Pulsed laser deposition and in situ diagnostics of the process applied to shape-memory alloys

NiTi films deposited by pulsed laser ablation on Si/SiO₂ are shown to exhibit structural and functional properties related to the shape-memory effect. Film characterization suggests that relevant temperatures for the solid-to-solid transformation responsible for the shape memory are in substantial agreement with those of the bulk target material, demonstrating a good congruency of the deposition process. Besides the technological interest for this class of thin films, our findings point out the suitability of laser ablation for metal alloy deposition. An investigation based on in situ ion-mass spectroscopy and covariance mapping analysis allows us to determine the main vapor-phase processes leading to the formation of stoichiometric clusters expected to play a relevant role in assisting the growth of NiTi thin films. Received: 6 August 2001 / Accepted: 11 April 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. Fax: +39-50/2214-333, E-mail: fuso@df.unipi.it     

Optical properties of SrTiO<Subscript>3</Subscript> thin films by pulsed laser deposition

SrTiO₃ thin films were prepared on a fused-quartz substrate by pulsed laser deposition (PLD). Dense and homogeneous films with a thickness of 260 nm were prepared. Optical constants (refractive index n and extinction coefficient k) were determined from the transmittance spectra using the envelope method. The optical band gap energy of the films was found to be 3.58 eV, higher than the 3.22 eV for bulk SrTiO₃, attributable to the film stress exerted by the substrate. The dispersion relation of the refractive index vs. wavelength follows the single electronic oscillator model. The refractive index and the packing density for the PLD-prepared SrTiO₃ thin films are higher than those for the SrTiO₃ films prepared by physical vapor deposition, sol–gel and RF sputtering. Received: 18 March 2002 / Accepted: 7 October 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +86-25/359-5535, E-mail: mszhang@nju.edu.cn     

Pulsed-laser-deposited epitaxial aluminum nitride films on (111) Si for surface acoustic-wave applications

Epitaxial (001) aluminum nitride (AlN) thin films on (111) Si substrates are prepared using pulsed-laser deposition. The epitaxial structure of the as-prepared thin films is characterized by checking the X-ray-diffraction θ-2 θ scan and pole-figure, using scanning electron microscopy, infrared radiation (IR) spectroscopy and Raman spectroscopy. The surface acoustic-wave resonance at 345 MHz for a 1.5 μm thick AlN film on a (111) Si substrate is observed using an inter-digital electrode. Received: 18 September 2001 / Accepted: 29 January 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-25/359-5535, E-mail: liujm@nju.edu.cn     

Production of biologically inert Teflon thin layers on the surface of allergenic metal objects by pulsed laser deposition technology

Allergic-type diseases are current nowadays, and they are frequently caused by certain metals. We demonstrated that the metal objects can be covered by Teflon protective thin layers using a pulsed laser deposition procedure. An ArF excimer laser beam was focused onto the surface of pressed PTFE powder pellets; the applied fluences were 7.5–7.7 J/cm². Teflon films were deposited on fourteen-carat gold, silver and titanium plates. The number of ablating pulses was 10000. Post-annealing of the films was carried out in atmospheric air at oven temperatures between 320 and 500 °C. The thickness of the thin layers was around 5 μm. The prepared films were granular without heat treatment or after annealing at a temperature below 340 °C. At 360 °C a crystalline, contiguous, smooth, very compact and pinhole-free thin layer was produced; a melted and re-solidified morphology was observed above 420 °C. The adhesion strength between the Teflon films and the metal substrates was determined. This could exceed 1–4 MPa depending on the treatment temperature. It was proved that the prepared Teflon layers can be suitable for prevention of contact between the human body and allergen metals and so for avoidance of metal allergy. Received: 12 June 2002 / Accepted: 13 June 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. E-mail: bhopp@physx.u-szeged.hu     

Femtosecond-laser-induced nanostructure formed on hard thin films of TiN and DLC

We report observation of nanostructures formed on thin TiN and DLC films that were irradiated by 800- and 267-nm, femtosecond (fs) Ti:sapphire laser pulses at an energy fluence slightly above the ablation threshold. On the ablated thin-film surfaces, the linearly polarized fs pulses produce arrays of fine periodic structures that are almost oriented to the direction perpendicular to the laser polarization, while the circularly polarized light forms fine-dot structures. The size of these surface structures is 1/10–1/5 of the laser wavelength and decreases with a decrease in the laser wavelength. Received: 3 September 2002 / Accepted: 4 September 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +81-778/62-3306, E-mail: yasuma@fukui-nct.ac.jp     

