(001) textured PbTiO3 thin films grown on redopingn-Si by metalorganic chemical vapor deposition under reduced pressure

(001) textured PbTiO₃ thin films have been deposited on (001) redopingn-Si substrates by metalorgnic chemical vapor deposition (MOCVD) under reduced pressure, and the film ferroelectricity has been measured using the substrate as bottom electrode directly. Besides this investigation, a set of analysis including AFM surface morphology, SEM cross section morphology, electron-probe element analysis, XRD 0-20 scan and high temperature X-ray diffraction have been carried out to study the microstructure and phase transition process of the PbTiO₃ thin film.     

Formation of the ferroelectric domains in epitaxial PbTiO3 thin films grown by metalorganic chemical vapor deposition

3 thin films have been prepared by metalorganic chemical vapor deposition under reduced pressure. The formation of ferroelectric domains in films grown on SrTiO₃ and LaAlO₃ substrates was investigated by synchrotron radiation and Rutherford backscattering spectroscopy. Single-domain (3000-Å thick) and multi-domain (4500-Å thick) PbTiO₃ films were produced on SrTiO₃. For multi-domain PbTiO₃ film, the c-domain presented epitaxial structure with its c-axis perpendicular to the substrate surface, while a-domains aligned four-fold symmetrically with c-domains by 2.79^° off the c-axis of c-domains. In the film, the measured lattice constants (a, b and c) of the a- and c-domains were different from each other, indicating that the films suffered a modulated strain during domain formation. In contrast, both the a and c domains of films on LaAlO₃ were alternatively aligned on substrate with the a-axis of the a-domain and the c-axis of c-domains perpendicular to the substrate surface. Two-dimensional distribution of these domains is proposed and the formation of these kinds of domains is discussed. The surface morphology and phase transition process of single and multi domain PbTiO₃ film on SrTiO₃ were studied by atomic force microscope (AFM) and high temperature X-ray diffraction, respectively. Received: 15 August 1996/Accepted: 21 January 1997     

用激光分子束外延在Si衬底上外延生长高质量的TiN薄膜

采用激光分子束外延技术,利用两步法,在Si单晶衬底上成功地外延生长出TiN薄膜材料.原子力显微镜分析结果显示, TiN薄膜材料表面光滑,在10 μm×10 μm范围内,均方根粗糙度为0842nm.霍耳效应测量结果显示,TiN薄膜在室温条件下的电阻率为36×10^-5Ω·cm,迁移率达到5830 cm²/V·S,表明TiN薄膜材料是一种优良的电极材料.X射线θ—2θ扫描结果和很高的迁移率均表明,高质量的TiN薄膜材料被外延在Si衬底 关键词： 激光分子束外延 TiN单晶薄膜 外延生长     

The growth and domain structure of YBa2Cu3Ox films on neodymium gallate substrates with a deviation of the normal to the surface from the [110] direction in NdGaO3

The growth, crystal structure, and electrophysical properties of YBa₂Cu₃O_x (YBCO) epitaxial films grown with and without a CeO₂ epitaxial sublayer on NdGaO₃ (NGO) substrates with the normal to the surface deviating from the [110] axis by 5° to 26.6° around the [001] axis are investigated. It is shown that the orientation of YBCO epitaxial films grown on such substrates is determined by the existence of symmetry-equivalent directions in the substrate and in the CeO₂ layer, as well as by the rate of film deposition. For a high deposition rate, YBCO films grow on the CeO₂ sublayer in the [001] orientation irrespective of the orientation of the substrate and the sublayer. It was found that when the angle of deviation of the substrate plane is from the (110) NGO plane, twinning of one or both twinning complexes in YBCO may be suppressed.     

