UNIT-V

1.AFM
HOW DOES THE AFM WORK?

AFM provides a 3D profile of the surface on a nanoscale, by measuring forces between a sharp probe (<10 nm) and surface at very short distance (0.2-10 nm probe-sample separation). The probe is supported on a flexible cantilever. The AFM tip gently touches the surface and records the small force between the probe and the surface

Schematic of the major components of an AFM showing the feedback loop for Tapping Mode operation.

Modes of operation
1. Contact Mode
In the so-called contact-AFM mode, the tip makes soft physical contact with thesurface of the sample. The deflection of the cantilever Dx is proportional to theforce acting on the tip, via Hooks law, F=-k. _x, where k is the spring constant ofthe cantilever. In contact-mode the tip either scans at a constant small height above the surface or under the conditions of a constant force. In the constant height mode the height of the tip is fixed, whereas in the constant-force

mode the deflection of the cantilever is fixed and the motion of the scanner in z-direction is recorded. By using contact-mode AFM, even atomic resolution images are obtained. For contact mode AFM imaging, it is necessary to have a cantilever which is soft enough to be deflected by very small forces and has a high enough resonant frequency to not be susceptible to vibrational instabilities. Silicon Nitride tips are used for contact mode. In these tips, there are 4 cantilever with different geometries attached to each substrate, resulting in 4 different spring constants (Figure 6).
Figure 6. Probe with four different cantilevers with different spring constants (N/m .

To avoid problems caused by capillary forces which are generated by a liquid contamination layer usually present on surfaces in air, the sample can be studied while immersed in a liquid. This procedure is especially beneficial for biological samples.

2.Non Contact Mode

In this mode, the probe operates in the attractive force region and the tip-sample interaction is minimized. The use of non-contact mode allowed scanning without influencing the shape of the sample by the tip-sample forces. In most cases, the cantilever of choice for this mode is the one having high spring constant of 20- 100 N/m so that it does not stick to the sample surface at small amplitudes. The tips mainly used for this mode are silicon probes.

Tapping Mode (intermittent contact Mode)

The force measured by AFM can be classified into long-range forces and shortrange forces. The first class dominates when we scan at large distances from the surface and they can be Van der Waals force, capillary forces (due to the water layer often present in an ambient environment). When the scanning is in contact with the surface the short range forces are very important, in particular the quantum mechanical forces (Pauli Exclusion Principle forces). In tapping modeAFM the cantilever is oscillating close to its resonance frequency. An electronic feedback loop ensures that the oscillation amplitude remains constant, such that a constant tip-sample interaction is maintained during scanning. Forces that act between the sample and the tip will not

only cause a change in the oscillation amplitude, but also change in the resonant frequency and phase of the cantilever. The amplitude is used for the feedback and the vertical adjustments of the piezoscanner are recorded as a height image. Simultaneously, the phase changes are presented in the phase image (topography). The advantages of the tapping mode are the elimination of a large part of permanent shearing forces and the causing of less damage to the sample surface, even with stiffer probes. Different components of the sample which exhibit difference adhesive and mechanical properties will show a phase contrast and therefore even allow a compositional analysis. For a good phase contrast, larger tip forces are of advantage, while minimization of this force reduces the contact area and facilitates high-resolution imaging. So in applications it is necessary to choose the right values matching the objectives. Silicon probes are used primarily for Tapping Mode applications. Table 1 is a summary of the main characteristics of the three modes explained before. In these modes we can work in different environments: air, liquid and vacuum. In contact mode the tip touches the sample surface, which leads to a high force and allows manipulation of the sample. The disadvantage is that the AFM tip may be contaminated by the sample. The opposite happens in the noncontact mode, where the tip stays at a distance above the sample. In tapping mode the tip touches the surface periodically therefore manipulation of the sample, as well as contamination of the tip is possible.

Operation mode Contact mode

tip loading force contact with sample surface manipulation sample contamination of AFM tip yes of yes low high yes

Non-contact mode
low no

Tapping mode
low periodical

no no

yes yes

Table 1. Properties of the different operation modes in AFM.

