Alessandro Alan Porporati

Raman spectroscopic analysis of phase-transformation and stress patterns in zirconia hip joints.

Confocal Raman piezo-spectroscopy has been used for the quantitative assessments of phase transformation and residual stresses in zirconia made artificial hip joints. This work can be considered to be a first step towards the development of a fully quantitative technique for the spectroscopic characterization of zirconia femoral heads and other zirconia parts for biomedical applications. After establishing reliable calibration procedures, Raman microprobe spectroscopy could be extended to provide quantitative assessments of zirconia metastability and microscopic stress fields along the z axis perpendicular to the joint surface. For the first time, we have directly visualized patterns of phase-transformation and related residual stresses on the very surface and along the subsurface of both in vitro tested and retrieved hip implants. These spectroscopic assessments may open a completely new perspective in understanding the micromechanical wear behavior of zirconia ceramics in biological environment and in developing new zirconia-based biomaterials with superior stability characteristics.

On the role of oxygen vacancies and lattice strain in the tetragonal to monoclinic transformation in alumina/zirconia composites and improved environmental stability☆

The aim of this paper is to clarify at the nanometer scale the relevant factors influencing the hydrothermal resistance to polymorphic transformation of alumina/zirconia composites, primary candidates for artificial joint applications. The topographic distribution of oxygen vacancies and lattice strain on the composite surface were visualized by means of cathodoluminescence spectroscopy and mapped as a function of exposure time in a thermally activated water vapor environment (i.e., simulating the exposure in human body). Systematically monitoring the optical activity of oxygen vacancies in both alumina and zirconia phases also revealed the effect of surface lattice strain accumulation on the kinetics of polymorphic transformation. From the presented data, an explicit role is evinced for surface oxygen vacancy formation in the alumina matrix, an important step in the complex cascade of mechanochemical events determining the superior environmental resistance of the composite.

Biaxial stress dependence of the electrostimulated near-band-gap spectrum of GaN epitaxial film grown on (0001) sapphire substrate

The biaxial piezospectroscopic coefficient (i.e., the rate of spectral shift with stress) of the electrostimulated near-band-gap luminescence of gallium nitride (GaN) was determined as Pi=-25.8 +/- 0.2 meV/GPa. A controlled biaxial stress field was applied on a hexagonal GaN film, epitaxially grown on (0001) sapphire using a ball-on-ring biaxial bending jig, and the spectral shift of the electrostimulated near-band-gap was measured in situ in the scanning electron microscope. This calibration method can be useful to overcome the lack of a bulk crystal of relatively large size for more conventional uniaxial bending calibrations, which has so far hampered the precise determination of the piezospectroscopic coefficient of GaN. The main source of error involved with the present calibration method is represented by the selection of appropriate values for the elastic stiffness constants of both film and substrate. The ball-on-ring calibration method can be generally applied to directly determine the biaxial-stress dependence of selected cathodoluminescence bands of epilayer/substrate materials without requiring separation of the film from the substrate. (c) 2006 American Institute of Physics.

Raman tensor elements for wurtzitic GaN and their application to assess crystallographic orientation at film/substrate interfaces

This study is aimed at establishing a method of polarized/confocal Raman spectroscopy capable of quantitatively assessing crystallographic orientation in wurtzitic GaN with a micron-scale resolution. First, Raman selection rules are explicitly put forward from a theoretical viewpoint in their complete form; then, experimentally retrieved intensities of the Raman signal as a function of Euler angles are fitted to the obtained theoretical dependencies in order to quantify a set of Raman tensor elements using experiments on known crystallographic planes of a wurtzitic GaN single-crystal. According to the above two procedures, a spectroscopic algorithm, incorporating the use of Raman tensor elements and Euler angles in tandem, becomes available for estimating unknown crystallographic orientations. As an application of the developed method, a confocal Raman probe was used to non-destructively unfold the relative orientation of a wurtzitic GaN epilayer with respect to (0001)-oriented sapphire substrate. The mic...

Spatially resolved crack-tip stress analysis in semiconductor by cathodoluminescence piezospectroscopy

A spatially resolved cathodoluminescence piezospectroscopic analysis is attempted for the high-resolution evaluation of the stress field developed ahead of the tip of an equilibrium crack propagating in a semiconductor. GaN was selected for this assessment as a paradigm semiconductor material. Quantitative measurements of in-plane luminescence probe response function (PRF) were preliminarily performed at different acceleration voltages upon scanning across a straight and atomically sharp interface between GaN and gold metal. Then, based on the knowledge of PRF, the convoluting effect due to the finite size of the electron probe could be corrected and an improved plot of the crack-tip stress field could be retrieved by a computer-aided data restoration procedure. The crack-tip stress intensity factor KI obtained by the cathodoluminescence piezospectroscopic method was compared with that obtained on the same crack path according to high-resolution measurements of crack-tip opening displacement. This study n...

