La0.7Ca0.3MnO3薄膜微观结构的HRTEM表征

利用透射电子显微镜研究了衬底温度600～800℃条件下采用脉冲激光法在(001)LaAlO3(LAO)衬底上制备的La0.7Ca0.3MnO3(LCMO)薄膜的微观结构。结果表明薄膜由大量柱状晶组成且与LAO衬底形成良好外延关系。LCMO薄膜与LAO衬底的取向关系可以描述为:(ⅰ)(100)f∥(001)s、[011]f∥[100]s;(ⅱ)(011)f∥(001)s、[100]f∥[100]s。LCMO显示层状畴结构,即在衬底上初始生长的薄膜为(ⅱ)型畴,在此之上生长的薄膜为(ⅰ)类和(ⅱ)类型畴的混合体。薄膜中可观察到一些反向畴与孪晶等缺陷。薄膜与衬底界面少见错配位错,薄膜以Stranski-Krastanov模式生长。     

Microstructure of Epitaxial La0.7Ca0.3MnO3 Thin Films Deposited by Direct Current Magnetron Sputtering on LaAlO3 Substrate

Transmission electron microscopy (TEM) and high resolution electron microscopy (HREM) have been used to study the microstructural properties of La_0.7Ca_0.3MnO₃ films on (001) LaAlO₃ substrates prepared by direct current magnetron sputtering technique. The as-grown thin films with different thickness are perfectly coherent with the substrates. The film suffers a tetragonal deformation in the area near the interface between the film and the substrate. With increasing thickness, the film is partially relaxed. It was found that La_0.7Ca_0.3MnO₃ films consist of two types of oriented domains described as: (1) (110)_f [001]_f||(001)_s[100]_s and (1¹10)_f [001]_f||(001)_s[100]_s and (2) (110)_f [001]_f||(001)_s[010]_s and (1¹10)_f [001]_f//(001)_s[010]_s. Upon annealing, the film is relaxed by the formation of mis¯t dislocations. Other than mis¯t dislocations, two types of threading dislocations with Burgers vector of <100> and <110> were also identified.     

Fully strained low-temperature epitaxy of TiN/MgO(001) layers using high-flux, low-energy ion irradiation during reactive magnetron sputter deposition

Epitaxial TiN layers, 0.3 μm thick, are grown on MgO(001) in the absence of applied substrate heating using very high flux, low-energy (below the lattice atom displacement threshold), ion irradiation during reactive magnetron sputter deposition in pure N₂ discharges. High-resolution x-ray diffraction, reciprocal lattice maps, and transmission electron microscopy analyses reveal that the TiN(001) films grow with an (001)_TiN||(001)_MgO and [100]_TiN||[100]_MgO orientation relationship to the substrate. The layers are fully coherent with no detectable misfit dislocations. For comparison, TiN/MgO(001) films grown at temperatures of 700-850 °C under similar conditions, but with no intentional ion irradiation, are fully relaxed with a high misfit dislocation density. Thus, the present results reveal that intense low-energy ion irradiation during film growth facilitates high adatom mobilities giving rise to low-temperature epitaxy, while the low growth temperature quenches strain-induced relaxation and suppresses misfit dislocation formation.     

Line defects, planar defects and voids in SrTiO3 films grown on MgO by pulsed laser and pulsed laser interval deposition

Two and three dimensional growth of SrTiO₃ films on (001) MgO substrate was achieved by pulsed laser interval and pulsed laser deposition respectively. The growth mode was monitored by in-situ reflection high energy electron diffraction. Interval deposition forces layer-by-layer growth of materials even with such a large lattice misfit (~ 7.9%). A titanium dioxide buffer monolayer was deposited to allow the film to wet the substrate to encourage two dimensional growth of the strontium titanate. A variety of defects was investigated using transmission electron microscopy and high resolution scanning transmission electron microscopy. Misfit dislocations, steps at the interface, Ti-rich defects and regularly shaped nano-holes connected by anti-phase boundaries were found to be the dominant defects in these films grown layer by layer. The edges of the nano-holes were mainly along [010] and [100] for a [001] growth direction. The large strain between the two crystal systems with large lattice mismatch leads to in-plane tensile stress during the layer-by-layer growth. The stress is relieved in part by the holes. The films with a three dimensional growth mode possess a uniform surface with dislocations as the dominant defects. The individual densities of the various defects, including a Ti-rich phase and misfit and threading dislocations, are determined by the kinetics of the deposition method.     