4.4. Advantages and Disadvantages of AFM Modes

Contact Mode AFM

Advantages: - High scan speeds. - Atomic resolution is possible. - Easier scanning of rough samples with extreme changes in vertical topography. Disadvantages: - Lateral forces can distort the image. - Capillary forces from a fluid layer can cause large forces normal to the tipsample interaction. - Combination of these forces reduces spatial resolution and can cause damage to soft samples. Non-contact Mode AFM Advantage: - Low force is exerted on the sample surface and no damage is caused to soft samples Disadvantages: - Lower lateral resolution, limited by tip-sample separation. - Slower scan speed to avoid contact with fluid layer. - Usually only applicable in extremely hydrophobic samples with a minimal fluid layer.
Tappping Mode AFM

Advantages: - Higher lateral resolution (1 nm to 5 nm). - Lower forces and less damage to soft samples in air. - Almost no lateral forces. Disadvantage: - Slower scan speed than in contact mode.
LIMITATIONS OF AFM

The AFM can be used to study a wide variety of samples (i.e. plastic, metals, glasses, semiconductors, and biological samples such as the walls of cells and bacteria). Unlike STM or scanning electron microscopy it does not require a conductive sample. However there are limitations in achieving atomic resolution. The physical probe used in AFM imaging is not ideally sharp. As a consequence, an AFM image does not reflect the true sample topography, but

rather represents the interaction of the probe with the sample surface. This is called tip convolution.

Scanning Electron Microscopy (SEM)

Susan Swapp, University of Wyoming

What is Scanning Electron Microscopy (SEM)

A typical SEM instrument, showing the electron column, sample chamber, EDS detector, electronics console, and visual display monitors.

The scanning electron microscope (SEM) uses a focused beam of high-energy electrons to generate a variety of signals at the surface of solid specimens. The signals that derive from electron-sample interactions reveal information about the sample including external morphology (texture), chemical composition, and crystalline structure and orientation of materials making up the sample. In most applications, data are collected over a selected area of the surface of the sample, and a 2-dimensional image is generated that displays spatial variations in these properties. Areas ranging from approximately 1 cm to 5 microns in width can be imaged in a scanning mode using conventional SEM techniques (magnification ranging from 20X to approximately 30,000X, spatial resolution of 50 to 100 nm). The SEM is also capable of performing analyses of selected point locations on the sample; this approach is especially useful in qualitatively or semi-quantitatively determining chemical compositions (using EDS), crystalline structure, and crystal orientations (using EBSD). The design and function of the SEM is very similar to the EPMA and considerable overlap in capabilities exists between the two instruments.

Fundamental Principles of Scanning Electron Microscopy (SEM)

Accelerated electrons in an SEM carry significant amounts of kinetic energy, and this energy is dissipated as a variety of signals produced by electron-sample interactions when the incident electrons are decelerated in the solid sample. These signals include secondary electrons (that produce SEM images), backscattered electrons (BSE), diffracted backscattered electrons (EBSD that are used to determine crystal structures and orientations of minerals), photons (characteristic X-rays that are used for elemental analysis and continuum X-rays), visible light (cathodoluminescence--CL), and heat.

Secondary electrons and backscattered electrons are commonly used for imaging samples: secondary electrons are most valuable for showing morphology and topography on samples and backscattered electrons are most valuable for illustrating contrasts in composition in multiphase samples (i.e. for rapid phase discrimination). X-ray generation is produced by inelastic collisions of the incident electrons with electrons in discrete ortitals (shells) of atoms in the sample. As the excited electrons return to lower energy states, they yield X-rays that are of a fixed wavelength (that is related to the difference in energy levels of electrons in different shells for a given element). Thus, characteristic Xrays are produced for each element in a mineral that is "excited" by the electron beam. SEM analysis is considered to be "non-destructive"; that is, x-rays generated by electron interactions do not lead to volume loss of the sample, so it is possible to analyze the same materials repeatedly.