金属有机化学气相沉积法制备钛酸铅铁电薄膜

利用低压ＭＯＣＶＤ工艺分别在（００１）取向的ＬａＡｌＯ_３，ＳｒＴｉＯ_３和重掺杂硅单晶衬底上制备ＰｂＴｉＯ_３铁电薄膜，并通过Ｘ射线衍射谱对薄膜的微结构进行分析．Ｘ射线θ－２θ扫描显示硅衬底上得到了ＰｂＴｉＯ_３多晶薄膜，另两种衬底上得到了择优取向的ＰｂＴｉＯ_３薄膜．ＬａＡｌＯ_３衬底上的ＰｂＴｉＯ_３薄膜有ａ和ｃ两个取向，也就是薄膜中存在着９０°畴结构，而生长在ＳｒＴｉＯ_３衬底上的ＰｂＴｉＯ_３薄膜中只存在ｃ方向的择优取向．由于薄膜的尺度效应，发现ｃ轴晶格常数与块材相比均缩短．Ｘ射线的φ扫描验证了后两类薄膜的外延特性，利用同步辐射的高强度和高能量分辨率用摇摆曲线方法研究了这两种外延薄膜的品质，进一步证明了ＳｒＴｉＯ_３衬底上的ＰｂＴｉＯ_３薄膜的单畴特性．利用重掺杂的硅衬底作底电极，测量显示直接生长于硅衬底上的ＰｂＴｉＯ_３多晶薄膜具有良好的铁电性能 关键词：     

Growth and conductivity of calcium cuprate films

Crystal and transport properties of epitaxial CaCuO₂ (CCO) films are studied for samples grown on (110)NdGaO₃, (001)SrTiO₃, and (001)LaAlO₃ substrates using the laser ablation technique. The resistivity is found to be dependent on the crystal quality of the films. The conductivity type varies depending on the doping. For lightly doped films with a resistance higher than 0.1 Ω cm, 3D hopping conductivity is observed. For low-resistance CCO films doped with Sr, a power law temperature dependence is found, which is inconsistent with the hopping conductivity. The influence of substrate tilting on the subsequent growth of CaCuO₂ films is studied. YBCO/CCO heterostructures preserve high critical temperatures and small widths of superconducting transitions, which is of special importance for growing Josephson heterostructures for superconducting electronics.     

Correlation between structural and mechanical properties of PbTiO3 thin films grown by pulsed-laser deposition

Tetragonal lead titanate (PbTiO₃, PT) thin films are grown on (1 0 0) MgO substrate by pulsed-laser deposition (PLD) for expected applications in integrated optics. The realisation of outstanding and reliable devices into integrated circuits requires sufficient mechanical resistance despite that the obtained PT films display interesting waveguiding properties associated with low optical losses. Two mechanical properties characteristic of elasticity and hardness of PT films are studied. The elastic modulus (E or Young's modulus) and the hardness (H) are measured by the nanoindentation technique. These mechanical properties are correlated to the crystalline quality of PT/MgO thin films. The films show epitaxial relationship with the MgO substrate and the orientation of crystallites perpendicularly to the surface substrate may be the consequence of a growth process along c-axis, a-axis or both. Differences on curves plotting hardness and elastic modulus as a function of indentation depth are observed as the curves are less dispersed for the films mainly c-axis oriented.     

Influence of the laser wavelength on the epitaxial growth and electrical properties of La0.8Sr0.2MnO3 films grown by excimer laser-assisted MOD

Epitaxial La_1−xSr_xMnO₃ (LSMO) films were prepared by excimer laser-assisted metal organic deposition (ELAMOD) at a low temperature using ArF, KrF, and XeCl excimer lasers. Cross-section transmission electron microscopy (XTEM) observations confirmed the epitaxial growth and homogeneity of the LSMO film on a SrTiO₃ (STO) substrate, which was prepared using ArF, KrF, and XeCl excimer lasers. It was found that uniform epitaxial films could be grown at 500 °C by laser irradiation. When an XeCl laser was used, an epitaxial film was formed on the STO substrate at a fluence range from 80 to 140 mJ/cm² of the laser fluence for the epitaxial growth of LSMO film on STO substrate was changed. When the LaAlO₃ (LAO) substrate was used, an epitaxial film was only obtained by ArF laser irradiation, and no epitaxial film was obtained using the KrF and XeCl lasers. When the back of the amorphous LSMO film on an LAO substrate was irradiated using a KrF laser, no epitaxial film formed. Based on the effect of the wavelength and substrate material on the epitaxial growth, formation of the epitaxial film would be found to be photo thermal reaction and photochemical reaction. The maximum temperature coefficient of resistance (TCR) of the epitaxial La_0.8Sr_0.2MnO₃ film on an STO substrate grown using an XeCl laser is 4.0%/K at 275 K. XeCl lasers that deliver stabilized pulse energies can be used to prepare LSMO films with good a TCR.     

