V Chapter Contrast in Electron Optical Images

Characteristic fringe contrast from stacking faults in silicon under varying diffraction conditions: (a) BF, (b) DF, ( c) & (d) Asymmetry of DF image for s 0.

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Contrast is based on 1. Mass thickness (t) applicable to shadowed replicas; provides valuable information on surface structure 2. Diffraction from localised regions useful for the study of crystal defects 3. Phase differences used to form interference fringes; under restricted conditions fringe spacing is the d spacing. basis for high resolution microscopy The size and positioning of the objective aperture for obtaining images based on diffraction contrast and phase contrast are shown in Fig. 5.1. The aperture covers the (000) spot or one of the intense diffracted spots for the formation of bright field and dark field images. The aperture is large and covers the (000) and several diffracted spots (Fig. 5.1b) for the formation of phase contrast images.

Fig. 5.1: Size and Position of Objective Aperture for (a) Diffraction and (b) Phase Interference Contrast Mass Thickness Contrast depends on t where is the density and t is the thickness. A bright field image of latex particles supported on an evaporated carbon film is shown in Fig. 5.2(a). The spherical latex particles appear dark. The contrast from these particles is considerably enhanced by shadowing with palladium, a heavy element. In this case a small amount of palladium is evaporated at angle; the particles cast a shadow in their vicinity, giving rise to a considerable difference in density (Fig. 5.2b). A phase contrast image of (111) Planes in a crystallised area of an amorphous Ge film is shown in Fig. 5.3.

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Fig. 5.2 (a) : Bright field image of latex particles on carbon, (b) Pd-shadowed images with enhanced contrast.

Fig. 5.3: Phase Contrast Image of (111) Planes in a crystallised area of an amorphous Ge film. Theories of Diffraction contrast Two theories have been postulated to explain the diffraction effects 1. Kinematical theory: Columnar approximation Two beam condition s >> 0 Absorption of electrons in sample neglected

2. Dynamical theory Takes absorption into account Takes s = 0 into account

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Neglecting absorption of electrons in the sample and for conditions of s>>0 (kinematic conditions), the intensity of the diffracted beam, Ig, can be expressed as

Ig = (/g)2 sin2(ts)/(s)2
where g is the extinction distance and is a constant for a given material, t is the thickness of the specimen and s is the deviation from Bragg diffraction conditions. g is related to the structure factor Fg by the relationship,

g = V(cos)/ Fg,
where V is the volume of the unit cell and Fg is the structure factor. The intensity of the directly transmitted electrons (It) is given by

It = 1 - I g
The intensity distribution in direct and diffracted waves is shown in Fig. 5.4. The expression for Ig indicates that even in perfect crystals change in thickness or deviation from diffraction conditions (change in s) can give rise to contrast - thickness and bend contours (Figs. 5.5 to 5.7).

Fig. 5.4: Intensity distribution in direct & diffracted waves

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Fig. 5.5: BF image of Al Showing Thickness Fringes: s ~ 0 and Electron Beam Direction is Close to [112].

Fig. 5.6: Thickness Fringes in a Wedge Shaped Aluminium Sample: (a) BF, (b) DF g [002], (c) Large tilt no fringes

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Fig. 5.7: Bend Contours in Stainless Steel Taking absorption of electrons in the specimen into account, the diffracted intensity (under dynamical conditions) is given by the equation,

Ig = sin2(ts')/(s')2
s' is the effective deviation parameter related s by the expression,

s' = [s2 + (1/)2]1/2 .

The variation in intensity with s under kinematical and dynamic conditions is shown in Fig. 5.8. When absorption is taken into account (the realistic condition), the diffracted intensity attains a peak value when s is slightly away from zero.

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Fig. 5.8: Variation of diffracted intensity with s (deviation from Bragg diffraction conditions) under kinematic and dynamical conditions. When defects are present, there is a change in the expression for intensity, with the introduction of an additional term g.R (g is the operating reflection and R is the displacement vector associated with the defect). R is the Burgers vector when the defects under consideration are dislocations. When g.R is equal to zero there is no change in the diffracted intensity, i.e. the defect is invisible. The images obtained from dislocations can vary depending on the diffraction conditions; in particular variations in s can cause Table 5.1: Contrast from dislocations for s ~ 0 and s >> 0. s~0 BF image shows oscillatory contrast, particularly prominent with small g Max. dislocation width, ~g/3 (~10 -20nm); large width poses problems in quantitative measurements Dislocation image coincides with dislocation core Image easily visible; stronger contrast for g.b = 2 than that for g.b = 1 Double images for g.b = 2 and single image for g.b = 1; can be used for b magnitude determination 77 s>> 0 BF image shows dark line in bright background with no oscillations Sharp narrow bright image; forms the basis for weak beam microscopy Image lies on one side of the line; image shift depends on (g.b)s Image becomes less intense and g.b = 1 can be mistaken for g.b = 0; for g.b = 2 strong visibility-

