5 Categories of Materials Characterization Techniques ImageSurfaceStructuralOrganicElemental
6 Image Analysis Optical microscopy Confocal microscopy SEM/EDX – Scanning Electron Microscopy with Energy Dispersive X-Ray detectorSPM – Scanning Probe MicroscopyAFM – Atomic Force MicroscopyTEM – Transmission Electron Microscopy
7 Surface Analysis AES – Auger Electron Spectroscopy XPS – X-Ray Photoelectron SpectroscopyTOF-SSIMS – Time of Flight Static Secondary Ion Mass SpectroscopyLEED – Low Energy Electron Diffraction
8 Structural Analysis XRD – X-Ray Diffraction XAX/EXAFS - X-ray Absorption Spectroscopy and Extended X-Ray Absorption Fine StructureRaman spectroscopyTEM – Transmission Electron MicroscopyEELS – Electron Energy Loss Spectroscopy (typically combined with TEM)
9 Organic Analysis FTIR – Fourier Transform Infrared Spectroscopy GC/MS – Gas Chromatography with Mass Spectroscopy (detector)HPLC – High Performance Liquid ChromatographyRaman spectroscopy (structural organic)
11 Industries Served Semiconductor (electronics) Magnetic storage (disks/drives)Biomedical device (biomaterials)Thin films (material coatings)Chemical / plastics (polymers)Clean energy technology (PV)Consumer Packaged Goods (CPG)
12 Types of Problems Materials characterization Process development Failure analysisQA/QCAuthenticityCompetitive analysis
13 Optical Microscopy First place you want to ‘look’ in failure analysis Metallography‘Inexpensive’ in comparison$1K to $10KContrast/dark field
14 Scanning Probe Microscopy (SPM) Family of Instruments “Scanning Probe Microscopy (SPM) is a branch of microscopy that forms images of surfaces using a physical probe that scans the specimen. An image of the surface is obtained by mechanically moving the probe in a raster scan of the specimen, line by line, and recording the probe-surface interaction as a function of position. SPM was founded with the invention of the scanning tunneling microscope in Many scanning probe microscopes can image several interactions simultaneously. The manner of using these interactions to obtain an image is generally called a mode.”
15 Metrology of Metals AFM can be used to understand surface morphology. This material was prepared using a spray / cast technique.
16 Metrology of Structures The pattern and depth of this micro lens can be determined using an AFM.This helps in both development and process control.
17 Scanning Electron Microscopy (SEM) “A scanning electron microscope (SEM) is a type of electron microscope that images a sample by scanning it with a high-energy beam of electrons in a raster scan pattern. The electrons interact with the atoms that make up the sample producing signals that contain information about the sample's surface topography, composition, and other properties such as electrical conductivity.”
22 Transmission Electron Spectroscopy (TEM) Transmission electron microscopy (TEM) is a microscopy technique whereby a beam of electrons is transmitted through an ultra thin specimen, interacting with the specimen as it passes through. An image is formed from the interaction of the electrons transmitted through the specimen; the image is magnified and focused onto an imaging device, such as a fluorescent screen, on a layer of photographic film, or to be detected by a sensor such as a CCD camera.
23 TEM Diagram SiC / Ytterbium dopant “Advanced structural ceramics offer important advantages over current materials used in high-temperature environments, such as increased thermal stability, oxidation resistance, and high strength. However, the inherently brittle nature of ceramics limits the use of materials like SiC and Si3N4 in applications such as ultra-high temperature turbine engines. the controlling factors for producing crack deflection, which leads to high toughness, include the stiffness of the grain boundary phase (present in liquid-phase sintered products) and the toughness of the interface between the grain boundary and the matrix grains. Both of these can be altered by the choice of dopants used during sintering. By tailoring the fracture properties of SiC, starting from the atomic level, we are working towards the goal of improving the fracture toughness and reliability of brittle materials. ”
24 Auger Electron Spectroscopy (AES) Surface sensitiveQualitativeSemi-quantitativeDepth profilingElemental mapping
25 Auger Electron Process Initial excitation eventSecondary internal eventEjection of Auger electron
26 Auger Survey Spectra 0 to 2000 eV Detects elements > Li Semi-quantitativeFairly fastConductive materialsSpatial resolution down to 100A on newer instruments
27 AES Elemental MappingSpatial resolution, fast data collection of AES, and surface sensitivity, allows x-y (image) mapping of elements.Helpful to show both distribution and spatial correlation of elements, inferring chemical bonding assignments.