Ti/La_(0.7)Ca_(0.3)MnO_3/Pt结构器件中“负”电阻开关特性研究

以Pt/Ti/SiO2/Si为衬底,制备了具有电阻转变特性的Ti/La0.7Ca0.3MnO3(LCMO)/Pt结构器件.X射线衍射分析表明LCMO薄膜呈纳米晶或非晶态,扫描电子显微镜及原子力显微镜分析表明LCMO薄膜表面平整、光滑致密.电学测试结果表明Ti/LCMO/Pt结构具有明显的双极型"负"电阻转变特性,低电阻态的导电过程为空间电荷限制电流机制,高电阻态的导电过程为Poole-Frenkel发射机制.利用氧化还原反应的随机性和TiOx中间层空间分布的不均匀性,定性地解释了高电阻态的不稳定性以及电流-电压曲线上的电流突变现象.     

Annealing effect on the structure and electronic transport properties in La5/8Ca3/8MnO3/ErMnO3 multilayer thin films

Ferromagnetic La5/8Ca3/8MnO3 (LCMO) and Ferroelectric ErMnO3 (EMO) multilayer thin films with sandwich structure (LCMO/EMO/LCMO) were grown on (LaAlO3)0.3(Sr2AlTaO6)0.7 (001) [LSAT (001)] substrates by pulsed laser deposition (PLD) method. For these films, the structural characterization was carried out by X-ray diffraction (XRD), and the temperature-dependence resistivity (p-T) showing the metal-insulator transition (Tp) also was measured. In the multilayer thin films the LCMO (002) peak move to lower Bragg angles after annealing at 900 degrees C for 30 hours under 1atm Oxygen pressure, and this condition is much different from the LCMO single layer films where the (002) peak moves to higher Bragg angle after annealing due to the lattice mismatch between the LCMO layer and the substrate. By increasing the thickness of LCMO, the multilayer samples show two MR peaks in a wide temperature range during the process of M-l transition. This phenomenon is attributed to a new (La5/8Ca3/8)xEr(1-x)MnO3 layer produced by the solubility between LCMO and EMO layers after high-temperature annealing. In this paper, we provide some evidence of dissolution between LCMO and EMO layers, and discuss the influence on structure and electronic transport properties in the composite thin films by annealing.     

Exchange coupling and exchange bias in La0.7Sr0.3MnO3-SrRuO3 superlattices

La(0.7)Sr(0.3)MnO(3)-SrRuO(3) superlattices with and without nanometrically thin SrTiO(3), BaTiO(3) and Ba(0.7)Sr(0.3)TiO(3) interlayers were grown by pulsed laser deposition. Transmission electron microscopy studies showed coherent growth of La(0.7)Sr(0.3)MnO(3), SrRuO(3) and SrTiO(3) layers with atomically sharp interfaces, even if individual layers were as thin as one or two unit cells. In contrast, misfit dislocations and unit cell high interfacial steps were observed at the interfaces between BaTiO(3) and one of the ferromagnetic layers. The presence of the interlayers as well as these extended defects had a significant influence on the magnetic properties of the superlattices, especially on the antiferromagnetic interlayer exchange coupling between the La(0.7)Sr(0.3)MnO(3) and SrRuO(3) layers and the exchange biasing. Surprisingly, exchange biasing was found to increase with decreasing strength of the antiferromagnetic interlayer exchange coupling. This was explained by different magnetization reversal mechanisms acting in the regimes of strong and weak interlayer exchange coupling.     