Andreev states and the Josephson effect in superconducting heterojunctions on thin YBa2Cu3Ox films

Conductance anomalies at low bias voltages and superconducting currents in Au/YBa₂Cu₃O_x and Nb/Au/YBa₂Cu₃O_x heterojunctions in which the c axis of the YBa₂Cu₃O_x (YBCO) epitaxial film is rotated in the (110) YBCO plane through 11° with respect to the normal to the substrate plane were studied experimentally. The films were prepared by laser deposition onto (7 2 10)-oriented NdGaO₃ substrates. The current-voltage characteristics of the heterojunctions exhibit conductance anomalies at low voltages. The behavior of these anomalies is studied at various temperatures and in various magnetic fields. The critical current and Shapiro steps observed in the current-voltage characteristics of Nb/Au/YBa₂Cu₃O_x were evidence of the Josephson effect in these heterojunctions. The experimental results are analyzed in terms of the model of the arising of bound states caused by Andreev reflection in superconductors with d-type symmetry of the superconducting order parameter.     

Stress dependence of growth mode change of epitaxial layered cobaltite γ-Na0.7CoO2

We report stress dependence of growth characteristics of epitaxial γ-Na_0.7CoO₂ films on various substrates deposited by pulsed laser deposition method. On the sapphire substrate, the γ-Na_0.7CoO₂ thin film exhibits spiral surface growth with multi-terraces and highly crystallized texture. For the γ-Na_0.7CoO₂ thin film grown on the (1 1 1) SrTiO₃ substrate, the nano-islands of ∼30 nm diameter on the hexagonal grains are observed. These islands indicate that the growth mode changes from step-flow growth mode to Stranski-Krastanow (SK) growth mode. On the (1 1 1) MgO substrate, the large grains formed by excess adatoms covering an aperture between hexagonal grains are observed. These experimental demonstrations and controllability could provide opportunities of strain effects of Na_xCoO₂, physical properties of thin films, and growth dynamics of heterogeneous epitaxial thin films.     

Film thickness dependence of electro-optic effect in epitaxial BaTiO3 thin films

Based on the phenomenological Landau-Devonshire theory, we investigate the film thickness dependence of ferroelectric and electro-optic properties of epitaxial BaTiO₃ thin films grown on SrTiO₃ and MgO substrates. By using the effective substrate lattice parameter concept, the film thickness dependence of misfit strain is incorporated into the theory. Therefore, the film thickness dependence of ferroelectric and electro-optic properties in epitaxial BaTiO₃ thin films can be explained. Moreover, a large quadratic electro-optic effect was obtained in the BaTiO₃ thin films, which is in good agreement with the experimental result of BaTiO₃ thin films on the MgO substrate.     

Features of the twin structure of YBa2Cu3O7−x epitaxial films

X-ray diffraction is used to investigate YBa₂Cu₃O_7?x (YBCO) films on NdGaO₃(110) and a ${{(100)CeO_2 } \mathord{\left/ {\vphantom {{(100)CeO_2 } {(1\bar 102)}}} \right. \kern-0em} {(1\bar 102)}}Al_2 O_3 $ heterostructure. Symmetric, asymmetric, and axial geometries for θ and θ/2θ scans are used to obtain diffraction spectra from different crystallographic planes. The orientational and quantitative twinning characteristics of the films are determined. While the crystallographic parameters of these two types of film (the films are c-axis oriented with c=11.67 Å) are similar, there are differences in the twin structure. In particular, the features of the NdGaO₃ structure lead to the appearance of an angle differing from 90° (90.20°) between the possible (110) and θ/2θ twin planes in a YBCO film and a different number of twin components in each system of twins. It is concluded from an analysis of the broadening of reflections, which are sensitive to twinning, that there is not twinning in a 60% film of YBCO on Al₂O₃ with a CeO₂ buffer layer.     