Elastic modulus-density relationship for amorphous boron suboxide thin films

Boron suboxide thin films have been deposited on Si(100) substrates by reactive RF magnetron sputtering of a sintered B target in an Ar/O₂ atmosphere. Elastic recoil detection analysis was applied to determine the film composition and density. Film structure was studied by X-ray diffraction and transmission electron microscopy. The elastic modulus, measured by nanoindentation, was found to decrease as the film density decreased. The relationship was affected by tuning the negative substrate bias potential and the substrate temperature during film growth. A decrease in film density, by a factor of 1.55, caused an elastic modulus reduction by a factor of 4.5, most likely due to formation of nano-pores containing Ar. It appears evident that the large scattering in the published data on elastic properties of films with identical chemical composition can readily be understood by density variations. These results are important for understanding the elastic properties of boron suboxide, but may also be qualitatively relevant for other B-based material systems. Received: 22 February 2002 / Accepted: 11 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +46-13/288-918, E-mail: denmu@ifm.liu.se     

Microstructure evolution in Pr-Co-C-Ti nanophase magnets

The microstructures of nanophase Pr-Co-C-(Ti) materials, which have improved magnetic properties, were investigated by means of transmission electron microscopy (TEM) to reveal their phase assemblage and grain-boundary structure. The phase assemblage was carefully controlled by the introduction of TiC nanoparticles and annealing. The optimal nanostructure contained uniformly distributed PrCo₅ and PrCo₂ nanophases without any magnetically soft phases, resulting in high coercivity and the characteristics of a single, hard magnetic phase. TEM analysis confirmed the presence of an amorphous grain-boundary phase surrounding the grains in alloys without TiC. In contrast, alloys with added TiC showed no amorphous phase and also showed higher coercivity compared to Co-Pr-C. Therefore, the variation of the grain boundary phases may be effective in changing the degree of exchange coupling. Controlling the formation of a uniform nanoscale microstructure, leading to improved magnetic properties, is discussed. Received: 5 September 2002 / Accepted: 10 September 2002 / Published online: 22 January 2003 RID="*" ID="*"Corresponding author. Fax: +1-630/252-7777, E-mail: ytang@anl.gov     

Photoluminescence behavior of pulsed laser deposited ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript> thin-film phosphors grown on various substrates

ZnGa₂O₄ thin-film phosphors have been grown on Si(100), Al₂O₃(0001) and MgO(100) substrates using pulsed laser deposition. The structural characterization was carried out on a series of ZnGa₂O₄ films grown on various substrates under various substrate temperatures and oxygen pressures. The films grown on these substrates not only have different crystallinity and surface morphology, but also different Zn/Ga composition ratio. The crystallinity and photoluminescence (PL) of the ZnGa₂O₄ films are highly dependent on the deposition conditions, in particular the stoichiometry ratio of Zn/Ga and the kind of substrate. The variation of Zn/Ga in the films also depends on not only the oxygen pressure but also the substrate temperature during deposition. The PL properties of pulsed laser deposited ZnGa₂O₄ thin films have indicated that Al₂O₃(0001) and MgO(100) are promising substrates for the growth of high-quality ZnGa₂O₄ thin films and that the luminescence brightness depends on the substrate. The luminescence spectra show a broad band extending from 350 to 600 nm and peaking at 460 nm. Received: 11 July 2002 / Accepted: 31 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +82-51-6206356, E-mail: jhjeong@pknu.ac.kr     

Nanostructures fabricated on metal surfaces assisted by laser with optical near-field effects

Nanostructures on metal film surfaces have been written directly using a pulsed ultraviolet laser. The optical near-field effects of the laser were investigated. Spherical silica particles (500–1000 nm in diameter) were placed on metal films. After laser illumination with a single laser shot, nanoholes were obtained at the original position of the particles. The mechanism for the formation of the nanostructure patterns was investigated and found to be the near-field optical resonance effect induced by the particles on the surface. The size of the nanohole was studied as a function of laser fluence and silica particle size. The experimental results show a good agreement with those of the relevant theoretical calculations of the near-field light intensity distribution. The method of particle-enhanced laser irradiation allows the study of field enhancement effects as well as its potentialapplications for nanolithography. Received: 10 December 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +65-777/1349, E-mail: HUANG_Sumei@dsi.a-star.edu.sg     

Growth of a textured quasicrystalline phase in Ti-Ni-Zr films prepared by pulsed laser deposition

The preparation in thin film form of the known icosahedral phase in Ti-Ni-Zr bulk alloys has been investigated as a function of substrate temperature. Films were deposited by pulsed laser deposition on sapphire substrates at temperatures ranging from room temperature to 350 °C. Morphological and structural modifications have been followed by grazing-incidence and θ–2θ X-ray diffraction, transmission electron diffraction and imaging. Chemical composition has been analyzed by electron probe microanalysis. The in-depth variation of composition has been studied by secondary neutral mass spectroscopy. We show that pulsed laser deposition at 275 °C makes the formation of a 1-μm-thick film of Ti-Ni-Zr quasicrystalline textured nanocrystallites possible. Received: 7 June 2001 / Accepted: 18 February 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +33-3/8357-6300, E-mail: brien@mines.u-nancy.fr     