Microstructural Characteristics of La0.7Ca0.3MnO3 Films and Multilayers

1. IntroductionEver since discovery of colossal magnetoresistance(CMR) in perovskite type Rel--.A.MnO3(Re=lajnthanides, A=alkaline earth elemellts), therehas been enormous illterest in these materials both inthe bulk and the filmsll~5]. A prominellt feature ofthese materials is a large maximum in the resistivitynear the ferromagnetic transition temperature (To).The resistance is dramatically decreased when an external magnetic field is applied, which leads to a verylarge (colossal) magneto…     

Morphology of strained and relaxed SiGe layers grown on high-index Si substrates

We have investigated the surface morphology of strained and relaxed SiGe layers grown on Si substrates with surface normals rotated off of the [001] axis towards [111] by 0, 13, and 25°. Atomic force microscopy has revealed surface corrugations in thin layers prior to plastic relaxation on each of the surfaces due to the initial deposition of the strained films. Thicker partially relaxed layers have previously been shown to contain networks of misfit dislocations which create patterns that are unique to each substrate orientation. We find on these relaxed layers that the surface corrugations are well aligned with the dislocation networks forming a modified crosshatch pattern on the off-axis substrates. More strikingly, though, we find that these corrugations are comprised of smaller nanostructured features which are also unique to each surface. Topographs of the unrelaxed surfaces show no such organization indicating a correspondence between the misfit dislocations and the surface corrugations.     

新型溶胶-凝胶工艺制备La0.5Ca0.5MnO3薄膜及性能分析

鉴于以醇盐为原料溶胶-凝胶制备La0.5Ca0.5MnO3薄膜工艺中存在诸多苛刻因素,本文以无机盐为原料采用溶胶-凝胶工艺在SiO2/Si(100)衬底上制备了La0.5Ca0.5MnO3薄膜.并用XRD、SEM和TEM等分析手段对薄膜进行了表征,通过不同磁场下电阻-温度(R-T)曲线,研究了样品的磁电阻(CMR)效应...     

铁磁(La0.7Ca0.3MnO3)/高温超导（YBa2Cu3O7）双层薄膜微结构的高分辨电镜研究

采用脉冲激光沉积法在LaAlO3(LAO)衬底上生长了YBa2Cu3O7/La0.7Ca0.3MnO3(YBCO/LC-MO)和La0.7Ca0.3MnO3/YBa2Cu3O7(LCMO/YBCO)两种外延薄膜,利用高分辨电子显微镜研究了其微观结构。在YBCO/LCMO/LAO薄膜中,LCMO以层-岛模式生长,并形成层状取向畴结构。YBCO层均由c轴取向晶粒组成,其中含有c/3平移畴界、额外CuO层及Y2O3第二相等缺陷结构。在LCMO/YBCO/LAO薄膜中,LAO衬底上初始生长的YBCO为c轴取向,至一定厚度(几个纳米)转为c与a轴混合生长。LCMO层在YBCO上外延生长并具有[100]m与[011]m混合取向畴结构。在LCMO/YBCO界面未观察到失配位错,因此二者界面属应变型界面。     

Electric resistance and magnetoresistance of 30-nm-Thick La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> films elastically compressed in the (110) plane

We have studied the structure, electric resistance, and magnetoresistance of 30-nm-thick (110)La_0.67Ca_0.33MnO₃ (LCMO) films grown by laser deposition on (001)-oriented LaAlO₃ substrates. The unit cell parameters a and b (along the [100] and [010]LCMO axes, respectively) of these manganite films are significantly (by ∼1.2%) increased as compared to the corresponding values in the pseudocubic unit cell of bulk stoichiometric LCMO crystals. At T < 150 K, the temperature dependence of the resistivity of LCMO films is well described by the relation ρ = ρ₁ + ρ₂ (H) T ^4.5. The value of ρ 2 decreases with increasing magnetic field and is close to the analogous coefficient for manganite films grown on substrates with small lattice misfit.     