31 X-Ray Photoelectron Spectroscopy (XPS) SSX-100 University of Toronto
32 The Photoelectric Process XPS spectral lines are identified by the shell from which the electron was ejected (1s, 2s, 2p, etc.).The ejected photoelectron has kinetic energy:KE=hv-BE-Following this process, the atom will release energy by the emission of an Auger Electron.Conduction BandValence BandL2,L3L1KFermiLevelFreeElectronIncident X-rayEjected Photoelectron1s2s2p
33 XPS Chemical ShiftsChemical shifts of photoelectrons allow for interpretation and assignment of chemical bonding states. In PET polymer the C-C, C-O, and O-C=O peaks are clearly resolved. The area under the curve is proportional to the number of atoms in that chemical state.NREL data
34 Al 2p XPS spectrum of native aluminum oxide XPS Chemical ShiftsThe chemical shift between aluminum metal and aluminum oxide is ~ 3 eV and clearly resolved. The oxide film thickness can be estimated from the oxide/metal peak ratio and the escape depth of the Al 2p photoelectronAl 2p XPS spectrum of native aluminum oxide
35 Time of Flight (TOF) SIMS Time of Flight – Secondary Ion Mass Spectroscopy and Time-of-flight mass spectrometry (TOFMS) is a method of mass spectrometry in which an ion's mass-to-charge ratio is determined via a time measurement. Ions are accelerated by an electric field of known strength. TOF-SIMS and AES surface analysis equipment can be used to detect and characterize micro-area contaminants or patterned features on magnetic media or read/write heads with sub-micron spatial resolution.
36 LEED – Low Energy Electron Diffraction “Low-energy electron diffraction (LEED) is a technique for the determination of the surface structure of crystalline materials by bombardment with a collimated beam of low energy electrons (20-200eV) and observation of diffracted electrons as spots on a fluorescent screen. LEED may be used both qualitatively and quantitatively in constructing a representation of surface structure and atomic positions.”
37 Infrared Spectroscopy “The infrared portion of the electromagnetic spectrum is usually divided into three regions; the near-, mid- and far- infrared, named for their relation to the visible spectrum. The higher energy near-IR, –4000 cm−1 (0.8–2.5 μm wavelength) can excite overtone or harmonic vibrations. The mid-infrared, ~4000–400 cm−1 (2.5–25 μm) may be used to study the fundamental vibrations and associated rotational-vibrational structure. The far-infrared, ~400–10 cm−1 (25–1000 μm), lying adjacent to the microwave region, has low energy and may be used for rotational spectroscopy. The names and classifications of these subregions are conventions, and only loosely based on the relative molecular or electromagnetic properties”. (Wikipedia)
42 Raman Spectroscopy http://en.wikipedia.org/wiki/Raman_spectroscopy Raman spectroscopy (named after C. V. Raman) is a spectroscopic technique used to study vibrational, rotational, and other low-frequency modes in a system. It relies on inelastic scattering, or Raman scattering, of monochromatic light, usually from a laser in the visible, near infrared, or near ultraviolet range.
43 XRD/XAX/EXAFSX-ray scattering techniques are a family of non-destructive analytical techniques which reveal information about the crystallographic structure, chemical composition, and physical properties of materials and thin films. These techniques are based on observing the scattered intensity of an X-ray beam hitting a sample as a function of incident and scattered angle, polarization, and wavelength or energy.
