Modern Techniques of Materials Characterisation



By :

B. Ramesh, (Ph.D.),
Associate Professor of Mechanical Engineering, St. Joseph’s College of Engineering, Jeppiaar Trust, Chennai-119 Ph.D. Research Scholar, College of Engineering, Guindy campus, Anna University, Chennai-25.

Compiled by : Mr. B. Ramesh, Associate Professor of Mechanical Engineering, St. Joseph’s College of Engineering, Jeppiaar Trust, Chennai-119

Modern Techniques of Materials Characterisation


OBJECTIVE: Characterisation of materials is very important for studying the structure of materials and to interpret their properties UNIT-I METALLOGRAPHIC TECHNIQUES 8 Specimen preparation techniques, components of microscope, Resolution, depth of focus, polarized light, phase contrast, differential interference microscopy, hot stage and quantitative metallographic techniques UNIT-II X-RAY DIFFRACTION TECHNIQUES 12 Crystallography basics, characteristic spectrum, Bragg’s law, Diffraction methods – Laue, rotating crystal and powder methods. Intensity of diffracted beams – structure factor calculations and other factors. Cameras- Laue, DebyeScherer cameras, Seeman-Bohlin focusing cameras. Diffractometer – general feature and optics, proportional, scintillating and Geiger counters. UNIT-III APPLICATION OF X-RAY DIFFRACTION 9 Determination of crystal structure, lattice parameter, phase diagram and residual stress – quantitative phase estimation, ASTM catalogue of Materials identification UNIT-IV ELECTRON MICROSCOPY 8 Construction and operation of Transmission electron microscope – Selected Area Electron Diffraction and image formation, specimen preparation techniques. Construction, modes of operation and application of Scanning electron microscope, Energy Dispersive Spectroscopy, Electron probe micro analysis (EPMA), Scanning Tunnelling Microscope (STM) and Atomic Force Microscope UNIT-V CHEMICAL AND THERMAL ANALYSIS 8 Basic principles, practice and applications of X-ray spectrometry, Wave dispersive X- ray spectrometry, Auger spectroscopy, Secondary ion mass spectroscopy – proton induced X-ray Emission spectroscopy, Differential thermal analysis, differential scanning calorimetry DSC and thermogravimetric analysis TGA Total: 45 TEXTBOOKS: 1. Cullity, B. D.,“ Elements of X-ray diffraction”, Addison-Wesley Company Inc., New York, 3rd Edition, 2000. 2. Cherepin and Malik, “Experimental Techniques in Physical Metallurgy", Asia Publishing Co. Bombay, 1968. REFERENCE BOOKS: 1. Brandon D. G, “Modern Techniques in Metallography”, Von Nostrand Inc NJ, USA, 1986.. 2. Thomas G., “Transmission electron microscopy of metals”, John Wiley, 1996. 3. Weinberg, F., “Tools and Techniques in Physical Metallurgy”, Volume I & II, Marcel and Decker, 1970 Compiled by : Mr. B. Ramesh, Associate Professor of Mechanical Engineering, St. Joseph’s College of Engineering, Jeppiaar Trust, Chennai-119

Modern Techniques of Materials Characterisation


Unit I
Laws of reflection

Fig. : Diagram of specular reflection If the reflecting surface is very smooth, the reflection of light that occurs is called specular or regular reflection. The laws of reflection are as follows: 1. The incident ray, the reflected ray and the normal to the reflection surface at the point of the incidence lie in the same plane. 2. The angle which the incident ray makes with the normal is equal to the angle which the reflected ray makes to the same normal.

Law of refraction
In optics and physics, Snell's law (also known as Descartes' law, the Snell–Descartes law, and the law of refraction) is a formula used to describe the relationship between the angles of incidence and refraction, when referring to light or other waves passing through
Compiled by : Mr. B. Ramesh, Associate Professor of Mechanical Engineering, St. Joseph’s College of Engineering, Jeppiaar Trust, Chennai-119

Associate Professor of Mechanical Engineering. Joseph’s College of Engineering. St. Named after Dutch mathematician Willebrord Snellius. Jeppiaar Trust. Snell's law states that the ratio of the sines of the angles of incidence and refraction is equivalent to the ratio of velocities in the two media. Since the velocity is lower in the second medium (v2 < v1). Ramesh. Fig. with n2 > n1. one of its discoverers. The law says that the ratio of the sines of the angles of incidence and of refraction is a constant that depends on the media. or equivalent to the opposite ratio of the indices of refraction: with each θ as the angle measured from the normal. such as water and glass. v as the velocity of light in the respective medium (SI units are meters per second. B. the Compiled by : Mr. Chennai-119 . : Refraction of light at the interface between two media of different refractive indices. The refractive index can be calculated by rearranging the formula accordingly.Modern Techniques of Materials Characterisation 4 a boundary between two different isotropic media. or m/s) and n as the refractive index (which is unitless) of the respective medium.

this is the angle of the real marginal ray in the system. The size of the finest detail that can be resolved is proportional to λ/NA. where λ is the wavelength of the light. In most areas of optics. Ramesh. Assuming quality (diffraction limited) optics. that is. In microscopy. Jeppiaar Trust. Compiled by : Mr. and up to 1. Joseph’s College of Engineering. In general. 1. B. the ray in the higher-index medium is closer to the normal. lenses with larger numerical apertures collect more light and will generally provide a brighter image.33 for pure water. The angular aperture of the lens is approximately twice this value (within the paraxial approximation). the numerical aperture (NA) of an optical system is a dimensionless number that characterizes the range of angles over which the system can accept or emit light. In microscopy. the numerical aperture of an optical system such as an objective lens is defined by where n is the index of refraction of the medium in which the lens is working (1. and especially in microscopy. and θ is the half-angle of the maximum cone of light that can enter or exit the lens. NA generally refers to object-space NA unless otherwise noted.Modern Techniques of Materials Characterisation 5 angle of refraction θ2 is less than the angle of incidence θ1. Associate Professor of Mechanical Engineering. Numerical aperture In optics. Chennai-119 . NA is important because it indicates the resolving power of a lens.0 for air. St.56 for oils). The exact definition of the term varies slightly between different areas of optics. The NA is generally measured with respect to a particular object or image point and will vary as that point is moved. A lens with a larger numerical aperture will be able to visualize finer details than a lens with a smaller numerical aperture. but will provide shallower depth of field.

[1][2] the second is the image-side conjugate of depth of field. depth of focus is relatively insensitive to focal length and subject distance. depth of focus increases with longer focal length or closer subject distance. : The numerical aperture with respect to a point P depends on the half-angle θ of the maximum cone of light that can enter or exit the lens. B. Chennai-119 . Depth of focus Depth of focus is a lens optics concept that measures the tolerance of placement of the image plane (the film plane in a camera) in relation to the lens. For distant subjects (beyond macro range). In the macro region. the depth of focus is symmetrical about the image plane. Refractive index The refractive index or index of refraction of a substance is a measure of the speed of light in that substance. Ramesh." Depth of focus vs depth of field While the phrase depth of focus was historically used. depth of focus indicates the tolerance of the film's displacement within the camera.[note 1] The velocity at which light travels in vacuum is a physical constant. In a camera. and is sometimes still used. Associate Professor of Mechanical Engineering. Joseph’s College of Engineering. Depth of field is the range of distances in object space for which object points are imaged with acceptable sharpness with a fixed position of the image plane (the plane of the film or electronic sensor). for a fixed fnumber. depth of focus is typically measured in microscopic units such as fractions of a millimeter or thousandths of an inch. St. It is expressed as a ratio of the speed of light in vacuum relative to that in the considered medium. Jeppiaar Trust. while depth of field decreases. The same factors that determine depth of field also determine depth of focus. The first is the distance over which the image plane can be displaced while a single object plane remains in acceptably sharp focus. though in most cases the distances are approximately equal. to mean depth of field. the depth of focus is greater on the far side of the image plane. and the fastest speed at which energy or information can be Compiled by : Mr. Both depth of field and depth of focus increase with smaller apertures. and is therefore sometimes referred to as "lens-to-film tolerance. Depth of focus can have two slightly different meanings.Modern Techniques of Materials Characterisation 6 Fig. Where depth of field often can be measured in macroscopic units such as meters and feet. with the second. in modern times it is more often reserved for the image-side depth.[2] With the first meaning. but these factors can have different effects than they have in depth of field.

vp.33 times as fast in a vacuum as it does in water. Associate Professor of Mechanical Engineering. of a wave phenomenon such as light or sound in a reference medium to the phase speed. of a medium is defined as the ratio of the speed.[1][2][3][4] A simple. meaning that light travels 1. B. light travels slower through any given material.33. or medium. that is not vacuum. Chennai-119 . St.Modern Techniques of Materials Characterisation 7 transferred. the refractive index of water is 1. Ramesh. However. Compiled by : Mr. : Refraction of light at the interface between two media. (See: light in a medium). The refractive index. Joseph’s College of Engineering. c. n. Jeppiaar Trust. of the wave in the medium in question: Fig. mathematical description of refractive index is as follows: n = velocity of light in a vacuum / velocity of light in medium Hence.

Chennai-119 . Associate Professor of Mechanical Engineering. is the decomposition of a ray of light (and other electromagnetic radiation) into two rays (the ordinary ray and the extraordinary ray) when it passes through certain types of material. Joseph’s College of Engineering. or double refraction. Jeppiaar Trust. contrast is determined by the difference in the color and brightness of the object and other objects within the same field of view.Modern Techniques of Materials Characterisation 8 Contrast Contrast is the difference in visual properties that makes an object (or its representation in an image) distinguishable from other objects and the background. B. : Changes in the amount of contrast in a photo Birefringence Birefringence. In visual perception of the real world. Compiled by : Mr. Ramesh. St. such as calcite crystals or boron nitride. Fig.

: Rays passing through a positively birefringent material. Liquid crystal materials as used in Liquid Crystal Displays (LCDs) are also birefringent.[1] The reason for birefringence is the fact that in anisotropic media the electric field vector and the dielectric displacement can be nonparallel (namely for the extraordinary polarisation). it is uniaxial). If the material has a single axis of anisotropy or optical axis (i. This effect can occur only if the structure of the material is anisotropic (directionally dependent). Jeppiaar Trust. so the ray polarized perpendicularly to the optic axis has a greater refractive index than the ray polarized parallel to it. Birefringence can also arise in magnetic. St. The optical axis is perpendicular to the direction of the rays. Joseph’s College of Engineering.[2] Fig. but substantial variations in magnetic permeability of materials are rare at optical frequencies. birefringence can be formalized by assigning two different refractive indices to the material for different polarizations. Chennai-119 . Ramesh. Associate Professor of Mechanical Engineering.Modern Techniques of Materials Characterisation 9 depending on the polarization of the light. materials. Compiled by : Mr. The birefringence magnitude is then defined by where ne and no are the refractive indices for polarizations parallel (extraordinary) and perpendicular (ordinary) to the axis of anisotropy respectively. although being linearly related. B. not dielectric.e.

Joseph’s College of Engineering. the two orthogonal components have exactly the same amplitude and are exactly ninety degrees out of phase. B. In the middle figure. Compiled by : Mr. or it may rotate as the wave travels (circular or elliptical polarization). In this case. The direction of this line depends on the relative amplitudes of the two components. so the direction of the electric vector (the vector sum of these two components) is constant. and gravitational waves exhibit polarization. and the path traced by the tip of the vector in the plane (purple): The same evolution would occur when looking at the electric field at a particular time while evolving the point in space.Modern Techniques of Materials Characterisation 10 Polarization Polarization (also polarisation) is a property of certain types of waves that describes the orientation of their oscillations. the polarization of light is described by specifying the orientation of the wave's electric field at a point in space over one period of the oscillation. acoustic waves (sound waves) in a gas or liquid do not have polarization because the direction of vibration and direction of propagation are the same. In the latter cases. depending on which way the electric vector rotates and the chosen convention. this special case is called linear polarization. with time(the vertical axes). the two orthogonal (perpendicular) components are in phase. The following figures show some examples of the evolution of the electric field vector (black). Electromagnetic waves. In this special case the electric vector traces out a circle in the plane. These cases are called right-hand circular polarization and left-hand circular polarization. the electric field may be oriented in a single direction (linear polarization). There are two possible phase relationships that satisfy this requirement: the x component can be ninety degrees ahead of the y component or it can be ninety degrees behind the y component. The direction the field rotates in depends on which of the two phase relationships exists. the oscillations can rotate either towards the right or towards the left in the direction of travel. In the leftmost figure above. in most cases it propagates as a transverse wave—the polarization is perpendicular to the wave's direction of travel. such as light. When light travels in free space. so this special case is called circular polarization. along with its x and y components (red/left and blue/right). at a particular point in space. Chennai-119 . In this case the ratio of the strengths of the two components is constant. Polarization state The shape traced out in a fixed plane by the electric vector as such a plane wave passes over it (a Lissajous figure) is a description of the polarization state. St. Associate Professor of Mechanical Engineering. Ramesh. Jeppiaar Trust. along the direction opposite to propagation. In this case one component is zero when the other component is at maximum or minimum amplitude. By convention. Since the tip of the vector traces out a single line in the plane.

of course. B.Modern Techniques of Materials Characterisation 11 Linear Circular Elliptical Another case is when the two components are not in phase and either do not have the same amplitude or are not ninety degrees out of phase. The circularly polarized modes are a more useful basis for the study of light propagation in stereoisomers. Jeppiaar Trust. Chennai-119 . This is shown in the above figure on the right. all the above is a very accurate description for most practical optical experiments which use TEM modes. including Gaussian optics. The Cartesian polarization decomposition is natural when dealing with reflection from surfaces. arbitrary. Plane waves of any polarization can be described instead by combining any two orthogonally polarized waves. Joseph’s College of Engineering. Compiled by : Mr. though their phase offset and their amplitude ratio are constant. St. Ramesh. birefringent materials.[2] This kind of polarization is called elliptical polarization because the electric vector traces out an ellipse in the plane (the polarization ellipse). Associate Professor of Mechanical Engineering. Though this section discusses polarization for idealized plane waves. for instance waves of opposite circular polarization. or synchrotron radiation. The "Cartesian" decomposition of the electric field into x and y components is.

Joseph’s College of Engineering. : Basic optical transmission microscope elements(1990's) Compiled by : Mr. If the polarization is consistent across the spectrum of the source. Associate Professor of Mechanical Engineering. One may then describe the light in terms of the degree of polarization. Components of a microscope Fig. Either by a external light source from above or through the lens with beam splitters. If there is partial correlation between the emitters. the light is partially polarized. St. B. Ramesh. Chennai-119 . The biological microscope usually is a transmission microscope with light coming from below. The orientation of the electric fields produced by these emitters may not be correlated. and the parameters of the polarization ellipse.Modern Techniques of Materials Characterisation 12 Unpolarized light Most sources of electromagnetic radiation contain a large number of atoms or molecules that emit light. and a completely polarized one. The metallurgical microscope usually is a reflection microscope with light coming from above. in which case the light is said to be unpolarized. partially polarized light can be described as a superposition of a completely unpolarized component. Jeppiaar Trust.

Associate Professor of Mechanical Engineering.Modern Techniques of Materials Characterisation 13 All modern optical microscopes designed for viewing samples by transmitted light share the same basic components of the light path. all rays of light from a point in the object plane would converge to the same point in the image plane. listed here in the order the light travels through them: • • • • Light source. a light or a mirror (7) Diaphragm and condenser lens (8) Objective (3) Ocular lens (eyepiece) (1) In addition the vast majority of microscopes have the same 'structural' components: • • • Objective turret (to hold multiple objective lenses) (2) Stage (to hold the sample) (9) Focus wheel to move the stage (4 . forming a clear image. 5 . Jeppiaar Trust. Joseph’s College of Engineering. Ramesh.coarse adjustment. The influences which cause different rays to converge to different points are called aberrations.fine adjustment) Aberrations : Summary of Aberrations In an ideal optical system. Chennai-119 . Compiled by : Mr. St. B.

Ramesh. Associate Professor of Mechanical Engineering. etchants. bases or other chemicals to dissolve unwanted materials such as metals. Jeppiaar Trust. soil conditioner. or methylated spirits for mild steels. This process has been used on a wide variety of metals with depths of metal removal as large as 12mm (0. 2% Nital is common etchant for plain carbon steels. Ammonium. desizing agents. etching. Compiled by : Mr. also known as chemical milling. also known as persulfuric acid. It is however very dangerous if it comes into contact with the body. a liquid at room temperature. is H2SO5. and potassium salts of H2SO5 are used in the plastics industry as polymerization initiators. B. or as Caro's acid. and for decolorizing and deodorizing oils. semiconductor materials or glass. Common etchants For aluminium • sodium hydroxide For steels • • • hydrochloric and nitric acids ferric chloride for stainless steels Nital (a mixture of nitric acid and ethanol.Modern Techniques of Materials Characterisation 14 Etchants : In industry. hydrochloric acid and hydrogen peroxide For silica • hydrofluoric acid (HF) is a very efficient etchant for silicon dioxide. sodium. is the process of using acids.5 in). Joseph’s College of Engineering. St. Peroxymonosulfuric acid. peroxysulfuric acid. For copper • • • • • • cupric chloride ferric chloride ammonium persulfate ammonia 25-50 % nitric acid. Chennai-119 . methanol.

and the image is shown directly on a computer screen without the need for eye-pieces. Ramesh. Associate Professor of Mechanical Engineering.Modern Techniques of Materials Characterisation 15 Optical microscope The optical microscope. Joseph’s College of Engineering. : Basic optical transmission microscope elements(1990's) Compiled by : Mr. Jeppiaar Trust. Optical microscopes are the oldest design of microscope and were designed around 1600. Chennai-119 . is a type of microscope which uses visible light and a system of lenses to magnify images of small samples. Alternatives to optical microscopy which do not use visible light include scanning electron microscopy and transmission electron microscopy. Basic optical microscopes can be very simple. B. often referred to as the "light microscope". Originally images were captured by photographic film but modern developments in CMOS and later charge-coupled device (CCD) cameras allow the capture of digital images. Components Fig. The image from an optical microscope can be captured by normal light-sensitive cameras to generate a micrograph. although there are many complex designs which aim to improve resolution and sample contrast. St. Historically optical microscopes were easy to develop and are popular because they use visible light so the sample can be directly observed by eye. Purely Digital microscopes are now available which just use a CCD camera to examine a sample.

Joseph’s College of Engineering. the optical configuration of the objective lens and eyepiece are matched to give the best possible optical performance. Typical magnification values of objective lenses are 4×. Jeppiaar Trust. At the lower end of the microscope tube one or more objective lenses are screwed into a circular nose piece which may be rotated to select the required objective lens. 5 . 5× and 10×. 10×. its function is to bring the image into focus for the eye. This occurs most commonly with apochromatic objectives. Objective The objective is a cylinder containing one or more lenses that are typically made of glass. Ramesh. St. The eyepiece is inserted into the top end of the body tube. Some high performance objective lenses may require matched eyepieces to deliver the best optical performance. listed here in the order the light travels through them: • • • • Light source. 60× and 100×. B. Associate Professor of Mechanical Engineering. Typical magnification values for eyepieces include 2×. Compiled by : Mr. In some high performance microscopes. Ocular (eyepiece) The ocular. a light or a mirror (7) Diaphragm and condenser lens (8) Objective (3) Ocular lens (eyepiece) (1) In addition the vast majority of microscopes have the same 'structural' components: • • • Objective turret (to hold multiple objective lenses) (2) Stage (to hold the sample) (9) Focus wheel to move the stage (4 . 50×. Eyepieces are interchangeable and many different eyepieces can be inserted with different degrees of magnification. its function is to collect light from the sample. Chennai-119 .fine adjustment) These entries are numbered according to the image on the right. is a cylinder containing two or more lenses. 5×. The stage usually has arms to hold slides (rectangular glass plates with typical dimensions of 25 mm by 75 mm. In the center of the stage is a hole through which light passes to illuminate the specimen. on which the specimen is mounted). or eyepiece. 40×. 20×.coarse adjustment. Stage The stage is a platform below the objective which supports the specimen being viewed.Modern Techniques of Materials Characterisation 16 All modern optical microscopes designed for viewing samples by transmitted light share the same basic components of the light path.

Most microscopes. The typical magnification of objective lenses depends on the intended application. to manage the quality and intensity of the illumination. The arm angle may be adjustable to allow the viewing angle to be adjusted. such as a diaphragm and/or filters. phase contrast and differential interference contrast microscopy additional optical components must be precisely aligned in the light path. For illumination techniques like dark field. 40×. normal groups of lens magnificaitons may be [4×. have their own controllable light source . Condenser The condenser is a lens designed to focus light from the illumination source onto the sample. 20×] for low magnification work and [10×.normally a halogen lamp. Other features may be lamp controls and/or controls for adjusting the condenser. 100×] for high magnification work. These objectives must be used with oil (immersion oil) between the objective lens and the sample. Objective lenses with higher magnifications normally have a higher numerical aperture and a shorter depth of field in the resulting image. Many different objective lenses with different properties and magnification are available. The refractive index of the immersion oil is higher than air and this allows the objective lens to have a larger Compiled by : Mr. Associate Professor of Mechanical Engineering. Ramesh. daylight is directed via a mirror. Typically there will be around three objective lenses: a low power lens for scanning the sample. Jeppiaar Trust. At its simplest. 10×. a medium power lens for normal observation and a high power lens for detailed observation. together with a smaller knurled wheel to control fine focus. Chennai-119 . typically a large knurled wheel to adjust coarse focus. The frame provides a mounting point for various microscope controls. Oil immersion objective Some microscopes make use of oil immersion lens. B. Frame The whole of the optical assembly is traditionally attached to a rigid arm which in turn is attached to a robust U shaped foot to provide the necessary rigidity. The condenser may also include other features. St. Joseph’s College of Engineering. however.Modern Techniques of Materials Characterisation 17 Light source Many sources of light can be used. Normally this will include controls for focusing. Objective lenses On a typical compound optical microscope there are a selection of lenses available for different applications.

the camera optics magnification and the enlargement factor. Jeppiaar Trust. the final magnification is the product of: the objective lens magnification. Immersion lenses are designed so that the refractive index of the oil and of the cover slip are closely matched so that the light is transmitted from the specimen to the outer face of the objective lens with minimal refraction. Chennai-119 . Associate Professor of Mechanical Engineering. The maximum normal magnifications of the occular and objective are 10× and 100× respectively giving a final magnification of 1000×. The larger numerical aperture allows collection of more light making detailed observation of faint details possible. The enlargement factor from the detector to the pixels on screen can then be calculated. the camera optics magnification and the enlargement factor of the film print relative to the negative. As with a film camera the final magnification is the product of: the objective lens magnification. An oil immersion lens usually has a magnification of 40 to 100×.Modern Techniques of Materials Characterisation 18 numerical aperture. In the case of digital cameras the size of the pixels in the CMOS or CCD detector and the size of the pixels on the screen have to be known. In the case of photographic film cameras the calculation is simple. Compiled by : Mr. Magnification and micrographs When using a camera to capture a micrograph the effective magnification of the image must take into account the size of the image. This is independent of whether it is on a print from a film negative or displayed digitally on a computer screen. Ramesh. Joseph’s College of Engineering. St. Magnification The actual power or magnification of a compound optical microscope is the product of the powers of the ocular (eyepiece) and the objective lens. B. A typical value of the enlargement factor is around 5× (for the case of 35mm film and a 6×4 inch print).

Chennai-119 . Headaches and tired eyes after using a microscope are usually signs that the eye is being forced to focus at a close distance rather than at infinity. Despite this. the basic operating principles of a microscope are quite simple. This creates an enlarged image of the subject. St. the first lens bringing the real image to a focus and the second lens enabling the eye to focus on the virtual image. a highly enlarged image can be seen. Here. In all microscopes the image is intended to be viewed with the eyes focused at infinity (mind that the position of the eye in the above figure is determined by the eye's focus). In most microscopes. This is brought very close to the specimen being examined so that the light from the specimen comes to a focus about 160 mm inside the microscope tube. The objective lens is.e. the quantity of interest is linear magnification. By carefully focusing a brightly lit specimen. It is this real image that is viewed by the eyepiece lens that provides further enlargement. a very high powered magnifying glass i.Modern Techniques of Materials Characterisation 19 Operation : Fig. Jeppiaar Trust. B. This image is inverted and can be seen by removing the eyepiece and placing a piece of tracing paper over the end of the tube. The essential principle of the microscope is that an objective lens with very short focal length (often a few mm) is used to form a highly magnified real image of the object. Associate Professor of Mechanical Engineering. the whole optical path has to be very accurately set up and controlled. at its simplest. Joseph’s College of Engineering. with one component lens near the front and one near the back of the eyepiece tube. In many designs. the virtual image comes to a focus between the two lenses of the eyepiece. and this number is generally Compiled by : Mr. the eyepiece is a compound lens. : Optical path in a typical microscope The optical components of a modern microscope are very complex and for a microscope to work well. Ramesh. This forms an air-separated couplet. a lens with a very short focal length.

