Piezoelectric Pb0.7La0.2TiO3 prepared by pulsed laser deposition on (100)InP

La-modified PbTiO₃ (PLT) thin films have been deposited by pulsed laser deposition on (100)InP substrates. The nominal target composition was selected to optimize piezoelectric properties of the material. It is shown that PLT deposition on as-received InP produces amorphous PLT films because of the presence of a native oxide on the substrate. PLT films deposited on bare InP have poor adhesion as a result of the surface reoxidation of the substrate due to the high oxygen pressure required for the deposition of stoichiometric PLT. To prevent substrate oxidation, several buffer oxides (CeO₂, ZrO₂, SrO, Y-stabilized ZrO₂, MgO, and SrTiO₃) have been grown in vacuum on (100)InP. Highest-quality heteroepitaxy was found with Y-stabilized ZrO₂ (YSZ), being 𘜄¢{100} YSZ𘜄¢{100} InP oriented. The PLT deposited on this buffer layer is oriented with the [101] direction perpendicular to the substrate surface plane.     

Controlling crystal quality and orientation of pulsed-laser-deposited BaTiO3 thin films by the kinetic energy of the film-forming particles

The deposition of BaTiO₃ thin films by pulsed excimer laser radiation (248 nm) on Pt/Ti/Si(111) and Pt/Ti/Si(100) substrates is investigated as a function of the processing variables laser fluence, processing gas pressure, and target-to-substrate distance under conditions of temporal and spatial properties of the involved vapour and plasma states. The kinetic energy of the species in the laser-generated plasma, as measured by time-of-flight optical emission spectroscopy and time-of-flight quadrupole mass spectrometry, is described as a function of the pressure of the processing gas, the distance from the target, and the laser fluence. The influence of the kinetic energy of the film-forming particles on the crystalline structure, defects, and orientation, and on the resulting electrical properties of the films is investigated. X-ray diffraction measurements and polarisation-dependent micro-Raman measurements reveal a c-axis orientation normal to the substrate surface, in the case of high particle energy (>50 eV), whereas at low kinetic energies (<30 eV) a [111]_pc or [110]_pc orientation is preferred. The ferroelectricity and the dielectric constant of the films, determined by impedance measurements, decrease with increasing kinetic energy of the film-forming particles from )_r=1000-2200 to )_r=200-700. This decrease correlates with the change of the orientation and with an increasing lattice constant of the films, indicating that particles with high kinetic energies produce crystal defects and stress in the growing film.     

Low-temperature preparation of SrxBi2+yTa2O9 ferroelectric thin film by pulsed laser deposition and its application to a metal–ferroelectric–nitride–oxide–semiconductor structure

Preferentially (105)-oriented Sr_xBi_2+yTa₂O₉ (SBT) thin films on SiN/SiO₂/p-Si(100) prepared by the pulsed laser deposition (PLD) method at a temperature as low as 400 °C, which is the lowest process temperature for growing SBT ferroelectric thin films on a silicon nitride film. Excess Bi promotes crystallization of the SBT film. A metal-ferroelectric-nitride-oxide-semiconductor (MFNOS) structure, which is very important in ferroelectric gate memory FET, has been fabricated by depositing the SBT film on silicon nitride-oxide-silicon. The MFNOS structures show capacitance-voltage (C-V) hysteresis corresponding to ferroelectric hysteresis. A memory window of the C-V hysteresis is improved, to be as high as 3.5 V in the SBT(400 nm)/SiN_x(7 nm)/SiO₂(18 nm)/Si compared with the window of 2.7 V in the SBT(400 nm)/SiO₂(27 nm)/Si (MFOS), where the thicknesses of their insulator layers are nearly the same. Little degradation is induced in the C-V characteristics of the SiN_x/SiO₂/p-Si structure when depositing the SBT film by PLD at low temperature. It is also found that the SiN_x layer acts as a diffusion barrier against component atoms in the SBT film during its deposition. Finally, the MFNOS structure prepared at the low temperature is very promising for a next-generation ferroelectric gate memory FET.     

