Lecture 9 Image Analysis

Nature Material: Macro, micro, nano

100X 10X 1000X 1,000,000X 10,000,000X 100,000,000X 1X 10,000X 100,000X 100 10 millimtre nanomtre nanomtres nanomtres 10 11 centimtre centimtres microns micron microns

Microstructural Features which concern us Grain Size Grain Shapes Precipitate Size: mostly in the micron regime Volume fraction and distribution of various phases Defects such as cracks voids Atom orientation within crystal Microstructrue ranging from crystal structure to engine components (e.g Si3N4)

Characteristics Information : SEM

Crystallographic Information !!
How the atoms are arranged in the object; direct relation between these arrangements and material properties

Scanning Electron Microscope (SEM)

The scanning electron microscope (SEM) is a type of electron microscope that takes images of the surface of samples by focusing a high energy beam of electrons onto the sample. The electrons interact with the atoms that make up the sample producing signals that give information about the sample. Electronic devices are used to capture or detect these signals and either allow them to expose film or, most common today, create an image on a computer screen. The type of signals made by an SEM can include secondary electrons, characteristic x-rays, and back scattered electrons. In an SEM, these signals come from the beam of electrons striking the surface of the specimen and interacting with the sample at or near its surface The SEM has allowed researchers to examine a much bigger variety of specimens The scanning electron microscope has many advantages over traditional microscopes. The SEM has a large depth of field, which allows more of a specimen to be in focus at one time. The SEM also has much higher resolution, so closely spaced specimens can be magnified at much higher levels Because the SEM uses electromagnets rather than lenses, the researcher has much more control in the degree of magnification. All of these advantages, as well as the actual strikingly clear images, make the scanning electron microscope one of the most useful instruments in research today. SEM micrographs have a very large depth of focus yielding a characteristic three-dimensional appearance useful for understanding the surface structure of a sample. Characteristic x-rays are the second most common imaging mode for an SEM. These characteristic x-rays are used to tell the chemical composition of the sample. Back-scattered electrons (BSE) that come from the sample may also be used to form an image.

Sample Preparation for SEM

SEM utilizes vacuum conditions and uses electrons to form an image, special preparations must be done to the sample. All water must be removed from the samples because the water would vaporize in the vacuum. All metals are conductive and require no preparation before being used. All non-metals need to be made conductive by covering the sample with a thin layer of conductive material. This is done by using a device called a "sputter coater. The sputter coater uses an electric field and argon gas. The sample is placed in a small chamber that is at a vacuum. Argon gas and an electric field cause an electron to be removed from the argon, making the atoms positively charged. Specimen at high vacuum requires sample fixation and dehydration or freezing. Minimized charging by coating sample with metal or carbon or lowering the operating kV

How does SEM work? What happens when the Electron Beam hits the sample? SEM Setup
Electron/Specimen Interactions When the electron beam strikes the sample, both photon and electron signals are emitted

SEM Imaging Modes

SE BSE

Secondary Electron Generation

Backscattered Electron Generation -SEM-BSE

-SEM-SE -sample electrons ejected by the primary beam [green line] -low energy -surface detail & topography

-primary beam electrons -high energy -composition and topography [specimen atomic number]

SEM-BSE image of a volcanic rock sample

SEM-SE image of volcanic glass shards

Identification of Fracture Mode

SEM micrographs of fractured surface of two BaTiO3 samples

D.Sarkar, B.Basu, M.J.Chu and S.J.Cho, R-Curve Behavior of Ti3SiC2, Ceramics International, 33 [5] 789 -793, 2007.

EDX
EDX is an analytical technique used for the elemental analysis or chemical characterization of a specimen. it relies on the investigation of a sample through interactions between electromagnetic radiation and matter, analyzing X-rays emitted by the matter in this particular case. Each element has a unique atomic structure allowing x-rays to be uniquely distinguished from each other. A graph is plotted (x-ray energy vs. count rate). The peaks correspond to characteristic elemental emissions.