Scanning Electron Microscopy (SEM) Instrumentation - How Does It Work?

Essential components of all SEMs include the following:

Electron Source ("Gun") Electron Lenses Sample Stage Detectors for all signals of interest Display / Data output devices Infrastructure Requirements: o o o o
Power Supply Vacuum System Cooling system Vibration-free floor

Room free of ambient magnetic and electric fields

SEMs always have at least one detector (usually a secondary electron detector), and most have additional detectors. The specific capabilities of a particular instrument are critically dependent on which detectors it accommodates.

Applications

The SEM is routinely used to generate high-resolution images of shapes of objects (SEI) and to show spatial variations in chemical compositions: 1) acquiring elemental maps or spot chemical analyses using EDS, 2)discrimination of phases based on mean atomic number (commonly related to relative density) using BSE, and 3) compositional maps based on differences in trace element "activitors" (typically transition metal and Rare Earth elements) using CL. The SEM is also widely used to identify phases based on qualitative chemical analysis and/or crystalline structure. Precise measurement of very small features and objects down to 50 nm in size is also accomplished using the SEM. Backescattered electron images (BSE) can be used for rapid discrimination of phases in multiphase samples. SEMs equipped with diffracted backscattered electron detectors (EBSD) can be used to examine microfabric and crystallographic orientation in many materials.

Strengths and Limitations of Scanning Electron Microscopy (SEM)?

Strengths
There is arguably no other instrument with the breadth of applications in the study of solid materials that compares with the SEM. The SEM is critical in all fields that require characterization of solid materials. While this contribution is most concerned with geological applications, it is important to note that these applications are a very small subset of the scientific and industrial applications that exist for this instrumentation. Most SEM's are comparatively easy to operate, with user-friendly "intuitive" interfaces. Many applications require minimal sample preparation. For many applications, data acquisition is rapid (less than

5 minutes/image for SEI, BSE, spot EDS analyses.) Modern SEMs generate data in digital formats, which are highly portable.

Limitations
Samples must be solid and they must fit into the microscope chamber. Maximum size in horizontal dimensions is usually on the order of 10 cm, vertical dimensions are generally much more limited and rarely exceed 40 mm. For most instruments samples must be stable in a vacuum on the order of 10-5 - 10-6 torr. Samples likely to outgas at low pressures (rocks saturated with hydrocarbons, "wet" samples such as coal, organic materials or swelling clays, and samples likely to decrepitate at low pressure) are unsuitable for examination in conventional SEM's. However, "low vacuum" and "environmental" SEMs also exist, and many of these types of samples can be successfully examined in these specialized instruments. EDS detectors on SEM's cannot detect very light elements (H, He, and Li), and many instruments cannot detect elements with atomic numbers less than 11 (Na). Most SEMs use a solid state xray detector (EDS), and while these detectors are very fast and easy to utilize, they have relatively poor energy resolution and sensitivity to elements present in low abundances when compared to wavelength dispersive x-ray detectors (WDS) on most electron probe microanalyzers (EPMA). An electrically conductive coating must be applied to electrically insulating samples for study in conventional SEM's, unless the instrument is capable of operation in a low vacuum mode.

X-ray Powder Diffraction (XRD)

What is X-ray Powder Diffraction (XRD)

X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase identification of a crystalline material and can provide information on unit cell dimensions. The analyzed material is finely ground, homogenized, and average bulk composition is determined.

