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.     

Working Pressure Dependence of Properties of Al2O3 Thin Films Prepared by Electron Beam Evaporation

The effects of working pressure on properties of Al2O3 thin films are investigated. Transmittance of the Al2O3 thin film is measured by a Lambda 900 spectrometer. Laser-induced damage threshold （LIDT） is measured by a Nd：YAG laser at 355 nm with a pulse width of 7ns. Microdefects were observed under a Nomarski microscope. The samples are characterized by optical properties and defect, as well as LIDT under the 355 nm Nd：YAG laser radiation. It is found that the working pressure has fundamental effect on the LIDT. It is the absorption rather than the microdefect that plays an important role on the LIDT of Al2O3 thin film.     

Influence of laser-ablation plume dynamics on the room-temperature epitaxial growth of CeO2 on silicon

High-quality epitaxial CeO₂ thin films were obtained on Si(001) buffered with a yttria-stabilised zirconia layer by pulsed laser deposition. Although the best structural properties were achieved at high substrate temperature, high-quality epitaxy was obtained even at room temperature. Epitaxial growth at low temperature is promoted by the high kinetic energy of particles reaching the substrate. The oxygen pressure and target-substrate distance had a strong influence on the crystallographic structure and surface morphology in low-temperature deposition. This behaviour is attributed to a change in the kinetic energy of the particles, which was evaluated from the plasma expansion velocity determined by an intensified CCD camera. If a shock wave forms, a minimum substrate temperature of 550 °C is necessary for epitaxial growth.     

Molecular dynamics simulation for the sputtering of an Al2O3 sample bombarded with MeV Si ions

Sputtering yield and kinetic energy distribution (KED) of Al particles from an Al₂O₃ sample bombarded with 1－5 MeV Si ions have been simulated using the molecular dynamics method. These have also been measured experimentally with a conventional time-of-flight facility. In the simulation, a new interatomic potential specific to the Al₂O₃ target was developed, and both the nuclear energy loss S_n and electronic energy loss S_e were taken into consideration. By carefully adjusting the simulation parameters, the simulated sputtering yields fit well with the experimental results, and the simulated KED of Al particles also fits roughly with the experimental KED after being modified theoretically.     

Pulsed laser deposition of tantalum pentoxide film

We report thin tantalum pentoxide (Ta₂O₅) films grown on quartz and silicon substrates by the pulsed laser deposition (PLD) technique employing a Nd:YAG laser (wavelength 5=532 nm) in various O₂ gas environments. The effect of oxygen pressure, substrate temperature, and annealing under UV irradiation using a 172-nm excimer lamp on the properties of the grown films has been studied. The optical properties determined by UV spectrophotometry were also found to be a sensitive function of oxygen pressure in the chamber. At an O₂ pressure of 0.2 mbar and deposition temperatures between 400 and 500 °C, the refractive index of the films was around 2.18 which is very close to the bulk Ta₂O₅ value of 2.2, and an optical transmittance around 90% in the visible region of the spectrum was obtained. X-ray diffraction measurements showed that the as-deposited films were amorphous at temperatures below 500 °C and possessed an orthorhombic (#-Ta₂O₅) crystal structure at temperatures above 600 °C. The most significant result of the present study was that oxygen pressure could be used to control the composition and modulate optical band gap of the films. It was also found that UV annealing can significantly improve the optical and electrical properties of the films deposited at low oxygen pressures (<0.1 mbar).     

Amorphization of Fe/Al: bulk and thin-film effects

The amorphous non-equilibrium state of the system Fe/Al is studied in bulk and thin-film systems. For bulk samples prepared by ion-beam mixing of laser-deposited multilayers, a bcc solid solution is found for alloys with up to 70 at. % Al. Around 75 at. % Al a Fe₂Al₅-like crystalline phase is found. An amorphous state with Fe₂Al₅-like short-range order is found for 80 at. % Al. In thin films, for example the amorphous Al-rich transition layer of a laser-deposited Fe/Al multilayer, the amorphous state can exist for up to 30 at. % Fe due to the high interfacial energy. By ion-beam mixing at low temperatures (about 140 K) an oversaturation with 40 at. % Fe can be achieved.     