Observation of defects and growth orientations of YBa2Cu3Ox thin films with YSZ buffer layers on Si

We have investigated defects and in-plate orientations of YBa₂Cu₃O_x thin films prepared by pulsed laser deposition (PLD) with YSZ as a buffer layer. The films showed c-axis oriented growth with the transition temperature T_co up to 87 K. Several types of defects including thermally induced cracks, grain boundaries and outgrowths were observed by scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). The grain boundary provided a favorable path for crack propagation. The outgrowths nucleated on the YSZ surface grew with stoichiometric composition. According to X-ray diffraction (XRD) and HRTEM studies the YSZ buffer layer grew with the orientation relationship, YSZ110//Si110 and YSZ(001)//Si(001) up to the YBCO/YSZ interface. The superconducting YBCO films on top grew mainly with YBCO100//Si110 and YBCO(001)//Si(001), with some minor portions of YBCO110//Si110 and YBCO(001)//Si(001).     

Role of bismuth precursor in crystallization of SrBi2Ta2O9 thin films

Crystallization of SrBi₂Ta₂O₉ (SBT) thin films was studied as a function of viscosity of bismuth precursor and baking temperature, in order to fabricate capacitors with improved ferroelectric properties. SBT thin films were deposited on to Pt substrates using a chemical solution deposition (CSD) technique. Post-deposition anneal at 750 °C for 1 h in oxygen atmosphere revealed a significant influence of baking temperature and the viscosity of bismuth precursor on the microstructure and the ferroelectric properties of SBT thin films. A high baking temperature (350 °C) and a low viscosity of bismuth precursor (8 cp) yielded larger amounts of Bi₂O₃ secondary phase, smaller SBT grains (104 nm), and lower remanent polarization (P_r=2.0 7c/cm²). Additionally, these films exhibited a very high rate of ageing (>45% reduction in P_r after 7 days). A modified CSD process is suggested, which could suppress the formation of Bi₂O₃ secondary phase. Films fabricated using modified CSD technique exhibited a much larger grain size of 165 nm, higher P_r of 7.2 7c/cm², and significantly improved ageing characteristics (<1% reduction in P_r after 7 days). A qualitative model to describe the ageing in SBT-based capacitors is also suggested.     

Differential friction force spectroscopy of micropatterned organosilane self-assembled monolayers

Frictional properties of organosilane self-assembled monolayers (SAMs) and hydrated silicon oxide (SiOH) surfaces on a single sample substrate were studied; the frictional force difference between the surfaces was measured by employing one as a standard. Using a lateral force microscope (LFM), differential frictional force microscopic data were obtained by measuring the difference in the friction forces of the two surfaces with respect to the vertical load force applied to the LFM probe. The SAMs were prepared from n-octadecyltrimethoxysilane [ODS, H₃C(CH₂)₁₇Si(OCH₃)₃], n-(6-aminohexyl) aminopropyltrimethoxysilane [AHAPS, H₂N(CH₂)₆NH(CH₂)₃Si(OCH₃)₃], 3,3,3-trifluoropropyltrimethoxysilane [FAS3, F₃C(CH₂)₂Si(OCH₃)₃] and heptadecafluoro-1,1,2,2-tetrahydro-decyl-1-trimethoxysilane [FAS17, F₃C(CF₂)₇(CH₂)₂Si(OCH₃)₃] by chemical vapor deposition. In the vertical force range of 0 to 600 nN, the SAMs showed no damage at all, and frictional force on the SAM surfaces increased linearly with the vertical force. The order of the frictional force magnitudes determined with the SiOH-terminated probe was SiOH > AHAPS > FAS3 > FAS17 > ODS. In addition, the frictional force difference did not become zero even at a vertical force of 0 nN, that is, the frictional differences could even be imaged by LFM through probe-sample adhesion.     