Microstructure of Fe film on Si grown by MOCVD

Fe epitaxial films were grown on Si(100) substrate by MOCVD using thermal decomposition of iron pentacarbonyl, Fe(CO)₅. X-ray diffraction and XPS spectroscopy were used to study the structure of the epitaxial film. The results indicate that single crystal Fe film and iron oxide-iron-silicon multilayer structure can be grown on Si (100) substrate. We have also discussed the relation between microstructure and MOCVD process.     

Investigation of BiFeO3 Multiferroic thin films prepared by metalloorganic chemical vapor deposition

BiFeO₃ thin oriented films are grown on SrTiO₃(001) and ZrO₂(Y₂O₃)(001) substrates by metalloorganic chemical vapor deposition (MOCVD) in the temperature range T= 500–800°C. Iron dipivaloylmethanate Fe(thd)₃ and triphenylbismuth Bi(C₆H₅)₃ are used as volatile precursors. It is shown that the high thermal stability of Bi(C₆H₅)₃ leads to significant deviations of the Bi: Fe ratio in the film from their ratio in the precursor flow. An increase in the residence time of the precursor flow in the reactor makes this ratio close to unity. The film-substrate epitaxial relations are determined. It is found that the film orientation on the ZrO₂(Y₂O₃)(001) substrate changes with increasing temperature. Optical second harmonic generation (SHG) measurements show the presence of ferroelectric ordering in the films. A significant decrease in the Curie temperature due to epitaxial stress is found. At the same time, the magnetization noticeably increases as compared to a BiFeO₃ single crystal.     

Interfaces in superconducting hybrid heterostructures with an antiferromagnetic interlayer

The structural, X-ray diffraction, and electrophysical studies of hybrid superconducting hetero-structures with an interlayer of cuprate antiferromagnetic Ca_{1 ? x} Sr _x CuO₂ (CSCO) with the upper electrode Nb/Au and the lower electrode Y_Ba₂Cu₃O_{7 ? δ} (YBCO) have been carried out. It has been experimentally shown that the epitaxial growth of two cuprates, YBCO and CSCO, results in the formation of an interface on which the enrichment of the CSCO interlayer with charge carriers proceeds to a depth of about 20 nm. In this case, the conduction of the enriched CSCO region proves to be closer to metallic, whereas the CSCO film deposited onto the NdGaO₃ substrate is a Mott insulator with hopping conduction.     

Magnetic properties of SrRu0.9Fe0.1O3 thin films grown on different surfaces of SrTiO3 substrates

We stabilized SrRu_0.9Fe_0.1O₃ single-crystalline films on SrTiO₃ (001) and SrTiO₃ (110) substrates using epitaxial strain during thin-film growth. X-ray diffraction (XRD) θ–2θ scans showed strong peaks demonstrating single-crystal quality. Fe doping in SrRuO₃ had negative effects on the ferromagnetic properties, such as decreasing the T_c and saturated magnetic moment, as well as weakening the ferromagnetism. The negative effects were reduced when a suitable surface of the cubic substrate was selected for thin-film SrRuO₃ growth. We found that the ferromagnetic properties, such as the T_c and saturated magnetic moment, differed depending on the substrate surface. The observed differences are discussed in terms of Ru–Ru nearest-neighbor distance.     

Thickness-dependent transport properties of Sr4Fe6O13 epitaxial thin films

High-quality epitaxial thin films of Sr₄Fe₆O₁₃ have been deposited on NdGaO₃(001) substrates by pulsed laser deposition. The transport properties have been characterized by impedance spectroscopy. The temperature dependence of conductivity suggests a mechanism of adiabatic hopping by small polarons, in agreement with previous results in bulk samples. The transport properties show a clear dependence on the film thickness with the thinner films (10 nm) presenting conductivity values in oxygen one order of magnitude higher than the thicker ones (313 nm). We correlate this behaviour with the thickness dependence of the epitaxial strain.     

