTiO3(011)

The morphology and microstructure of all-epitaxial (Bi,La)₄Ti₃O₁₂/Pb(Zr_0.4Ti_0.6)O₃/(Bi,La)₄Ti₃O₁₂ (BLT/PZT/BLT) tri-layered ferroelectric films, grown on (011)-oriented SrTiO₃ (STO) substrates by pulsed laser deposition, are investigated by transmission electron microscopy (TEM). X-ray diffraction and electron diffraction patterns demonstrate that the epitaxial relationship between BLT, PZT and STO can be described as ; . Cross-sectional TEM images show that the growth rate of BLT is nearly two times that for PZT at the same growth conditions, and 90° ferroelectric domain boundaries lying on {110} planes are observed in the PZT layer. The 90° ferroelectric domains in the PZT layer extend up to 600 nm in length. Long domains penetrate into the neighboring columnar grain through the columnar grain boundary, whereas others are nucleating at the columnar grain boundaries. The roughness of the PZT/BLT interfaces appears to depend on the viewing direction, i.e., it is different for different azimuthal directions. Planar TEM investigations show that the grains in the top BLT layer have a rod-like morphology, preferentially growing along the [110]_BLT direction. The grain width is rather constant at about 90 nm, whereas the length of the grains varies from 150 to 625 nm. These morphological details point to the important role the crystal anisotropy of BLT plays for the growth and structure of the tri-layered films. PACS 81.15-z; 68.37.Lp; 77.84.-s     

Synthesis of free-standing Ga_2O_3 films for flexible devices by water etching of Sr_3Al_2O_6 sacrificial layers

Flexible electronic devices have attracted much attention due to their practical and commercial value. Integration of thin films with soft substrate is an effective way to fabricate flexible electronic devices. Ga_2O_3 thin films deposited directly on soft substrates would be amorphous mostly. However, the thickness of the thin film obtained by mechanical exfoliation method is difficult to control and the edge of the film is fragile and easy to be damaged. In this work, we fabricated free-standing Ga_2O_3 thin films using the water-soluble perovskite Sr_3Al_2O_6 as a sacrificial buffer layer. The obtained Ga_2O_3 thin films were polycrystalline. The thickness and dimension of the films were controllable. A flexible Ga_2O_3solar-blind UV photodetector was fabricated by transferring the free-standing Ga_2O_3 film on a flexible polyethylene terephthalate substrate. The results displayed that the photoelectric performances of the flexible Ga_2O_3 photodetector were not sensitive to bending of the device. The free-standing Ga_2O_3 thin films synthesized through the method described here can be transferred to any substrates or integrated with other thin films to fabricate electronic devices.     

Growth and transport properties of topological insulator Bi_2Se_3 thin film on a ferromagnetic insulating substrate

Exchange coupling between topological insulator and ferromagnetic insulator through proximity effect is strongly attractive for both fundamental physics and technological applications. Here we report a comprehensive investigation on the growth behaviors of prototype topological insulator Bi_2Se_3 thin film on a single-crystalline LaCoO_3 thin film on SrTiO_3 substrate, which is a strain-induced ferromagnetic insulator. Different from the growth on other substrates, the Bi_2Se_3 films with highest quality on LaCoO_3 favor a relatively low substrate temperature during growth. As a result, an inverse dependence of carrier mobility with the substrate temperature is found. Moreover, the magnetoresistance and coherence length of weak antilocalization also have a similar inverse dependence with the substrate temperature, as revealed by the magnetotransport measurements. Our experiments elucidate the special behaviors in Bi_2Se_3/LaCoO_3 heterostructures,which provide a good platform for exploring related novel quantum phenomena, and are inspiring for device applications.     

Effects of Thickness and Temperature on Thermoelectric Properties of Bi_2Te_3-Based Thin Films

Bi_2Te_3 thin films and GeTe/B_2Te_3 superlattices of different thicknesses are prepared on the silicon dioxide substrates by magnetron sputtering technique and thermally annealed at 573 K for 30 min. Thermoelectric(TE)measurements indicate that optimal thickness and thickness ratio improve the TE performance of Bi_2Te_3 thin films and GeTe/B_2Te_3 superlattices, respectively. High TE performances with figure-of-merit(ZT) values as high as 1.32 and 1.56 are achieved at 443 K for 30 nm and 50 nm Bi_2Te_3 thin films, respectively. These ZT values are higher than those of p-type Bi_2Te_3 alloys as reported. Relatively high ZT of the GeTe/B_2Te_3 superlattices at 300-380 K were 0.62-0.76. The achieved high ZT value may be attributed to the unique nano-and microstructures of the films,which increase phonon scattering and reduce thermal conductivity. The results indicate that Bi_2Te_3-based thin films can serve as high-performance materials for applications in TE devices.     