In practice. Compiled by : Mr. Spherical aberration can be minimised by careful choice of the curvature of the surfaces for a particular application: for instance. nonspherical surfaces are used are called aspheric lenses. Ramesh. Spherical aberration causes beams parallel to. and there is always some degree of distortion or aberration introduced by the lens which causes the image to be an imperfect replica of the object. St. Spherical aberration Spherical aberration occurs because spherical surfaces are not the ideal shape with which to make a lens. B. today. Associate Professor of Mechanical Engineering. There are several different types of aberration which can affect image quality. but distant from. and a second weak tube lens which then forms a real image in its focal plane. Jeppiaar Trust. but advances in technology have greatly reduced the manufacturing cost for such lenses. Chennai-119 . but they are by far the simplest shape to which glass can be ground and polished and so are often used. This manifests itself as a blurring of the image. Lenses in which closer-to-ideal. the lens axis to be focused in a slightly different place than beams close to the axis. a planoconvex lens which is used to focus a collimated beam produces a sharper focal spot when used with the convex side towards the beam source. Careful design of the lens system for a particular application ensures that the aberration is minimized.[3] Aberrations of lenses Lenses do not form perfect images. this magnification is carried out by means of two lenses: the objective lens which creates an image at infinity. These were formerly complex to make and often extremely expensive.Modern Techniques of Materials Characterisation 20 inscribed on the objective lens casing. Joseph’s College of Engineering.

Chennai-119 . Rays which pass through the centre of the lens of focal length f are focused at a point with distance f tan θ from the axis. Joseph’s College of Engineering. a bundle of parallel rays passing through the lens at a fixed distance from the centre of the lens are focused to a ring-shaped image in the focal plane. where rays pass through the lens at an angle to the axis θ. An apochromat is a lens or lens system which has Compiled by : Mr.Modern Techniques of Materials Characterisation 21 Coma Another type of aberration is coma. though it does not produce perfect correction. either further from the axis (positive coma) or closer to the axis (negative coma). f is dependent upon n. it follows that different wavelengths of light will be focused to different positions. In general. Lenses in which both spherical aberration and coma are minimised are called bestform lenses. Jeppiaar Trust. The use of achromats was an important step in the development of the optical microscope. Since. Chromatic aberration of a lens is seen as fringes of colour around the image. known as a comatic circle. St. It can be minimised by using an achromatic doublet (or achromat) in which two materials with differing dispersion are bonded together to form a single lens. which derives its name from the comet-like appearance of the aberrated image. Ramesh. n. coma can be minimised (and in some cases eliminated) by choosing the curvature of the two lens surfaces to match the application. with the wavelength of light. from the formulae above. Associate Professor of Mechanical Engineering. B. Chromatic aberration Chromatic aberration is caused by the dispersion of the lens material—the variation of its refractive index. The sum of all these circles results in a V-shaped or comet-like flare. Coma occurs when an object off the optical axis of the lens is imaged. As with spherical aberration. This reduces the amount of chromatic aberration over a certain range of wavelengths. Rays passing through the outer margins of the lens are focused at different points.

B. Associate Professor of Mechanical Engineering. such as specialised coatings or lenses made from the crystal fluorite.Modern Techniques of Materials Characterisation 22 even better correction of chromatic aberration. Different lens materials may also be used to minimise chromatic aberration. This naturally occurring substance has the highest known Abbe number. St. Joseph’s College of Engineering. Jeppiaar Trust. combined with improved correction of spherical aberration. Chennai-119 . Ramesh. indicating that the material has low dispersion. Compiled by : Mr. Apochromats are much more expensive than achromats.

Placing this lens the distance f from a flat image sensor. : Field curvature: the image plane is not flat. Fig. named for Joseph Petzval. which take hemispherical views. and astigmatism. image magnification decreases with distance from the optical axis. Most photographic lenses are designed to minimize field curvature. Compiled by : Mr. Jeppiaar Trust. The apparent effect is that of an image which has been mapped around a sphere (or barrel). Barrel distortion In "barrel distortion". Ramesh. image points near the optical axis will be in perfect focus. dropping off by the cosine of the angle they make with the optical axis. St. but rays off axis will come into focus before the image sensor. Consider an "ideal" singleelement lens system for which all planar wave fronts are focused to a point a distance f from the lens. utilize this type of distortion as a way to map an infinitely wide object plane into a finite image area. and so effectively have a focal length that increases with ray angle. Joseph’s College of Engineering. Fisheye lenses. B. describes the optical aberration in which a flat object normal to the optical axis (or a non-flat object past the hyperfocal distance) cannot be brought into focus on a flat image plane. Associate Professor of Mechanical Engineering. This is less of a problem when the imaging surface is spherical. barrel and pincushion distortion. Chennai-119 . Petzval field curvature. as in the human eye.Modern Techniques of Materials Characterisation 23 Other types of aberration Other kinds of aberration include field curvature.

St. binoculars. Jeppiaar Trust. image magnification increases with the distance from the optical axis. : Pincushion distortion simulation Compiled by : Mr. A certain amount of pincushion distortion is often found with visual optical instruments.g. Fig.Modern Techniques of Materials Characterisation 24 Fig. e. B. like a pincushion. The visible effect is that lines that do not go through the centre of the image are bowed inwards. towards the centre of the image. Chennai-119 . Ramesh. where it serves to eliminate the globe effect. Joseph’s College of Engineering. Associate Professor of Mechanical Engineering. : Barrel distortion simulation Pincushion distortion In "pincushion distortion".

which is wavelength dependent and gives rise to colours. In order to make phase variations observable.. it is necessary to combine the light passing through the sample with a reference so that the resulting interference reveals the phase structure of the sample.e. Changes in amplitude give rise to familiar absorption of light. In optical microscopy many objects such as cell parts in protozoans. interaction with this medium causes its amplitude and phase to change in a way which depends on properties of the medium. this technique allows phase of the light passing through the object under study to be inferred from the intensity of the image produced by the microscope. As light travels through a medium other than vacuum. This phase contrast technique proved to be such an advancement in microscopy that Zernike was awarded the Nobel prize (physics) in 1953. so changes in phase are not easily observed. When in use. (Staining is a difficult and time consuming procedure which sometimes. Using the phase-contrast technique makes these structures visible and allows their study with the specimen still alive. This was first realized by Frits Zernike during his study of diffraction gratings. i. Compiled by : Mr. and that to maximize the contrast achieved with the technique. St. it is necessary to introduce a phase shift to this reference so that the no-phase-change condition gives rise to completely destructive interference. hence they are sometimes called "phase objects". The same holds in a typical microscope. although the phase variations introduced by the sample are preserved by the instrument (at least in the limit of the perfect imaging instrument) this information is lost in the process which measures the light. This type of microscope made it possible to study the cell cycle. The human eye measures only the energy of light arriving on the retina. Associate Professor of Mechanical Engineering. Chennai-119 . Ramesh. Joseph’s College of Engineering. Jeppiaar Trust.Modern Techniques of Materials Characterisation 25 Phase contrast microscopy Phase contrast microscopy is an optical microscopy illumination technique in which small phase shifts in the light passing through a transparent specimen are converted into amplitude or contrast changes in the image. destroys or alters the specimen. B. yet often these changes in phase carry a large amount of information. The necessary phase shift is introduced by rings etched accurately onto glass plates so that they introduce the required phase shift when inserted into the optical path of the microscope. This is the phase-contrast technique. A phase contrast microscope does not require staining to view the slide. but not always.) The difference in densities and composition within the imaged objects however often give rise to changes in the phase of light passing through them. He later realised that the same technique can be applied to optical microscopy. bacteria and sperm tails are essentially fully transparent unless stained. During these studies he appreciated both that it is necessary to interfere with a reference beam.

Condenser annulus 2. Chennai-119 . Phase-contrast microscopy is a mode available on most advanced light microscopes and is most commonly used to provide contrast of transparent specimens such as living cells or small organisms. Associate Professor of Mechanical Engineering. Phase plate 4. Description 1. Ramesh. St. B.Modern Techniques of Materials Characterisation 26 Background The technique was invented by Frits Zernike in the 1930s for which he received the Nobel prize in physics in 1953. Primary image plane Compiled by : Mr. Object plane 3. Joseph’s College of Engineering. Jeppiaar Trust.

Recentring and rotational alignment of the cross by means of the telescope was nevertheless needed for each change in magnification. and recombined before observation. Ramesh.e. The interference of the two parts at recombination is sensitive to their optical path difference (i. they enter the objective as parallel rays. Associate Professor of Mechanical Engineering. Joseph’s College of Engineering. Two selected light rays. The advantage claimed here was that only a single slit aperture was needed for all phase objective magnifications. St. transparent samples. DIC works on the principle of interferometry to gain information about the optical density of the sample. Chennai-119 . to see otherwise invisible features. To complete the phase setup. Baker. the back focal plane is a conjugated aperture plane to the condenser's front focal plane (also location of the condenser annulus). also known as Nomarski Interference Contrast (NIC) or Nomarski microscopy. the product of refractive index and Compiled by : Mr. B. A relatively complex lighting scheme produces an image with the object appearing black to white on a grey background. get focused by the field lens exactly inside the opening of the condenser annular ring. Differential interference contrast microscopy Differential interference contrast microscopy (DIC). is an optical microscopy illumination technique used to enhance the contrast in unstained. the two light rays are then refracted in such way that they exit the condenser as parallel rays. London) in which the conventional annular form of the two elements was replaced by a cross-shaped transmission slit in the substage and corresponding crossshaped phase plates in the conjugate plane in the objectives. Jeppiaar Trust. Since this location is precisely in the front focal plane of the condenser.Modern Techniques of Materials Characterisation 27 A practical implementation of phase-contrast illumination consists of a phase ring (located in a conjugated aperture plane somewhere behind the front lens element of the objective) and a matching annular ring. Only through correctly centering the two elements can phase contrast illumination be established. This image is similar to that obtained by phase contrast microscopy but without the bright diffraction halo. Assuming that the two rays in question are neither refracted nor diffracted in the specimen plane (location of microscope slide). which is located in the primary aperture plane (location of the condenser's aperture). An interesting variant in phase contrast design was once implemented (by the microscope maker C. which are emitted from one point inside the lamp's filament. DIC works by separating a polarised light source into two orthogonally polarized mutually coherent parts which are spatially displaced (sheared) at the sample plane. Since all parallel rays are focused in the back focal plane of the objective. a phase plate is positioned inside the back focal plane in such a way that it lines up nicely with the condenser annulus. A phase centering telescope that temporarily replaces one of the oculars is used. first to focus the phase element plane and then center the annular illumination ring with the corresponding ring of the phase plate.

Chennai-119 . Joseph’s College of Engineering. : The components of the basic differential interference contrast microscope setup. Compiled by : Mr. emphasising lines and edges though not providing a topographically accurate image.Modern Techniques of Materials Characterisation 28 geometric path length). B. St. the contrast is proportional to the path length gradient along the shear direction. Adding an adjustable offset phase determining the interference at zero optical path difference in the sample. Associate Professor of Mechanical Engineering. Jeppiaar Trust. The light path Fig. giving the appearance of a three-dimensional physical relief corresponding to the variation of optical density of the sample. Ramesh.

29 2. These two illuminations are. The rays travel through adjacent areas of the sample. the sampling and reference rays. which. separated by the shear. The polarised light enters the first Nomarski-modified Wollaston prism and is separated into two rays polarised at 90° to each other. Main article: Wollaston prism Wollaston prisms are a type of prism made of two layers of a crystalline substance. such as quartz. Polarised light is required for the technique to work. with one lying slightly offset with respect to the other. not quite aligned. Joseph’s College of Engineering. one with 0° polarisation and the other with 90° polarisation. Chennai-119 . The sample is effectively illuminated by two coherent light sources. around 0. The two light beams should be parallel between condenser and objective 4. This Compiled by : Mr.Modern Techniques of Materials Characterisation 1. Fig. and so allows greater flexibility when setting up the microscope. Jeppiaar Trust. The separation is normally similar to the resolution of the microscope. as the prism can be actively focused. splits the light according to its polarisation. Unpolarised light enters the microscope and is polarised at 45°. They will experience different optical path lengths where the areas differ in refractive index or thickness. 3.2 μm apart. Associate Professor of Mechanical Engineering. due to the variation of refractive index depending on the polarisation of the light. however. Ramesh. The Nomarski prism causes the two rays to come to a focal point outside the body of the prism. : The route of light through a DIC microscope. St. The two rays are focused by the condenser for passage through the sample. B. These two rays are focused so they will pass through two adjacent points in the sample.

B. such as a smear from a tissue culture or individual water borne single-celled organisms. silicon nitride and Compiled by : Mr. The second prism recombines the two rays into one polarised at 135°. 5. such as tissue slices. The main limitation of DIC is its requirement for a transparent sample of fairly similar refractive index to its surroundings. interference occurs between rays of light that went through adjacent points which therefore have a slightly different phase. This is vital later. would be bright field images of the sample. The combination of the rays leads to interference. refraction and scattering by the sample) means an image of the sample will now be carried by both the 0° and 90° polarised light. Ramesh. These. Chennai-119 . The light also carries information about the image invisible to the human eye. The different polarisations prevent interference between these two images at this point.g. Its resolution[specify] and clarity in conditions such as this are unrivaled among standard optical microscopy techniques. One non-biological area where DIC is useful is in the analysis of planar silicon semiconductor processing.this means that instead of interference occurring between 2 rays of light that passed through the same point in the specimen. Because the difference in phase is due to the difference in optical path length. 6. silicon dioxide. The rays travel through the objective lens and are focused for the second Nomarskimodified Wollaston prism.. DIC is unsuitable (in biology) for thick samples. The thin (typically 100-1000 nm) films in silicon processing are often mostly transparent to visible light (e. the phase of the light. this recombination of light causes "optical differentiation" of the optical path length. Associate Professor of Mechanical Engineering. and highly pigmented cells.Modern Techniques of Materials Characterisation 30 causes a change in phase of one ray relative to the other due to the delay experienced by the wave in the more optically dense material. if looked at individually. The passage of many pairs of rays through pairs of adjacent points in the sample (and their absorbance. Advantages and disadvantages DIC has strong advantages in uses involving live and unstained biological samples. brightening or darkening the image at that point according to the optical path difference. the images do not quite line up because of the offset in illumination . This prism overlays the two bright field images and aligns their polarisations so they can interfere. generating the image seen. Joseph’s College of Engineering. St. Jeppiaar Trust. However. DIC is also unsuitable for most non biological uses because of its dependence on polarisation. slightly offset from each other. which many physical samples would affect.

However analysis of DIC images must always take into account the orientation of the Wollaston prisms and the apparent lighting direction. Chennai-119 . This also enables the determination of whether a feature is a pit in the substrate material or a blob of foreign material on top. Joseph’s College of Engineering. Ramesh. is outstanding in resolution and almost entirely free of artifacts unlike phase contrast. This is. B. however. when used under suitable conditions. Etched crystalline features gain a particularly striking appearance under DIC. St. Associate Professor of Mechanical Engineering. Jeppiaar Trust. as features parallel to this will not be visible.Modern Techniques of Materials Characterisation 31 polycrystalline silicon). and defects in them or contamination lying on top of them become more visible. Image quality. Compiled by : Mr. easily overcome by simply rotating the sample and observing changes in the image.

Associate Professor of Mechanical Engineering. is given by EA = E1 . Emission of an Auger electron is an alternative to the emission of a characteristic X-ray.Modern Techniques of Materials Characterisation 32 Unit IV Primary electron : A primary electron is usually a high energy electron which starts outside the crystal (e. E2 = energy of atom with outer-shell vacancy. Backscattered electrons usually have energies close to that of the primary electron beam. Binding energy : Compiled by : Mr.E3. Back scattered electron: A backscattered electron is a high energy primary electron which suffers large angle (> 90°) scattering and re-emerges from the entry surface of a specimen. and E3 = binding energy of emitted (Auger) electron. EA. Jeppiaar Trust. In practice the phrase most commonly refers to low-energy electrons (kinetic energy less than 50eV) emitted from the specimen in a scanning electron microscope (SEM). Ramesh. giving surface sensitive information. It may be elastically scattered or may excite various processes in the crystal by being inelastically scattered. St. Joseph’s College of Engineering. where E1 = energy of atom with inner-shell vacancy. Secondary electron : A secondary electron arises as a result of the interaction of a primary electron with a specimen. Auger electron : An Auger electron has characteristic energy related to the electronic transitions within the atom which have caused it to be emitted.g. B. The energy of an Auger electron. In principle the term refers to all electrons emitted from a specimen after it has been bombarded with primary electrons.E2 . in the beam of an electron microscope). Secondary electrons of various types can be emitted from a solid following its bombardment with primary electrons. They are of greatest interest to SEM users. Chennai-119 . X-rays or other radiation.

g.Ebinding. Associate Professor of Mechanical Engineering. e. Chennai-119 .L3 = EK . Cathodoluminescence : Cathodoluminescence is the emission of light in response to irradiation by electrons.g. Joseph’s College of Engineering. L) electron jumps in to fill an inner-shell (e. Compiled by : Mr. Its energy is the difference between the energies of the atom with an inner-shell vacancy and the same atom with an outer-shell vacancy. St.EL2 . It has an energy characteristic of the atom and can therefore be used for analytical purposes. L3 Auger electron.g. B. Ramesh. L3 Characteristic X-ray : A characteristic X-ray can be emitted from an excited atom when an outer-shell (e. It will have characteristic energy EK-L2. The emission of the excess energy when an atom de-excites (decays or relaxes) can alternatively be achieved by the production of an Auger electron.g. K (1s) electrons in aluminium = 1559 eV Auger emission example: If a K-shell electron is knocked out of an atom. the resulting inner-shell (K) vacancy can be filled by an outer-shell (e. Jeppiaar Trust.Modern Techniques of Materials Characterisation 33 The binding energy of a particular electron is the energy which would be required to remove it from the atom to an infinite distance. L2) electron. If the resulting energy difference is lost be the emission of an L3 electron this will be known as a K-L2. K) vacancy.

Ramesh. Chennai-119 . Jeppiaar Trust. Associate Professor of Mechanical Engineering. Compiled by : Mr. B. Joseph’s College of Engineering. St. Auger electrons (not shown) emerge from a very thin region of the sample surface (maximum depth about 50 Å) than do secondary electrons (50-500 Å).Modern Techniques of Materials Characterisation 34 Figure :Generalized illustration of interaction volumes for various electron-specimen interactions.

A very thin specimen. The captured electrons are then converted by electronic to a image displayed on a monitor. Image is a two dimensional projection of Image is of the surface of the sample. beam passes through SEM thin Electron beam scans over surface of sample. The electron beam knocks electrons away from the specimen and a sensor captures the electrons. Specimen stage halfway down column. 2 nm 200 000 X A SEM (scanning electron microscope) images using the electrons reflected from a specimen. An electron beam is then directed through the specimen and produced a negative image on a plate coated with a phosphorus coating.2 nm Magnification: 500 000 X A TEM (transmission electron microscope) images using the electrons that pass through it. Image shown on fluorescent screen. Jeppiaar Trust.Modern Techniques of Materials Characterisation 35 Differences between TEM and SEM: TEM Electron sample. The image from an SEM thus looks somewhat like a normal photo (we’re used to imaging using the light reflected from objects). TEM grids. Pictures of this electronic image can also be printed. This is the type where you insert a specimen into the scanning chamber and an electron beam scans the surface of the speciman. Specially prepared thin samples or Sample can be any thickness and is mounted on an particulate material are supported on aluminum stub. coated in gold. Specimen stage in the chamber at the bottom of the column. Resolution : 0. A SEM is a 'Scanning Electron Microscope'. Ramesh. B. Compiled by : Mr. A TEM image takes a bit more interpretation as we’re not used to seeing images of light that’s passed through things A TEM is a 'Transmission Electron Microscope'. Chennai-119 . Image shown on TV monitor. the sample. Joseph’s College of Engineering. St. Photographs are taken of the image by opening a trap door in the plate and exposing negative film or electronic sensors for a digital image. Associate Professor of Mechanical Engineering. is inserted in the specimen chamber of the microscope.

The STM captures images using quantum tunneling. Unlike the STM. the AFM is more complex than the STM. St. B. Summary 1.Modern Techniques of Materials Characterisation 36 Difference Between AFM and STM AFM vs STM AFM refers to Atomic Force Microscope and STM refers to Scanning Tunneling Microscope. When talking of AFM. Jeppiaar Trust. When compared to STM. AFM captures precise images by moving a nanometer sized tip across the surface of the image. the Scanning Tunneling Microscope was the first to be developed. The STM images indirectly by calculating the quantum degree tunneling between he probe and sample. The probe makes a direct contact with the surface or calculates the incipient chemical bonding in AFM. The AFM suits well with liquid and gas environments whereas STM operates only in high vacuum. the tip is kept at a short distance from the surface. The development of these two microscopes is considered a revolution in the atomic and molecular fields. Compiled by : Mr. This is why AFM is widely used in nano-technology. the AFM does not measure the tunneling current but only measures the small force between the surface and the tip. 2. Of the two microscopes. the probe makes a direct contact with the surface or calculates the incipient chemical bonding in AFM. The STM captures images using quantum tunneling. Joseph’s College of Engineering. it captures precise images by moving a nanometer sized tip across the surface of the image. The STM images indirectly by calculating the quantum degree tunneling between he probe and sample. the Atomic Force Microscope is applicable to both conductors and insulators. Ramesh. When talking of the dependence between force and distance. Unlike the STM. It has also been seen that the AFM resolution is better than the STM. Chennai-119 . the AFM gives a more topographic contrast direct height measurement and better surface features. When Scanning Tunneling Microscope is normally applicable to conductors. Another difference that can be seen is that the tip in AFM touches the surface gently touches the surface whereas in STM. Associate Professor of Mechanical Engineering.

the Atomic Force Microscope is applicable to both conductors and insulators. St. When Scanning Tunneling Microscope is normally applicable to conductors. The tip in AFM touches the surface gently touches the surface whereas in STM. Ramesh. 4. Chennai-119 . 5. This is why AFM is widely used in nanotechnology. An image of the surface is obtained by mechanically moving the probe in a raster scan of the specimen. measuring. INVENTED: Scanning Tunneling Microscopy (STM) was invented in 1981 and was developed by Gerd Binnig and Heinrich Rohrer. RESOLUTION: STM gives better resolution than AFM because of the exponential dependence of the tunneling current on distance. STM is a powerful instrument that is used for imaging surfaces at the atomic level while AFM is one of the primary tools for imaging. The AFM suits well with liquid and gas environments whereas STM operates only in high vacuum. line by line.Modern Techniques of Materials Characterisation 37 3. and recording the probe-surface interaction as a function of position. Associate Professor of Mechanical Engineering. the Scanning Tunneling Microscope was the first to be developed. Atomic Force Microscopy (AFM) was invented in 1985 and was also developed by Gerd Binnig and Heinrich Rohrer. the tip is kept at a short distance from the surface. The force-distance dependence in AFM is much more complex when characteristics such Compiled by : Mr. 7. IMAGE: STM gives two-dimensional image of the atoms. and manipulating matter at the Nano-scale. AFM resolution is better than the STM. B. 6. AFM gives three-dimensional surface profile of the Nano-objects. Of the two microscopes. STM Vs AFM Scanning Tunneling Microscopy (STM) and Atomic Force Microscopy (AFM) or scanning force microscopy (SFM) are inventions of Scanning Probe microscopy a technique that forms images of surfaces using a physical probe that scans the specimen. Joseph’s College of Engineering. Jeppiaar Trust.

Compiled by : Mr. While in AFM Interaction between probe and material surface is monitored is van der Waals force. AFM does not record the tunneling current but the small force between the tip and the surface. TIP USED: STM uses a sharpened conducting tip (metallic tip). While in AFM Tip and substrate are actually in physical contact. 38 CONSISTED OF: STM uses a sharpened conducting tip. Ramesh. AFM relies on movement due to the electromagnetic forces between atoms. which is reflected from the cantilever. ATTACHMENT OF TIP: Tip is not attached to a tiny leaf spring in case of Scanning tunneling microscopy. AFM uses a conductive AFM cantilever. often with the use of a laser beam. While AFM's Tip is not kept at a short distance from the surface but it gently touches the surface. the cantilever. which has a low spring constant. INTERACTION: In case of STM Interaction between probe and material surface is monitored is tunneling current. Associate Professor of Mechanical Engineering. TIP SPACE: STM's Tip is kept at a short distance from the surface. Joseph’s College of Engineering. Bending of this cantilever is detected. B. MOUNTED ON: Tip mounts on the scanner when we have scanning tunneling microscope. PHYSICAL CONTACT: In STM Tip and substrate are in very close proximity but not actually in physical contact. St. TUNNELING CURRENT: STM record the tunneling current. Chennai-119 . Sample mounts on the scanner when we have atomic force microscope.Modern Techniques of Materials Characterisation as tip shape and contact force are considered. AFM uses a conductive AFM cantilever (typically silicon or silicon nitride with a tip radius of curvature on the order of nanometers) with a sharp tip (probe) at its end that is used to scan the specimen surface. Jeppiaar Trust. DEPENDED ON: STM relies on electrical current between the tip and the surface. In Atomic force microscope Tip is attached to a tiny leaf spring.