Interfaces with vapor-evaporated polyaniline thin films

Interfaces with vapor-deposited polyaniline thin films are investigated using angle-resolved X-ray photoemission spectroscopy. We demonstrate that a diffuse interface is formed with sodium deposited on top of polyaniline, and the distribution of sodium atoms, in the near surface region of the polyaniline thin film, is quite uniform. In comparison, the interface between polyaniline and another polymer, PVDF-TrFE, is rather abrupt and a flat-band model can be applied to the interface band structure. Received: 29 November 2002 / Accepted: 16 December 2002 / Published online: 28 March 2003 RID="*" ID="*"Corresponding author. Fax: +1-402/472-2879, Email: pdowben@unl.edu     

Structural and optical properties of Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric thin films prepared by chemical solution methods

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films have been grown on Pt/Ti/SiO₂/Si substrates by chemical solution methods. X-ray diffraction analysis shows that BLT thin films are polycrystalline with (171)-preferential orientation. Atomic force microscopy investigation shows that they have large grains about 120 nm in size. A Pt/BLT/Pt capacitor has been fabricated and showed excellent ferroelectricity, with a remnant polarization and coercive field of 24 μC/cm² and 116 kV/cm, respectively. The capacitor shows no polarization fatigue up to 10⁹ switching cycles. The optical constants (n,k) of the BLT thin films in the wavelength range 0.35–1.7 μm were obtained by spectroscopic ellipsometry measurements, and the band-gap energy was found to be about 3.25 eV. Received: 16 October 2001 / Accepted: 6 January 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-21/65830-734, E-mail: gswang@mail.sitp.ac.cn     

Ion-beam synthesis and growth mechanism of diamond-like materials

Opposite to most other deposition methods, the dominating nucleation and growth mechanism during ion-beam deposition of energetic ions in the range between 10 eV and 10 keV occurs in a region of a few nanometers below the surface of the growing film. This process is called ‘subplantation’ – emphasizing the implantation of ions into a subsurface region. Ordering and phase formation is a result of the interaction of the deposited ions with the solid state that takes place within the short time scale of femto- and picoseconds. This extreme non-equilibrium process can result in metastable amorphous or crystalline structures. This review will present several examples of the influence of the deposition parameters on the properties of diamond-like materials synthesized using mass-selected ion-beam deposition. Furthermore, several existing models of the deposition process will be presented and critically discussed. Received: 11 November 2002 / Accepted: 12 November 2002 / Published online: 4 April 2003 RID="*" ID="*"Corresponding author. Fax: +49-551/39-4493, E-mail: carsten.ronning@phys.uni-goettingen.de     

Layer-resolved microscopy of magnetic domains in multi-layered systems

Photoelectron emission microscopy in connection with magnetic circular dichroism in soft X-ray absorption can be used for the microscopic imaging of magnetic domains in layered thin film structures consisting of several magnetic layers. Due to the element-selectivity of the method, the different magnetic layers in such a structure can be imaged separately, provided that they contain different elements. This has been applied for the investigation of Co/Cu/Ni trilayers, epitaxially grown on Cu (001). The magnetic coupling between the Co and Ni layers can be directly visualized from comparing layer-resolved magnetic domain images of both layers. As a consequence of the competition between the anisotropy energies of the two magnetic layers and the magnetic coupling energy, spin-reorientation transitions between collinear and non-collinear magnetic configurations are observed. Apart from this globally observable magnetic interlayer coupling a micromagnetic coupling mechanism is also evident from the layer-resolved domain images. It is caused by magnetostatic interaction of local stray fields from domain walls. Received: 22 August 2002 / Accepted: 2 October 2002 / Published online: 5 February 2003 RID="*" ID="*"Corresponding author. Fax: +49-345/5511-223, E-mail: kuch@mpi-halle.de     

Influence of substrate temperature on the chemical and microstructural properties of MO-CVD ZrTiO<Subscript>4</Subscript> thin films