Orientation dependence of ferroelectricity in pulsed-laser-deposited epitaxial bismuth-layered perovskite thin films

Thin films of bismuth-layered perovskites such as SrBi₂Ta₂O₉, Bi₄Ti₃O₁₂, and BaBi₄Ti₄O₁₅ with preferred orientations were grown by pulsed laser deposition on epitaxial conducting LaNiO₃ electrodes on single-crystalline (100) SrTiO₃ or on top of epitaxial buffer layers on (100) silicon. A morphology and structure investigation by X-ray diffraction analysis, scanning probe microscopy, and scanning and transmission electron microscopy showed that the films consisted of both c-axis-oriented regions and mixed (110)-, (100)-, and (001)-oriented regions. The regions with mixed orientation featured rectangular as well as equiaxed crystalline grains protruding out of a smooth c-oriented background. A closer examination revealed that the regions with mixed orientation actually consisted of a c-axis-oriented sublayer growing directly on the epitaxial LaNiO₃ electrode, on top of which the growth of either (110)-, (100)-, or (001)-oriented grains took place. Macroscopic as well as microscopic measurements of the ferroelectric properties of regions with pure c-orientation and of regions with mixed orientations showed a clear relationship between their ferroelectric properties and their morphology and crystallographic orientation. In the regions with mixed orientation, the films exhibited saturated ferroelectric hysteresis loops with well-defined remnant polarisation P_r and coercive field E_c. The regions having c-axis orientation with a smooth surface morphology in contrast exhibited a linear P-E curve with no hysteretic behaviour for SrBi₂Ta₂O₉ and BaBi₄Ti₄O₁₅ and a weak ferroelectric behaviour for Bi₄Ti₃O₁₂. This clearly showed that the ferroelectric properties of bismuth-layered ferroelectric oxides depended on the crystalline orientation of the film and that the observed ferroelectric hysteresis loops in SrBi₂Ta₂O₉ and BaBi₄Ti₄O₁₅ films were solely due to the (100)- and (110)-oriented grains. The size of the (110)- and (100)-oriented grains being of the order of 100 nm and spontaneous polarisation having been observed and switched in a controlled manner is a demonstration that ferroelectricity can exist in structures of submicrometer size. These results might have a technological impact due to the relevance of bismuth-layered ferroelectric oxides for the fabrication of non-volatile FeRAM memories.     

Texture control and its impact on the properties of SrBi2Ta2O9 thin films prepared by pulsed laser deposition

SrBi₂Ta₂O₉ (SBT) ferroelectric thin films with different preferred orientations were deposited by pulsed laser deposition (PLD). Several methods have been developed to control the preferred orientation of SBT thin films. For SBT films deposited directly on Pt/TiO₂/SiO₂/Si substrates and in situ crystallized at the deposition temperature, the substrate temperature has a significant impact on the orientation and the remnant polarization (Pr) of the films; a higher substrate temperature benefits the formation of (115) texture and larger grain size. The films deposited on Pt/TiO₂/SiO₂/Si substrates at 830 °C are (115)-oriented and exhibit 2Pr of 6 μC/cm². (115)- and (200)-predominant films can be formed by using a La_0.85Sr_0.15CoO₃ (LSCO) buffer layer or by annealing amorphous SBT films deposited on Pt/TiO₂/SiO₂/Si substrates at 450 °C using rapid thermal annealing (RTA). These films exhibit good electric properties; 2Pr of the films are up to 12 μC/cm² and 17 μC/cm², respectively. The much larger 2Pr of the films deposited on the LSCO buffer layer and of the films obtained by RTA than 2Pr of the films deposited on Pt/TiO₂/SiO₂/Si substrates at 830 °C is attributed to a stronger (200) texture. Received: 30 January 2001 / Accepted: 30 May 2001 / Published online: 25 July 2001     

Growth and characterization of ferroelectric SrBi2Ta2O9 single crystals via high-temperature self-flux solution method

SrBi₂Ta₂O₉ (SBT) single crystals were produced by the high-temperature self-flux solution method using a Bi₂O₃ flux modified with B₂O₃. The processing conditions were optimized to obtain large and translucent SBT crystals with a layered habit and typical dimensions of approximately 7 × 5 × 0.2 mm. X-ray diffraction and x-ray topography measurements revealed that the major faces of the crystals with natural rectangular platelet morphology are perfectly (001)-oriented with edges directed along the [110] directions. The high quality of the crystals was confirmed by rocking curves (half-width of 0.04° for the (0018) reflection) and by ferroelectric measurements. The anisotropy in the dielectric and ferroelectric properties was investigated both along the [110] (ab plane) and the [001] (c axis) directions. The growth mechanism, morphology, and dielectric anisotropy of the SBT crystal platelets are discussed based on its crystallographic structure. This article was submitted by the authors in English     