Distinct orientation of AlN thin films deposited on sapphire substrates by laser ablation

We report the experimental characterization of the charged species produced in excimer laser ablation of a superconducting intermetallic compound (YNi₂B₂C). By using energy-selective time-of-flight mass spectrometry, we have obtained direct measurements of both mass spectra and kinetic energy distributions of ions. The investigation has been carried out in the laser fluence range 1-5 J cm^-2, which is typical of laser ablation thin film deposition. High kinetic energies of the charged component (up to 0.4 keV) have been observed even at moderate laser fluences.     

The effect of different ambient gases, pressures, and substrate temperatures on TiO2 thin films grown on Si(100) by laser ablation technique

Pure titanium dioxide (TiO₂) thin films were deposited on single-crystal Si(100) substrates by laser ablation. We investigated the effects of ambient gas (O₂ or Ar), pressures, and substrate temperatures on film quality. From the annealing experiment of the deposited TiO₂ thin film under Ar or O₂ ambient gas, we see the chemical effect of ambient gas on film quality. The crystallinity of the deposited TiO₂ thin film is best at 700 °C in the substrate temperature range attempted, 400-700 °C, and at pressures of 0.1 Torr and below. The rutile phase is dominant under most experimental conditions. Only under very extreme conditions did we obtain a thin film of the anatase phase.     

Study of pulsed laser deposition of RuO2 and SrRuO3 thin films

In this study, the pulsed laser ablation of RuO₂ and SrRuO₃ (SRO) is investigated by observing the fluorescence from excited atoms in the plume by using a framing streak camera. Vaporization, phase explosion and boiling are suggested to play the main roles in the processes for the interaction between the laser beam and target. Collisions and adiabatic expansion are also suggested before particles move forward with shifted Maxwellian spatial distribution. In O₂ pressure, numerous collisions between fast and slow atoms occur and result in the exchange of speeds. The structural and electrical (conductivity and work-function) properties of RuO₂ and SRO thin films are measured. Epitaxial SRO growth was obtained at growth temperatures down to 350 °C. Ferroelectric and high- dielectric thin-film capacitors with RuO₂ or SRO thin film electrode are also studied.     

Al<Subscript>2</Subscript>O<Subscript>3</Subscript> plasma production during pulsed laser deposition

A Nd:YAG laser operating in second harmonic (532 nm), 3 ns pulse duration, 150 mJ pulse energy, and 10 Hz repetition rate, is employed to irradiate Al₂O₃ target placed in high vacuum. The produced plasma is investigated by an ion collector used in time-of-flight configuration and by a mass quadrupole spectrometer, in order to determine the equivalent plasma temperature and the atomic and molecular composition. Pulsed laser deposition technique has been used to produce thin films on different substrates placed close to the target. Different surface analyses, such as energy dispersive X-ray fluorescence (EDXRF), X-ray photoelectron spectroscopy (XPS) and surface profilometry are employed to characterize the produced films. Measurements of ablation yield, plasma equivalent temperature, acceleration voltage and characterization of grown thin films are presented and discussed.     

Influence of the plasma parameters on the properties of aluminum oxide thin films deposited by laser ablation

The plasma produced by the ablation of a high purity Al₂O₃ target, using the fundamental line (1064 nm) of a Nd:YAG laser, was characterized. The laser fluence was varied in order to study its effect on the characteristics of the produced plasma as well as on the properties of the material deposited. Optical emission spectroscopy (OES) was used to determine the type of excited species present in the plasma. The mean kinetic energy of the ions and the maximum plasma density were determined from the time of flight (TOF) curves, obtained with a planar Langmuir probe. The obtained results reveal that the fast peak in the probe curve could be attributed to Al III, while the slow peak corresponds to the Al II. Aluminum oxide thin films were then deposited under the same conditions of the diagnosed plasma, in an attempt to correlate the plasma parameters with the properties of the deposited material. It was found that when Al II ion energies are lower than 461.0 eV the films deposited have structural characteristics similar to that of α-Al₂O₃, whereas at ion energies greater than 461.0 eV amorphous material was obtained.     