Fundamental Principles of X-ray Powder Diffraction (XRD)

Constructive interference occurs only when n l = AB + BC AB=BC n l = 2AB Sinq=AB/d

AB=dsinq n l =2dsinq l = 2dhklsinqhkl

Max von Laue, in 1912, discovered that crystalline substances act as three-dimensional diffraction gratings for X-ray wavelengths similar to the spacing of planes in a crystal lattice. X-ray diffraction is now a common technique for the study of crystal structures and atomic spacing. X-ray diffraction is based on constructive interference of monochromatic X-rays and a crystalline sample. These X-rays are generated by a cathode ray tube, filtered to produce monochromatic radiation, collimated to concentrate, and directed toward the sample. The interaction of the incident rays with the sample produces constructive interference (and a diffracted ray) when conditions satisfy Bragg's Law (n=2d sin ). This law relates the wavelength of electromagnetic radiation to the diffraction angle and the lattice spacing in a crystalline sample. These diffracted X-rays are then detected, processed and counted. By scanning the sample through a range of 2angles, all possible diffraction directions of the lattice should be attained due to the random orientation of the powdered material. Conversion of the diffraction peaks to d-spacings allows identification of the mineral because each mineral has a set of unique d-spacings. Typically, this is achieved by comparison of d-spacings with standard reference patterns. All diffraction methods are based on generation of X-rays in an X-ray tube. These X-rays are directed at the sample, and the diffracted rays are collected. A key component of all diffraction is the angle between the incident and diffracted rays. Powder and single crystal diffraction vary in instrumentation beyond this.

X-ray Powder Diffraction (XRD) Instrumentation - How Does It Work?

X-ray diffractometers consist of three basic elements: an X-ray tube, a sample holder, and an X-ray detector. X-rays are generated in a cathode ray tube by heating a filament to produce electrons, accelerating the electrons toward a target by applying a voltage, and bombarding the target material with electrons. When electrons have sufficient energy to dislodge inner shell electrons of the target material, characteristic X-ray spectra are produced. These spectra consist of several components, the most common being K and K. K consists, in part, of K1 and K2. K1 has a slightly shorter wavelength and twice the intensity as K2. The specific wavelengths are characteristic of the target material (Cu, Fe, Mo, Cr). Filtering, by foils or crystal monochrometers, is required to produce monochromatic X-rays needed for diffraction. K1and K2 are sufficiently close in wavelength such that a weighted average of the two is used. Copper is the most common target material for single-crystal diffraction, with CuK radiation = 1.5418. These X-rays are collimated and directed onto the sample. As the sample and detector are rotated, the intensity of the reflected X-rays is recorded. When the geometry of the incident X-rays impinging the sample satisfies the Bragg Equation, constructive interference occurs and a peak in intensity occurs. A detector records and processes this X-ray signal

and converts the signal to a count rate which is then output to a device such as a printer or computer monitor.

X-ray powder diffractogram. Peak positions occur where the X-ray beam has been diffracted by the crystal lattice. The unique set of d-spacings derived from this patter can be used to 'fingerprint' the mineral. Details The geometry of an X-ray diffractometer is such that the sample rotates in the path of the collimated X-ray beam at an angle while the X-ray detector is mounted on an arm to collect the diffracted Xrays and rotates at an angle of 2. The instrument used to maintain the angle and rotate the sample is termed a goniometer. For typical powder patterns, data is collected at 2 from ~5 to 70, angles that are preset in the X-ray scan.

Applications
X-ray powder diffraction is most widely used for the identification of unknown crystalline materials (e.g. minerals, inorganic compounds). Determination of unknown solids is critical to studies in geology, environmental science, material science, engineering and biology. Other applications include:

characterization of crystalline materials identification of fine-grained minerals such as clays and mixed layer clays that are difficult
to determine optically

determination of unit cell dimensions measurement of sample purity

With specialized techniques, XRD can be used to:

determine crystal structures using Rietveld refinement determine of modal amounts of minerals (quantitative analysis) characterize thin films samples by:

o o o o

determining lattice mismatch between film and substrate and to inferring stress and strain determining dislocation density and quality of the film by rocking curve measurements measuring superlattices in multilayered epitaxial structures determining the thickness, roughness and density of the film using glancing incidence X-ray reflectivity measurements make textural measurements, such as the orientation of grains, in a polycrystalline sample

Strengths and Limitations of X-ray Powder Diffraction (XRD)?