Nanoscale Materials
Nanowires and Nanotubes Lateral dimension: 1 100 nm Nanowires and nanotubes exhibit novel physical, electronic and optical properties due to Two dimensional quantum confinement Structural one dimensionality High surface to volume ratio Potential application in wide range of nanodevices and systems Nanoscale sensors and actuators Photovoltaic devices solar cells Transistors, diodes and LASERs

Nanowire Solar Cell: The nanowires create a surface that is able to absorb more sunlight than a flat surface

Nanoscale Materials
Nanoscale materials have feature size less than 100 nm utilized in nanoscale structures, devices and systems Nanoparticles and Structures

Gold nanoparticles
TU Dresden/ESRF, 2008

Silver nanoparticles
Northwestern Univ., 2002

A 3-dimensional nanostructure A stadium shaped quantum corral made by positioning iron grown by controlled nucleation atoms on a copper surface IBM of Silicon-carbide nanowires on Corp., 1993. Gallium catalyst particles
Univ. of Cambridge, 2007

Nanofluids
Nanofluids are engineered colloids = base fluid (water, organic liquid) + nanoparticles Nanoparticle size: 1-100 nm

Nanoparticle materials: Al2O3, ZrO2, SiO2, CuO, Fe3O4, Au, Cu, C (diamond, PyC, fullerene) etc.
Previous studies suggest significant enhancement of: Thermal conductivity (+40%) Single-phase convective heat transfer (+40%)

Critical Heat Flux (+100%)

Aluminum Oxide Particles in Water

Transmission electron microscopy (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 it. An image is formed from the electrons transmitted through the specimen, magnified and focused by an objective lens and appears on an imaging screen, a fluorescent screen in most TEMs, plus a monitor, or on a layer of photographic film, or to be detected by a sensor such as a CCD camera. The first practical transmission electron microscope was built by Albert Prebus and James Hillier at the University of Toronto in 1938 using concepts developed earlier by Max Knoll and Ernst Ruska.

Resolution of the TEM is limited primarily by spherical aberration, but a new generation of aberration correctors have been able to partially overcome spherical aberration to increase resolution. Software correction of spherical aberration for the High Resolution.
An aberration is something that deviates from the normal way

Basic Principle of TEM

Electron source, electromagnetic lens system, sample holder, and imaging system
Electron Source The electron source consists of a cathode and an anode. The cathode is a tungsten filament which emits electrons when being heated. A negative cap confines the electrons into a loosely focused beam. The beam is then accelerated towards the specimen by the positive anode. Electrons at the rim of the beam will fall onto the anode while the others at the center will pass through the small hole of the anode. The electron source works like a cathode ray tube.

Electromagnetic lens system After leaving the electron source, the electron beam is tightly focused using electromagnetic lens and metal apertures. The system only allows electrons within a small energy range to pass through, so the electrons in the electron beam will have a well-defined energy. 1.Magnetic Lens: Circular electro-magnets capable of generating a precise circular magnetic field. The field acts like an optical lens to focus the electrons. 2.Aperture: A thin disk with a small (2-100 micrometers) circular through-hole. It is used to restrict the electron beam and filter out unwanted electrons before hitting the specimen.

Sample Holder The sample holder is a platform equipped with a mechanical arm for holding the specimen and controlling its position. Imaging system The imaging system consists of another electromagnetic lens system and a screen. The electromagnetic lens system contains two lens systems, one for refocusing the electrons after they pass through the specimen, and the other for enlarging the image and projecting it onto the screen. The screen has a phosphorescent plate which glows when being hit by electrons. Image forms in a way similar to photography. Working principle TEM works like a slide projector. A projector shines a beam of light which transmits through the slide. The patterns painted on the slide only allow certain parts of the light beam to pass through. Thus the transmitted beam replicates the patterns on the slide, forming an enlarged image of the slide when falling on the screen.