The depth of focus. although at relatively low quality. requiring several minutes for a typical scan. The AFM is one of the primary tools for imaging. measuring. • AFM gives three-dimensional image while STM only gives two-dimensional image. and manipulating matter at the Nano-scale. Joseph’s College of Engineering.Modern Techniques of Materials Characterisation 39 VISUALIZATION: STM can visualize and even manipulate atoms. Depth of field and depth of focus The depth of field. STM is being used for the conductance of single molecule. ADVANTAGES & DISADVANTAGES: • In STM the two parameters are integrally linked for voltage calculation. • AFM offers the advantage that the writing voltage and tip-to-substrate spacing can be controlled independently. Dob is the range of distance along the optical axis in which the specimen can move without the image appearing to lose sharpness. • An AFM cannot scan images as fast as a STM. USED FOR: STM is a powerful instrument that is used for imaging surfaces at the atomic level.e. This is the advantage of AFM over STM. Jeppiaar Trust. This depends on magnification. DNA and proteins etc. • Resolution of STM is higher than AFM. St. Ramesh. STM gives true atomic resolution. MT. Both depth of field and depth of focus are strongly dependent on changes in aperture (hence the semiangle  and working distance (dob). Chennai-119 . ) Compiled by : Mr.. Associate Professor of Mechanical Engineering. This obviously depends on the resolution of the microscope. Dim is the extent of the region around the image plane in which the image will appear to be sharp. B. AFM can easily image non-conducting objects i. while a STM is capable of scanning at near real-time.

Associate Professor of Mechanical Engineering. B. As a result. and thus will not form part of the image. This produces the classic appearance of a dark. Joseph’s College of Engineering. the field around the specimen (i. Chennai-119 .htm 40 Dark field microscopy Dark field microscopy (dark ground microscopy) describes microscopy methods. Ramesh. darkfield describes an illumination technique used to enhance the contrast in unstained samples. in both light and electron microscopy.e. Light Microscopy Applications In optical microscopy. It works by illuminating the sample with light that will not be collected by the objective lens.Modern Techniques of Materials Characterisation http://www. Compiled by : background with bright objects on it. Jeppiaar Trust. almost black. which exclude the unscattered beam from the image. The light's path The steps are illustrated in the figure where an upright microscope is used. where there is no specimen to scatter the beam) is generally dark.

different effects are visible in each. 5. features are visible where either a shadow is cast on the surface by the incident light. Light enters the microscope for illumination of the sample. The condenser lens focuses the light towards the sample. while the directly transmitted light simply misses the lens and is not collected due to a direct illumination block (see figure).Modern Techniques of Materials Characterisation Fig. possibly by the presence of pits or scratches. 2. Dark field microscopy techniques are almost entirely free of artifacts. Joseph’s College of Engineering. the patch stop (see figure) blocks some light from the light source. Considering the simplicity of the setup. The main limitation of dark field microscopy is the low light levels seen in the final image.Dark field microscopy is a very simple yet effective technique and well suited for uses involving live and unstained biological samples. In bright field microscopy. Jeppiaar Trust. : Diagram illustrating the light path through a dark field microscope. or a part of the surface is less reflective. Compiled by : Mr. due to the nature of the process. Only the scattered light goes on to produce the image. such as a smear from a tissue culture or individual water-borne single-celled organisms. B. leaving an outer ring of illumination. The light enters the sample. while the directly transmitted light is omitted. 3. and vice versa. While the dark field image may first appear to be a negative of the bright field image. Advantages and disadvantages . Ramesh. Chennai-119 . while some is scattered from the sample. The scattered light enters the objective lens. Associate Professor of Mechanical Engineering. 6. However the interpretation of dark field images must be done with great care as common dark features of bright field microscopy images may be invisible. A specially sized disc. 4. St. Most is directly transmitted. the quality of images obtained from this technique is impressive. 41 1. This means the sample must be very strongly illuminated. but the light that reflects off the sides of the feature will be visible in the dark field images. which can cause damage to the sample. Raised features that are too smooth to cast shadows will not appear in bright field images.

illuminated from below and observed from above) white light and contrast in the sample is caused by absorbance of some of the transmitted light in dense areas of the sample. Joseph’s College of Engineering. The light path therefore consists of: • • • • Transillumination light source. Bright field illumination is useful for samples which have an intrinsic colour. Performance Bright field microscopy typically has low contrast with most biological samples as few absorb light to a great extent.e. Bright field microscopy is the simplest of a range of techniques used for illumination of samples in light microscopes and its simplicity makes it a popular technique. commonly a halogen lamp in the microscope stand. Limitations • • Very low contrast of most biological samples. Compiled by : Mr. Chennai-119 . Light path The light path of a bright field microscope is extremely simple. for example chloroplasts in plant cells. St. Low apparent optical resolution due to the blur of out of focus material. no additional components are required beyond the normal light microscope setup. Bright field microscopy may use critical or Köhler illumination to illuminate the sample. The typical appearance of a bright field microscopy image is a dark sample on a bright background. Sample illumination is transmitted (i. Jeppiaar Trust.. hence the name. B. Bright field microscopy is a standard light microscopy technique and therefore magnification is limited by the resolving power possible with the wavelength of visible light. Ramesh. Oculars and/or a camera to view the sample image. Objective lens which collects light from the sample and magnifies the image. Associate Professor of Mechanical Engineering. Stains are often required to increase contrast which prevents use on live cells in many situations. Summary Advantages • Simplicity of setup with only basic equipment required. Condenser lens which focusses light from the light source onto the sample.Modern Techniques of Materials Characterisation 42 Bright field microscopy Bright field microscopy is the simplest of all the optical microscopy illumination techniques.

• Dark field illumination. 1. Ramesh. endospore stains). Use of a colored (usually blue) or polarizing filter on the light source to highlight features not visible under white light. such as simple stains (Methylene blue. flagellar stains. Joseph’s College of Engineering. Immersion oil has the same refraction as glass and improves the resolution of the observed specimen.559 μm/pixel. live cells cannot be viewed. Associate Professor of Mechanical Engineering. B. Safranin. Use of sample staining methods for use in microbiology. sample contrast comes from light scattered by the sample. Chennai-119 . Comparison of transilumination techniques used to generate contrast in a sample of tissue paper. Enhancements • • • • Reducing or increasing the amount of the light source via the iris diaphragm. The use of filters is especially useful with mineral samples. Therefore. Compiled by : Mr. St.Modern Techniques of Materials Characterisation • 43 The sample has to be stained before viewing. Jeppiaar Trust. Crystal violet) and differential stains (Negative stains. Use of an oil immersion objective lens and a special immersion oil placed on a glass cover over the specimen.

crystal orientation. Alternate modes of use allow for the TEM to observe modulations in chemical identity. materials science as well as pollution and semiconductor research. TEM forms a major analysis method in a range of scientific fields. virology. the image is magnified and focused onto an imaging device. Ramesh. or to be detected by a sensor such as a CCD camera. interacting with the specimen as it passes through. The first TEM was built by Max Knoll and Ernst Ruska in 1931. Chennai-119 . Transmission electron microscopy Transmission electron microscopy (TEM) is a microscopy technique whereby a beam of electrons is transmitted through an ultra thin specimen. Associate Professor of Mechanical Engineering. requiring expert analysis of observed images. such as a fluorescent screen. in both physical and biological sciences. St. At higher magnifications complex wave interactions modulate the intensity of the image. due to the thickness and composition of the material. sample contrast comes from absorbance of light in the sample. Uses: Compiled by : Mr. B. At smaller magnifications TEM image contrast is due to absorption of electrons in the material. owing to the small de Broglie wavelength of electrons. An image is formed from the interaction of the electrons transmitted through the specimen. with this group developing the first TEM with resolving power greater than that of light in 1933 and the first commercial TEM in 1939. This enables the instrument's user to examine fine detail—even as small as a single column of atoms. which is tens of thousands times smaller than the smallest resolvable object in a light microscope.Modern Techniques of Materials Characterisation 44 • Bright field illumination. electronic structure and sample induced electron phase shift as well as the regular absorption based imaging. TEMs find application in cancer research. TEMs are capable of imaging at a significantly higher resolution than light microscopes. on a layer of photographic film. Jeppiaar Trust. Joseph’s College of Engineering.

Because even for very thin samples one is looking through many atoms.Modern Techniques of Materials Characterisation 45 The transmission electron microscope is used to characterize the microstructure of materials with very high spatial resolution. Ramesh. Chennai-119 .025Å. one does not usually see individual atoms. or recorded on film or digital camera. St. and magnetic microstructure can be obtained by a combination of electron-optical imaging (sub-Ångstrom in the Titan. electron diffraction. crystal phases and composition. The electrons are accelerated at several hundred kV. the Titan provides significant in situ capabilities. B. Information about the morphology. giving wavelengths much smaller than that of light: 200kV electrons have a wavelength of 0. Joseph’s College of Engineering. and small probe capabilities. allowing for the investigation of how material structure can evolve due to different environmental factors. 2. However. The electrons are focused with electromagnetic lenses and the image is observed on a fluorescent screen. whereas the resolution of the optical microscope is limited by the wavelength of light. The trade-off for this diverse range of structural information and high resolution is the challenge of producing very thin samples for electron transmission.5 Å point resolution in the Tecnai). crystal structure and defects. Associate Professor of Mechanical Engineering. Jeppiaar Trust. to about 1-2 Å. Further. Principles of operation: The transmission electron microscope uses a high energy electron beam transmitted through a very thin sample to image and analyze the microstructure of materials with atomic scale resolution. that of the electron microscope is limited by aberrations inherent in electromagnetic lenses. Rather the high resolution imaging mode of the microscope images the crystal lattice of a material as an interference pattern between the transmitted Compiled by : Mr.

are also invaluable for giving information about the morphology. Restrictions on Samples: Sample preparation for TEM generally requires more time and experience than for most other characterization techniques. The TEM is also capable of forming a focused electron probe. combined with electron diffraction. Ramesh. Joseph’s College of Engineering. with atomic scale resolution. where the resolution is on the order of one micron due to beam spreading in the bulk sample. grinding and polishing using special devices (t-tool. For example surface oxide films may be introduced during ion milling and the strain state of a thin film may change if the substrate is removed. Artifacts are common in TEM samples. grain boundaries. and defects in a material. disc shaped sample with a hole in the middle. which operate at intermediate magnification. Chennai-119 . as unlike neutron or X-Ray radiation the Compiled by : Mr. lithographic patterning of walls and pillars for cross-section viewing. The high brightness field-emission gun improves the sensitivity and resolution of x-ray compositional analysis over that available with more traditional thermionic sources. due both to the thinning process and to changing the form of the original material. which can be positioned on very fine features in the sample for microdiffraction information or analysis of x-rays for compositional information. A thin. The entire specimen must fit into a 3mm diameter cup and be less than about 100 microns in thickness. carbon). as small as 20 Å. chemical etching and electropolishing. B. is typical. Finally the microscope is equipped with a special imaging lens allowing for the observation of micromagnetic domain structures in a field-free environment. Jeppiaar Trust. A TEM specimen must be approximately 1000 Å or less in thickness in the area of interest. the edges of the hole being thin enough for TEM viewing. interfaces. and the final thinning done by ion milling.Modern Techniques of Materials Characterisation 46 and diffracted beams. Associate Professor of Mechanical Engineering. The latter is the same signal as that used for EMPA and SEM composition analysis (see EMPA facility). The brightfield/darkfield imaging modes of the microscope. TEM specimens are required to be at most hundreds of nanometers thick. tripod). on the order of the probe size. Other specimen preparation possibilities include direct deposition onto a TEM-thin substrate (Si3N4. because the sample is so thin. and focused ion beam (FIB) sectioning for site specific samples. The initial disk is usually formed by cutting and grinding from bulk or thin film/substrate material. crystal phases. This allows one to observe planar and line defects. The spatial resolution for this compositional analysis in TEM is much higher. Conversely the signal is much smaller and therefore less quantitative. etc. Most artifacts can either be minimized by appropriate preparation techniques or be systematically identified and separated from real information. St. Sample preparation Sample preparation in TEM can be a complex procedure. direct dispersion of powders on such a substrate.

many generic techniques have been used for the preparation of the required thin sections. The stain absorbs electrons or scatters part of the electron beam which otherwise is projected onto the imaging system. lead. Constraints on the thickness of the material may be limited by the scattering cross-section of the atoms from which the material is comprised. such as powders or nanotubes. or uranium may be used prior to TEM observation to selectively deposit electron dense atoms in or on the sample in desired cellular or protein regions.[35] In material science and metallurgy the specimens tend to be naturally resistant to vacuum. an effect that increases roughly with atomic number squared (z2). Joseph’s College of Engineering. requiring an understanding of how heavy metals bind to biological tissues. small. This may be achieved via an electric arc deposition process using a sputter coating device. or etched so some portion of the specimen is thin enough for the beam to penetrate. to ensure constant sample thickness across the region of interest. Polishing needs to be done to a high quality. Ramesh. or cubic boron nitride polishing compound may be used in the final stages of Compiled by : Mr. Tissue sectioning By passing samples over a glass or diamond edge. thin sections can be readily obtained using a semi-automated method. B. similarly TEM samples of biological tissues can utilize high atomic number stains to enhance contrast. biological specimens can be fixated using either a negative staining material such as uranyl acetate or by plastic embedding. As such. Preparation of TEM specimens is specific to the material under analysis and the desired information to obtain from the specimen. Additionally inorganic samples have been studied. Chennai-119 . Jeppiaar Trust. Compounds of heavy metals such as osmium. where the coating thickness is several nanometers.Modern Techniques of Materials Characterisation 47 electron beam interacts readily with the sample.[14] High quality samples will have a thickness that is comparable to the mean free path of the electrons that travel through the samples.[36] This method is used to obtain thin. [37] To prevent charge build-up at the sample surface. such as aluminium. Mechanical milling Mechanical polishing may be used to prepare samples. St. such as carbon. can be quickly prepared by the deposition of a dilute sample containing the specimen onto support grids or films. A diamond. but still must be prepared as a thin foil. Associate Professor of Mechanical Engineering. In the biological sciences in order to withstand the instrument vacuum and facilitate handling. Alternately samples may be held at liquid nitrogen temperatures after embedding in vitreous ice. Sample staining Details in light microscope samples can be enhanced by stains that absorb light. tissue samples need to be coated with a thin layer of conducting material. minimally deformed samples that allow for the observation of tissue samples. Materials that have dimensions small enough to be electron transparent. although this usage is limited owing to the heavy damage induced in the less soft samples. which may be only a few tens of nanometers.

particularly metallic specimens. Associate Professor of Mechanical Engineering. As TEM specimens are typically ~100 nm thick. Because FIB can be used to micro-machine samples very precisely.[38] Selected area (electron) diffraction: Selected area (electron) diffraction (abbreviated as SAD or SAED). is a crystallographic experimental technique that can be performed inside a transmission electron microscope (TEM). additional fine methods such as ion etching may be required to perform final stage thinning. The sample may be rotated to promote even polishing of the sample surface. such as an acid. These samples are thinned using a chemical etchant. Unlike inert gas ion sputtering. Ramesh. the atoms act as a diffraction grating to the electrons. to prepare the sample for TEM observation. The sputtering rate of such methods is on the order of tens of micrometers per hour. and may include systems to detect when the sample has been thinned to a sufficient level of optical transparency. some fraction of Compiled by : Mr. rather than particle-like (see waveparticle duality). Chennai-119 . B. which are diffracted.Modern Techniques of Materials Characterisation 48 polishing to remove any scratches that may cause contrast fluctuations due to varying sample thickness. This is used to perform a finishing polish of specimens polished by other means. Even after careful mechanical milling. That is. the electrons pass through the sample easily. and the electrons typically have an energy of 100-400 kiloelectron volts. Joseph’s College of Engineering. Acceleration energies for gases such as argon are typically a few kilovolts. limiting the method to only extremely fine polishing. In a TEM. Devices to control the thinning process may allow the operator to control either the voltage or current passing through the specimen. FIB makes use of significantly more energetic gallium ions and may alter the composition or structure of the material through gallium implantation. St. such as a semiconductor or metal. Ion etching uses an inert gas passed through an electric field to generate a plasma stream that is directed to the sample surface. Jeppiaar Trust. Because the wavelength of high-energy electrons is a fraction of a nanometer. Chemical etching Certain samples may be prepared by chemical etching. FIB is a relatively new technique to prepare thin samples for TEM examination from larger specimens. electrons are treated as wave-like. In this case. a thin crystalline specimen is subjected to a parallel beam of high-energy electrons. it is possible to mill very thin membranes from a specific area of interest in a sample. More recently focussed ion beam methods have been used to prepare samples. Ion etching Ion etching is a sputtering process that can remove very fine quantities of material. and the spacings between atoms in a solid is only slightly larger.

Ramesh. Chennai-119 . This is a thin strip of metal that will block the beam. by moving the aperture hole to the section of the sample the user wishes to examine. Joseph’s College of Engineering. St. whereas x-ray diffraction typically samples areas several centimeters in size. A diffraction pattern is made under broad. while others continue to pass through the sample without deflection. and only this section will contribute to the SADP on the screen. parallel electron illumination. Jeppiaar Trust. It is similar to x-ray diffraction. An aperture in the image plane is used to select the diffracted region of the specimen. The effect is to block all of the electron beam except for the small fraction passing through one of the holes. each spot corresponding to a satisfied diffraction condition of the sample's crystal structure. This is important. If more than one crystal contributes to the SADP. determined by the crystal structure of the sample. As a result. the same crystal will stay under illumination. SAD can be used to identify crystal structures and examine crystal defects. in order to examine the crystallographic orientation between them. it is useful to select a single crystal for analysis at a time. Fig. but unique in that areas as small as several hundred nanometers in size can be examined. but different diffraction conditions will be activated. It may also be useful to select two crystals at a time. B. this particular area is selected by the aperture.Modern Techniques of Materials Characterisation 49 them will be scattered to particular angles. and different diffraction spots will appear or disappear. Associate Professor of Mechanical Engineering. If the sample is tilted. the image on the screen of the TEM will be a series of spots—the selected area diffraction pattern. : SADP of a single austenite crystal in a piece of steel SAD is referred to as "selected" because the user can easily choose from which part of the specimen to obtain the diffraction pattern. Located below the sample holder on the TEM column is a selected area aperture. for example. As such. and can be moved by the user. which can be inserted into the beam path. it can be difficult or impossible to analyze. in polycrystalline specimens. giving siteCompiled by : Mr. As a diffraction technique. SADP. It contains several different sized holes.

SAD is used primarily in material science and solid state physics. with lattice reflections showing as sharp diffraction spots. Jeppiaar Trust. and is one of the most commonly used experimental techniques in those fields. twinning and certain crystalline defects [1]. Chennai-119 . interfaces. Ramesh. St. Joseph’s College of Engineering. SAD patterns are a projection of the reciprocal lattice. Scanning process and image formation Compiled by : Mr. By tilting a crystalline sample to low-index zone axes. Other uses of SAD include analysis of: lattice matching. The electrons interact with the atoms that make up the sample producing signals that contain information about the sample's surface topography. Scanning electron microscope The scanning electron microscope (SEM) is a type of electron microscope that images the sample surface by scanning it with a high-energy beam of electrons in a raster scan pattern.Modern Techniques of Materials Characterisation 50 selective diffraction analysis. SAD patterns can be used to identify crystal structures and measure lattice parameters. SAD is essential for setting up DF imaging conditions. Associate Professor of Mechanical Engineering. composition and other properties such as electrical conductivity. B.

When the primary electron beam interacts with the sample. emission of secondary electrons by inelastic scattering and the emission of electromagnetic radiation. typically in the final lens. each of which can be Compiled by : Mr.5 keV to 40 keV. Other types of electron emitters include lanthanum hexaboride (LaB6) cathodes. is focused by one or two condenser lenses to a spot about 0. Associate Professor of Mechanical Engineering. Tungsten is normally used in thermionic electron guns because it has the highest melting point and lowest vapour pressure of all metals. an electron beam is thermionically emitted from an electron gun fitted with a tungsten filament cathode. The size of the interaction volume depends on the electron's landing energy. The electron beam. The beam passes through pairs of scanning coils or pairs of deflector plates in the electron column. which may be of the cold-cathode type using tungsten single crystal emitters or the thermally-assisted Schottky type. which can be used in a standard tungsten filament SEM if the vacuum system is upgraded and field emission guns (FEG). which deflect the beam in the x and y axes so that it scans in a raster fashion over a rectangular area of the sample surface. thereby allowing it to be heated for electron emission. the electrons lose energy by repeated random scattering and absorption within a teardrop-shaped volume of the specimen known as the interaction volume. St. The energy exchange between the electron beam and the sample results in the reflection of high-energy electrons by elastic scattering.Modern Techniques of Materials Characterisation 51 Fig. Joseph’s College of Engineering. which typically has an energy ranging from 0. and because of its low cost. In a typical SEM. which extends from less than 100 nm to around 5 µm into the surface. B. the atomic number of the specimen and the specimen's density. : Schematic diagram of an SEM. using emitters of zirconium oxide. Jeppiaar Trust.4 nm to 5 nm in diameter. Chennai-119 . Ramesh.

Conductive materials in current use for specimen coating include gold. O-osmium). and the resulting image is therefore a distribution map of the intensity of the signal being emitted from the scanned area of the specimen. B. T-thiocarbohydrazide. even when there is enough specimen conductivity to prevent charging. Joseph’s College of Engineering. Metal objects require little special preparation for SEM except for cleaning and mounting on a specimen stub. Ramesh. this causes scanning faults and other image artifacts. Jeppiaar Trust. The improvement in resolution arises because backscattering and secondary electron emission near the surface are enhanced and thus an image of the surface is formed.Modern Techniques of Materials Characterisation 52 detected by specialized detectors. especially with samples of low atomic number (Z).[6][7] Nonconducting specimens may be imaged uncoated using specialized SEM instrumentation such as the "Environmental SEM" (ESEM) or field emission gun (FEG) SEMs operated at low voltage. deposited on the sample either by low vacuum sputter coating or by high vacuum evaporation. at least at the surface. Associate Professor of Mechanical Engineering. The raster scanning of the CRT display is synchronised with that of the beam on the specimen in the microscope. gold/palladium alloy. St. chromium and graphite. Nonconductive specimens tend to charge when scanned by the electron beam. For conventional imaging in the SEM. The image may be captured by photography from a high resolution cathode ray tube. osmium. commonly gold. but in modern machines is digitally captured and displayed on a computer monitor and saved to a computer's hard disk. Chennai-119 . are to increase signal and surface resolution. and some can tilt an object of that size to 45°. They are therefore usually coated with an ultrathin coating of electrically-conducting material. and electrically grounded to prevent the accumulation of electrostatic charge at the surface. Environmental SEM instruments place the specimen in a relatively high pressure chamber where the working distance is short and the electron optical column is differentially pumped to keep vacuum adequately low at the electron gun. The high pressure region around the sample in the ESEM neutralizes charge and provides an Compiled by : Mr.[5] iridium. platinum. and especially in secondary electron imaging mode. Coating prevents the accumulation of static electric charge on the specimen during electron irradiation. tungsten. An alternative to coating for some biological samples is to increase the bulk conductivity of the material by impregnation with osmium using variants of the OTO staining method (O-osmium. specimens must be electrically conductive. The beam current absorbed by the specimen can also be detected and used to create images of the distribution of specimen current. Electronic amplifiers of various types are used to amplify the signals which are displayed as variations in brightness on a cathode ray tube. Several models of SEM can examine any part of a 6-inch (15 cm) semiconductor wafer. Sample preparation All samples must also be of an appropriate size to fit in the specimen chamber and are generally mounted rigidly on a specimen holder called a specimen stub. Two reasons for coating.