Studies of structure and composition of a Pt-based basic electrode for deposition of PZT ferroelectric films on silicon substrates

In this study it has been found that a TiO₂/Ti double adhesion layer is used for SiO₂/Si substrate and a YSZ layer is used for SiO₂/Si and Si substrates to achieve high residual polarization of PZT layers on platinum. Epitaxial deposition of YSZ on Si(100) provides an atomically smooth platinum layer textured in the [100] direction. The produced PZT films are mostly textured in the [111] direction; their residual polarization is 5–15 μC/cm².     

Improved initial epitaxial growth of superconducting YBa2Cu3O7 thin films on Y–ZrO2 substrates with a La1.85Sr0.15CuO4 buffer layer

Epitaxial thin films of YBa₂Cu₃O₇ (YBCO) have been deposited on Y–ZrO₂ (YSZ) substrates by means of the pulse laser deposition technique. It has been found that the initial epitaxy of YBCO thin films grown on YSZ can be significantly improved by using La_1.85Sr_0.15CuO₄ (LSCO) as a buffer layer. X-ray diffraction measurements show that the epitaxial YBCO films have single in-plane orientation with YBCO [100]LSCO [100] and LSCO [100]YSZ [110]. The real-time resistance measurements reveal that with LSCO buffer layers the initial formation of the YBCO ultra-thin films changes from the island growth to the layer-by-layer growth.     

Pulsed-laser deposition of Ta-doped PZT ferroelectric films for memory applications using conductive oxide La0.25Sr0.75CoO3 and SrRuO3 electrodes

New methods for fabricating highly 𘚡¢-oriented and complete 𘜏¢-textured Pb(Ta_0.05Zr_0.48Ti_0.47)O₃ (PTZT) films on Pt/TiO₂/SiO₂/Si(001) substrates by pulsed-laser deposition have been developed using conductive oxide La_0.25Sr_0.75CoO₃ and SrRuO₃ electrodes. The 𘚡¢-preferred orientated PTZT ferroelectric capacitor was not subjected to loss of its polarization after 1᎒¹⁰ switching cycles at an applied voltage of 5 V and a frequency of 1 MHz, and the 𘜏¢-textured PTZT film capacitor retains 94.7% of its polarization after 1.5᎒¹⁰ switching cycles at 5 V and 50 kHz. The PTZT capacitors using these conductive oxide electrodes have low leakage current dominated by Schottky field emission mechanism.     

SrTiO3(110) thin films grown directly on different oriented silicon substrates

We have grown (110)-oriented SrTiO₃ (STO) thin films on silicon without any buffer layer, by means of pulsed laser deposition technique. The crystal structures of the grown films were examined by X-ray diffraction analysis including θ–2θ scan and rocking curve as well as Laue diffraction methods. STO films with single (110) out-of-plane orientation were formed on all (100), (110) and (111)-oriented Si substrates. The in-plane alignments for the epitaxial STO films grown directly on Si (100) were found as STO[001]//Si[001] and STO[11̄0]//Si[010]. The results should be of interest for better understanding of the growth of perovskite oxide thin films on silicon wafers. PACS 77.55.+f; 68.55.JK; 81.15Fg     

Ruthenium oxide and strontium ruthenate electrodes for ferroelectric thin-films capacitors

Metallic ruthenium and ruthenium oxides, such as SrRuO₃ and RuO₂, are potential electrode materials for ferroelectric capacitors. The electrical properties (e.g. leakage currents) of such thin film devices are dependent on the electronic properties of the electrode/ferroelectric junctions and therefore also on the electrode work functions. During growth and processing of film-electrode layer structures the formation of sub-oxides within the electrode is possible, with their work functions being unknown. In order to obtain information for predicting device properties, we have systematically analysed the valence bands and work functions of RuO_x and SrRuO_y thin films with different oxidation states by using photoelectron spectroscopy techniques. The results suggest that Ru⁰ and Ru⁴⁺ ions are present in co-existence at the surfaces of oxygen-deficient polycrystalline films (inhomogeneous oxidation). For both oxygen-deficient materials the work function coincides with that of metallic ruthenium (4.6ǂ.1 eV). Only for fully oxidised ruthenium oxide and strontium ruthenate films (no Ru⁰ present at the surface) is the work function increased to 5.0 or 4.9 eV, respectively. As an example of importance for new dynamic random access memory applications, the junctions of Ba_1-xSr_xTiO₃ with SrRuO_y and RuO_x are discussed.     