changes in images. This is illustrated in Figs. 5.9 to 5.12. Oscillatory contrast associated with dislocations (Fig. 5.9) at s ~ 0 disappears when large values of s are used. Double images obtained when g.b = 2 and s ~ 0 should not be confused with superdislocations found in ordered alloys (Fig. 5.10). The image of a dislocation in a centro-symmetic crystal reverses top to bottom and side to side if g is reversed (Fig. 5.11). A dislocation dipole (closely spaced pair of dislocations of opposite sign) gives images which have a centre of inversion (Fig. 5.12).

Fig. 5.9: Influence of Variation in s on Contrast from Dislocations: (a) & (b) Oscillations for small s, ( c) & (d) Large s Minimised oscillations.

Fig. 5.10: BF Image Double Images for dislocations (a) when g.b = 2 and s ~ 0 and (b) s> 0.

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Fig. 5.11: BF Image Influence of Reversing g on dislocation Images (Stainless Steel)

Fig. 5.12: BF Image (Stainless Steel): Effect of Reversal of g on Contrast from a Dislocation Dipole The applications of transmission electron microscopy for the study of dislocations are illustrated with steels (Fig. 5.13 and 5.14). The dislocation structure in retained austenite in a martensitic steel is shown in Fig. 5.13(a). The dislocations are wavy in nature; their density can be estimated by standard quantitative microscopy techniques and from determination of the thickness of the electron microscope sample (thin foil). The microstructure of the same steel shows helical dislocations in the tempered condition (Fig. 5.13b); note that helical dislocations are formed by the condensation of point defects or their clusters on screw dislocations. Cold working leads to a significant increase in dislocation density and the microstructure is characterized by heavily dislocated regions. Annealing of the cold worked metal proceeds through the stages of recovery and recrystallisation where the rearrangement of dislocations and formation of

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strain-free grains take place at the expense of the heavily strained regions. This is illustrated in Fig. 5.14

(a)

(b)

Fig. 5.13: (a) Fe-4Mo-0,2C martensitic steel solution treated and rapidly cooled with dislocations in retained austenite, (b) Fe-4Mo-0.2C martensitic steel tempered, with dislocation helices in ferrite

Fig. 5.14: (a) Austenitic stainless steel, cold worked and lightly annealed showing recrystallized and deformed grains and some stacking fault ribbons, (b) "302AA" austenitic stainless steel, cold worked, annealed at 704C for 1h, showing deformed and recrystallized grains.

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Contrast from perfect dislocations As pointed out earlier contrast from line defects depends on g.b. As an illustration we can consider unit or perfect dislocations in a FCC crystal. The Burgers vector of unit dislocations lying on the (111) plane are a/2[110], a/2[101], a/2[011], a/2[1-10], a/2[01-1] and [1-10]. ( -1 should read as bar 1). The dot product g.b is zero for certain values of g and b. In this condition the dislocation is invisible. While the screw dislocation is invisible, there may be a faint residual contrast from the edge dislocation. This will be illustrated for three operating reflections, [111], [200] and [220) and for the unit dislocations lying on the (111) plane of a FCC crystal. The details are shown in Table 5.2. Table 5.2 Values of g.b for unit dislocations in FCC structure B a/2[110] a/2[101] a/2[011] a/2[1-10] a/2[10-1] a/2[0-11] g.b for g (111) a a a 0 0 0 g.b for g (200) a a 0 -a a 0 g.b for g (220) 2a A A 0 A -a

Note that when imaging with (111) reflection, half the dislocations will be invisible or faintly visible. The invisibility criterion can be used to work out the Burgers vector of a dislocation line; the vector is given by the cross product of the indices of two reflections for which the dislocation is invisible. Recall the discussion on tilting experiments in Chapter IV for exciting various reflections. Partial dislocations and stacking faults Partial dislocations can be of the Shockley and Frank type. In a FCC crystal the formation of Shockley partials occurs by the shear of atoms a shown in Fig. 5.15. Movement along the [110] direction can be split up into two components both of which have indices of the type [112]. Thus the unit dislocation splits into two partials with Burgers vector [112]. This is an energetically favoured process as can be seen from the equations given below: For a unit dislocation lying on the (111) plane with Burgers vector a/2[10-1], the splitting process can be written as

a/2 [10-1] a/6 [2-1-1] + a/6 [11-2]

Note that all the directions shown above are normal to [111], the plane normal. Since the energy of the dislocation is proportional to the burgers vector square, the above splitting up process is energetically favoured. It may also be seen that the region between the partials is faulted, i.e. the partials surround a region of stacking fault.