Chennai-119 . or subjected to analog-to-digital conversion and displayed and saved as a digital image. image resolution less than 0.5 nm is possible. three-dimensional appearance. and more secondary electrons will be emitted. If the beam enters the sample perpendicular to the surface. Low voltage SEM of non-conducting specimens can be operationally difficult to accomplish in a conventional SEM and is typically a research application for specimens that are sensitive to the process of applying conductive coatings. which results in images with a well-defined. The amplified electrical signal output by the photomultiplier is displayed as a two-dimensional intensity distribution that can be viewed and photographed on an analogue video display.Modern Techniques of Materials Characterisation 53 amplification of the secondary electron signal. and then further accelerated towards a phosphor or scintillator positively biased to about +2. these electrons originate within a few nanometers from the sample surface. This process relies on a raster-scanned primary beam. Ramesh.[17] The electrons are detected by an EverhartThornley detector[18] which is a type of scintillator-photomultiplier system. As the angle of incidence increases. Associate Professor of Mechanical Engineering. St. The secondary electrons are first collected by attracting them towards an electrically-biased grid at about +400 V. Low-voltage SEM is typically conducted in an FEG-SEM because the FEG is capable of producing high primary electron brightness even at low accelerating potentials. B. Operating conditions must be adjusted such that the local space charge is at or near neutral with adequate low voltage secondary electrons being available to neutralize any positively charged surface sites. The brightness of the signal depends on the number of secondary electrons reaching the detector. The accelerated secondary electrons are now sufficiently energetic to cause the scintillator to emit flashes of light (cathodoluminescence) which are conducted to a photomultiplier outside the SEM column via a light pipe and a window in the wall of the specimen chamber. Thus steep surfaces and edges tend to be brighter than flat surfaces. This requires that the primary electron beam's potential and current be tuned to the characteristics of the sample specimen. then the activated region is uniform about the axis of the beam and a certain number of electrons "escape" from within the sample. Jeppiaar Trust. Detection of secondary electrons The most common imaging mode collects low-energy (<50 eV) secondary electrons that are ejected from the k-orbitals of the specimen atoms by inelastic scattering interactions with beam electrons. the "escape" distance of one side of the beam will decrease. Joseph’s College of Engineering. Detection of backscattered electrons Compiled by : Mr. Embedding in a resin with further polishing to a mirror-like finish can be used for both biological and materials specimens when imaging in backscattered electrons or when doing quantitative X-ray microanalysis. Using this technique. Due to their low energy.000 V.

which is normally positioned to one side of the specimen. Ramesh. strong topographic contrast is produced by collecting back-scattered electrons from one side above the specimen using an asymmetrical. atomic number contrast is produced. Dedicated backscattered electron detectors are positioned above the sample in a "doughnut" type arrangement.Modern Techniques of Materials Characterisation 54 Fig. St. Semiconductor detectors can be made in radial segments that can be switched in or out to control the type of contrast produced and its directionality. is inefficient for the detection of backscattered electrons because few such electrons are emitted in the solid angle subtended by the detector.composition Bottom: secondary electron analysis . Associate Professor of Mechanical Engineering. directional BSE detector. and because the positively biased detection grid has little ability to attract the higher energy BSE electrons. and thus appear brighter in the image. Comparison of SEM techniques: Top: backscattered electron analysis . Since heavy elements (high atomic number) backscatter electrons more strongly than light elements (low atomic number). the resulting contrast appears as illumination of the topography from that side. BSE detectors are usually either of scintillator or semiconductor types. B. concentric with the electron beam. Compiled by : Mr. However.topography Backscattered electrons (BSE) consist of high-energy electrons originating in the electron beam. maximising the solid angle of collection. .[17] The Everhart-Thornley detector. Jeppiaar Trust. Chennai-119 . Joseph’s College of Engineering. that are reflected or back-scattered out of the specimen interaction volume by elastic scattering interactions with specimen atoms. When all parts of the detector are used to collect electrons symmetrically about the beam. BSE are used to detect contrast between areas with different chemical compositions.

The detector consists primarily of a scintillator inside a Faraday cage inside the specimen chamber of the microscope. Thornley who in 1960 published their design to increase the efficiency of existing secondary electron detectors by adding a light pipe to carry the photon signal from the scintillator inside the evacuated specimen chamber of the SEM to the photomultiplier outside the chamber. the emission of light when atoms excited by high-energy electrons return to their ground state. Joseph’s College of Engineering. Everhart-Thornley detector The Everhart-Thornley Detector (E-T detector or ET detector) is a secondary electron detector used in scanning electron microscopes (SEMs).000 eVs) to accelerate the incoming electrons to it where they can be converted to light photons. Other electrons within the specimen chamber are not attracted by this low voltage and will only reach the detector if their direction of travel takes them to it. Jeppiaar Trust. Cathodoluminescence is most commonly experienced in everyday life as the light emission from the inner surface of the cathode ray tube in television sets and computer CRT monitors. or can analyse the wavelengths emitted by the specimen and display an emission spectrum or an image of the distribution of cathodoluminescence emitted by the specimen in real colour. A low positive voltage is applied to the Faraday cage to attract the relatively low energy (less than 50 eVs by definition) secondary electrons. Ramesh. However. A. is analogous to UV-induced fluorescence. St. The direction of their travel is focused to the lightguide by a metal coating on the scintillator acting as a mirror. B. The scintillator has a high positive voltage (in the nature of 10. The EverhartThornley Detector with its lightguide and highly efficient photomultiplier is the most frequently used detector in SEMs.Modern Techniques of Materials Characterisation 55 Backscattered electrons can also be used to form an electron backscatter diffraction (EBSD) image that can be used to determine the crystallographic structure of the specimen. Everhart and Richard F. Chennai-119 . The E-T secondary electron detector can be used in the SEM's back-scattered electron mode by either turning off the Faraday cage or by applying a negative voltage to the Faraday cage. It is named after its designers. In the light pipe the photons travel outside of the microscope's vacuum chamber to a photomultiplier tube for amplification. better back-scattered electron images come from dedicated BSE detectors rather than from using the E-T detector as a BSE detector. Rajchman by changing the electron multiplier to a photomultiplier. CL detectors either collect all light emitted by the specimen. and some materials such as zinc sulfide and some fluorescent dyes. exhibit both phenomena. In the SEM. M. Associate Professor of Mechanical Engineering. Thomas E. [1] Prior to this Everhart had improved a design for a secondary electron detection by Vladimir Zworykin and J. Cathodoluminescence Cathodoluminescence. Compiled by : Mr.

and the difference in energy between the higherenergy shell and the lower energy shell may be released in the form of an X-ray. Joseph’s College of Engineering. or a beam of X-rays. To stimulate the emission of characteristic X-rays from a specimen.Modern Techniques of Materials Characterisation 56 Energy-dispersive X-ray spectroscopy Energy-dispersive X-ray spectroscopy (EDS or EDX) is an analytical technique used for the elemental analysis or chemical characterization of a sample. The number and energy of the X-rays emitted from a specimen can be measured by an energy-dispersive spectrometer. ejecting it from the shell while creating an electron hole where the electron was. and of the atomic structure of the element from which they were emitted. Its characterization capabilities are due in large part to the fundamental principle that each element has a unique atomic structure allowing X-rays that are characteristic of an element's atomic structure to be identified uniquely from one another. an atom within the sample contains ground state (or unexcited) electrons in discrete energy levels or electron shells bound to the nucleus. It is one of the variants of X-ray fluorescence spectroscopy which relies on the investigation of a sample through interactions between electromagnetic radiation and matter. a high-energy beam of charged particles such as electrons or protons (see PIXE). The incident beam may excite an electron in an inner shell. is focused into the sample being studied. Chennai-119 . Jeppiaar Trust. Associate Professor of Mechanical Engineering. Compiled by : Mr. analyzing X-rays emitted by the matter in response to being hit with charged particles. St. An electron from an outer. this allows the elemental composition of the specimen to be measured. As the energy of the X-rays are characteristic of the difference in energy between the two shells. higher-energy shell then fills the hole. B. Ramesh. At rest.

Ramesh. Technological variants Principle of EDS The excess energy of the electron that migrates to an inner shell to fill the newly-created hole can do more than emit an X-ray. the X-ray detector. the pulse processor.Modern Techniques of Materials Characterisation Fig. Scanning electron microscopes are equipped with a cathode and magnetic lenses to create and focus a beam of electrons. This ejected species is called an Auger electron. the excess energy is transferred to a third electron from a further outer shell. which measures the signals and passes them onto an analyzer for data display and analysis. St. A detector is used to convert X-ray energy into voltage signals. instead of X-ray emission. Jeppiaar Trust. prompting its ejection. Joseph’s College of Engineering. EDS systems are most commonly found on scanning electron microscopes (SEM-EDS) and electron microprobes. However. Often. B. Chennai-119 . this information is sent to a pulse processor. and the analyzer. and the method for its analysis is known as Compiled by : Mr.: EDS spectrum of the mineral crust of Rimicaris exoculata[1] 57 Equipment: the connection with SEM There are four primary components of the EDS setup: the beam source. A number of free-standing EDS systems exist. and since the 1960s they have been equipped with elemental analysis capabilities. Associate Professor of Mechanical Engineering.

The SDD consists of a high-resistivity silicon chip where electrons are driven to a small collecting anode. and Li) [2]. Jeppiaar Trust. Chennai-119 . Information on the quantity and kinetic energy of ejected electrons is used to determine the binding energy of these now-liberated electrons. 5. Ramesh. called the silicon drift detector (SDD). This allows for even higher count rate collection. Emerging technology There is a trend towards a newer EDS detector. In WDS. EDS detectors cannot detect elements with atomic number less than 4. Over-voltage settings in EDS alter the peak sizes – raising over-voltage on the SEM shifts the spectrum to the larger energies. These X-rays are emitted in any direction. Ti Kβ and V Kα.[3] The accuracy of the spectrum can also be affected by the nature of the sample. Further benefits of large area chips include Compiled by : Mr. Faster analytical capabilities and more precise X-ray maps or particle data collected in seconds. thereby utilizing shorter processing times and allowing very high throughput. Better resolution than traditional Si(Li) detectors at high count rates. X-rays can be generated by any atom in the sample that is sufficiently excited by the incoming beam. WDS differs from EDS in that it uses the diffraction patterns created by light-matter interaction as its raw data. Because the capacitance of the SDD chip is independent of the active area of the detector. 2.Modern Techniques of Materials Characterisation 58 Auger electron spectroscopy (AES). Ability to be stored and operated at relatively high temperatures. while EDS gathers a spectrum of all elements. noise from the amplifiers and microphonics. This can result in reduced accuracy in inhomogeneous and rough samples. EDS is often contrasted with its spectroscopic counterpart. Mn Kβ and Fe Kα). that is H.e. Benefits of the SDD include: 1. Associate Professor of Mechanical Engineering. The likelihood of an X-ray escaping the specimen. depends on the energy of the X-ray and the amount and density of material it has to pass through. WDS has a much finer spectral resolution than EDS. Accuracy of EDS Accuracy of EDS spectrum can be affected by many factors. Windows in front of the detector can absorb low-energy X-rays (i. and thus being available to detect and measure. He. Joseph’s College of Engineering. which is element-specific and allows chemical characterization of a sample. utilizing ejected electrons in a manner similar to that of AES. much larger SDD chips can be utilized (40 mm2 or more).g. X-ray photoelectron spectroscopy (XPS) is another close relative of EDS. Also many elements will have overlapping peaks (e. High count rates and processing. eliminating the need for liquid nitrogen cooling. within limits. WDS (wavelength dispersive X-ray spectroscopy). St. Lower dead time (time spent on processing X-ray event). WDS also avoids the problems associated with artifacts in EDS (false peaks. of a sample. The advantage lies in the extremely low capacitance of this anode. and so they may not all escape the sample. making higher-energy peaks larger and lower-energy peaks smaller. B. 3.. only one element can be analyzed at a time. 4.

Joseph’s College of Engineering. also known as an electron probe microanalyzer (EPMA) or electron micro probe analyzer (EMPA). The EDS microcalorimeter relies highly on two components: an absorber. the X-rays can then be detected by the electron microprobe. the latter measures the subsequent change in temperature due to the influx of heat (in essence. Chennai-119 . It works similarly to a scanning electron microscope: the sample is bombarded with an electron beam. a different type of EDS detector. In recent years. Reduced sample damage and 3.[2] The size of the electron beam determines the trade-off between resolution and scan time. Ramesh. This enables the abundances of elements present within small sample volumes (typically 10-30 cubic micrometers or less) to be determined. Innovative engineering solutions are necessary for further improvement of spectroscopic microanalysis. based upon a microcalorimeter. emitting x-rays at wavelengths characteristic to the elements being analyzed. poor collection efficiencies and small detector areas. This new model allegedly has the simultaneous detection capabilities of EDS as well as the high spectral resolution of WDS. and a thermistor. The count rate is hampered by its reliance on the time constant of the calorimeter’s electrical circuit. a thermometer). 2. The detector area must be small in order to keep the heat capacity as small as possible and maximize thermal sensitivity (resolution). St.Modern Techniques of Materials Characterisation 59 1.[1] The concentrations of elements from boron to plutonium can be measured at levels as low as 100 parts per million (ppm). The EDS microcalorimeter has suffered from a number of drawbacks. the Cameca SX100 with five oversized PET crystals for trace element analysis) can accurately measure elemental concentrations of approximately 10 ppm How it works A beam of electrons is fired at a sample. The former absorbs X-rays emitted from the sample and converts this energy into heat. Smaller beam interaction and improved spatial resolution for high speed maps. Jeppiaar Trust. B. including low count rates. The collection efficiency is a function of the absorber material and remains to be optimized. Recent improvements on EMPAs (e.g. The beam causes each element in the sample to emit X-rays at a characteristic frequency. Associate Professor of Mechanical Engineering. has become commercially available. Minimizing SEM beam current allowing for optimization of imaging under analytical conditions. is an analytical tool used to nondestructively determine the chemical composition of small volumes of solid materials.[3] Compiled by : Mr. Electron microprobe An electron microprobe (EMP).

: A Cambridge Scientific Instrument Company "Microscan" electron probe microanalyzer based on a design by David Wittry. Fig. Ramesh. backscattered electron production. St. B. Specific X-ray wavelengths are selected and counted. Among these effects are: phonon excitation (heat). The anode plate has central aperture and electrons that pass through it are collimated and focused by a series of magnetic lenses and apertures. either by wave-length dispersive spectrometry (WDS) or energy Compiled by : Mr. The resulting approximately 1 micrometre diameter electron beam may be rastered across the sample or used in spot mode to excite various effects from the sample. characteristic X-ray radiation. Chennai-119 . This model is housed at the Cambridge Museum of Technology The characteristic X-rays are used for chemical analysis. continuum Xray radiation (bremsstrahlung). and Auger electron production. cathodoluminescence (visible light fluorescence). Associate Professor of Mechanical Engineering. secondary electrons (plasmon production). Jeppiaar Trust.Modern Techniques of Materials Characterisation 60 Detailed description Low-energy electrons are produced from a tungsten filament or lanthanum hexaboride crystal cathode and accelerated by a positively biased anode plate to 10 to 30 thousand electron volts (keV). Joseph’s College of Engineering.

Changes in these parameters are recorded by titanium as the crystal grows. and glasses. The electron microprobe is widely used for research. ceramics. can be readily determined. Since these fossils are often compressed into a 2D film. This information may illuminate geologic processes. orogenic events (mountain building). soft parts of organisms may be preserved. but measurable amount of titanium into their structure as a function of temperature. volcanism. Palaeontology In exceptionally preserved fossils. Variations in chemical composition within a material (zoning). and the amount of titanium available in their environment. Chemical composition is determined by comparing the intensities of characteristic X-rays from the sample material with intensities from known composition (standards). and comets. The resulting chemical information is gathered in textural context. Count from the sample must be corrected for matrix effects (absorption and secondary fluorescence) to yield chemical compositions. Most rocks are aggregates of small mineral grains. This technique is also used for the study of extraterrestrial rocks (i. lithification. Chennai-119 . including the temperature. such as crystallization. quality control. Associate Professor of Mechanical Engineering. B. The change in elemental composition from the center (also known as core) to the edge (or rim) of a mineral can yield information about the history of the crystal's formation. In contrast. metamorphism. and chemistry of the surrounding medium. EDS uses a solid state semiconductor detector to accumulate Xrays of all wavelengths produced from the sample. and provides chemical data which is vital to understanding the evolution of the planets. pressure. It is particularly useful for assessing the composition of individual particles or grains and chemical changes on the scale of a few micrometres to millimeters. WDS is the more precise technique because its superior X-ray peak resolution. plate tectonics. Uses Material sciences and engineering The technique is commonly used for analyzing the chemical composition of metals. such as a mineral grain or metal. such as those of the Burgess shale. WDS utilizes Bragg diffraction from crystals to select X-ray wavelengths of interest and direct them to gas-flow or sealed proportional detectors. asteroids. and failure analysis. for example. it Compiled by : Mr. incorporate a small. Mineralogy and Petrology This technique is most commonly used by mineralogists and petrologists. While EDS yields more information and typically requires a much shorter counting time. pressure. meteorites). St.e. Joseph’s College of Engineering. Jeppiaar Trust. alloys. Ramesh. Quartz crystals. These grains may preserve chemical information adopted during their formation and subsequent alteration.Modern Techniques of Materials Characterisation 61 dispersive X-ray spectroscopy (EDS).

If the tip is moved across the sample in the x-y plane. At close range. Elemental mapping showed that they had a similar composition to the gut. In this situation. This Compiled by : Mr. B. the tip's bias and position with respect to the sample can be varied (with the details of this variation depending on the experiment) and data is obtained from the resulting changes in current. and various other liquid or gas ambients. which is turned off when the tip and sample are sufficiently close. applied voltage.[4] The STM is based on the concept of quantum tunneling. creating a current that can be measured.1 nm lateral resolution and 0. individual atoms within materials are routinely imaged and manipulated. the voltage bias will cause electrons to tunnel between the tip and sample. the changes in surface height and density of states cause changes in current.[1][2] For an STM. Gerd Binnig and Heinrich Rohrer (at IBM Zürich).[3] With this resolution.[4] Information is acquired by monitoring the current as the tip's position scans across the surface. and is usually displayed in image form. a bias (voltage difference) applied between the two can allow electrons to tunnel through the vacuum between them. maintaining tip-sample separation W typically in the 4-7 Å range. When a conducting tip is brought very near to the surface to be examined. The resulting tunneling current is a function of tip position. Associate Professor of Mechanical Engineering. These changes are mapped in images. good resolution is considered to be 0. favouring the second interpretation.[5] Scanning tunneling microscope A scanning tunneling microscope (STM) is an instrument for imaging surfaces at the atomic level. fine control of the tip in all three dimensions when near the sample is typically piezoelectric. Once tunneling is established. which is the equilibrium position between attractive (3<W<10Å) and repulsive (W<3Å) interactions[4]. Procedure First. Chennai-119 . Joseph’s College of Engineering. water. the Nobel Prize in Physics in 1986. and sophisticated electronics. Jeppiaar Trust. as it requires extremely clean and stable surfaces.Modern Techniques of Materials Characterisation 62 can be difficult to deduce what features were what: a famous example is that of triangular extensions in Opabinia. Ramesh. St. only low voltages (5-15V) can be used in such specimens. and the local density of states (LDOS) of the sample. excellent vibration control. a voltage bias is applied and the tip is brought close to the sample by some coarse sample-to-tip control. STM can be a challenging technique.[4] Because of the thin nature of the carbon films.01 nm depth resolution. which were interpreted as either legs or extensions of the gut. Its development in 1981 earned its inventors. and at temperatures ranging from near zero kelvin to a few hundred degrees Celsius. The STM can be used not only in ultra high vacuum but also in air. sharp tips.

this leads to an image made of current changes over the surface. The benefit to using a constant height mode is that it is faster.Modern Techniques of Materials Characterisation 63 change in current with respect to position can be measured itself. with color optionally added in post-processing in order to visually emphasize important features. Ramesh. Jeppiaar Trust. z.[10] Compiled by : Mr. as the piezoelectric movements require more time to register the change in constant current mode than the voltage response in constant height mode[6]. In constant current mode. Associate Professor of Mechanical Engineering. of the tip corresponding to a constant current can be measured [4]. These two modes are called constant height mode and constant current mode. St. information on the electronic structure at a given location in the sample can be obtained by sweeping voltage and measuring current at a specific location[3]. In constant height mode. this means contrast on the image is due to variations in charge density [6]. or the height. the density of states at an impurity site can be compared to the density of states far from impurities. Joseph’s College of Engineering. All images produced by STM are grayscale.[8][9] This can be used to scan surface diffusion. the voltage and height are both held constant while the current changes to keep the voltage from changing. The advantage of STM over other measurements of the density of states lies in its ability to make extremely local measurements: for example. This leads to a height variation and thus the image comes from the tip topography across the sample and gives a constant charge density surface. B. Chennai-119 . which can be related to charge density[6]. This type of measurement is called scanning tunneling spectroscopy (STS) and typically results in a plot of the local density of states as a function of energy within the sample.[7] Framerates of at least 1 Hz enable so called Video-STM (up to 50 Hz is possible). respectively. feedback electronics adjust the height by a voltage to the piezoelectric height control mechanism[5]. In addition to scanning across the sample.

Ramesh. coarse sample-to-tip control. Associate Professor of Mechanical Engineering. magnetic levitation was used to keep the STM free from vibrations. Therefore it has been essential to develop processes for consistently obtaining sharp. Additionally.y scanner. now mechanical spring or gas spring systems are often used[4]. mechanisms for reducing eddy currents are sometimes implemented.Modern Techniques of Materials Characterisation 64 Instrumentation Fig. St. Additionally. and platinum-iridium tips by mechanical shearing[3]. Recently. Tungsten tips are usually made by electrochemical etching. and computer[5]. proper vibration isolation or an extremely rigid STM body is imperative for obtaining usable results. image artifacts can occur if the tip has two tips at the end rather than a single atom. piezoelectric controlled height and x. usable tips. carbon nanotubes have been used in this instance. vibration isolation system. Chennai-119 . Compiled by : Mr. B. Due to the extreme sensitivity of tunnel current to height. though gold is also used[3]. Joseph’s College of Engineering. Jeppiaar Trust. this leads to “double-tip imaging. In the first STM by Binnig and Rohrer. [11] The tip is often made of tungsten or platinum-iridium. The resolution of an image is limited by the radius of curvature of the scanning tip of the STM.” a situation in which both tips contribute to the tunneling[3]. : Schematic view of an STM The components of an STM include scanning tip.

Quate and Gerber invented the first atomic force microscope (also abbreviated as AFM) in 1986. currents can even be passed through the tip to probe the electrical conductivity or transport of the underlying surface. with demonstrated resolution on the order of fractions of a nanometer. and manipulating matter at the nanoscale. measuring. : Block diagram of atomic force microscope Compiled by : Mr. the scanning tunneling microscope. but this is much more challenging with very few research groups reporting reliable data. a development that earned them the Nobel Prize for Physics in 1986. The information is gathered by "feeling" the surface with a mechanical probe. St. The precursor to the AFM. Ramesh. electric potentials can also be scanned using conducting cantilevers.Modern Techniques of Materials Characterisation 65 Maintaining the tip position with respect to the sample. Jeppiaar Trust. The computer may also be used for enhancing the image with the help of image processing[12][13] as well as performing quantitative measurements. The first commercially available atomic force microscope was introduced in 1989. was developed by Gerd Binnig and Heinrich Rohrer in the early 1980s at IBM Research . Piezoelectric elements that facilitate tiny but accurate and precise movements on (electronic) command enable the very precise scanning. more than 1000 times better than the optical diffraction limit. The AFM is one of the foremost tools for imaging. Associate Professor of Mechanical Engineering.[14] Atomic force microscopy Atomic force microscopy (AFM) or scanning force microscopy (SFM) is a very highresolution type of scanning probe microscopy.Zurich. Joseph’s College of Engineering. In newer more advanced versions. B. Fig. Binnig. Chennai-119 . scanning the sample and acquiring the data is computer controlled[5]. In some variations.

scanning joule expansion microscopy. Associate Professor of Mechanical Engineering. Typically. This eliminates Compiled by : Mr.. capillary forces. solvation forces. the deflection is measured using a laser spot reflected from the top surface of the cantilever into an array of photodiodes. If the tip was scanned at a constant height.y and z directions. photothermal microspectroscopy. electrostatic forces. MFM).. Using a Wheatstone bridge. Other methods that are used include optical interferometry. causing damage. Alternatively a 'tripod' configuration of three piezo crystals may be employed. strain in the AFM cantilever due to deflection can be measured. and the x and y directions for scanning the sample. and ~30 micrometers The AFM consists of a cantilever with a sharp tip (probe) at its end that is used to scan the specimen surface. Along with force. St. etc. capacitive sensing or piezoresistive AFM cantilevers. forces that are measured in AFM include mechanical contact force. forces between the tip and the sample lead to a deflection of the cantilever according to Hooke's law. Hence. a risk would exist that the tip collides with the surface. These cantilevers are fabricated with piezoresistive elements that act as a strain gauge. with each responsible for scanning in the x.). Joseph’s College of Engineering. Traditionally. B. Depending on the situation. magnetic forces (see magnetic force microscope. Casimir forces. the sample is mounted on a piezoelectric tube. but this method is not as sensitive as laser deflection or interferometry.Modern Techniques of Materials Characterisation 66 Basic principles Electron micrograph of a used AFM cantilever image width ~100 micrometers. additional quantities may simultaneously be measured through the use of specialized types of probe (see scanning thermal microscopy. van der Waals forces. chemical bonding. Chennai-119 . Jeppiaar Trust. The cantilever is typically silicon or silicon nitride with a tip radius of curvature on the order of nanometers. Ramesh. that can move the sample in the z direction for maintaining a constant force. When the tip is brought into proximity of a sample surface. etc. in most cases a feedback mechanism is employed to adjust the tip-to-sample distance to maintain a constant force between the tip and the sample.