In the last few years, intensive research activity has been focused on the development of suitable synthesis methods for high-permittivity materials, used for the realization of next-generation microdevices able to fulfil the previsions of the Technology Roadmap of Semiconductors. The use of high-permittivity materials can overcome the difficulties concerning the production of SiO₂-based ultra-thin dielectrics, such as the generation of pinholes and the non-uniformity of the film, which may result in a malfunction in high-density systems. Recently, zirconium titanate thin films were discovered to have very interesting dielectric properties, which suggests a use for them in microwave integrated systems, such as receivers or DRAMs, since they are monophasic, have little dissipation and show a good thermal stability and a high value for the dielectric constant, independent of frequency in the range from kilohertz to a few gigahertz. Real application is possible only in strict connection with the development of a suitable preparation method which allows production with controlled and reproducible characteristics. In this work, the synthesis and characterization of Zr_xTi_1-xO₄ (ZT) thin films grown via MO-CVD is described, studying the influence of growth parameters on their structural, chemical and physical properties. Received: 17 June 2002 / Accepted: 24 June 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. Fax: +39-06/9067-2445, E-mail: Pad@mlib.cnr.it     

Nanoscale effects in focused ion beam processing

Focused ion beams with diameters of 8 to 50 nm are used for material processing in the nanoscale regime. In this paper, effects of the ion beam–solid interaction determining the formation of small structures by ion-beam sputtering and chemically assisted material deposition and etching are investigated. In the case of decreasing feature size, angle-dependent sputtering, a non-constant sputter rate, and scattered ions play an important role. The impact on side-wall angle, aspect ratio, and shape of the bottom of the etched structures is discussed. In beam tail regions, these effects will be especially pronounced, leading to material swelling instead of material removal. Ion beam assisted etching and deposition will face additional effects. For small structures, gas depletion becomes a significant drawback. The impact on gas depletion and the competition with sputtering are discussed. Received: 21 August 2002 / Accepted: 21 August 2002 / Published online: 12 February 2003 RID="*" ID="*"Corresponding author. Fax: +49-9131/761360, E-mail: frey@iis-b.fhg.de     

Application of SCM for the microcharacterization of semiconductor devices

The article presents an overview of the current status of scanning capacitance microscopy (SCM) with respect to applications in the failure analysis of modern semiconductor devices. Examples for top-down and cross-sectional SCM imaging and the importance of an optimized sample preparation for improved SCM results will be discussed. An outlook on SCM requirements for future-technology generations highlights the usefulness of high aspect ratio tips for SCM measurements. Received: 2 September 2002 / Accepted: 2 September 2002 / Published online: 5 March 2003 RID="*" ID="*"Corresponding author. E-mail: gunnar.zimmermann@infineon.com     

High refractive index and transparent heavy metal oxide glassy thin films

Heavy metal oxide thin films of the ternary system Nb₂O₅–GeO₂–PbO have been prepared by pulsed laser deposition in an O₂ environment from either glassy or crystalline bulk samples. The range of ([Pb]+[Nb]) content in which the films are optically homogeneous and transparent is much broader (0.5–1.0) than that of the bulk samples considered in the present work (0.55–0.62). The imaginary part of the refractive index is very low in all cases (k<10^-3), whereas the real part increases linearly with the ([Pb]+[Nb]) content up to values as high as 2.35. The optical energy gap has been found to be strongly dependent on [Pb], whereas it is almost independent of [Nb]. This dependence is discussed in terms of the role of Pb and Nb as network modifiers or formers. Received: 5 August 2002 / Accepted: 8 August 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +34-91/564-5557, E-mail: j.gonzalo@io.cfmac.csic.es     

Formation of metal membranes by direct duplication of etched ion-track templates

A method for direct electrochemical metal duplication of pores in ion-track polymer membranes is described. It allows fabrication of metallic membranes using any metal, which is readily deposited by electroplating from aqueous solutions. The metal is deposited on one side of the template membrane, facing the anode, which is made conductive by a thin metal cladding layer. During electroplating, the lateral tapping of the pores is prevented by applying a counter-solution from the opposite non-metallized side of the plastic membrane, which increases dramatically the deposition overvoltage in the vicinity of the pore orifices. Such metallic membranes can be generated with pore diameters in the nano- and micrometer range and with densities from single pores up to 10⁶–10⁷ pores/cm². They can replace plastic filters in cases when an application of polymer material is not desirable. They could be advantageous particularly in catalysis as well as in biological science and technology. Further, they may be useful as apertures and collimators for different kinds of radiation. Received: 14 February 2002 / Accepted: 21 May 2002 / Published online: 22 November 2002 RID="*" ID="*"Corresponding author. Fax: +49-6159/712-179, E-mail: r.neumann@gsi.de     

Spiral and curved periodic crack patterns in sol-gel films

Thin silicate sol-gel films with four different crack patterns were created reproducibly by controlling the film deposition parameters. The crack geometry, periodicity, and amplitude were studied experimentally as a function of the film thickness, curing time, and temperature. Direct evidence was found that the physical interplay between stress relief through film cracking and stress relief through film warping results in sawtooth, spiral, closed loop, or straight line crack trajectories. Received: 25 March 2002 / Accepted: 1 July 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +1-941-359-4396, Email: sendova@ncf.edu