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Fig. 5.15: Dissociation of dislocations in close packed structure. A second type of partial dislocations is FCC crystals is the Frank partial formed by the condensation of a disc of vacancies or interstitials on the close packed planes. This is illustrated in Fig. 5.16 where vacancies have condensed on a part of one of the (111) planes. The resulting configuration is an intrinsic stacking fault surrounded by edge-type of dislocations. The Burgers vector of this dislocation (Frank partial) is [111].

Fig. 5. 16: Formation of a Frank partial dislocation in FCC structure by the condensation of vacancies.

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The formation of planar can be due to one of the following effects: 1. introducing a shear; e.g. glide of a Shockley partial with Burgers vector a/6<112> in a FCC crystal, or 2. by a displacement inclined to but necessarily perpendicular to the plane. The displacement vector RF indicates relative displacement between the region and above and below the fault. The phase change, , of the electrons in the faulted region is given by = 2g.R; the values of RF in a FCC crystal are a/3<111> or a/6 <112>. Hence can take two values, 2/3 (h+k+l) or 2/6 (h+k+2l); in either case the phase difference is 2n or 2/3. The fault is invisible when the phase change is 0 or 2n. Fringe contrast occurs when the fault is inclined to the foil. A micrograph of stacking faults in silicon is shown in Fig. 5.17. Note the visibility and invisibility of the faults on changing the operating reflection.

Fig. 5.17: BF Stacking Faults in Silicon: Fringe Contrast Visible On B and C when g is 022; A is not visible. Note Change in (b) when g is changed to 220. The contrast from stacking faults surrounded by Shockley partials can be considered based on the splitting equations: a/2 [ 11 0 ] a/2 [1 01] a/2 [0 11] a/6 [ 211] + a/6 [12 1] ..(1) a/6[211] + a/6 [1 12] ..(2) a/6 [1 21 ] + a/6 [ 1 12] (3)

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a/2 [11 0] a/2 [1 01] a/2 [0 11]

a/6 [211] + a/6 [12 1]

(4)

a/6 [211] + a/6 [1 1 2] (5) a/6 [1 21] + a/6 [1 12] .(6)

For the operating reflection [200], the values of g.b for eq.(1) are a/2[2] Visible a/6[4] + visible a/6[2] invisible

and for fault = 2/3. Hence based on the first equation one partial and fault are visible. The other partial is invisible. Similar calculations can be made for other splitting equation. Note that the use of g [220] will make the fault invisible in certain case ie. = 0. In order to distinguish between a 1/3 <111> and a 1/6 <112> stacking fault, it is necessary to determine the Burger vector of the bounding partials. Contrast from precipitates A precipitate particle is visible when it diffracts differently from the matrix or produces strain in the matrix. Precipitate structure factor contrast arises when the structure factor of the precipitate is different from that of the matrix. Note that since extinction distance is dependent on structure factor, differences in the latter will give rise to displacement of fringes. This mechanism is useful in imaging small coherent precipitates such as GP zones. Precipitate orientation contrast arises when the matrix and precipitate diffract electrons with different intensities due to differences in crystal structure. The diffraction spots from the precipitate can be used for the formation of dark field images which give useful information on orientation of the particles. A coherent precipitate with lattice parameter slightly different from that of the matrix causes coherency strains in the surrounding regions of the matrix. In this case the image shows a line of no contrast normal to the operating reflection (Fig. 5.18).