Strengths
Powerful and rapid (< 20 min) technique for identification of an unknown mineral In most cases, it provides an unambiguous mineral determination Minimal sample preparation is required XRD units are widely available Data interpretation is relatively straight forward

Limitations
Homogeneous and single phase material is best for identification of an unknown Must have access to a standard reference file of inorganic compounds (d-spacings, hkls) Requires tenths of a gram of material which must be ground into a powder For mixed materials, detection limit is ~ 2% of sample For unit cell determinations, indexing of patterns for nonisometric crystal systems is complicated Peak overlay may occur and worsens for high angle 'reflections'

TEM

Transmission Electron Microscope In Transmission Electron Microscope (TEM), a thin specimen is irradiated with an electron

beam of uniform current density : the electron energy is in the range of 60 -150 KeV (usually, 100 keV), or 200 KeV-1 MeV in case of the high voltage electron microscope (HVEM) or high resolution transmission electron microscope (HRTEM).

The electrons are emitted in the electron gun by the 'thermionic emission' from tungsten cathodes or LaB6 rods or by the field emission from the pointed tungsten filaments. The latter are used when high gun brightness is needed. A two-stage condenser-lens system permits the variation of

the illuminated aperture, and the area of the specimen is imaged with a three- or four-stage lens system onto a fluorescent screen. The image can be recorded in emulsion inside the vacuum. The lens aberrations of the objective lens are so great that it is necessary to work with very small objective apertures, of the order of 10-25 mrad, to achieve a resolution of the order of 0.2 nm 0.5 nm. The bright-field contrast is produced either by the adsorption of the electrons scattered through the angles, which are larger than the objective aperture (i.e. scattering contrast), or by the interference between the scattered wave and the incident wave at the image point (i.e. phase contrast). The phase of the electron waves behind the specimen is modified by the wave aberration of the objective lens. This aberration, and the energy spread of the electron gun, which is of the order of 1-2 eV, limits the contrast transfer (i.e. Fourier transform) of high spatial frequencies. The electrons interact strongly with the atoms by elastic and inelastic scattering. The specimen must therefore be very thin, typically of the order of 5 nm - 0.5 m for 100 KeV electrons, depending on the density and the elemental composition of the object, and the resolution desired. The special preparation techniques are needed for this purpose. The TEM can provide high resolution, because the elastic scattering is an interaction process that is highly localized to the region occupied by the screened Coulomb potential of an atomic nucleus, whereas the inelastic scattering is more diffuse. It spreads out over about a nanometer. A further capability of the modern TEM is the formation of very small electron probes, 2 nm - 5 nm in diameter, by means of a three-stage condenser-lens system, the last lens field of which is the objective pre-field in front of the specimen. This enables the instrument to operate in a scanning transmission mode with a resolution determined by the electron probe-diameter. This has the advantage for imaging thick or crystalline specimens, and for recording secondary electrons and back-scattered electrons, cathode-luminescence and electron-beam-induced currents. The main advantage of equipping a TEM with a STEM attachment is the formation of a very small electron probe, with which the elemental analysis and micro-diffraction can be performed on extremely small areas. The X-ray production in thin foils is confined to small volumes excited by the electron probe, which is only slightly broadened by the multiple scattering. Therefore, a better spatial resolution is obtainable for the segregation effects at crystal interfaces or precipitates, for example, than in an X-ray micro-analyser with the bulk specimens, where the spatial resolution is limited to 0.1- 1 mm by the diameter of the electron-diffusion cloud.

2.6.4. Sample Preparation for TEM Study For TEM study, the cylindrical specimen of 3 mm diameter and 1 mm high, which is a suitable size for the fabrication of TEM specimens, is cut directly from the bulk sintered pellets of alpha silicon carbide. The specimens are prepared from these samples by mechanical thinning to 75 m, which is followed by dimpling and subsequent low-energy (5 to 6 kV) and low angle (15) Ar+ ion beam milling. The films are then examined in a transmission electron microscope (Model - TEM-400CX, JEOL,Japan), which was operated at an accelerating voltage of 100 KeV.