Epitaxial Properties of Co-Doped ZnO Thin Films Grown by Plasma Assisted Molecular Beam Epitaxy

High quality Co-doped ZnO thin films are grown on single crystalline Al2O3（0001） and ZnO（0001） substrates by oxygen plasma assisted molecular beam epitaxy at a relatively lower substrate temperature of 450℃. The epitaxial conditions are examined with in-situ reflection high energy electron diffraction （RHEED） and ex-situ high resolution x-ray diffraction （HRXRD）. The epitaxial thin films are single crystal at film thickness smaller than 500nm and nominal concentration of Co dopant up to 20%. It is indicated that the Co cation is incorporated into the ZnO matrix as Co^2＋ substituting Zn^2＋ ions. Atomic force microscopy shows smooth surfaces with rms roughness of 1.9 nm. Room-temperature magnetization measurements reveal that the Co-doped ZnO thin films are ferromagnetic with Curie temperatures Tc above room temperature.     

Room-Temperature Ferromagnetism in Zn1-xMnxO Thin Films Deposited by Pulsed Laser Deposition

Zn1-xMnxO （x = O.Olq3.1） thin films with a Curie temperature above 300K are deposited on Al2O3 （0001） substrates by pulsed laser deposition. X-ray diffraction （XRD）, ultraviolet （UV）-visible transmission and Raman spectroscopy are employed to characterize the microstructural properties of these films. Room temperature ferromagnetism is observed by superconducting quantum interference device （SQUID）. The results indicate that Mn doping introduces the incorporation of Mn^2＋ ions into the ZnO host matrix and the insertion of Mn^2＋ ions increases the lattice defects, which is correlated with the ferromagnetism of the obtained films. The doping concentration is also proven to be a crucial factor for obtaining highly ferromagnetic Zn1-xMnxO films.     

Microstructure and electrical properties of textured Sr0.51Ba0.48La0.01Nb2O6 thin films

Sr_0.51Ba_0.48La_0.01Nb₂O₆ (SBLN) thin films were prepared on platinized silicon substrates by pulsed laser deposition (PLD) combined with annealing technique. The preferred orientation, surface morphology, composition, and interfacial properties of the SBLN thin films were characterized by X-ray diffraction, atomic force microscopy, transmission electron microscopy, X-ray energy dispersive spectroscopy, and automatic spreading resistance measurement. The ferroelectric properties were confirmed by P - E hysteresis loops. The frequency variation of the dielectric constant was measured as well.     

UV laser ablation of alumina ring faces for mechanical seal applications

Al₂O₃ seal ring faces were treated by KrF excimer laser irradiation. Surface characteristics induced by laser irradiation depend upon laser fluence, the number of laser pulses, the frequency and duration of the laser pulses, the rotation rate of the ring, and the processing atmosphere. Microstructural analyses of the surface and cross section of the laser-processed seal faces showed that, at low fluence (1.8 J/cm²), the surface is covered by scale due to the melting/resolidification processes. At high fluence (7.5 J/cm²), there is no continuous scaling on the surfaces. Material is removed by decomposition/vaporisation and the ablation depth is linearly dependent on the number of pulses; on the surface, a network of microcracks forms. The evolution of surface morphology and roughness is discussed with reference to composition, the microstructure and physical and optical properties of Al₂O₃, and laser processing parameters.     