Stabilization of Ferromagnetic Order in La(0.7)Sr(0.3)MnO(3)-SrRuO(3) Superlattices

The study of spatially confined complex oxides is of wide interest, since correlated electrons at interfaces might form exotic phases. Here La(0.7)Sr(0.3)MnO(3)/SrRuO(3) superlattices with coherently grown interfaces were studied by structural techniques, magnetization, and magnetotransport measurements. Magnetization measurements showed that ferromagnetic order in ultrathin La(0.7)Sr(0.3)MnO(3) layers is stabilized in the superlattices down to layer thicknesses of at least two unit cells. This stabilization is destroyed, if the ferromagnetic layers are separated by two unit cell thick SrTiO(3) layers. The resistivity of the superlattices showed metallic behavior and was dominated by the conducting SrRuO(3) layers, the off-diagonal resistivity showed an anomalous Hall effect from both SrRuO(3) and La(0.7)Sr(0.3)MnO(3) layers. This shows that the La(0.7)Sr(0.3)MnO(3) layers are not only ferromagnetic but also highly conducting; probably a conducting hole gas is induced at the interfaces that stabilizes the ferromagnetic order. This result opens up an alternative route for the fabrication of two-dimensional systems with long-range ferromagnetic order.     

Synthesis and characterization of pure and doped (Na, Ca, Sr) nanograined LaMnO3 magnetoresistive ceramics

Pure and Na, Ca, and Sr doped lanthanum manganites (LaMnO3, La0.85Na0.15MnO3, La0.7Ca0.3 MnO3, La0.7Sr0.3MnO3) were prepared in form of bulk nano-structured materials through a two-step process. Nanometric powders were synthesized by the Pechini method and subsequently densified by Spark Plasma Sintering at 1273 K for 5 minutes under a pressure of 140 MPa. The method allowed the preparation of single phase manganites with a theoretical density above 98% together with a very limited growth of the grain size. Grain sizes below 70 nm were obtained for all materials except La0.85Na0.15MnO3 which showed a much larger grain size. Curie temperatures (Tc) and magnetoresistivity properties of the samples were measured by a Superconducting Quantum Interference Device (SQUID). The decrease in the resistivity below Tc occurred in a much wider range of temperature compared to ceramics having micron-size grains.     

Stability of strained thin films with interface misfit dislocations: A multiscale computational study

The stability of thin single-crystal, internal-defect-free Fe films on Mo(110) and W(110) substrates is investigated through calculations of energetics including contributions from the misfit strain, interfacial misfit dislocations, film surface and interface. The misfit dislocation model is developed through the Peierls-Nabarro framework, employing ab initio calculations of the corrugation potential at the film/substrate interface as an input to the model. The surface and interfacial energies for pseudomorphic films are calculated as a function of film thickness from 1 to 10 layers, employing first-principles spin-polarized density-functional theory calculations in the generalized gradient approximation. First-principles calculations are also employed to obtain the Fe surface stress used in the Peierls-Nabarro model to account for the strain dependence of the surface energy. It is found that the competition between the misfit strain, misfit dislocations, film surface and interfacial energies gives rise to a driving force for solid-state dewetting of a single-crystal, internal-defect-free film, i.e., an instability of a flat film that leads to formation of thicker and thinner regions. The details of the energetics are presented to demonstrate the robustness of the mechanism. Our findings indicate that misfit dislocations and their configurations play a significant role in a morphological evolution of metallic thin films.     

Nucleation and growth of GeTe films on KCl and SnTe substrates

The nucleation and growth of GeTe films on KCl or SnTe substrates is found to follow the same mechanism on both substrates. Nucleation occurs through the formation of three-dimensional nuclei of almost equal sizes, bounded by edges along the [110] and [1$\text{1}$0] directions. The growth continues through the lateral extension of the nuclei. The overgrowth layer is anisotropic strainwise, due to the difference in lattice misfit along [110] and [1$\text{1}$0]. This angular misfit is responsible for an increase in the equilibrium energy by 5%. The excess strain is accommodated by misfit dislocations forming a network parallel to the [110] and [1$\text{1}$0] directions, the dislocations being of the edge orientation with Burger's vector equal to $\text{1}\text{2}\text{a<110>}$ and with a different linear density in the two directions. Annealing the system GeTe/SnTe results in a substantial decrease in the density of dislocations due to cross diffusion of Ge and Sn respectively, which forces the dislocations to climb to the surface.     