TEMs work the same way except that they shine a beam of electrons (like the light in a slide projector) through the specimen (like the slide). However, in TEM, the transmission of electron beam is highly dependent on the properties of material being examined. Such properties include density, composition, etc. For example, porous material will allow more electrons to pass through while dense material will allow less. As a result, a specimen with a non-uniform density can be examined by this technique. Whatever part is transmitted is projected onto a phosphor screen for the user to see. The following movie will help you to understand more about the operation of a TEM:

Imaging Mode of TEM:

Bright Field Mode Dark Field Mode

Diffraction Mode

Preparation of Specimen
In a TEM, the specimen you want to look at must be of such a low density that it allows electrons to travel through the tissue There are different ways to prepare your material for that purpose. You can cut very thin slices of your specimen from a piece of tissue either by fixing it in plastic or working with it as frozen material. Another way to prepare your specimen is to isolate it and study a solution of for example viruses or molecules in the TEM.

TEM Sample Prep for Materials

How to Measure SAED (Selected Area Electron Diffraction) Think of TEM as a diffraction camera
Rdhkl=lL Au (111) ring [2.35 d-spacing]
R is measured d inter atomic distance l is the electron wavelength L is the camera length (lL is the camera constant) Transmitted Beam

L
Diffracted Beam

With 200KV, (111) ring should distance R from the transmitted beam

Electron Diffraction
Four conditions in Back Focal Plane (BFP) of the objective lens:
No sample Amorphous Polycrystal Single crystal No reflections (only transmitted beam) Transmitted beam + random scattering Transmitted beam + rings Transmitted beam + spots

Metal particles Polymer mix

Bright field TEM of FeNbO4 and (1 wt %) Pt impregnated FeNbO4. (Inset) SAED pattern of FeNbO4

Electron Diffraction

Particle Size : 30-60nm

TiO2 Nanoscale Rods

TEM images of Cu on ZnO (a model methanol catalyst)

TEM Characterization of TiO2 Nanoparticles

20nm

(a) dark field image

(b) bright field image

(c) diffraction patterns

The structure of all as-grown samples is anatase. The particle sizes from TEM range between 15 and 25 nm.
(d) lattice image (d) Lattice Image

Crystallite Size is Different than Particle Size

A particle may be made up of several different crystallites Crystallite size often matches grain size, but there are exceptions
Crystallite size is usually measured from X-ray diffraction patterns and grain size by other experimental techniques like transmission electron microscopy. Most materials are polycrystalline; they are made of a large number of single crystals crystallites. Grain boundaries are interfaces where crystals of different orientations meet. A grain boundary is a single-phase interface, with crystals on each side of the boundary being identical except in orientation. The term "crystallite boundary" is sometimes, though rarely, used. Grain boundary areas contain those atoms that have been perturbed from their original lattice sites, dislocations, and impurities that have migrated to the lower energy grain boundary.

Crystallite is the average size of the particle whereas the particle size denotes the individual size of the particle

Scanning Probe Microscopy

atomic force microscope
sharp probe moves over surface of specimen at constant distance up and down movement of probe as it maintains constant distance is detected and used to create image

scanning tunneling microscope

steady current (tunneling current) maintained between microscope probe and specimen up and down movement of probe as it maintains current is detected and used to create image of surface of specimen

Transmission Electron Microscopy Study of TiO2 Phase Transformation

As-deposited

700 oC

800 oC

TEM diffraction patterns for annealed and as-deposited 12-nm sample.

Dark Field Imaging

If the transmitted beam is excluded from the image formation process
off-axis imaging tilted beam imaging

Bright Field Imaging

If the main portion of the near-forward scattered beam is used to form the image
transmitted beam 000 beam zero-order beam

Probable Questions: 1. What is the basic working principle of TEM? 2. How SAED pattern detects the state of material and their planes?

3. Why EPMA is an important technique to analyze the microstructure?

4. How dhkl value can be calculated from HRTEM image? 5. How XRD and TEM analysis can correlate and identify nanomaterials?