B. Jeppiaar Trust. In newer designs. In the dynamic mode. Associate Professor of Mechanical Engineering.Modern Techniques of Materials Characterisation 67 some of the distortion effects seen with a tube scanner. The resulting map of the area s = f(x. St. Imaging modes The primary modes of operation for an AFM are static mode and dynamic mode. possible imaging modes are divided into static (also called contact) modes and a variety of dynamic (or non-contact) modes where the cantilever is vibrated. Consequently. The AFM can be operated in a number of modes. In general. the cantilever is "dragged" across the surface of the sample and the contours of the surface are measured directly using the deflection of the cantilever. However. The oscillation amplitude. Ramesh. Because the measurement of a static signal is prone to noise and drift. low stiffness cantilevers are used to boost the deflection signal. Contact mode In the static mode operation. the static tip deflection is used as a feedback signal. the cantilever is externally oscillated at or close to its fundamental resonance frequency or a harmonic. attractive forces can be quite strong. causing the tip to "snap-in" to the surface. phase and resonance frequency are modified by tip-sample interaction forces. Chennai-119 . depending on the application. Joseph’s College of Engineering. close to the surface of the sample. Compiled by : Mr. In static mode. In contact mode. the tip is mounted on a vertical piezo scanner while the sample is being scanned in X and Y using another piezo block. the force between the tip and the surface is kept constant during scanning by maintaining a constant deflection. this technique is typically called "contact mode".y) represents the topography of the sample. Thus static mode AFM is almost always done in contact where the overall force is repulsive. These changes in oscillation with respect to the external reference oscillation provide information about the sample's characteristics.

Jeppiaar Trust. : AFM . The cantilever is instead oscillated at a frequency slightly above its resonance frequency where the amplitude of oscillation is typically a few nanometers (<10 nm). whereas in non-contact mode an AFM will oscillate above the adsorbed fluid layer to image both the liquid and surface.y) data point allows the scanning software to construct a topographic image of the sample surface. Chennai-119 . Joseph’s College of Engineering. Associate Professor of Mechanical Engineering. An AFM operating in contact mode will penetrate the liquid layer to image the underlying surface. which are strongest from 1 nm to 10 nm above the surface. This makes noncontact AFM preferable to contact AFM for measuring soft samples. or any other long range force which extends above the surface acts to decrease the resonance frequency of the cantilever. In the case of rigid samples.non-contact mode In this mode. St. Measuring the tip-to-sample distance at each (x.Modern Techniques of Materials Characterisation 68 Non-contact mode Fig. Non-contact mode AFM does not suffer from tip or sample degradation effects that are sometimes observed after taking numerous scans with contact AFM. B. However. the images may look quite different. contact and non-contact images may look the same. The van der Waals forces. Ramesh. if a few monolayers of adsorbed fluid are lying on the surface of a rigid sample. Compiled by : Mr. This decrease in resonance frequency combined with the feedback loop system maintains a constant oscillation amplitude or frequency by adjusting the average tip-to-sample distance. the tip of the cantilever does not contact the sample surface.

In dynamic contact mode. Dynamic contact mode (also called intermittent contact or tapping mode) was developed to bypass this problem. changes in the oscillation frequency provide information about tip-sample interactions. Joseph’s College of Engineering. Amplitude modulation can be operated either in the non-contact or in the intermittent contact regime. most samples develop a liquid meniscus layer. Stiff cantilevers provide stability very close to the surface and. Chennai-119 . Because of this.[2] In ambient conditions. Jeppiaar Trust. : Single polymer chains (0. Associate Professor of Mechanical Engineering. as a result.4 nm thick) recorded in a tapping mode under aqueous media with different pH.[3] In tapping mode. In frequency modulation. the cantilever is driven to oscillate up and down at near its resonance frequency by a small piezoelectric element mounted in the AFM tip holder similar to non-contact mode. Tapping mode Fig. changes in the phase of oscillation can be used to discriminate between different types of materials on the surface. Amplitude modulation has also been used in the non-contact regime to image with atomic resolution by using very stiff cantilevers and small amplitudes in an ultra-high vacuum environment.[1] In amplitude modulation. changes in the oscillation amplitude or phase provide the feedback signal for imaging. Frequency can be measured with very high sensitivity and thus the frequency modulation mode allows for the use of very stiff cantilevers. the cantilever is oscillated such that the separation distance between the cantilever tip and the sample surface is modulated. St. Compiled by : Mr. Ramesh. B. keeping the probe tip close enough to the sample for short-range forces to become detectable while preventing the tip from sticking to the surface presents a major problem for non-contact dynamic mode in ambient conditions. In amplitude modulation. However. the amplitude of this oscillation is greater than 10 nm.Modern Techniques of Materials Characterisation 69 Schemes for dynamic mode operation include frequency modulation and the more common amplitude modulation. this technique was the first AFM technique to provide true atomic resolution in ultra-high vacuum conditions.

4 nm thick chains of synthetic polyelectrolytes) under liquid medium. This makes it possible to study biological macromolecules and even living organisms. While an electron microscope needs an expensive vacuum environment for proper operation. It has been shown to give true atomic resolution in ultra-high vacuum (UHV) and. most AFM modes can work perfectly well in ambient air or even a liquid environment. an AFM's usefulness has limitations. the conformation of single molecules can remain unchanged for hours. electrostatic forces. Due to the interaction of forces acting on the cantilever when the tip comes close to the surface.[2] Advantages and disadvantages Just like any other tool. samples viewed by AFM do not require any special treatments (such as metal/carbon coatings) that would irreversibly change or damage the sample. B. In principle. When determining whether or not analyzing a sample with an AFM is appropriate. With proper scanning parameters. St. there are various advantages and disadvantages that must be considered. Van der Waals force. Joseph’s College of Engineering. etc. This method of "tapping" lessens the damage done to the surface and the tip compared to the amount done in contact mode. The servo adjusts the height to maintain a set cantilever oscillation amplitude as the cantilever is scanned over the sample. Chennai-119 . Additionally. Whereas the AFM can only image a maximum height on the order of 10-20 micrometers and a maximum scanning Compiled by : Mr. 0. An electronic servo uses the piezoelectric actuator to control the height of the cantilever above the sample. A tapping AFM image is therefore produced by imaging the force of the intermittent contacts of the tip with the sample surface. Advantages AFM has several advantages over the scanning electron microscope (SEM). In one pass. AFM can provide higher resolution than SEM.Modern Techniques of Materials Characterisation 70 typically 100 to 200 nm. Ramesh. cause the amplitude of this oscillation to decrease as the tip gets closer to the sample. Tapping mode is gentle enough even for the visualization of supported lipid bilayers or adsorbed single polymer molecules (for instance. Jeppiaar Trust. in liquid environments. dipole-dipole interaction. Unlike the electron microscope which provides a two-dimensional projection or a two-dimensional image of a sample. Disadvantages A disadvantage of AFM compared with the scanning electron microscope (SEM) is the single scan image size. High resolution AFM is comparable in resolution to scanning tunneling microscopy and transmission electron microscopy. the AFM provides a three-dimensional surface profile. Associate Professor of Mechanical Engineering. more recently. the SEM can image an area on the order of square millimeters with a depth of field on the order of millimeters.

Traditionally. Jeppiaar Trust. St. Compiled by : Mr. an AFM cannot scan images as fast as a SEM. Specially made cantilevers and AFMs can be used to modulate the probe sideways as well as up and down (as with dynamic contact and non-contact modes) to measure sidewalls. there is the possibility of image artifacts. they cannot normally measure steep walls or overhangs. These image artifacts are unavoidable however. Joseph’s College of Engineering. Such filtering could "flatten" out real topographical features. Chennai-119 . their occurrence and effect on results can be reduced through various methods. lower lateral resolution and additional artifacts.Modern Techniques of Materials Characterisation 71 area of about 150×150 micrometers. although at relatively low quality. or even by the sample itself. As with any other imaging technique. z axes that may require software enhancement and filtering. Ramesh. a poor operating environment. at the cost of more expensive cantilevers. y. To eliminate image distortions induced by thermal drift. requiring several minutes for a typical scan. However. One method of improving the scanned area size for AFM is by using parallel probes in a fashion similar to that of millipede data storage. several fast-acting designs [11][12] were suggested to increase microscope scanning productivity including what is being termed videoAFM (reasonable quality images are being obtained with videoAFM at video rate: faster than the average SEM). The scanning speed of an AFM is also a limitation. newer AFMs utilize closed-loop scanners which practically eliminate these problems. Some AFMs also use separated orthogonal scanners (as opposed to a single tube) which also serve to eliminate part of the cross-talk problems. which could be induced by an unsuitable tip.[9][10] AFM images can also be affected by hysteresis of the piezoelectric material[13] and crosstalk between the x. while a SEM is capable of scanning at near real-time. Due to the nature of AFM probes. Associate Professor of Mechanical Engineering. B. However. several methods have been introduced. The relatively slow rate of scanning during AFM imaging often leads to thermal drift in the image [9][10] making the AFM microscope less suited for measuring accurate distances between topographical features on the image.

Most metals encountered in everyday life are polycrystals.a single. St. Chennai-119 . Jeppiaar Trust. or ions are arranged in an orderly repeating pattern extending in all three spatial dimensions. Associate Professor of Mechanical Engineering. or "rock crystal".[2][3] The word once referred particularly to quartz. molecules. Joseph’s College of Engineering. The process of crystal formation via mechanisms of crystal growth is called crystallization or solidification. Ramesh.Modern Techniques of Materials Characterisation 72 Unit II & III Crystal A crystal or crystalline solid is a solid material whose constituent atoms.[1] from κρύος (kruos). B. Crystals are often symmetrically intergrown to form crystal twins. Crystal structure Insulin crystals grown in outer space Halite (sodium chloride) . frost". The scientific study of crystals and crystal formation is known as crystallography. Compiled by : Mr. meaning "rock-crystal" but also "ice". large crystal. "icy cold. The word crystal is derived from the Ancient Greek word κρύσταλλος (krustallos).

Jeppiaar Trust. Energy-resolved measurements yield the dynamic structure factor. or glassy material. A noncrystalline material. The types and structures of these defects can contain a profound effect on the properties of the materials. and graphite. Most crystalline materials have a variety of crystallographic defects. although there are distinct differences between crystalline solids and amorphous solids: most notably. Covalently bonded crystals are also very common. Associate Professor of Mechanical Engineering. Structure factor (crystallography) In condensed matter physics and crystallography. In most cases. Polymer materials generally will form crystalline regions. Chennai-119 .Modern Techniques of Materials Characterisation 73 The process of forming a crystalline structure from a fluid or from materials dissolved in the fluid is often referred to as the crystallization process. amorphous or single-crystal metals must be produced synthetically. notable examples being diamond. Crystalline structures occur in all classes of materials. Weak van der Waals forces can also play a role in a crystal structure. While the cooling process usually results in the generation of a crystalline material. Almost all metal exists in a polycrystalline state. It is also often referred to as an amorphous solid. The physical properties of the ice depend on the size and arrangement of the individual crystals. often with great difficulty. forming a polycrystalline structure. the conditions under which it is being solidified. or grains. but the lengths of the molecules usually prevent complete crystallization. and the same may be said of metals solidifying from a molten state. In the old example referenced by the root meaning of the word crystal. vitreous. The static structure factor is measured without resolving the energy of scattered photons/electrons/neutrons. Which crystal structure the fluid will form depends on the chemistry of the fluid. the fluid may be frozen in a noncrystalline state. is called an amorphous. the process of forming a glass does not release the latent heat of fusion. St. and also on the ambient pressure. Ionically bonded crystals can form upon solidification of salts. electron and neutron diffraction experiments. the static structure factor (or structure factor for short) is a mathematical description of how a material scatters incident radiation. under certain conditions. this type of bonding loosely holds together the hexagonal-patterned sheets in graphite. water being cooled undergoes a phase change from liquid to solid beginning with small ice crystals that grow until they fuse. this involves cooling the fluid so rapidly that atoms cannot travel to their lattice sites before they lose mobility. Compiled by : Mr. B. for example. either from a molten fluid or upon crystallization from a solution. which has no long-range order. The structure factor is a particularly useful tool in the interpretation of interference patterns obtained in X-ray. with all types of chemical bonds. Joseph’s College of Engineering. silica. Ramesh.

electrons and neutrons. of an element depends on the type of radiation considered. called simple cubic (sc). and index 001 represents a plane orthogonal to n. i. Jeppiaar Trust. Chennai-119 . plus a number of other variants listed below. the atomic form factors for the two cases are not the same. Scattering from a crystal A crystal is a periodic arrangement of atoms in a particular pattern. The atomic form factor. Each of the atoms may scatter incident radiation such as X-rays. body-centered cubic (bcc). there is more than one atom per cubic unit cell. there will be a difference in phase when considering the scattered amplitude from two atoms. k. the cubic (or isometric) crystal system is a crystal system where the unit cell is in the shape of a cube. a family of lattice planes is determined by three integers ℓ. There are three main varieties of these crystals. m. or scattering power. Joseph’s College of Engineering. the primitive unit cell often is not. This is the diffraction pattern caused by the crystal. B. their greatest common divisor should be 1. St. Note that although the unit cell in these crystals is conventionally taken to be a cube. The structure factor describes the way in which an incident beam is scattered by the atoms of a crystal unit cell. taking into account the different scattering power of the elements through the term fj. In particular. negative integers are written with a bar. and face-centered cubic (fcc.Modern Techniques of Materials Characterisation 74 In crystallography. also known as cubic close-packed or ccp). Ramesh. The integers are usually written in lowest terms. index 010 represents a plane orthogonal to direction m. They are written (hkl). Associate Professor of Mechanical Engineering. This phase shift is taken into account by the complex exponential term.e. Because of the periodic arrangement of the atoms. Miller indices are a notation system in crystallography for planes and directions in crystal (Bravais) lattices. l) in the basis of the reciprocal lattice vectors. and n. Miller index 100 represents a plane orthogonal to direction ℓ. Compiled by : Mr. the interference of waves scattered from different atoms may cause a distinct pattern of constructive and destructive interference to form. This is one of the most common and simplest shapes found in crystals and minerals. Since the atoms are spatially distributed in the unit cell. and each index denotes a plane orthogonal to a direction (h. This is related to the fact that in most cubic crystal systems. Because electrons interact with matter through different processes than for example X-rays. the Miller indices. as in 3 for −3. By convention.

the atoms in the basis are at the origin with indices (0. with indices given by (1/2.1/2.0).1/2).1/2. B. St. (0.Modern Techniques of Materials Characterisation 75 Structure factors for specific lattice types Face-centered cubic (FCC) In the case of a monoatomic FCC crystal. An argument similar to the one above gives the expression with the result Compiled by : Mr. Chennai-119 . Associate Professor of Mechanical Engineering.0. (1/2.1/2). Joseph’s College of Engineering. Ramesh.0.0) and at the three face centers . Jeppiaar Trust. .

Dislocation In materials science. when brought together. the surrounding planes are not straight. Two dislocations of opposite orientation.Modern Techniques of Materials Characterisation 76 The most intense diffraction peak from a material that crystallizes in the FCC structure is typically the (111). Jeppiaar Trust. Joseph’s College of Engineering. can cancel each other (this is the process of annihilation). The theory was originally developed by Vito Volterra in 1905. the defect in the stack is only noticeable at the edge of the half sheet. In such a case. The mathematical theory explains why dislocations behave as stable particles: they can be moved about. B. but maintain their identity as they move. a dislocation is a crystallographic defect or irregularity. but instead bend around the edge of the terminating plane so that the crystal structure is perfectly ordered on either side. Ramesh. within a crystal structure. Some types of dislocations can be visualized as being caused by the termination of a plane of atoms in the middle of a crystal. Films of FCC materials like gold tend to grow in a (111) orientation with a triangular surface symmetry. but a single dislocation typically cannot "disappear" on its own. Associate Professor of Mechanical Engineering. Mixed dislocations are intermediate between these. Compiled by : Mr. Figure 1: An edge-dislocation (b = Burgers vector) Mathematically. The analogy with a stack of paper is apt: if a half a piece of paper is inserted in a stack of paper. St. Chennai-119 . There are two primary types: edge dislocations and screw dislocations. sometimes called a soliton. dislocations are a type of topological defect. The presence of dislocations strongly influences many of the properties of materials.

A crystalline material consists of a regular array of atoms. Ramesh. this extra plane passes through planes of atoms breaking and joining bonds with them until it reaches the grain boundary. Dislocations found in real materials typically are mixed. B. Jeppiaar Trust. Chennai-119 . meaning that they have characteristics of both. dislocation line in blue. Figure B Schematic diagram (lattice planes) showing an edge dislocation. with the atoms represented by spheres. distorting nearby planes of atoms. Edge dislocations An edge dislocation is a defect where an extra half-plane of atoms is introduced mid way through the crystal. One approach is to begin by considering a 3-d representation of a perfect crystal lattice. each of the trays of oranges are the lattice planes). The viewer may then start to simplify the representation by visualising planes of atoms instead of the atoms themselves (Figure A). Burgers vector in black. (Figure B represents the "extra half-plane" concept of an edge type dislocation). and the Burgers vector which describes the magnitude and direction of distortion to the lattice. a line direction. A simple schematic diagram of such atomic planes can be used to illustrate lattice defects such as dislocations. the Burgers vector is perpendicular to the line direction.Modern Techniques of Materials Characterisation Dislocation geometry 77 Figure A Crystal lattice showing atoms and lattice planes Two main types of dislocation exist: edge and screw. When enough force is applied from one side of the crystal structure. Associate Professor of Mechanical Engineering. Joseph’s College of Engineering. In an edge dislocation. which is the direction running along the bottom of the extra half plane. The dislocation has two properties. St. Compiled by : Mr. arranged into lattice planes (imagine stacking oranges in a grocers.

the boundary of the cut is a screw dislocation. St. Jeppiaar Trust. Associate Professor of Mechanical Engineering.[citation needed] Compiled by : Mr. Perhaps the closest analogy is a spiral-sliced ham. A screw dislocation is much harder to visualize. Screw dislocations 78 Fig.: Top right: edge dislocation. Chennai-119 . the Burgers vector is parallel to the line direction. B. Bottom right: screw dislocation. It comprises a structure in which a helical path is traced around the linear defect (dislocation line) by the atomic planes in the crystal lattice (Figure C). Joseph’s College of Engineering. If the cut only goes part way through the crystal. and then slipped. Imagine cutting a crystal along a plane and slipping one half across the other by a lattice vector. In pure screw dislocations. Figure C Schematic diagram (lattice planes) showing a screw dislocation.Modern Techniques of Materials Characterisation The stresses caused by an edge dislocation are complex due to its inherent asymmetry. Ramesh. the halves will fit back together without leaving a defect.

Calculate the interplanar spacing (that is. St. this simple model results in an infinite value for the core of the dislocation at r=0 and so it is only valid for stresses outside of the core of the dislocation. b is the Burgers vector.Modern Techniques of Materials Characterisation 79 Despite the difficulty in visualization. The formula for interplanar spacing is: d = a / (sqrt (h^2 + k^2 + l^2)) d: interplanar spacing a: lattice parameter h. l: plane indices A crystal is made up of a large number of parallel equidistant planesnpassing through the lattice planes can be chosen in various number of ways.[1] Mixed dislocations In many materials. This equation suggests a long cylinder of stress radiating outward from the cylinder and decreasing with distance. Inter-planar spacing distance for a cubic crystal Consider a cubic crystal having a lattice parameter (the length of the cube edge) of 0. Please note. Associate Professor of Mechanical Engineering. the distance between neighboring planes that are parallel to one another) among the (110) planes. the stresses caused by a screw dislocation are less complex than those of an edge dislocation. as symmetry allows only one radial coordinate to be used:[1] where μ is the shear modulus of the material. The distance between the parallel planes whose miller indices are same is called as interplanar distance 'd'. These stresses need only one equation. and r is a radial coordinate. Jeppiaar Trust. k. consisting of both screw and edge character. dislocations are found where the line direction and Burgers vector are neither perpendicular nor parallel and these dislocations are called mixed dislocations. The set of planes are represented by certain numbers called Miller indices. Compiled by : Mr. The perpendicular distance between adjacent planes is called interplanar spacing. Chennai-119 . B.4nm. Ramesh. Joseph’s College of Engineering.

M. The value of the parameter is usually expressed as LMP=T(C + log t) where C is a material specific constant often approximated as 20.M. is a parametric relation used to extrapolate experimental data on creep and rupture life of engineering materials. parameter. St. which in generalized form is P(L. h C = constant usually of order 20 According to the L. Creep-stress rupture data for high-temperature creep-resistant alloys are often plotted as log stress to rupture versus a combination of log time to rupture and temperature. One of the most common time–temperature parameters used to present this kind of data is the Larson-Miller (L.) = T[logtr + C] T = temperature. Ramesh. t is the time in hours and T is the temperature in Kelvin. the equation can be used to relate the difference in rupture life to differences in temperature for a given stress.) parameter. Jeppiaar Trust.Modern Techniques of Materials Characterisation Larson-Miller parameter 80 The Larson-Miller relation. Compiled by : Mr. time and temperature using a correlative approach based on the Arrhenius rate equation.M. also widely known as the Larson-Miller Parameter and often abbreviated LMP. Associate Professor of Mechanical Engineering. B. Joseph’s College of Engineering. Using the assumption that activation energy is independent of applied stress. K or °R tr = stress-rupture time. at a given stress level the log time to stress rupture plus a constant of the order of 20 multiplied by the temperature in kelvins or degrees Rankine remains constant for a given material. LMP = T * (C + log(t)) where the quantity LMP is known as the Larson-Miller parameter. Chennai-119 . The Larson-Miller parameter is a means of predicting the lifetime of material vs. The Larson-Miller model is used for experimental tests so that results at certain temperatures and stresses can predict rupture lives of time spans that would be impractical to reproduce in the laboratory. The equation was developed during the 1950s while Miller and Larson were employed by GE performing research on turbine blade life. The material constant C is typically found to be in the range of 20 to 22 for metals.

X-Ray Electromagnetic radiation of short wavelength produced when high-speed electrons strike a solid target An X-ray is a form of electromagnetic radiation with a wavelength approximately in the range of 5 pm to 10 nanometers (corresponding to frequencies in the range 30 PHz to 60 EHz).001 nanometre) produced by the deceleration of charged particles or the transitions of Compiled by : Mr.1 nm are called soft X-rays. Associate Professor of Mechanical Engineering. not its wavelength: X-ray photons are generated by energetic electron processes. gamma rays by transitions within atomic nuclei. Joseph’s College of Engineering. and a new photon of wavelength λ′ emerges at an angle θ. which recoils and is ejected from its atom (which becomes ionized). Hard X-rays overlap the range of long-wavelength (low energy) gamma rays. X-rays with a wavelength approximately longer than 0. Ramesh. The inelastic scattering of photons in matter results in a decrease in energy (increase in wavelength) of an X-ray or gamma ray photon. Jeppiaar Trust. they are called hard X-rays.Modern Techniques of Materials Characterisation 81 Compton scattering Compton scattering is a type of scattering that X-rays and gamma rays undergo in matter. Chennai-119 . and the rest of the energy is taken by the scattered. B. At wavelengths shorter than this. Part of the energy of the X/gamma ray is transferred to a scattering electron. St. however the distinction between the two terms depends on the source of the radiation. Fig. called the Compton effect. collides with a target at rest. Electromagnetic radiation of extremely short wavelength (100 nanometres to 0. "degraded" photon. X-rays are primarily used for diagnostic medical imaging and crystallography. Xrays are a form of ionizing radiation and as such can be dangerous.: A photon of wavelength λ comes in from the left.

Chennai-119 . which results in a beam of X-rays. For example. or X-ray image intensifiers. The beam is projected on matter. the excited atoms within emit characteristic "secondary" (or fluorescent) Xrays. Associate Professor of Mechanical Engineering. the highest intensity being around 60deg to 90deg from the beam due to the angle of the anode target to the approaching X-ray photons. to locate foreign objects in the body. The electrons that make up the beam are emitted from a heated cathode filament. The point where the electron beam strikes the target is called the focal spot. This window allows the X-ray to exit the tube with little attenuation while maintaining a vacuum seal required for the X-ray tube operation. The resulting pattern of the radiation is then ultimately detected by a detection medium including rare earth screens (which surround photographic film). Most of the kinetic energy contained in the electron beam is converted to heat. dental cavities. There is a small round window in the X-ray tube directly above the angled target. X-rays travel at the speed of light and exhibit phenomena associated with waves. They were discovered in 1895 by Wilhelm Conrad Röntgen. X-radiation can be produced by a variety of phenomena. Joseph’s College of Engineering. B. they lie between gamma rays and ultraviolet radiation. Some of the X-ray beam will pass through the object. electrons. [1] At the focal spot. and cancer. They are used in medicine to diagnose bone fractures. the accelerations (or decelerations) may give off X-radiation. they are used to analyze and detect flaws in structures. but experiments indicate that they can also behave like particles (see waveparticle duality). the excess heat is dissipated via a heat sink. who named them X-rays for their unknown nature. while some are absorbed. Jeppiaar Trust. gamma rays. The electrons are then focused and accelerated by an electrical field towards an angled anode target. or X-rays. X-ray machines work by applying controlled voltage and current to the X-ray tube. On the electromagnetic spectrum. X-ray generation X-ray generation can occur whenever charged particles pass within certain distances of each other without being in fixed orbits. X-ray photons are emitted in all directions from the target surface. St. Ramesh.Modern Techniques of Materials Characterisation 82 electrons in atoms. X-ray photons are produced by an electron beam that is accelerated to a very high speed and strikes a target. and to stop the spread of malignant tumours. but around 1% of the energy is converted into X-ray photons. semiconductor detectors. Compiled by : Mr. or protons bombard materials. when high-energy X-rays. In industry.