44 X-Ray DiffractionX-ray diffraction yields the atomic structure of materials and is based on the elastic scattering of X-rays from the electron clouds of the individual atoms in the system. The most comprehensive description of scattering from crystals is given by the dynamical theory of diffraction (Wikipedia X-ray scattering techniques)
45 X-Ray Diffractometer“Powder diffraction (XRD) is a technique used to characterize the crystallographic structure, crystallite size (grain size), and preferred orientation in polycrystalline or powdered solid samples. Powder diffraction is commonly used to identify unknown substances, by comparing diffraction data against a database maintained by the International Centre for Diffraction Data. It may also be used to characterize heterogeneous solid mixtures to determine relative abundance of crystalline compounds and, when coupled with lattice refinement techniques, can provide structural information on unknown materials. Powder diffraction is also a common method for determining strains in crystalline materials. “
46 Inductively Coupled Plasma (ICP) MS Inductively coupled plasma mass spectrometry (ICP-MS) is a type of mass spectrometry that is highly sensitive and capable of the determination of a range of metals and several non-metals at concentrations below one part in 1012 (part per trillion). It is based on coupling together an inductively coupled plasma as a method of producing ions (ionization) with a mass spectrometer as a method of separating and detecting the ions.
47 X-Ray Fluorescence (XRF) X-ray fluorescence (XRF) is the emission of characteristic "secondary" (or fluorescent) X-rays from a material that has been excited by bombarding with high-energy X-rays or gamma rays. The phenomenon is widely used for elemental analysis and chemical analysis, particularly in the investigation of metals, glass, ceramics and building materials, and for research in geochemistry, forensic science and archaeology.
53 Quality Assurance / Quality Control (QA/QC) An XPS lubricant thickness map shows the presence of a void in the 2 nm lubricant coating on a 95 mm diameter hard disk media.
54 BiomedicineOrally disintegrating tablets (ODTs) are dosage forms formulated in such a way as to improve a pharmaceutical product’s in vivo oral disintegration and dissolution rates. In order to achieve rapid disintegration rates, the tablet formula must provide a high porosity, low density and low hardness. Particle size and distribution were evaluated with a number of techniques including FE-SEM (Field Emission Scanning Electron Microscopy).
55 Coatings for biomedical stents and prosthetic implantable devices “There are many types of coatings used in the manufacturing and preparation of biomedical devices. Some coatings protect the device from corrosion while others protect from complications such as tissue trauma, infection, or even rejection. Drug delivery coatings are also becoming common. Other biomedical devices, including angioplasty balloons, are freestanding membranes that must be of uniform and fixed thickness in order to function properly. Thickness measurement methods of these coatings vary, but one thing is certain - the most commonly used methods (such as weighing a part before and after coating) do not detect incomplete coverage or coating non-uniformities that can lead to device failure.”https://www.filmetrics.com/biomedical
56 Authenticity Testing Counterfeit devices Second shift manufacturing SemiconductorsConsumer goodsSecond shift manufacturingLicensed vendor/processMay not follow process exactlyB-lot material sold as A-lotRejected material under another brand
57 Surface Treatments Control friction, lubrication, and wear Improve corrosion resistance (passivation)Change physical property, e.g., conductivity, resistivity, and reflectionAlter dimension (flatten, smooth, etc.)Vary appearance, e.g., color and roughnessReduce cost (replace bulk material)
58 Surface Treatment of NiTi Biomedical Devices and Biomedical Implants – SJSU Guna Selvaduray
59 Surface Treatment of NiTi Biomedical Devices and Biomedical Implants – SJSU Guna Selvaduray
60 Surface Treatment of NiTi XPS spectra of the Ni(2p) and Ti(2p) signals from Nitinol undergoing surface treatments show removal of surface Ni from electropolish, and oxidation of Ni from chemical and plasma etch. Mechanical etch enhances surface Ni.Biomedical Devices and Biomedical Implants – SJSU Guna Selvaduray
61 Consumer Applications AFM is used to understand the glossing characteristics of paper surfaces. In this example ink jet paper was examined to understand the pooling distribution of a polymer coating. Surface coating characteristics affect both the adsorption of ink to the surface, as well as the reflection of scattered light. Each parameter contributes to the total image quality.100 X 100µ close contact scan mode
62 LIMS for Laboratory Data Laboratory Information Management Systems => data storage/organizationKnowledge Management for analytical services and materials characterizationRecord key results of experimentsSearch archives for context/referenceIt is a competitive advantage for any lab
63 Wrap Up – 5 Step Instrument Rubric What is the physics?What is the information?What types of materials?What industries/labs use it?For what types of problems?
64 Why do Materials Characterization? Learn about a materialLearn about a processSee why something went wrongCompetitive analysisAuthenticity testingQA/QC / process checksDevelop a reference / standards libraryLearn to use an instrument really well!