High-resolution stress assessments of interconnect/dielectric electronic patterns using optically active point defects of silica glass as a stress sensor

A piezospectroscopic (PS) cathodoluminescence (CL) study has been carried out on a Cu-Ta∕SiOx (carbon-doped) model chip prepared on a Si substrate. The PS approach was applied to CL spectra arising from optically active point defects in dielectric silica. The red CL emission arising from nonbridging oxygen hole centers (NBOHC) in the carbon-doped SiOx dielectric layer was calibrated and used as a stress sensor. This approach enabled us to locate the trace of the residual stress tensor, as locally developed during manufacturing process in the dielectric interlayers between Cu-Ta interconnects. A minimally invasive electron beam allowed probing local residual stress fields with an improved spatial resolution as compared to more conventional photostimulated PS techniques applied to the Si substrate. In addition, a two-dimensional deconvolution procedure was attempted to retrieve the “true” residual stress distribution piled up between adjacent Cu-Ta lines, according to a theoretical model for embedded struct...

Electron probe response function and piezo-spectroscopic behaviour of semiconductor materials in presence of highly graded stress fields

The response function of the electron probe and the stress dependence of cathodoluminescence spectra emitted by selected semiconductor materials have been evaluated by scanning across sharp bi-material interfaces and along highly graded residual stress fields generated at the tip of an equilibrium crack, respectively. These microscopic procedures can be made fully quantitative provided that the crack opening displacement of the investigated crack is preliminarily measured in a scanning electron microscope for an in situ estimate of the crack-tip stress intensity factor. Taking advantage of the high scanning flexibility of the electron probe, capable of nanometric lateral displacements, spectral shifts typical of the K-dominated zone along the axis of crack propagation were recorded as a function of distance from the crack-tip. A plot of equi-biaxial stress versus spectral band shift was then obtained whose slope represents the piezo-spectroscopic coefficient of the selected material band. A theoretical analysis was attempted to analyse the in-plane interaction between sample and electron probe and to put forward suitable conditions for a reliable assessment of highly graded stress fields. Conditions were worked out into generalized plots as a function of spectroscopic and mechanical parameters for GaN, 3C–SiC and GaAs, as paradigm semiconductor materials.

Spatially resolved residual stress assessments of GaN film on sapphire substrate by cathodoluminescence piezospectroscopy

Two cathodoluminescence piezospectroscopic (CL/PS) approaches for measuring the residual stress distribution in thin films are critically examined and compared using an intrinsic GaN film sample (2.5μm in thickness) grown on a (0001)-oriented sapphire substrate. The first approach invokes an analytical model to fit experimental stress distributions as retrieved in both film and substrate at the edge of an artificially created cross section of the sample. Such an edge-stress distribution takes into account both the thermal expansion mismatch between the film and substrate and the mechanistics of film growth process. In the second approach, we directly and nondestructively measure the bulk residual stress field from the sample top surface on the film side using an increase in electron beam voltage (maintaining a constant beam power) as a means for screening the film subsurface. In this latter case, the combined effects of self-absorption and misfit dislocations on the GaN spectrum severely affect the CL/PS ...

Stress dependence of the near-band-gap cathodoluminescence spectrum of GaN determined by spatially resolved indentation method

A microscopic procedure has been proposed for evaluating the stress dependence of the (room-temperature) cathodoluminescence (CL) excitonic band emitted from the (0001) crystallographic plane of GaN in a field-emission-gun scanning electron microscope. The room-temperature near-band-gap emission (generally referred to as the excitonic band) mainly consisted of a band arising from free exciton (FX). However, an asymmetric morphology was found for the band, which thus needed to be deconvoluted into the main FX band and a shoulder. The spectral location at intensity maximum of the overall excitonic band under stress-free conditions was observed at room temperature at around 365nm. Experimentally measured spectral shifts were precisely retrieved nearby the tip of a Vickers indentation microcrack, while CL intensity probe response functions were collected at different acceleration voltages at a sharp interface between a GaN film and its sapphire substrate. Based on these assessments, the magnitude of the piezo...

Deformation potentials of Si-doped GaAs from microscopic residual stress fields

Underlying physics has been put forward and an experimental verification given for in situ determination of deformation potentials in Si-doped GaAs through a quantitative assessment of micro-/nanoscopic surface stress fields. Highly localized spectroscopic stress assessments could be achieved using a field emission scanning electron microscope as an energy source for stimulating cathodoluminescence emission from a Si-doped GaAs wafer. The deformation potentials were obtained from the local (elastic) residual strain fields stored in the neighborhood of an indentation print. The three independent GaAs deformation potentials could be obtained from a single measurement set and from mixed strain fields including tensile and compressive strains, while all the previously published characterizations were made in compression and on different samples. For these reasons, the deformation potentials determined in this study may prove more reliable and valid in a wider strain range as compared to those from previously ...