Nanocrystalline growth and diagnostics of TiC and TiB2 hard coatings by pulsed laser deposition

Nanocrystalline coatings of TiC and TiB₂ were grown by pulsed laser deposition on Si(100) and on X155 steel at low substrate temperatures ranging from 40 °C to 650 °C. A pulsed KrF excimer laser was used with the deposition chamber at a base pressure of 10^-6 mbar. The morphology and structure of the films, studied with SEM, XRD, and TEM, showed that nanocrystalline films with a fine morphology of TiC and TiB₂ were deposited with a grain size of 10 nm-70 nm at all substrate temperatures. The growth of the polycrystalline coatings possessed a columnar morphology with a 𘜄¢ preferred orientation. The hardness of the coatings was determined to be 40 GPa and the elastic modulus, 240 GPa. The composition and the kinetics of the plume produced during the pulsed laser deposition of TiC and TiB₂ was studied under film growth conditions. The mass analysis of ions of the ejected material was performed by time-of-flight mass spectroscopy (TOF-MS) and showed the presence of Ti⁺ and C⁺ during TiC ablation and B⁺, B₂⁺, and Ti⁺ during TiB₂ ablation. The kinetic energies (KE) of the ions depended on the laser fluence which was between 0.5 eV and 340 eV. The kinetic energy and the evolution of the plasma was studied with a streak camera. The velocity of the plasma was of the order of 10⁶ cm/sec and was linearly dependent on the energy fluence of the laser. The emission spectroscopy of the plasma plume confirmed the atomic neutral and single excited species of Ti. These results show that coating growth basically occurs by the recombination of the ionic species at the surface of the substrate.     

SbOx Thin Films Used for Write-Once Blue Laser Recording

SbOx thin films are deposited by reactive dc-magnetron sputtering from an antimony metal target in Ar＋O2 with the relative O2 content 7%. It is found that the as-deposited films can represent a two-component system comprising amorphous Sb and amorphous Sb2 O3. The crystallization of Sb is responsible for the changes of optical properties of the films. The results of the static test show that the SbOx thin films have good writing sensitivity for blue laser beams and the recording marks are very clear and circular. High reflectivity contrast of about 41% is obtained at a writing power 6mW and writing pulse width 300ns. In addition, the films show a good stability after reading 10000 times.     

Structural and Magnetic Characteristics of Nanogranular Co–Al2O3 Single- and Multilayer Films Formed by the Solid-State Synthesis

The results of structural and magnetic investigations of nanogranular Co–Al₂O₃ films formed from Co₃O₄/Al thin-film layered structures upon vacuum annealing are reported. The Co₃O₄/Al films have been obtained by sequential reactive magnetron sputtering of a metallic cobalt target in a medium consisting of the Ar + O₂ gas mixture and magnetron sputtering of an aluminum target in the pure argon atmosphere. It is shown that such a technique makes it possible to obtain nanogranular Co–Al₂O₃ single- and multilayer thin films with a well-controlled size of magnetic grains and their distribution over the film thickness.

     

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     

High-quality epitaxial LaNiO3 thin films on SrTiO3(100) and LaAlO3(100)

LaNiO₃ thin films have been deposited by pulsed laser deposition on SrTiO₃(100) and LaAlO₃(100) substrates. The processing conditions have been investigated in order to optimize electrical resistivity, crystal quality, and surface morphology. Excellent properties are achieved at moderate substrate temperature and relatively low oxygen pressure, without the need for annealing. Thickness exerts an important influence on electrical transport, as the electrical resistivity increases quickly in films thicker than a few tens of nanometer. The surface of the films on LaAlO₃ is very flat in all the studied thickness range, but the films on SrTiO₃ develop a pattern of boundaries and even cracks as the thickness is higher. Below the critical thickness, high-quality epitaxial films with very smooth surface and low electrical resistivity are obtained under the optimum conditions of substrate temperature and oxygen pressure. The optimum processing conditions are different depending on the substrate, and control is especially critical in films deposited on SrTiO₃.