Features of island nanostructures formed by melting Sn, Bi and Sn-Bi thin films on C substrates

We report the results of studying the morphological structure of island systems formed by melting Sn, Bi and eutectic Sn-Bi polycrystalline films 2-70 nm thick deposited on carbon substrates. Substrate coverage with a film is found to be non-uniform against film mass thickness after its melting and crystallization. The interval of film thickness is determined where the island systems with narrow enough particle size distribution are formed under melting.     

Bi1.8Nd0.2Ti4O11的温致及压致软模相变研究

 采用背用散射的方法，测量了Bi_1.8Nd_0.2Ti₄O₁₁的拉曼光谱。实验结果表明，该掺杂样品发生温致和压致软模相变的温度和压力分别为200 ℃和3.35 GPa。文中讨论了相变点移动的原因及高频声子模随温度和压力的变化。     

掺铋BaF2晶体的制备及其近红外发光研究

通过温度梯度法制备了Bi₂O₃:BaF₂以及BiF₃:BaF₂晶体.在Bi₂O₃:BaF₂晶体中观察到了发光峰位于961 nm,半高宽202 nm的超宽带红外发光.在BiF₃:BaF₂晶体中检测到Bi²⁺和Bi³⁺可见区的发光,但是没有观察到红外发光.通过γ射线辐照实现了BiF₃:BaF₂晶体的近红外发光, 发光峰位于1135 nm,半高宽192 nm.讨论了Bi₂O₃和BiF₃掺杂BaF₂晶体的红外发光的机理. 关键词： 近红外发光 铋 氟化钡晶体 γ辐照     

存储器用铁电薄膜及电极材料的研究

铁电体独特的自发电极化双稳性质和非线性光学性质使其在光电子器件中得到广泛应用．为了实现器件的小型化和与微电子、光电子工艺兼容，铁电薄膜已成为一个研究热点．自发电极化的大小和取向以及外电场、缺陷和铁电薄膜／电极界面与自发电极化的交互作用决定了铁电薄膜的性质和服役行为．文章以铁电存储器和光电子器件应用为背景，选择了具有重大应用前景的Bi4-xLaxTi3O12（BLT）、SrBi2Ta2O9（SBT）、PbZrxTi1-xO3（PET）和LiNbO3（LN）铁电薄膜以及相关的La（Sr，Co）O3（LSCO）和LaNiO3（LNO）等电极材料为研究对象，研究了缺陷电荷和电畴的交互作用和它们在交变外电场中的动力学行为，探明了铁电薄膜疲劳现象的物理本质；从晶格结构与缺陷的观察研究入手，探索了材料铁电性质的起源和优化材料铁电性质的途径；从铁电薄膜／电极界面结构与性质的研究入手，寻找更有效、更稳定的电极材料与结构，从而为器件应用打下了基础；在研究外电场对铁电薄膜生长机制影响的基础上，找到了利用外电场调控铁电薄膜结构的新途径，发展了新的、与半导体器件和光电子器件工艺兼容的制膜方法．     

Imaging of ferroelectric vinylidene fluoride and trifluoroethylene copolymer films by scanning tunneling microscopy

In this paper, we reported the possibility to image non-conducting P(VDF-TrFE) copolymer films by STM. The films had the thickness of ∼25.0 nm and were spin-coated onto Au or graphite substrates. For films deposited on Au substrates, STM images showed grain structures of ∼100 nm, much larger than the grains of bare Au substrate. With increased scan rate, the film surface was damaged by STM tip and extreme protrusions and holes were observed. For films deposited on graphite substrates, we only obtained an image of very flat plane and could not observe the topography of the film surface. It seemed that the tip had pierced through the uppermost P(VDF-TrFE) layers and only imaged the layers nearest to the substrate. Asymmetrical current-voltage curves were observed from copolymer films deposited on HOPG. Experimental results were discussed.     

Insertion of Platinum Oxide into Nanotube of Sodium Titanate

A new method for preparing PtO _x -inserted sodium titanate nanotube was reported. By suction of H₂PtCl₆ ethanol solution into the nanotubes first and annealed at 653 K for 3 h afterwards, Pt nanoparticles formed in the nanotubes. The size of Pt nanoparticles is controlled by the dimensions of nanotubes. Some of them are spherical, some are nanorods. XPS and XRD results revealed that during annealing the following complex reaction happened:

$Na_1.1H_0.9Ti_2O_4(OH)_2 + H_2PtCl_6+ O_2 \rightarrow TiO_2(anatase) + PtO_x(x=1,2)+NaCl+ HCl\!\uparrow\!\!.$