Joseph’s College of Engineering. and allowed for more accurate control of the X-ray unit. Ramesh. known as the beam. usually perpendicular to the path of the electron beam. called high speed switching. higher quality results. The rest of the energy is released as heat. The smooth. for example 30 to 150 kilovolts (kV). As with any vacuum tube. through the tube. Compiled by : Mr. In the late 1980s a different method of control was emerging. About 1% of the energy generated is emitted/radiated. Until the late 1980s. and the spikes are characteristic K lines for rhodium atoms. Associate Professor of Mechanical Engineering. ions and nuclei within the anode material. Electrons from the cathode collide with the anode material. Chennai-119 . tungsten will be deposited from the target onto the interior surface of the tube. is connected across cathode and anode to accelerate the electrons. and reduced X-ray exposures. A high voltage power source. as X-rays. This followed the electronics technology of switching power supplies (aka switch mode power supply).Modern Techniques of Materials Characterisation X-ray tube function 83 Spectrum of the X-rays emitted by an X-ray tube with a rhodium target. St.[1] In many applications. thus establishing a flow of electrical current. continuous curve is due to bremsstrahlung. Over time. there is a cathode. X-ray generators were merely highvoltage. which emits electrons into the vacuum and an anode to collect the electrons. usually tungsten. the current flow (typically in the range 1mA to 1A) is able to be pulsed on for between about 1ms to 1s. The X-ray spectrum depends on the anode material and the accelerating voltage. and accelerate other electrons. molybdenum or copper. operated at 60 kV. and taking snapshots of motion. This enables consistent doses of x-rays. B. Jeppiaar Trust. AC to DC variable power supplies.

thermionic emission or Richardson-Dushman effect and "cold electronic emission". Ramesh. At this point. the tube becomes unstable even at lower voltages. are adjusted by controlling the current flow and exposure time. When field emission is used without qualifiers it typically means the "cold emission. Chennai-119 . and replaced with a new tube assembly.Modern Techniques of Materials Characterisation 84 including the glass surface. or result in promotion of electrons from the valence to conduction band of semiconductors. the emission of electrons in strong static (or quasi-static) electric fields. Field emission can happen from solid and liquid surfaces. Simply put. i. but it is most Compiled by : Mr. This arcing causes an effect called "crazing" on the interior glass of the X-ray window.[2] Eventually. and thus the contrast of the image. The terminology is historical because related phenomena of surface photoeffect. The old tube assembly is shipped to a company that reloads it with a new X-ray tube." Field emission in pure metals occurs in high electric fields: the gradients are typically higher than 1000 volts per micron and strongly dependent upon the work function. the high voltage controls X-ray penetration. the tungsten deposit may become sufficiently conductive that at high enough voltages. St. Aluminum filters are installed in the path of the X-ray beam to remove "soft" (non-penetrating) radiation. or individual atoms into vacuum or open air. were discovered and studied independently from 1880s to 1930s. Jeppiaar Trust. and installing aluminum filters of varying thicknesses. the tube assembly (also called the "tube head") is removed from the X-ray system. The tube current and exposure time affect the dose and therefore the darkness of the image. As time goes on. The range of photonic energies emitted by the system can be adjusted by changing the applied voltage.[13] The CNT field emission cathodes have onset voltages about an order of magnitude lower than devices that rely on diamond or diamond-like carbon films. Joseph’s College of Engineering. a contraction of the German brems for braking.e. The arc will jump from the cathode to the tungsten deposit. which has much lower power efficiency. and must be replaced. B. Field electron emission for X-ray generation Oxford Instruments have worked together with NASA on carbon nanotube (CNT)-based X-ray sources that employ field emission as the electron source. Electron sources based on field emission have a number of applications. This will slowly darken the tube and was thought to degrade the quality of the X-ray beam. or dose. and then to the anode. but research has suggested there is no effect. The number of emitted X-ray photons. rather than thermionic emission. arcing occurs. and strahlung for radiation.[13] Field emission (FE) (also known as electron field emission) is an emission of electrons induced by external electromagnetic fields. Associate Professor of Mechanical Engineering. The X-Ray photon-generating effect is generally called the Bremsstrahlung effect.

e. St. and gamma rays. from radio waves to infrared light. then an awkward mathematical problem arises over the resulting differential equation: it is known to be mathematically impossible in principle to solve this equation exactly in terms of the usual functions of mathematical physics. Field emission was explained by quantum tunneling of electrons in the late 1920s. moving near the speed of light) charged particles through magnetic fields. To get even an approximate solution. Chennai-119 .. If one inserts a more realistic barrier model into the simplest form of the Schrödinger equation. which are located in the straight sections of the storage ring. The theory of field emission from bulk metals was proposed by Fowler and Nordheim.Modern Techniques of Materials Characterisation 85 commonly an undesirable primary source of vacuum breakdown and electrical discharge phenomena. which engineers work to prevent. Associate Professor of Mechanical Engineering. Simple solvable models of the tunneling barrier lead to equations (including the original 1928 Fowler-Nordheim-type equation) that get predictions of emission current density too low by a factor of 100 or more. B. It is distinguished by its characteristic polarization and spectrum. This may be achieved artificially in synchrotrons or storage rings. FowlerNordheim equations apply only to field emission from bulk metals and (with suitable modification) to other bulk crystalline solids.[1] A family of approximate equations. This was one of the triumphs of the nascent quantum mechanics.[citation needed] A consequence of these (and other) difficulties has been a heritage of misunderstanding and disinformation that still persists in some current field emission research literature. but generated by the acceleration of ultrarelativistic (i. and even the corrected theory that was put in place in the 1950s has been formally incomplete until very recently. Devices which eliminate induced charges are termed charge-neutralizers. or insertion devices. or in any simple way. Strictly. Synchrotron X-ray generation Synchrotron radiation is electromagnetic radiation. a mathematical error was made in the original application of these methods to field emission. Jeppiaar Trust. it is necessary to use special approximate methods known in physics as "semi-classical" or "quasi-classical" methods. but they are often used – as a rough approximation – to describe field emission from other materials. field electron emission is a paradigm example of what physicists mean by tunneling. "Fowler–Nordheim equations". Unfortunately. This article tries to present a basic account of field emission "for the 21st century and beyond" that is free from these confusions. which mark the corners of the storage ring. is named after them. In some respects. The radiation produced may range over the entire electromagnetic spectrum. Ramesh. The spectrum and energy of X-rays differ between the two types. Joseph’s College of Engineering. These beamlines may originate at bending magnets. similar to cyclotron radiation. or naturally by fast electrons moving through magnetic fields in space. The radiation is projected at a tangent to the electron storage ring and captured by beamlines. Examples of applications for surface field emission include construction of bright electron sources for high-resolution electron microscopes or to discharge spacecraft from induced charges. The Compiled by : Mr. X-rays. visible light. it is also a paradigm example of the intense mathematical difficulties that can arise. ultraviolet light. Worse.

Modern Techniques of Materials Characterisation


beamline includes X-ray optical devices which control the bandwidth, photon flux, beam dimensions, focus, and collimation of the rays.

First synchrotron function, F(x), x is usually a ratio of the frequency over a critical frequency. The maximum is at 1/3 of the critical frequency, where the bulk of emission takes place. For X-ray generation or at lower frequencies, x is usually a ratio of frequencies, that is, the frequency over a critical frequency (critical frequency is the frequency at which most of the synchrotron radiation is radiated). This is needed when calculating the spectra for different types of synchrotron emission. It takes a spectrum of electrons (or any charged particle) generated by a separate process (such as a power law distribution of electrons and positrons from a constant injection spectrum) and converts this to the spectrum of photons generated by the input electrons/positrons.

The effective temperature, or black body temperature, of the Sun (5777 K) is the temperature a black body of the same size must have to yield the same total emissive power. A spectral distribution comparison between blackbody radiation and synchrotron radiation for the same critical wavelength indicates that the synchrotron spectrum has a steeper dropoff at higher frequencies (shorter wavelengths, higher energy) and a shallower dropoff with increasing wavelength (lower frequencies, lower energy).[14] Electromagnetic radiation is produced in a continuum whenever a charged particle loses energy by passing through a magnetic field or passes another charged particle, as by an electron passing a proton. When the electron assumes an energy level around the proton or changes energy levels the spectrum becomes blackbody radiation (Planckian distribution).

Compiled by : Mr. B. Ramesh, Associate Professor of Mechanical Engineering, St. Joseph’s College of Engineering, Jeppiaar Trust, Chennai-119

Modern Techniques of Materials Characterisation


Bragg’s Law
Definition: When a beam of X-rays (wavelength λ) strikes a crystal surface in which the layers of atoms or ions are separated by a distance d, the maximum intensity of the reflected ray occurs when sinθ = nλ/2d, where θ (known as the Bragg angle) is the complement of the angle of incidence and n is an integer. The law enables the structure of many crystals to be determined. It was discovered in 1912 by Sir William Lawrence Bragg. Significance of bragg’s law: Bragg's law was used to explain the interference pattern of X-rays scattered by crystals, diffraction has been developed to study the structure of all states of matter with any beam, e.g., ions, electrons, neutrons, and protons, with a wavelength similar to the distance between the atomic or molecular structures of interest. The condition for maximum intensity contained in Bragg's law above allow us to calculate details about the crystal structure. Derivation of bragg’s law: Consider figure 5, the maximum intensity of diffraction is achieved when both waves, reflected by the electrons in the atom, are in phase. The rays of the incident beam are always in phase and parallel up to the point at which the top beam strikes the top layer at point z4.

Compiled by : Mr. B. Ramesh, Associate Professor of Mechanical Engineering, St. Joseph’s College of Engineering, Jeppiaar Trust, Chennai-119

Modern Techniques of Materials Characterisation


Figure 5 - Deriving Bragg's Law using the reflection geometry and applying trigonometry. The lower beam must travel the extra distance (AB + BC) to continue travelling parallel and adjacent to the top beam4. The second beam continues to the next layer where it is scattered by atom B. The second beam must travel the extra distance AB + BC if the two beams are to continue travelling adjacent and parallel. This extra distance must be an integral (n) multiple of the wavelength (  for the phases of the two beams to be the same: ) n= AB +BC (2) Recognising d as the hypotenuse of the right triangle Abz, we can use trigonometry to relate d and  to the distance (AB + BC). The distance AB is opposite  so, AB = d sin n = 2AB n = 2d sin Because AB = BC equation 2 becomes, (4) (1) Substituting equation 3 in equation 4 we have, and Bragg's Law has been derived. The location of the surface does not change the derivation of Bragg's Law4. 

Compiled by : Mr. B. Ramesh, Associate Professor of Mechanical Engineering, St. Joseph’s College of Engineering, Jeppiaar Trust, Chennai-119

Modern Techniques of Materials Characterisation


In X-ray diffraction a beam strikes a crystal and diffracts into many specific directions. The angles and intensities of the diffracted beams indicate a three-dimensional density of electrons within the crystal. X-rays produce a diffraction pattern because their wavelength is typically the same order of magnitude (0.1-10.0 nm) as the spacing between the atomic planes in the crystal.

Fig. :Symmetrically spaced atoms cause re-radiated X-rays to reinforce each other in the specific directions where their path-length difference, 2d sin θ, equals an integer multiple of the wavelength λ Each atom, re-radiates a small portion of an incoming beam's intensity as a spherical wave. If the atoms are arranged symmetrically (as is found in a crystal) with a separation d, these spherical waves will be in synch (add constructively) only in directions where their path-length difference 2d sin θ is equal to an integer multiple of the wavelength λ. The incoming beam therefore appears to have been deflected by an angle 2θ, producing a reflection spot in the diffraction pattern. X-ray diffraction is a form of elastic scattering; the outgoing X-rays have the same energy, and thus same wavelength, as the incoming X-rays, only with altered direction. By contrast, inelastic scattering occurs when energy is transferred from the incoming Xray to an inner-shell electron exciting it to a higher energy level. Such inelastic scattering reduces the energy (or increases the wavelength) of the outgoing beam. Inelastic scattering is useful for probing such electron excitation, but not in determining the distribution of atoms within the crystal. Longer-wavelength photons (such as ultraviolet radiation) would not have sufficient resolution to determine the atomic positions. At the other extreme, shorter-wavelength
Compiled by : Mr. B. Ramesh, Associate Professor of Mechanical Engineering, St. Joseph’s College of Engineering, Jeppiaar Trust, Chennai-119

using a powder or polycrystalline specimen. St. to satisfy Bragg's law. discover the different techniques used in x-ray diffraction.e. Similar diffraction patterns can be produced by scattering electrons or neutrons. in which a beam of X-rays strikes a single crystal. Diffraction can occur whenever Bragg's law is satisfied. Associate Professor of Mechanical Engineering. This problem can be overcome by continuously varying  or  over a range of values. The first — and often most difficult — step is to obtain an adequate crystal of the material under Compiled by : Mr. For single crystals of sufficient purity and regularity. With monochromatic radiation. X-ray diffraction data can determine the mean chemical bond lengths and angles to within a few thousandths of an Ångström and to within a few tenths of a degree. Ramesh. The atoms in a crystal are not static. Jeppiaar Trust.matter. When they land on a piece of film or other detector. Procedure The technique of single-crystal X-ray crystallography has three basic steps. B. Xray crystallography allows measuring the size of these oscillations. since it corresponds to the reflection of the X-rays from one set of evenly spaced planes within the crystal. white radiation).uk/diffraction/x-ray/x_ray_methods. producing scattered beams. or • by rotating the crystal or. the strengths and angles of these beams are recorded as the crystal is gradually rotated. There would therefore be very little information in a single crystal diffraction pattern from using monochromatic respectively. an arbitrary setting of a single crystal in an x-ray beam will not generally produce any diffracted beams. these beams make a diffraction pattern of spots. http://www.[89] Each spot is called a reflection. but oscillate about their mean positions. usually by less than a few tenths of an Ångström. Chennai-119 . difficult to focus. X-rays are usually not diffracted from atomic nuclei. Joseph’s College of Engineering. producing particle-antiparticle pairs. By selecting combinations of x-ray ranges and specimen types.Modern Techniques of Materials Characterisation 90 photons such as gamma rays are difficult to produce in large numbers.htm Single-crystal X-ray diffraction The oldest and most precise method of X-ray crystallography is single-crystal X-ray diffraction. and interact too strongly with matter. Practically this is done by: • using a range of x-ray wavelengths (i.

small molecules are also easier to crystallize than macromolecules. its unit cell. Jeppiaar Trust. Such crystal structures are generally less well-resolved (more "smeared out"). the atoms and chemical bonds appear as tubes of electron density. In the second step. Ramesh. usually of a single wavelength (monochromatic X-rays). the crystal is placed in an intense beam of X-rays. Two limiting cases of X-ray crystallography—"small-molecule" and "macromolecular" crystallography—are often discerned. Associate Professor of Mechanical Engineering. the intensity of every spot is recorded at every orientation of the crystal. with each set covering slightly more than half a full rotation of the crystal and typically containing tens of thousands of reflections. the atomic-level picture provided by X-ray crystallography becomes less well-resolved (more "fuzzy") for a given number of observed reflections. such crystal structures are usually so well resolved that the atoms can be discerned as isolated "blobs" of electron density. with no significant internal imperfections such as cracks or twinning. pure in composition and regular in structure. X-ray crystallography has proven possible even for viruses with hundreds of thousands of atoms. B. Limitations As the crystal's repeating unit. Multiple data sets may have to be collected. macromolecular crystallography often involves tens of thousands of atoms in the unit cell. Compiled by : Mr. St. As the crystal is gradually rotated. Joseph’s College of Engineering. becomes larger and more complex. By contrast. previous reflections disappear and new ones appear.1 mm in all dimensions). Small-molecule crystallography typically involves crystals with fewer than 100 atoms in their asymmetric unit. these data are combined computationally with complementary chemical information to produce and refine a model of the arrangement of atoms within the crystal. producing the regular pattern of reflections.Modern Techniques of Materials Characterisation 91 study. Chennai-119 . In general. however. The crystal should be sufficiently large (typically larger than 0. refined model of the atomic arrangement — now called a crystal structure — is usually stored in a public database. rather than as isolated atoms. In the third step. The final.

Associate Professor of Mechanical Engineering. St. the diffraction spots lie on horizontal lines. Chennai-119 . Explore the rotating crystal method by clicking on the start button repeatedly. a single crystal is mounted with an axis normal to a monochromatic x-ray beam. As the crystal rotates. When the film is laid out flat. A cylindrical film is placed around it and the crystal is rotated about the chosen axis. B. : Workflow for solving the structure of a molecule by X-ray crystallography. The reflected beams are located on the surface of imaginary cones. Jeppiaar Trust. Rotating Crystal method: In the rotating crystal method. sets of lattice planes will at some point make the correct Bragg angle for the monochromatic incident beam. Joseph’s College of Engineering. Compiled by : Mr. and at that point a diffracted beam will be formed. Ramesh.Modern Techniques of Materials Characterisation 92 Fig. The chief use of the rotating crystal method is in the determination of unknown crystal structures.

Compiled by : Mr. St. The film intersects the cone. The Bragg angle is fixed for every set of planes in the crystal. the back-reflection and the transmission Laue method. or transmitted through. Each set of planes picks out and diffracts the particular wavelength from the white radiation that satisfies the Bragg law for the values of d and  involved.htm 93 Laue method: The Laue method is mainly used to determine the orientation of large single crystals. White radiation is reflected from. with the diffraction spots generally lying on an hyperbola. Each curve therefore corresponds to a different wavelength. Chennai-119 . The beams which are diffracted in a backward direction are recorded. the film is placed between the x-ray source and the crystal. The diffracted beams form arrays of spots.Modern Techniques of Materials Characterisation http://www. You can study these below: Back-reflection Laue In the back-reflection Laue reflections from planes of the same zone all lie on the surface of an imaginary cone whose axis is the zone axis. The spots lying on any one curve are reflections from planes belonging to one zone. Jeppiaar Trust. that lie on curves on the film. Associate Professor of Mechanical Engineering. Ramesh. Experimental There are two practical variants of the Laue method. One side of the cone of Laue reflections is defined by the transmitted beam. Joseph’s College of Engineering. a fixed crystal.matter.

The Greninger chart is used for back-reflection patterns and the Leonhardt chart for transmission patterns. using special charts. If a monochromatic x-ray beam is directed at a single crystal. attributed to a particular plane. i. Compiled by : Mr. Powder method: The powder method is used to determine the value of the lattice parameters accurately. the spots become distorted and smeared out. b and c which define the unit cell for the crystal. If the crystal has been bent or twisted in anyway. Each spot can be indexed. Ramesh.Modern Techniques of Materials Characterisation Transmission Laue In the transmission Laue method. The film intersects the cone. Joseph’s College of Engineering.e. Associate Professor of Mechanical Engineering. the film is placed behind the crystal to record beams which are transmitted through the crystal. Lattice parameters are the magnitudes of the unit vectors a. St. with the diffraction spots generally lying on an ellipse. 94 Crystal orientation is determined from the position of the spots. Jeppiaar Trust. Chennai-119 . then only one or two diffracted beams may result. One side of the cone of Laue reflections is defined by the transmitted beam. B. The Laue technique can also be used to assess crystal perfection from the size and shape of the spots.

Compiled by : Mr. Each diffraction line is made up of a large number of small spots. each from a separate crystal.e. forwards and backwards. Each cone intersects the film giving diffraction lines. Associate Professor of Mechanical Engineering. the diffracted beams are seen to lie on the surface of several cones. A circle of film is used to record the diffraction pattern as shown. by chance.Modern Techniques of Materials Characterisation If the sample consists of some tens of randomly orientated single crystals. Each spot is so small as to give the appearance of a continuous line. The lines are seen as arcs on the film. the diffraction lines appear speckled. The cones may emerge in all directions. a powdered sample) show that the diffracted beams form continuous cones.. Ramesh. For every set of crystal planes. Jeppiaar Trust. 95 A sample of some hundreds of crystals (i. Every crystal plane is thus capable of diffraction. If the crystal is not ground finely enough.. Joseph’s College of Engineering. This arrangement is achieved practically in the Debye Scherrer camera illustrated here. B. Chennai-119 . one or more crystals will be in the correct orientation to give the correct Bragg angle to satisfy Bragg's equation. St.

Investigate the powder diffraction method using the simulation here. Associate Professor of Mechanical Engineering. Ramesh. Chennai-119 . Jeppiaar Trust. Compiled by : Mr. B.Modern Techniques of Materials Characterisation 96 Debye Scherrer camera: A very small amount of powdered material is sealed into a fine capillary tube made from glass that does not diffract Joseph’s College of Engineering. These cones intersect a strip of photographic film located in the cylindrical camera to produce a characteristic set of arcs on the film. http://www. X-rays enter the camera through a collimator. The powder diffracts the x-rays in accordance with Braggs law to produce cones of diffracted beams. The specimen is placed on the sample turntable.matter.htm Figure 6 – A photograph of a Debye-Scherrer camera with the front cover removed. by clicking on the start button The knobs on the top are for positioning and fixing the film. St. The specimen is placed in the Debye Scherrer camera and is accurately aligned to be in the centre of the camera.

flattened and processed. this causes the highest angle back-reflected arcs to be doubled. Compiled by : Mr. The sample is known to have a cubic structure. • When the film is laid flat. then develop and fix it. • For back reflections. Joseph’s College of Engineering. but we don't know which one. Associate Professor of Mechanical Engineering. We remove the film strip from the Debye camera after exposure. where 2 > 90° you can measure S2 as the distance from the beam entry point. it is always clear which hole is for the transmitted beam and which is for the incident beam in the film. to the centre of the hole for the transmitted direct beam. Jeppiaar Trust. This is the distance along the film. S1 can be measured. From noting this. it shows the diffraction lines and the holes for the incident and transmitted beams. B. Chennai-119 . Indexing a powder pattern: We shall now consider the powder patterns from a sample crystal.Modern Techniques of Materials Characterisation 97 Powder diffraction film: When the film is removed from the camera. Ramesh. From the strip of film we make measurements of the position of each diffraction line. From the results it is possible to associate the sample with a particular type of cubic structure and also to determine a value for its lattice parameter. from a diffraction line.e. There are always two arcs in the x-ray beams Ka and Kb. St. i.

Compiled by : Mr. B. Associate Professor of Mechanical Engineering. then the experimental values of sin2 should form a pattern related to the values of h. Ramesh.  and sin2. St.Modern Techniques of Materials Characterisation 98 • The distance S1 corresponds to a diffraction angle of 2. d. The angle between the diffracted and the transmitted beams is always 2. k and l for the structure. Integer values are then assigned. corresponds to a diffraction angle of  =  So we can find  . W. • If all the diffraction lines are considered. Joseph’s College of Engineering. • We now multiply the values of sin2 by some constant value to give nearly integer values for all the h2+ k2+ l2 values. We know that the distance between the holes in the film. Chennai-119 . for cubic crystals is given by: where a is the lattice parameter this gives: • From the measurements of each arc we can now generate a table of S1. Jeppiaar Trust. from: or • We know Bragg's Law: n = 2dsin and the equation for interplanar spacing.

Jeppiaar Trust. St. using the table shown below: • For some structures e. or all odd in the table above). Inorganic. • It is then possible to identify certain structures. Joseph’s College of Engineering. Associate Professor of Mechanical Engineering. Chennai-119 • . For greater accuracy the value is averaged over all the lines. Organic. Compiled by : Mr. Powder method of XRD : APPLICATIONS X-ray powder diffraction has opened up new avenues in the studies of structures. bcc. • For each line we can also calculate a value for a. so some of the arcs may be missing. It has a number of applications.g. This comparison is done with the help of a powder diffraction file that contains the patterns of some standard compounds divided into subdivisions-Minerals.Modern Techniques of Materials Characterisation 99 • The integer values of h2+ k2+ l2 are then equated with their hkl values to index each arc. the lattice parameter. • Qualitative analysis: From the pattern. not all planes reflect.the planes have hkl values: all even. Ramesh. in this case fcc (. fcc. B. the d-spacings are recorded and the relative intensities of the 10 strongest lines are measured and are compared with the patterns of the known compounds. Quantitative Analysis: For a two-component mixture the relative concentration of each of the components can be obtained by measuring the relative intensities of the strong non overlapping lines each belonging to the two components.