Defect microstructures in epitaxial PbZr0.2Ti0.8O3 films grown on (001) SrTiO3 by pulsed laser deposition

Transmission electron microscopy has been used to investigate the character and distribution of the microstructural features in epitaxial (001) ferroelectric PbZr_0.2Ti_0.8O₃ films grown on (001) SrTiO₃ substrates by pulsed laser deposition. The TEM observations revealed that the films were predominantly c-oriented with embedded a ₁- and a ₂-oriented domains lying on {101} planes. The substrate/film interfaces contained arrays of edge-type misfit dislocations and there were extraordinarily high densities ( ) of threading dislocations in the films. The character and distribution of these features are consistent with the following relaxation sequence. Firstly, the lattice misfit between the phases is accommodated at the growth temperature by the introduction of misfit dislocations at the edges of island nuclei, and some of these dislocations are forced away from the interface to form threading segments upon island coalescence. Next, the film adopts the c-orientation upon cooling through the Curie temperature with a ₁- and a ₂-oriented domains being formed to ameliorate the self-strain of the transformation. Finally, some redistribution of the embedded domains and misfit dislocations occurs in response to stresses caused by expansion coefficient differences. The impact of these defects on the electrical and electromechanical properties of epitaxial ferroelectric properties is discussed.     

壳聚糖／纳米La0．7Ca0．3Fe0．25Co0．75O3复合膜的制备及表征

采用甘氨酸一硝酸盐燃烧法成功的制备了La0．7Ca0．3Fe0．25Co0．75O3钙钛矿型复合氧化物,并通过扫描电镜、红外光谱、XRD现代分析手段对其进行了分析,结果表明La0．7Ca0．3Fe0．25Co0．75O3纳米晶体复合氧化物呈球形,粒径为19．1nm。利用溶胶-凝胶法在壳聚糖溶液中制备壳聚糖／La0．7Ca0．3Fe0．25Co0．75O3薄膜,并通过以上分析手段,对膜的表面形貌、成分变化、La0．7Ca0．3Fe0．25Co0．75O3的形态、粒子尺寸等进行分析,研究其成膜前后的变化。结果表明壳聚糖与La0．7Ca0．3Fe0．25Co0．75O3之间存在较强的氢键相互作用,这种分子问的相互作用扰乱了壳聚糖原有的晶体结构,在壳聚糖与La0．7Ca0．3Fe0．25Co0．75O3复合过程中产生了新的分子排列,从而使两组分之间形成了良好的分散与相容。     

Structural characterization of a Cu/MgO(001) interface using CS-corrected HRTEM

Epitaxial Cu(001) layers were deposited on MgO(001) substrates by magnetron sputtering and the atomic structure of the Cu-MgO interface was characterized by spherical aberration (C_S)-corrected high-resolution transmission electron microscopy (HRTEM). The interface structure and the misfit dislocation network were determined by imaging in both the <100> and <110> directions. The dislocation network was found to lie along the <100> directions with a Burgers vector of ½ a_Cu <100> deduced from HRTEM images and geometrical phase analysis. The dislocations do not fully accommodate the lattice mismatch, yielding residual stress at the interface and an elongation of the Cu lattice along the [001] direction.     

Reflection high energy electron diffraction and X-ray studies of AlN films grown on Si(111) and Si(001) by organometallic chemical vapour deposition

The crystallinity of AlN films on silicon substrates grown by organometallic chemical vapour deposition was investigated using X-ray diffraction and reflection high energy electron diffraction (RHEED). Single-crystal films of good quality with atomically smooth surfaces can be epitaxially grown on Si(111) substrates. Epitaxial films can also be grown on Si(001) substrates. These films have previously been reported to have a fibre structure. Different RHEED patterns were observed from the films on Si(111) and Si(001). It is established that the films grown on Si(001) consist of two types of crystallite with the following orientations: [11$\text{2}$0]_AlN//[110]_Si and [11$\text{2}$0]_AlN//[1$\text{1}$0]_Si The thickness dependence of the crystallinity was also investigated. The standard deviation σ of the X-ray rocking curve for the films grown on Si(111) is less than that for the films on Si(001) and is independent of the film thickness. The σ values for the films on Si(001) decrease markedly with increasing film thickness. On the basis of these observations, the growth mechanism of AlN epitaxial films on Si(111) and Si(001) is discussed.