Characterization of bicrystalline epitaxial LaNiO3 films fabricated on MgO (1 0 0) substrates by pulsed laser deposition

A series of metallic LaNiO₃ (LNO) thin films were deposited on MgO (1 0 0) substrates by pulsed laser deposition (PLD) under the oxygen pressure of 20 Pa at different substrate temperatures from 450 to 750 °C. X-ray diffraction (XRD) was used to characterize the crystal structure of LNO films. θ-2θ scans of XRD indicate that LNO film deposited at a substrate temperature of 700 °C has a high orientation of (l l 0). At other substrate temperatures, the LNO films have mixed phases of (l l 0) and (l 0 0). Furthermore, pole figure measurements show that LNO thin films, with the bicrystalline structure, were epitaxially deposited on MgO (1 0 0) substrates in the mode of LNO (1 1 0)//MgO (1 0 0) at 700 °C. Reflection high-energy electric diffraction (RHEED) and atomic force microscopy (AFM) were also performed to investigate the microstructure of LNO films with the high (l l 0) orientation. RHEED patterns clearly confirm this epitaxial relationship. An atomically smooth surface of LNO films at 700 °C was obtained. In addition, bicrystalline epitaxial LNO films, fabricated at 700 °C, present a excellent conductivity with a lower electrical resistivity of 300 μ Ω cm. Thus, the obtained results indicate that bicystalline epitaxial LNO films could serve as a promising candidate of electrode materials for the fabrication of ferroelectric or dielectric films.     

SUPERCONDUCTING PROPERTIES AND STRUCTURAL PERFECTION OF EPITAXIAL YBa2Cu3O7-x THIN FILMS

High quality epitaxial YBa₂Cu₃O_7-x thin films have been succcessfully prepared by dc magnetron sputtering deposition, on (100) and (110) aligned SrTiO₃, LaAlO₃ and yttria-stabilized zirconia (YSZ) substrates. The films showed zero resistance around 90 K and had a J_c (at 77 K, H=0) over 10⁶A/cm². It was found that superconducting properties and structures of the films were strongly dependent on oxygen pressure and substrate temperature. The epitaxial structure of the films have been studied by X-ray diffraction. Rutherford backscattering and channeling spectroscopy, X-ray double-crystal diffraction and transmission election microscopy. The experimental results demonstrated that the epitaxial YBa₂Cu₃O_7-x films had excellent superconducting properties and quite perfect structure.     

Microstructure of epitaxial SrRuO3 thin films on MgO substrates

SrRuO₃ thin films have been grown on singular (1 0 0) MgO substrates using pulsed laser deposition (PLD) in 30 Pa oxygen ambient and at a temperature of 400-700 °C. Ex situ reflection high-energy electron diffraction (RHEED) as well as X-ray diffraction (XRD) θ/2θ scan indicated that the films deposited above 650 °C were well crystallized though they had a rough surface as shown by atom force microscopy (AFM). XRD Φ scans revealed that these films were composed of all three different types of orientation domains, which was further confirmed by the RHEED patterns. The heteroepitaxial relationship between SrRuO₃ and MgO was found to be [1 1 0] SRO//[1 0 0] MgO and 45°-rotated cube-on-cube [0 0 1] SRO//[1 0 0] MgO. These domain structures and surface morphology are similar to that of ever-reported SrRuO₃ thin films deposited on the (0 0 1) LaAlO₃ substrates, and different from those deposited on (0 0 1) SrTiO₃ substrates that have an atomically flat surface and are composed of only the [1 1 0]-type domains. The reason for this difference was ascribed to the effect of lattice mismatch across the film/substrate interface. The room temperature resistivity of SrRuO₃ films fabricated at 700 °C was 300 μΩ cm. Therefore, epitaxial SrRuO₃ films on MgO substrate could serve as a promising candidate of electrode materials for the fabrication of ferroelectric or dielectric films.