Associate Professor of Mechanical Engineering. Jeppiaar Trust. Ramesh. Determination of particle size: As the size of the crystallite decreases. St. a 3-D pattern is reduced to a 1-D pattern and analysis is done.[1] • Single-crystal X-ray diffraction is a technique used to solve the complete structure of crystalline materials. The individual peak intensities are difficult to obtain because in powder diffraction. ranging from simple inorganic solids to complex macromolecules. Such accuracy is sometimes difficult to obtain. the angular spread of the reflection increases. it produces separate lines on the powder pattern corresponding to the component. Powder method of XRD :LIMITATIONS • • • • Single crystal methods depend upon mathematical algorithms and accurate peak intensities to solve structures. we can for example determine the structure of different clays as a cement material by comparing with acceptable clay and thus relate structure to properties. The most comprehensive description of scattering from crystals is given by the dynamical theory of diffraction. But both rotating the sample about its normal and rocking it about each data point can overcome this. it is difficult to analyze the pattern. such as proteins. Identification and raw material evaluation: For some complex materials. If one of the components precipitates. The symmetry of crystals cannot be obtained accurately in powder diffraction pattern. X-ray diffraction techniques-specific applications X-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. Chennai-119 . Joseph’s College of Engineering. This leads to both accidental and exact peak overlap.Modern Techniques of Materials Characterisation • 100 • • • Structure of alloys: An alloy is a mixture of two or more elements. In addition. If the composition is uniform it produces a typical powder diffraction pattern. Stress Determination in metals: If there is a stress in a metal then the angle of the diffraction cone changes because of a change in the d-spacing due to stress. B. But since similar materials exhibit similar patterns. Preferred orientation can lead to inaccurate peak intensities. The half height width can be used a measure of the mean particle size of the sample. Compiled by : Mr. stress invariably broadens diffraction peaks unless it is absolutely uniform on an atomic scale. By measuring the changes in the cone angle accurate measurements of stress can be made.

neon or argon with halogens added) briefly conducts electricity when a particle or photon of radiation makes the gas conductive. X-ray rocking curve analysis is used to quantify grain size and mosaic spread in crystalline materials. It employs parallelbeam optics. An effect of the finite crystallite sizes is seen as a broadening of the peaks in an X-ray diffraction as is explained by the Scherrer Equation. Ramesh. Thin film diffraction and grazing incidence X-ray diffraction may be used to characterize the crystallographic structure and preferred orientation of substrateanchored thin films. They are notable for being used to detect if objects emit nuclear radiation Description Geiger counters are used to detect ionizing radiation (usually beta particles and gamma rays. It may also be used to characterize heterogeneous solid mixtures to determine relative abundance of crystalline compounds and. crystallite size (grain size). when coupled with lattice refinement techniques. Joseph’s College of Engineering. though sensitivity can be lower for high energy gamma radiation than with certain other types of detector. High-resolution X-ray diffraction is used to characterize thickness. by comparing diffraction data against a database maintained by the International Centre for Diffraction Data. and are better absorbed by the detector. Examples of this are the X-ray Pancake Geiger Tube). Powder diffraction is also a common method for determining strains in crystalline materials. such as Rietveld refinement. Geiger counter A Geiger counter. can provide structural information on unknown materials. Chennai-119 . B. and preferred orientation in polycrystalline or powdered solid samples. which is then often displayed by a needle or lamp and/or audible clicks. Good alpha and beta scintillation counters also exist. A better device for detecting gamma rays is a sodium iodide scintillation counter. An inert gas-filled tube (usually helium. Associate Professor of Mechanical Engineering. Jeppiaar Trust. St. allowing most high energy gamma photons to pass through undetected (lower energy photons are easier to detect. Powder diffraction is commonly used to identify unknown substances. but Geiger detectors are still favored as general purpose alpha/beta/gamma portable contamination Compiled by : Mr. Some Geiger counters can be used to detect gamma radiation. is a type of particle detector that measures ionizing radiation. but certain models can detect alpha particles). Modern instruments can report radioactivity over several orders of magnitude. also called a Geiger-Müller counter. crystallographic structure. The tube amplifies this conduction by a cascade effect and outputs a current pulse. X-ray pole figure analysis enables one to analyze and determine the distribution of crystalline orientations within a crystalline thin-film sample. because the density of the gas in the device is usually low. and strain in thin epitaxial films.Modern Techniques of Materials Characterisation • 101 • • • • Powder diffraction (XRD) is a technique used to characterise the crystallographic structure.

Types and applications A modern digital Geiger counter is used with applications ranging from nuclear medicine. A Geiger counter and metal detector combined for detecting both metal and radioactive materials for security purpose. where the gas used is boron trifluoride and a plastic moderator is used to slow the neutrons. due to their low cost and robustness. St. B. contamination monitoring.Modern Techniques of Materials Characterisation 102 and dose rate instruments. Joseph’s College of Engineering. Chennai-119 . Ramesh. Associate Professor of Mechanical Engineering. A variation of the Geiger tube is used to measure neutrons. This creates an alpha particle inside the detector and thus neutrons can be counted. Jeppiaar Trust. Compiled by : Mr. mining. and national security.

and medical therapy with isotopes and x-rays. St. Although useful. Gas detectors with the ability to both detect radiation and determine particle energy levels (due to their construction. Chennai-119 . as opposed to energy). For example. a counter using a GM tube can only detect the presence and intensity of radiation (particle frequency. Joseph’s College of Engineering. and associated electronics) are called proportional counters.5 mg/cm2 Axial Xe/CH4 Mylar/Al 6 m Scintillation Be/Al 0. medicine. astronomy. B. a thin mica window on a GM Tube (shown here) will allow for the detection of alpha radiation.Modern Techniques of Materials Characterisation 103 The configuration of GM tubes determines the types of radiation that it can detect. Associate Professor of Mechanical Engineering. The Geiger–Müller tube is one form of a class of radiation detectors called gaseous detectors or simply gas detectors. Some proportional counters can detect the position and or angle of the incident radiation as well. particle physics. Characteristics of counters Geiger Window Thickness Position Filling Mica 3 mg/cm2 Radial Ar/Br Proportional Gas Flow Mica 2. and in industry. Some of the proportional counters have many electrodes and are called multi-wire proportional counters or simply MWPCs. test gas.2 mm Radial -- Axial Ar/CH4 Compiled by : Mr. Other devices detecting radiation include: • • • • • • • • • • • • ionization chambers dosimeters photomultipliers semiconductor detectors and variants including CCDs microchannel plates scintillation counters solid-state track detectors cloud chambers bubble chambers spark chambers neutron detectors microcalorimeters The Geiger-Müller counter has applications in the fields of nuclear physics. Radiation detectors have also been used extensively in nuclear physics. Jeppiaar Trust. cheap and robust. geophysics (mining). Ramesh. whereas GM Tubes without a thin mica window are too thick for the alpha and low energy beta radiation to pass through and be detected.

containing several more strongly different directions of propagation. Chennai-119 . Jeppiaar Trust. Furthermore. A topograph thus represents a two-dimensional spatial intensity mapping of reflected X-rays. or divergent/convergent.5 106 0. Associate Professor of Mechanical Engineering.8 Resolution % (Fe Quantum counting efficiency ) dependent dependent dependent reasonably independent of *Can be extended to 50 Å by use of ultra-thin windows. i. X-ray diffraction topography is one variant of X-ray imaging. Diffraction topography Diffraction topography (short: "topography") is an X-ray imaging technique based on Bragg diffraction. topography can be applied without preparing or otherwise damaging the sample. it is therefore one variant of nondestructive testing. be composed of a mixture of wavelengths ("white beam" topography). Topography is used for monitoring crystal quality and visualizing defects in many different crystalline materials. Ramesh. and for iteratively optimizing growth conditions. consist one single wavelength of X-rays or neutrons. Basic principle of topography The basic working principle of diffraction topography is as follows: An incident.4 l0 4 5 0. the incident beam may be either parallel. Joseph’s College of Engineering.5-4 0. consisting only of "rays" propagating all along nearly the same direction.2 14 l0 4 Cosmic background (c/s) 0. i. The beam may be either monochromatic. B. topographs therefore reveal the irregularities in a nonideal crystal lattice. St. It has proved helpful e. for monitoring growth and the crystal quality achieved.g. or polychromatic. or neutrons) impinges on a sample.5-4 200 106 0.e.e.2 106 10 15 104 2 -- 10 3 5 0. when developing new crystal growth methods. sometimes. Compiled by : Mr. neutrons) diffracted by a crystal. making use of diffraction contrast rather than absorption contrast which is usually used in radiography and computed tomography (CT).Modern Techniques of Materials Characterisation Pre-amplifier Auto-amplification Useful range (Å) Dead time (Micro seconds) Max. This intensity mapping reflects the distribution of scattering power inside the crystal. useful count rate unnecessary 109 0. spatially extended beam (mostly of X-rays.7-10* 0. Diffraction topographic images ("topographs") record the intensity profile of a beam of X-rays (or. the spatial fine structure of a Bragg spot.1-3 0. i. In many cases.5 106 0.e.

Modern Techniques of Materials Characterisation


When the beam hits the crystalline sample, Bragg diffraction occurs, i.e. the incident wave is reflected by the atoms on certain lattice planes of the sample, on condition that it hits those planes at the right Bragg angle. Diffraction from sample can take place either in reflection geometry (Bragg case), with the beam entering and leaving through the same surface, or in transmission geometry (Laue case). Diffraction gives rise to a diffracted beam, which will leave the sample and propagate along a direction differing from the incident direction by the scattering angle . The cross section of the diffracted beam may or may not be identical to the one of the incident beam. In the case of strongly asymmetric reflections, the beam size (in the diffraction plane) is considerably expanded or compressed, with expansion occurring if the incidence angle is much smaller than the exit angle, and vice-versa. Independently of this beam expansion, the relation of sample size to image size is given by the exit angle alone: The apparent lateral size of sample features parallel to the exit surface is downscaled in the image by the projection effect of the exit angle. A homogeneous sample (with a regular crystal lattice) would yield a homogeneous intensity distribution in the topograph (a "flat" image). Intensity modulations (topographic contrast) arise from irregularities in the crystal lattice, originating from various kinds of defects such as
• • • • • • • • • • •

voids and inclusions in the crystal phase boundaries (regions of different crystallographic phase, polytype, ...) defective areas, non-crystalline (amorphous) areas / inclusions cracks, surface scratches stacking faults dislocations, dislocation bundles grain boundaries, domain walls growth striations point defects or defect clusters crystal deformation strain fields

In many cases of defects such as dislocations, topography is not directly sensitive to the defects themselves (atomic structure of the dislocation core), but predominantly to the strain field surrounding the defect region.
Compiled by : Mr. B. Ramesh, Associate Professor of Mechanical Engineering, St. Joseph’s College of Engineering, Jeppiaar Trust, Chennai-119

Modern Techniques of Materials Characterisation


XRD 1. X-ray Diffraction

X-ray powder diffraction (XRD) is one of the most dominant techniques for qualitative and quantitative analysis of crystalline compounds. The technique supplies information that cannot be obtained any other method. The information obtained includes nature of crystalline phase’s present, structural make-up of phases, degree of crystallinity, and amount of amorphous content, micro-strain size and orientation of crystallites. 1. Principles of Operation

Once a solid sample is irradiated by a parallel beam of monochromatic X-rays, the atomic lattice of the sample operates as a three dimensional diffraction stridents causing the X-ray beam to be diffracted to particular angles. The diffraction pattern, that includes angles (positions) and intensities of the diffracted beam, presents several practical clues about the sample which are discussed below: Angles are utilized to compute the inter-planar atomic spacing (d-spacing). Because every crystalline material will give a distinctive diffraction pattern and can perform as a unique ‘fingerprint’, the position (d) and intensity (I) information are used to identify the nature of material by comparing them with patterns for over 80,000 data entries in the International Powder Diffraction File (PDF) database, complied by the Joint Committee for Powder Diffraction Standards (JCPDS). Through this method, identification of any crystalline compounds, even in a complex sample, can be determined. The position (d) of diffracted peaks also supplies information about how the atoms are coordinated within the crystalline compound, which represents unit cell size or lattice parameter. The intensity information is used to evaluate the type and nature of atoms. Determination of lattice parameter assists understanding extent of solid solution including absolute or partial substitution of one element for another, as in some alloys in a sample. Width of the diffracted peaks is used to establish crystallite size and micro-strain in the sample. The‘d’ and ‘I’ from a phase can also be utilized to quantitatively approximate the amount of that phase in a multi-component mixture. 1. Quantitative analysis

Compiled by : Mr. B. Ramesh, Associate Professor of Mechanical Engineering, St. Joseph’s College of Engineering, Jeppiaar Trust, Chennai-119

Modern Techniques of Materials Characterisation


As stated earlier, XRD can be utilized not only for qualitative identification but also for quantitative approximation of diverse crystalline phases. This is one of the significant advantages of X-ray diffraction techniques. Numerous methods have been proposed and successfully applied to quantify crystalline phases in mixtures. They include external standard methods, the reference-intensity-ratio (RIR) method, chemical methods and the full-pattern fitting Rietveld method. Upon accessible methods, the Rietveld method is probably the most precise and reliable method. The Rietveld method is a full-pattern fitting least squares refinement technique and has been successfully applied for quantification and characterization of inorganic and organic compounds. It has also been used for crystal structure refinement, to determine size and strain of crystallites. Internal Standard The Internal Standard Method is the procedure of choice for analyzing powdered systems. A known quantity of a reference powder is added to the unknown. Any number of constituents in a mixture may be quantified independently. The mixture may contain amorphous (noncrystalline) components. The mass absorption coefficient of the mixture need not be known in advance. The Internal Standard Method is applied broadly to any mineral or materials systems for which the chemistry is unknown. External Standard The External Standard Method may be applied to solid systems, such as alloys, plasma sprayed coatings, or oxide layers. This method allows the quantification of one or more components in a system that may contain an amorphous fraction. The mass absorption coefficient must, however, be known in advance, requiring either full elemental chemistry or prior knowledge of the chemistry, as in the case of plasma spray coatings or alloys. Direct Comparison This procedure requires no standards, but is only applicable to fully crystalline mixtures. All of the components in the system must be quantified for solution. The Direct Comparison Method is the common method used for retained austenite determination.

Unit V
Compiled by : Mr. B. Ramesh, Associate Professor of Mechanical Engineering, St. Joseph’s College of Engineering, Jeppiaar Trust, Chennai-119

e. once the very close relationship E = hν for photons was realized (h is the Planck constant).Modern Techniques of Materials Characterisation 108 Spectroscopy was originally the study of the interaction between radiation and matter as a function of wavelength (λ). the instrument that performs such measurements is a spectrometer. Jeppiaar Trust. Spectroscopy/spectrometry is often used in physical and analytical chemistry for the identification of substances through the spectrum emitted from or absorbed by them. which are used either to measure the chemical composition and physical properties of astronomical objects or to measure their velocities from the Doppler shift of their spectral lines Fig. by a prism. it also can refer to a response to an alternating field or varying frequency (ν). A plot of the response as a function of wavelength—or more commonly frequency—is referred to as a spectrum. Ramesh.g. B. Detecting photoelectrons that are ejected by x-rays is called x-ray photoelectron spectroscopy (XPS) or electron spectroscopy for chemical analysis (ESCA). Historically. Detecting electrons that are ejected from higher orbitals to conserve energy during electron transitions is called Auger electron spectroscopy (AES). Later the concept was expanded greatly to comprise any measurement of a quantity as a function of either wavelength or frequency. Associate Professor of Mechanical Engineering. molecular. see also spectral linewidth. electrons or synchrotron radiation will eject an electron from an inner-shell orbital of an atom. In general an excitation source such as x-rays. Chennai-119 . St. Thus. or spectrograph. spectrophotometer. Joseph’s College of Engineering. or ionic) species. spectroscopy referred to the use of visible light dispersed according to its wavelength. In this case. A further extension of the scope of the definition added energy (E) as a variable. Most large telescopes have spectrographs. Spectrometry is the spectroscopic technique used to assess the concentration or amount of a given chemical (atomic. Spectroscopy/spectrometry is also heavily used in astronomy and remote sensing.: Animation of the dispersion of light as it travels through a triangular prism Electron spectroscopy is an analytical technique to study the electronic structure and its dynamics in atoms and molecules. Compiled by : Mr.

cutting or scraping in air or UHV to expose the bulk chemistry. It cannot detect hydrogen (Z = 1) or helium (Z = 2) because the diameter of these orbitals is so small. reducing the catch probability to almost zero. Associate Professor of Mechanical Engineering. an abbreviation for Electron Spectroscopy for Chemical Analysis. Chennai-119 . medical implants. XPS is a surface chemical analysis technique that can be used to analyze the surface chemistry of a material in its "as received" state. XPS is routinely used to analyze inorganic compounds. glues. XPS detects all elements with an atomic number (Z) of 3 (lithium) and above. B. make-up. woods. paints. Ramesh. XPS requires ultra high vacuum (UHV) conditions. bio-materials. Jeppiaar Trust. or after some treatment. Compiled by : Mr. semiconductors. • • • • XPS is also known as ESCA.Modern Techniques of Materials Characterisation 109 Experimental applications include high-resolution measurements on the intensity and angular distributions of emitted electrons as well as on the total and partial ion yields. Joseph’s College of Engineering. glasses. Depth profiling is accomplished by combining an electron spectroscopy with a sputtering source that removes surface layers. XPS spectra are obtained by irradiating a material with a beam of X-rays while simultaneously measuring the kinetic energy and number of electrons that escape from the top 1 to 10 nm of the material being analyzed. plant parts. viscous oils. exposure to ultraviolet light. Detections limits of parts per million (ppm) are possible. Detection limits for most of the elements are in the parts per thousand range. teeth. bones. polymers. Ejected electrons can escape only from a depth of approximately 3 nanometers or less. ion modified materials and many others. papers. chemical state and electronic state of the elements that exist within a material. exposure to reactive gases or solutions. X-ray photoelectron spectroscopy X-ray photoelectron spectroscopy (XPS) is a quantitative spectroscopic technique that measures the elemental composition. ion beam etching to clean off some of the surface contamination. elements. catalysts. St. exposure to heat to study the changes due to heating. making electron spectroscopy most useful to study surfaces of solid materials. metal alloys. ceramics. for example: fracturing. but require special conditions: concentration at top surface or very long collection time (overnight). exposure to ion beam implant. empirical formula. inks.

Ramesh.: Wide-scan survey spectrum for all elements. Associate Professor of Mechanical Engineering. B.: Basic components of a monochromatic XPS system. Jeppiaar Trust. Compiled by : Mr.Modern Techniques of Materials Characterisation 110 Fig. Joseph’s College of Engineering. St. Fig. Chennai-119 .

Associate Professor of Mechanical Engineering. Joseph’s College of Engineering. B. St. Compiled by : Mr. : High-resolution spectrum for Si(2p) signal.Modern Techniques of Materials Characterisation 111 Fig. Jeppiaar Trust. Ramesh. Chennai-119 .

Commercial XPS instruments in the year 2005 used either a highly focused 20 to 200 micrometer beam of monochromatic aluminium Kα X-rays or a broad 10–30 mm beam of non-monochromatic (polychromatic) magnesium X-rays."Photoelectric Effect. special design. St. Ramesh. Associate Professor of Mechanical Engineering. Joseph’s College of Engineering. a privately built XPS system or a synchrotron-based light source combined with a custom designed electron analyzer. XPS instruments can analyze volatile liquids or gases. materials at low or high temperatures or materials at roughly 1 torr vacuum. A few.Modern Techniques of Materials Characterisation 112 Fig. but there are relatively few of these types of XPS systems. B. Compiled by : Mr.: Rough schematic of XPS physics . Jeppiaar Trust. Chennai-119 . XPS is used to measure: • • • • • • elemental composition of the surface (top 1–10 nm usually) empirical formula of pure materials elements that contaminate a surface chemical or electronic state of each element in the surface uniformity of elemental composition across the top surface (or line profiling or mapping) uniformity of elemental composition as a function of ion beam etching (or depth profiling) XPS can be performed using either a commercially built XPS system.

AES has become a practical and straightforward characterization technique for probing chemical and compositional surface environments and has found applications in metallurgy. Chennai-119 . pronounced [oʒe] in French) is a common analytical technique used specifically in the study of surfaces and. more generally. gas-phase chemistry. Jeppiaar Trust. Joseph’s College of Engineering. and throughout the microelectronics industry. Auger is credited with the discovery in most of the scientific community. Ephoton is the energy of the X-ray photons being used. B. the electron binding energy of each of the emitted electrons can be determined by using an equation that is based on the work of Ernest Rutherford (1914): where Ebinding is the binding energy (BE) of the electron. but studied so as to explain anomalies in x-ray spectroscopy data. which is based on the analysis of energetic electrons emitted from an excited atom after a series of internal relaxation events. as it has come to be called. in the area of materials science.[2][3][4][5] Compiled by : Mr. St. [1] Until the early 1950s Auger transitions were considered nuisance effects by spectroscopists. Ekinetic is the kinetic energy of the electron as measured by the instrument and φ is the work function of the spectrometer (not the material). Underlying the spectroscopic technique is the Auger effect.Modern Techniques of Materials Characterisation 113 Because the energy of a particular X-ray wavelength is known. Associate Professor of Mechanical Engineering. Ramesh. The Auger effect was discovered independently by both Lise Meitner and Pierre Auger in the 1920s. Though the discovery was made by Meitner and initially reported in the journal Zeitschrift für Physik in 1922. Since 1953 however. exists in the surface or the bulk of the sample Empirical formula of a material that is free of excessive surface contamination The chemical state identification of one or more of the elements in the sample The binding energy of one or more electronic states The thickness of one or more thin layers (1–8 nm) of different materials within the top 12 nm of the surface The density of electronic states Auger electron spectroscopy Auger electron spectroscopy (AES. not containing much relevant material information. XPS is routinely used to determine: • • • • • • • What elements and the quantity of those elements that are present within the top 1-12 nm of the sample surface What contamination. if any.

As this is an unstable state. first outer shell. Chennai-119 . EB. When an atom is probed by an external mechanism.Modern Techniques of Materials Characterisation 114 Electron transitions and the Auger effect The Auger effect is an electronic process at the heart of AES resulting from the inter. St. Ramesh. Figure 1 illustrates two schematic views of the Auger process. Jeppiaar Trust. The transition energy can be coupled to a second outer shell electron which will be emitted from the atom if the transferred energy is greater than the orbital binding energy. often however. The apostrophe (tic) denotes a slight modification to the binding energy of the outer shell electrons due to the ionized nature of the atom. B. whereby the electron moving to the lower energy level loses an amount of energy equal to the difference in orbital energies. Joseph’s College of Engineering. such as a photon or a beam of electrons with energies in the range of 2 keV to 50 keV. the core hole can be filled by an outer shell electron. Associate Professor of Mechanical Engineering. Compiled by : Mr. measured from the vacuum level. and second outer shell electron energies. EC' are respectively the core level. this energy modification is ignored in order to ease calculations.[2][3][4][5][6][7] An emitted electron will have a kinetic energy of: Ekin = ECore State − EB − EC' where ECore State. analysis of the ejected electrons can yield information about the chemical composition of a surface.and intrastate transitions of electrons in an excited atom. a core state electron can be removed leaving behind a hole.[3] Since orbital energies are unique to an atom of a specific element.