(100) and (110) SiSiO2 interface studies by MeV ion backscattering

Thin oxide layers on (110) and (100) Si have been studied by ion scattering experiments in a channeling grazing exit angle geometry. Oxides are found to be stoichiometric SiO₂ to within 10 Å of the (100) substrate surface, and 7 Å of the (110). The transition interface region between single crystal Si and the SiO₂ layer is abrupt and is characterized by approximately one to two monolayers of Si which is out of registration with the substrate lattice for the (110) case. The possibility of a layer of O-deficient oxide is also explored.     

Preparation and characterization of ferroelectric SrBi2Ta2O9 thin films on Si using Al2O3 buffer layers

SrBi₂Ta₂O₉ (SBT) thin films were prepared on p-type Si(100) substrates with Al₂O₃ buffer layers. Both the SBT films and the Al₂O₃ buffer layers were deposited by a pulsed laser deposition technique using a KrF excimer laser. An Al prelayer was used to prevent Si surface oxidization in the initial growth stage. It is shown that Al₂O₃ buffer layers effectively prevented interdiffusion between SBT and Si substrates. Furthermore, the capacitance–voltage (C-V) characteristics of the SBT/Al₂O₃/Si heterostructures show a hysteresis loop with a clockwise trace, demonstrating the ferroelectric switching properties of SBT films and showing a memory window of 1.6 V at 1 MHz. Received: 17 July 2000 / Accepted: 16 August 2000 / Published online: 30 November 2000     

Synthesis and characterization of laser ablated TiNi films

TiNi thin films with BaTiO₃ and PbZr_0.52Ti_0.48O₃ (PZT) as buffer layers were deposited on Si(100) substrates by the pulsed laser deposition (PLD) method. Buffer layers (BaTiO₃ and PZT) were deposited at 600 °C in oxygen (O₂) environment and TiNi films were deposited on the top of the buffer layer in presence of 15 mTorr nitrogen (N₂) at various deposition temperatures (50, 300, and 500 °C). Synthesis and characterization of TiNi films were investigated from the crystallographic point of view by using X-ray diffractometer (XRD) and atomic force microscope (AFM) techniques. It is found that buffer layer of BaTiO₃ and PZT have improved the crystallinity of TiNi films deposited at higher temperatures. The TiNi/PZT film was uniform compared to TiNi/BaTiO3 film with the exception of agglomerates that appeared throughout the layer.     

Si衬底上分子束外延Ge,Si时的反射式高能电子衍射强度振荡观察

本文观察了在Si(100)和Si(111)衬底上分子束外延Si,Ge时的反射式高能电子衍射(RHEED)强度振荡现象。其振荡特性表明,外延一定厚度的缓冲层可以改善表面的平整性,较慢的生长速率或中断生长一段时间有利于外延膜晶体质量的提高。Si(100)上外延Si或Ge时,沿[100]和[110]方位观测到的振荡特性均为单原子模式,起因于表面存在双畴(2×1)再构;而Si(111)上外延Ge时,[112]方位观测到的振荡为双原子层模式,但在[110]方位观察到不均匀周期的强度振荡行为。两种衬底上保持RHEED     

Anisotropy of Hc2 in single crystal Nb3Sn and V3Si at high magnetic fields: Limitations of linear chain model

The anisotropy of H_c2 for single crystal Nb₃Sn and V₃Si in the low temperature tetragonal phase was measured in high magnetic fields. At ～ 8K, δ = [H_c2[100]-H_c2[110])/H_c2] ≈0.05 for Nb₃Sn and δ ≈ 0.02 for V₃Si. The data do not show evidence of a highly anisotropic Fermi surface for Nb₃Sn or V₃Si.