The energy level of the core hole will often determine which transition types will be favored.5[EB(Z) + EB(Z + 1)] − 0. For single energy levels. put forth by Jenkins and Chung. giving rise to characteristic peaks in an Auger spectrum. one in the 2s orbital and the other in the 2p orbital. (b) illustrates the same process using spectroscopic notation. i. giving rise to strong KLL type peaks in an Auger spectrum. While useful in practice. Joseph’s College of Engineering. they are also less energetic and thus harder to locate on an Auger spectrum. The final atomic state thus has two holes.e. and a combination of both for intermediate elements. (a) illustrates sequentially the steps involved in Auger deexcitation. which is historically linked to X-ray notation. One of the most tractable descriptions. Figure 1(b) illustrates this transition with the corresponding spectroscopic notation. ranging from initial excitation energy to relative interaction rates. Thus for a KL1L2. Energy levels are labeled using a number of different schemes such as the j-j coupling method for heavy elements (Z ≥ 75).[2][3] while Coster–Kronig transitions are faster.[3][8][9] The j-j coupling method. Ramesh.[2] The result are transitions of the type LMM and KLL along with faster Coster–Kronig transitions such as LLM. KL1L2. The types of state-to-state transitions available to electrons during an Auger event are dependent on several factors. Jeppiaar Trust. the Russell-Saunders L-S method for lighter elements (Z < 20). K represents the core level hole.Modern Techniques of Materials Characterisation 115 Figure 1. An electron from the 2s level fills in the 1s hole and the transition energy is imparted to a 2p electron which is emitted. both phenomenological and analytical. the strongest electronelectron interactions are between levels which are close together. ℓ quantum numbers) or energy levels within the same shell (same n. Fortunately. St. Several models. and L2. transitions can occur from the L levels. Two views of the Auger process. is almost always used to denote Auger transitions. L1 the relaxing electron's initial state.[3] Finally. but are less probable. As the atomic number Z increases.3 the emitted electron's initial energy state. KLL and LMM peaks are some of the most commonly identified transitions during surface analysis. Higher level transitions can also occur.3. An incident electron creates a core hole in the 1s level. yet are often dominated by a few characteristic transitions. B. Because of the interaction between an electron's spin and orbital angular momentum (spin-orbit coupling) and the concomitant energy level splitting for various shells in an atom. K. so too does the number of potential Auger transitions.5[EC(Z) + EC(Z + 1)] Ei(Z) are the binding energies of the ith level in element of atomic number Z and Ei(Z + 1) are the energies of the same levels in the next element up in the periodic table. valence band electrons can also fill core holes or be emitted during KVV-type transitions.3 transition. estimates the energy of Auger transition ABC as: EABC = EA(Z) − 0. Associate Professor of Mechanical Engineering. a more rigorous model accounting for effects such as screening and relaxation probabilities between energy levels gives the Auger energy as: EABC = EA − EB − EC − F(BC:x) + Rxin + Rxex Compiled by : Mr. Chennai-119 . there are a variety of transition pathways for filling a core hole. For multi-level shells. different ℓ number). transitions are available from higher energy orbitals (different n. have been developed to describe the energetics of Auger transitions.

An electron beam is focused onto a specimen and emitted electrons are deflected around the electron gun and pass through an aperture towards the back of the CMA. Surface sensitivity in AES arises from the fact that emitted electrons usually have energies ranging from 50 eV to 3 keV and at these values. Such measures prevent electron scattering off of residual gas atoms as well as the formation of a thin "gas (adsorbate) layer" on the surface of the specimen which degrades analytical performance. B. An optional ion gun can be integrated for depth profiling experiments.Modern Techniques of Materials Characterisation 116 where F(BC:x) is the energy of interaction between the B and C level holes in a final atomic state x and the R's represent intra. Experimental setup and quantification Instrumentation Figure 2. Joseph’s College of Engineering. In this configuration. focused electrons are incident on a sample and emitted electrons are deflected into a cylindrical mirror analyzer (CMA). St. The escape depth of electrons is therefore localized to within a few nanometers of the target surface. Jeppiaar Trust. most AES setups are run under ultra-high vacuum (UHV) conditions.[3] Auger electron energies can be calculated based on measured values of the various Ei and compared to peaks in the secondary electron spectrum in order to identify chemical species.and extra-atomic transition energies accounting for electronic screening. AES experimental setup using a cylindrical mirror analyzer (CMA). Associate Professor of Mechanical Engineering.[6][7] A typical AES setup is shown schematically in figure 2. giving AES an extreme sensitivity to surface species. This technique has been used to compile several reference databases used for analysis in current AES setups. These electrons are then directed into an electron multiplier for analysis. [7] Because of the low energy of Auger electrons. Varying voltage at the sweep supply allows derivative mode plotting of the Auger data. Ramesh. In Compiled by : Mr. electrons have a short mean free path in a solid. Chennai-119 .

e. B. detecting the signal at frequency ω will give a value for I' or .[6][7] Plotting in derivative mode also emphasizes Auger fine structure which appear as small secondary peaks surrounding the primary Auger peak. but this concern is usually ignored. Jeppiaar Trust. not to be confused with high energy satellites which are discussed later. arise from the presence of the same element in multiple different chemical states on a surface (i. AES is often run in a derivative mode which serves to highlight the peaks by modulating the electron collection current via a small applied AC voltage. The peak in derivative mode is not the true Auger peak. These secondary peaks. but rather the point of maximum slope of N(E). Since this ΔV = ksin(ωt). St. Joseph’s College of Engineering. Ramesh.[7] Compiled by : Mr. Associate Professor of Mechanical Engineering. Since the intensity of the Auger peaks may be small compared to the noise level of the background.Modern Techniques of Materials Characterisation 117 the detection unit. the collection current becomes I(V + ksin(ωt)). Taylor expanding gives: Using the setup in figure 2. Collected Auger electrons are plotted as a function of energy against the broad secondary electron background spectrum. Figure 3 illustrates a derivative spectrum from a copper nitride film clearly showing the Auger peaks. Adsorbate layers) or from relaxation transitions involving valence band electrons of the substrate. Chennai-119 . Auger electrons are multiplied and the signal sent to data processing electronics.

Electron yield. Compiled by : Mr. Auger spectrum of a copper nitride film in derivative mode plotted as a function of energy. in turn. ω. Joseph’s College of Engineering.[4][6] Since the Auger effect is not the only mechanism available for atomic relaxation. St. depends on several critical parameters such as electron-impact crosssection and fluorescence yield. there is a competition between radiative and non-radiative decay processes to be the primary de-excitation pathway.Modern Techniques of Materials Characterisation 118 Figure 3. Different peaks for Cu and N are apparent with the N KLL transition highlighted. Associate Professor of Mechanical Engineering. ωX. Jeppiaar Trust. B. Quantitative analysis Semi-quantitative compositional and element analysis of a sample using AES is dependent on measuring the yield of Auger electrons during a probing event. is a sum of the non-radiative (Auger) and radiative (photon emission) processes. The Auger yield. ωA. is thus related to the fluorescence (x-ray) yield. Ramesh. by the relation. Chennai-119 . The total transition rate.

[1] Compiled by : Mr. For K-level based transitions. Similar plots can be obtained for L and M shell transitions.[6] The yield limits effectively prescribe a cutoff for AES sensitivity. Ramesh. For heavier elements. Neither H nor He can be detected with this technique. indicating an increased difficulty in measuring the Auger peaks for large Z-values.e.and M-level transitions. Fluorescence and Auger electron yields as a function of atomic number for K shell vacancies. Auger transitions (red curve) are more probable for lighter elements. Chennai-119 . AES data can be measured for Z ≤ 50. x-ray yield becomes greater than Auger yield. such as uranium and americium. intrashell) transitions are ignored in this analysis.[6] Attempts to relate the fluorescence and Auger yields to atomic number have resulted in plots similar to figure 4. B. A clear transition from electron to photon emission is evident in this chart for increasing atomic number. using the Auger effect.Modern Techniques of Materials Characterisation 119 Figure 4. Associate Professor of Mechanical Engineering. where WX is the X-ray transition probability and WA is the Auger transition probability. Jeppiaar Trust. Joseph’s College of Engineering. Auger effects are dominant for Z < 15 while for L. AES is sensitive to the lighter elements. but complex techniques can be utilized to identify heavier elements. Coster– Kronig (i. Conversely. while X-ray yield (dotted blue curve) becomes dominant at higher atomic numbers. Auger peaks can be detected for elements as light as lithium (Z = 3). St. Lithium represents the lower limit for AES sensitivity since the Auger effect is a "three state" event necessitating at least three electrons. and unlike X-ray fluorescence.

spatially resolved chemical images. T the transmission of the analyzer. Ratios of the acquired data to standards can eliminate common terms. Sputtering removes thin outer layers of a surface so that AES can be used to determine the underlying composition. Precise expressions for the transition probability. Uses and limitations There are a number of electron microscopes that have been specifically designed for use in Auger spectroscopy. dΩ the solid angle. I(t) the electron excitation flux at depth t. based on first-order perturbation Hamiltonians. Jeppiaar Trust. Ramesh. especially the Auger yield which is related to the transition probability. sputtering is sometimes used with Auger spectroscopy to perform depth profiling experiments. Early approximations (in cm2) of the cross-section were based on the work of Worthington and Tomlin. While this value of σax is calculated for an isolated atom. rm can be established empirically and encompasses electron interactions with the matrix such as ionization due to backscattered electrons. while elemental identification is best obtained from comparison of pure samples. is the quantum mechanical overlap of the initial and final state wave functions. Chennai-119 .[4] Often.[1][3][5][7] SAM images are obtained by stepping a focused electron beam across a sample surface and measuring the intensity of the Auger peak above the background of scattered electrons. and C a function of the primary electron beam energy. [3][4][5][6] Depth profiles Compiled by : Mr. so most analyses compare measured yields with external standards of known composition.[3][6][7] Comparison techniques work best for samples of homogeneous binary materials or uniform surface layers. The intensity map is correlated to a gray scale on a monitor with whiter areas corresponding to higher element concentration. especially experimental setup characteristics and material parameters. B.α)] where α is the angle to the surface normal of the incident electron beam. with b acting as a scaling factor between 0. St. Ep. a simple modification can be made to account for matrix effects: σ(E) = σax[1 + rm(Ep. Associate Professor of Mechanical Engineering. Joseph’s College of Engineering.25 and 0.35. λ the electron escape depth. and can be used to determine element composition. In addition. can be found in Thompson and Baker. Thus the total yield can be written as: Here Nx is the number of x atoms per volume. all of these terms are not known. θ the analyzer angle.Modern Techniques of Materials Characterisation 120 Another critical quantity that determines yield of Auger electrons at a detector is the electron impact cross-section. and δt is the thickness of the layer being probed. these are termed scanning Auger microscopes (SAM) and can produce high resolution. Encompassed in these terms.

Modern Techniques of Materials Characterisation 121 are shown as either Auger peak height vs. AES is also used extensively as an evaluation tool on and off fab lines in the microelectronics industry. this type of approach limits SAM applications as well as the amount of sample material available for probing. B. AES data can be obscured by the presence of characteristic energy losses in a sample and higher order atomic ionization events. A related technique involves thinning or "dimpling" a non-conductive layer with Ar+ ions and then mounting the sample to a conductive backing prior to AES. Ramesh. they are difficult to extract from the background and in the presence of plasmon losses. However. though none of them are ideal and still make quantification of AES data difficult. such as secondary ion mass spectrometry (SIMS). Joseph’s College of Engineering. Origin of the satellites is usually attributed to multiple ionization events in an atom or ionization cascades in which a series of Compiled by : Mr. as these methods usually involve surface bombardment with either electrons or ions (i. The most common setup to minimize charging effects includes use of a glancing angle (~10°) electron beam and a carefully tuned bombarding energy (between 1. Control of both the angle and energy can subtly alter the number of emitted electrons vis-à-vis the incident electrons and thereby reduce or altogether eliminate sample charging. additional analysis through chemical sensitive surface techniques like x-ray photoelectron spectroscopy (XPS) is often required to disentangle the peaks. especially when evaluating solid specimens.5 keV and 3 keV). To complicate matters. As Auger spectra are normally weak and spread over many eV of energy. there are several factors that can limit the applicability of this technique. St. deconvolution of the two peaks becomes extremely difficult. are not applicable to AES.e.[2] Sometimes an Auger spectrum can also exhibit "satellite" peaks at welldefined off-set energies from the parent peak. Associate Professor of Mechanical Engineering.[2][5][6] In addition to charging effects. For such spectra. Electrons ejected from a solid will generally undergo multiple scattering events and lose energy in the form of collective electron density oscillations called plasmons.[3][6] One such technique involves depositing conductive pads near the analysis area to minimize regional charging. Precise depth milling through sputtering has made profiling an invaluable technique for chemical analysis of nanostructured materials and thin films. neutralization methods employed in other surface analysis techniques. depth.[2][7] If plasmon losses have energies near that of an Auger peak. As a result. Jeppiaar Trust. giving rise to a net polarity at the surface. with claims that the thinning process leaves elemental artifacts on a surface and/or creates damaged layers that distort bonding and promote chemical mixing in the sample.[10][11][12][13] Despite the advantages of high spatial resolution and precise chemical sensitivity attributed to AES. the compositional AES data is considered suspect. flood gun). Chennai-119 . the less intense Auger process may become dwarfed by the plasmon peak.[2][3] Charging results when the number of secondary electrons leaving the sample is different to the number of incident electrons. One of the most common limitations encountered with Auger spectroscopy are charging effects in non-conducting samples.[14][15] This method has been debated. Both positive and negative surface charges severely alter the yield of electrons emitted from the sample and hence distort the measured Auger peaks. while the versatility and sensitivity of the Auger process makes it a standard analytical tool in research labs. sputter time or atomic concentration vs. Several processes have been developed to combat the issue of charging.

these are distinguished from one another by the property which is measured: • • • • • • • • • Differential thermal analysis (DTA): temperature difference Differential scanning calorimetry (DSC): heat difference Thermogravimetric analysis (TGA): mass Thermomechanical analysis (TMA): dimension Dilatometry (DIL): volume Dynamic mechanical analysis (DMA) : mechanical stiffness & damping Dielectric thermal analysis (DEA): dielectric permittivity & loss factor Evolved gas analysis (EGA) : gaseous decomposition products Thermo-optical analysis(TOA) : optical properties Simultaneous Thermal Analysis (STA) generally refers to the simultaneous application of Thermogravimetry (TGA) and Differential scanning calorimetry (DSC) to one and the same sample in a single instrument. and ease of use have brought AES from an obscure nuisance effect to a functional and practical characterization technique in just over fifty years. St. which usually distort focusing in most of analysers known. Joseph’s College of Engineering. vapor pressure of the sample. heating rate.[2][3] The presence of satellites can distort the true Auger peak and/or small peak shift information due to chemical bonding at the surface. AES will continue to be a cornerstone of surface-sensitive electron-based spectroscopies. thermal contact to the sample crucible and sensor. well known CMA. Ramesh. Jeppiaar Trust. With applications both in the research laboratory and industrial settings. etc. Chennai-119 . Auger electron spectroscopy is a widely used surface analysis technique that has been successfully applied to many diverse fields ranging from gas phase chemistry to nanostructure characterization. Associate Professor of Mechanical Engineering. Sensitivity.Modern Techniques of Materials Characterisation 122 electrons are emitted as relaxation occurs for multiple core level holes. quantitative detail. Several methods are commonly used . Several studies have been undertaken to further quantify satellite peaks.). gas flow rate. Very new class of high-resolving electrostatic energy analyzers recently developed – the face-field analyzers (FFA)[17] can be used for remote electron spectroscopy of distant surfaces or surfaces with large roughness or even with deep dimples. These instruments are designed as if to be specifically used in combined scanning electron microscopes (SEMs). The information gathered can even be enhanced by coupling the STA instrument to an Evolved Gas Analyzer (EGA) like Fourier transform infrared spectroscopy (FTIR) or Mass Spectometry (MS). for example. B. Thermal analysis Thermal analysis is a branch of materials science where the properties of materials are studied as they change with temperature. radiation effect.[1] Compiled by : Mr. The test conditions are perfectly identical for the TGA and DSC signals (same atmosphere. "FFA" in principle have no perceptible end-fields.[16] Despite these sometimes substantial drawbacks.

Joseph’s College of Engineering. the weight loss curve may require transformation before results may be interpreted. Again. Measurements may be carried out in air or under an inert gas (e. interpretation is limited without further modifications and deconvolution of the overlapping peaks may be required. atmosphere). Ramesh. Associate Professor of Mechanical Engineering. St. Thermogravimetric analysis Thermogravimetric analysis or thermal gravimetric analysis (TGA) is a type of testing that is performed on samples to determine changes in weight in relation to change in temperature. As many weight loss curves look similar. Many of the basic engineering data for modelling such systems comes from measurements of heat capacity and Thermal conductivity.g. nitrogen or helium). less-common.measurements are often made at different temperatures so that these experiments can be considered to come under the auspices of Thermal Analysis. the level of inorganic and organic components in materials.Modern Techniques of Materials Characterisation 123 Other. B. Chennai-119 . Reducing or reactive atmospheres have also been used and measurements are even carried out with the sample surrounded by water or other liquids. In addition to controlling the temperature of the sample. The essence of all these techniques is that the sample's response is recorded as a function of temperature (and time). Compiled by : Mr. and temperature change. methods measure the sound or light emission from a sample. Thermal Analysis is also often used as a term for the study of Heat transfer through structures. By controlling the temperature of the heated tip and/or the sample a form of spatially resolved thermal analysis can be carried out. it is also important to control its environment (e. Inverse gas chromatography is a technique which studies the interaction of gases and vapours with a surface .g. to determine degradation temperatures. TGA is commonly employed in research and testing to determine characteristics of materials such as polymers. absorbed moisture content of materials. Jeppiaar Trust. More advanced temperature profiles have been developed which use an oscillating (usually sine or square wave) heating rate (Modulated Temperature Thermal Analysis) or modify the heating rate in response to changes in the system's properties (Sample Controlled Thermal Analysis). It is usual to control the temperature in a predetermined way . Atomic force microscopy uses a fine stylus to map the topography and mechanical properties of surfaces to high spatial resolution.either by a continuous increase or decrease in temperature at a constant rate (linear heating/cooling) or by carrying out a series of determinations at different temperatures (stepwise isothermal measurements). Such analysis relies on a high degree of precision in three measurements: weight. A derivative weight loss curve can be used to tell the point at which weight loss is most apparent. or the mechanical relaxation in a stressed specimen. temperature. or the electrical discharge from a dielectric material.

B. degradation).g.. Simultaneous TGA-DTA/DSC measures both heat flow and weight changes (TGA) in a material as a function of temperature or time in a controlled atmosphere. Chennai-119 . and solvent residues. It is also often used to estimate the corrosion kinetics in high temperature oxidation. Simultaneous measurement of these two material properties not only improves productivity but also simplifies interpretation of the results. The complementary information obtained allows differentiation between endothermic and exothermic events which have no associated weight loss (e.[1] The sample is placed in a small electrically heated oven with a thermocouple to accurately measure the temperature.g. A different process using a quartz crystal microbalance has been devised for measuring smaller samples on the order of a microgram (versus milligram with conventional TGA). St. Ramesh. Joseph’s College of Engineering. Fig. melting and crystallization) and those which involve a weight loss (e. Equipment The analyzer usually consists of a high-precision balance with a pan (generally platinum) loaded with the sample. The atmosphere may be purged with an inert gas to prevent oxidation or other undesired reactions.: A typical TGA system Compiled by : Mr. Associate Professor of Mechanical Engineering.Modern Techniques of Materials Characterisation 124 decomposition points of explosives.. Jeppiaar Trust. A computer is used to control the instrument.

Ramesh. Fig. A method known as hi-resolution TGA is often employed to obtain greater accuracy in areas where the derivative curve peaks. curve smoothing and other operations may be done such as to find the exact points of inflection. Chennai-119 .Modern Techniques of Materials Characterisation 125 Methodology Analysis is carried out by raising the temperature of the sample gradually and plotting weight (percentage) against temperature. Jeppiaar Trust. Associate Professor of Mechanical Engineering. After the data are obtained. St. Several modern TGA devices can vent burnoff to an infrared spectrophotometer to analyze composition. temperature increase slows as weight loss increases. B. The temperature in many testing methods routinely reaches 1000°C or greater. Joseph’s College of Engineering. This is done so that the exact temperature at which a peak occurs can be more accurately identified. In this method. but the oven is so greatly insulated that an operator would not be aware of any change in temperature even if standing directly in front of the device. : Thermogram of calcium oxalate Compiled by : Mr.

Joseph’s College of Engineering. Apparatus A DTA consists of a sample holder comprising thermocouples. a temperature programmer. Changes in the sample. Ramesh. St. the material under study and an inert reference are made to undergo identical thermal cycles. Chennai-119 .Modern Techniques of Materials Characterisation 126 Differential thermal analysis Differential thermal analysis (or DTA) is a thermoanalytic technique. can be detected relative to the inert reference. crystallization. and a recording system. there will be a brief deflection of the voltmeter if the sample is undergoing a phase transition. but be incorporated as latent heat in the material changing phase.[5][6][7][8] DTA may be used in cement chemistry. a furnace. Thus. The area under a DTA peak is the enthalpy change and is not affected by the heat capacity of the sample. As the temperature is increased.[13][14] Compiled by : Mr. or against temperature (DTA curve or thermogram).[11] DTA curves may also be used to date bone remains[12] or to study archaeological materials. Jeppiaar Trust. which provides both mass loss and thermal information. heat change measurements and decomposition in various atmospheres.[9] mineralogical research[10] and in environmental studies. simultaneously with mass loss. even these instruments are being replaced by true TGA-DSC instruments that can provide the temperature and heat flow of the sample. either exothermic or endothermic. DTA is widely used in the pharmaceutical[3][4] and food industries.[2] Today's Instruments In today’s market most manufactures no longer make a true DTA but rather have incorporated this technology into a Thermogravimetric analysis(TGA). The key feature is the existence of two thermocouples connected to a voltmeter. Associate Professor of Mechanical Engineering. B. sample containers and a ceramic or metallic block. melting and sublimation. Applications A DTA curve can be used only as a finger print for identification purposes but usually the applications of this method are the determination of phase diagrams. while the other is placed in a sample of the material under study. a DTA curve provides data on the transformations that have occurred. similar to differential scanning calorimetry. One thermocouple is placed in an inert material such as Al2O3. such as glass transitions. With today’s advancements in software. In DTA. while recording any temperature difference between sample and reference.[1] This differential temperature is then plotted against time. This occurs because the input of heat will raise the temperature of the inert substance.

such as glass transitions. There are two different conventions: exothermic reactions in the sample shown with a Compiled by : Mr. Both the sample and reference are maintained at nearly the same temperature throughout the experiment. Many modern commercial DTA are called heat flux DSC. For example. Whether less or more heat must flow to the sample depends on whether the process is exothermic or endothermic.S. St. The technique was developed by E. Generally. DSC curves The result of a DSC experiment is a curve of heat flux versus temperature or versus time. Joseph’s College of Engineering. In this technique it is the heat flow to the sample and reference that remains the same rather than the temperature. differential scanning calorimeters are able to measure the amount of heat absorbed or released during such transitions. DSC may also be used to observe more subtle phase changes. It is widely used in industrial settings as a quality control instrument due to its applicability in evaluating sample purity and for studying polymer curing. Likewise. Associate Professor of Mechanical Engineering. When the sample and reference are heated identically phase changes and other thermal processes cause a difference in temperature between the sample and reference. Chennai-119 . the temperature program for a DSC analysis is designed such that the sample holder temperature increases linearly as a function of time. Watson and M. The reference sample should have a well-defined heat capacity over the range of temperatures to be scanned. This is due to the absorption of heat by the sample as it undergoes the endothermic phase transition from solid to liquid. By observing the difference in heat flow between the sample and reference. Ramesh. more or less heat will need to flow to it than the reference to maintain both at the same temperature. O'Neill in 1960.[3][4][5] DTA An alternative technique. Jeppiaar Trust. as the sample undergoes exothermic processes (such as crystallization) less heat is required to raise the sample temperature. B.[1] and introduced commercially at the 1963 Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy.[2] Detection of phase transitions The basic principle underlying this technique is that. is differential thermal analysis (DTA). The term DSC was coined to describe this instrument which measures energy directly and allows precise measurements of heat capacity. which shares much in common with DSC. as a solid sample melts to a liquid it will require more heat flowing to the sample to increase its temperature at the same rate as the reference. Both DSC and DTA provide similar information.J. when the sample undergoes a physical transformation such as phase transitions.Modern Techniques of Materials Characterisation 127 Differential scanning calorimetry Differential scanning calorimetry or DSC is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature.

Chennai-119 .[4] Applications Fig. This curve can be used to calculate enthalpies of transitions. B. St. This is known as the crystallization temperature (Tc).[3] Compiled by : Mr. At some point the molecules may obtain enough freedom of motion to spontaneously arrange themselves into a crystalline form. Ramesh. Using this technique it is possible to observe fusion and crystallization events as well as glass transition temperatures Tg. and results in a peak in the DSC signal.:A schematic DSC curve demonstrating the appearance of several common features Differential scanning calorimetry can be used to measure a number of characteristic properties of a sample. depending on the kind of technology used in the experiment. an amorphous solid will become less viscous. It can be shown that the enthalpy of transition can be expressed using the following equation: ΔH = KA where ΔH is the enthalpy of transition.[3][4][5][6] Glass transitions may occur as the temperature of an amorphous solid is increased. as well as other chemical reactions. This is done by integrating the peak corresponding to a given transition. The calorimetric constant will vary from instrument to instrument. DSC can also be used to study oxidation. The ability to determine transition temperatures and enthalpies makes DSC a valuable tool in producing phase diagrams for various chemical systems. Jeppiaar Trust. This transition from amorphous solid to crystalline solid is an exothermic process. As the temperature increases the sample eventually reaches its melting temperature (Tm). The melting process results in an endothermic peak in the DSC curve. and can be determined by analyzing a well-characterized sample with known enthalpies of transition. Associate Professor of Mechanical Engineering. These transitions appear as a step in the baseline of the recorded DSC signal. no formal phase change occurs. K is the calorimetric constant. This is due to the sample undergoing a change in heat capacity.[3][5] As the temperature increases.Modern Techniques of Materials Characterisation 128 positive or negative peak. and A is the area under the curve. Joseph’s College of Engineering.

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