Fig. 5.18: Cu-Co alloy: (a) strain contrast from spherical Co particles, no contrast perpendicular to g, (b) loss of contrast after irradiation with 450 keV electrons. 84

High Resolution Microscopy High resolution electron microscopy offers the following advantages: Resolution of object details finer than 1 nm (10A) Imaging the interior structure of the sample as opposed to surface structure in atomic resolution STM While X-ray diffraction provides average information, HREM gives localized information Direct imaging of atomic structure, in particular structural defects, interfaces, dislocations Image formation in HREM is an interference phenomenon. A parallel coherent incident electron beam is diffracted by the thin crystal placed in the object plane of the objective lens. The lens forms a magnified and inverted image in the image plane. The electron beams converge and form a Fraunhoufer diffraction pattern in the back focal plane of the objective lens (Fig.5.19). High resolution image depends strongly on defocus, astigmatism, beam tilt, crystal tilt. All these factors cause the lattice fringes to become more or less intense or make them move. Consider a two beam-condition at exactly the Braggs condition, (S=0), i.e. the direct unscattered beam 000 and one diffracted beam, g , which can be described as plane wave

1 = A{exp(2ik.r)} and 2 = B{exp(2ik.r)}

Fig. 5.19: Image formation by a lens without aberrations

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The intensity of the image formed is given by: Ig = A2 + B2 - 2AB sin2[g.r] where r is a real space vector, A and B are the amplitudes of the two waves (assuming that they are real) and g = k - k. Therefore in the image we see a sinusoidal oscillation in the intensity with the periodicity r = 1/ [g] (Fig. 5.20),

In the back focal plane

In the image plane Fringe spacing 1/g

Fig. 5.20: Formation of fringes in the image plane with spacing 1/g If we include an array of reflections centered on the 000 beam, the image formed will be a cross grating of sine fringes generated by the interference between all the beams included in the aperture. These lattice fringes are not necessarily direct images of the structure because the phase relationship between the beams is distorted be the aberrations of the lenses. Practical aspects of HREM: Suitable and well aligned microscope Specimen should be as thin as possible Resolution depends on wave length of electrons and spherical aberration coefficient of objective lens; choice is use either high voltage or very low Cs. To minimize damage to specimen, use medium voltage (200-300 keV) and Cs lens of 0.5 mm; disadvantage of using low Cs is limited tilting possibilities (max 15)

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 Choice of the microscope depends on the interplanar spacing of the specimen studied; higher Cs enough for crystals with large d Contrast transfer function (CTF) provides information on resolvable d spacings Electron source is also important in HREM; LaB6 normally used as it has a much lower work function than W and hence the density of electrons is higher; this leads to reduced exposure time. FEG provides brighter and smaller probe and high spatial coherence (parallelism) of the beam and much lower energy spread. Information is transferred with higher spatial frequency (lower distance in direct space) ( see Table 5.3). Table 5.3: Characteristics of the electron sources Characteristic Temp, K Energy spread, eV Spot size, m Brightness, A/m2/sr Current, A/m2 2700 3.0 50 109 5x104 W 1700 1.5 10 5x1010 106 LaB6 300 0.3 <0.01 1012 1010 FEG

Electron beam conditions fro many beam imaging: Illuminating electron beam is axial Beam incident along a low order zone axis of the crystal Optimum objective size aperture Specimen is very thin Image observed at defocus value given by the equation

The steps involved in obtaining the images are Assume that the specimen is available in the form a sharp wedge crushed sample mounted on a C grid Specimen examined at a magnification of about 10000X to locate an area that is very thin, clean and undistorted. Take SAD and tilt sample to make a zone axis parallel to the optic axis Insert objective aperture at the centre of the pattern Correct astigmatism by observing the granular structure of a microgrid film. Take photographs changing the defocus slowly; compare with computer-simulated images. For an unknown structure an image appearing with high contrast (close to the Scherzer focus) and a series of through-focus images are recorded

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 Diffraction pattern taken to check how far from the orientation has deviated from the zone axis during this procedure Examples of applications Main area of applications is in the study of nanomaterials; examples of formation of nanoaluminium crystals in an Al-Ni-Gd alloy, carbon nanotube during pyrolysis of deoiled asphalt and carbon nanotubes are shown in Figs. 5.21, 5.22 and 5.23 respectively.

Fig. 5.21: Development of Al nanocrystal in Al90Ni5Gd5 during a DSC scan (a) BF image at 290C, (b) DF image of (a), (c) BF image 330C, (d) dark field image of (c)

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Fig. 5.22: Formation of carbon nanotube during catalytic pyrolysis of de-oiled asphalt (a) TEM image, (b) High resolution image

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Fig. 5.23: Single walled Carbon nanotube (a) TEM of as -received sample (b) SEM, (c ) TEM nano screws, (d) enlarged(c), (e) Straight nano-Wire (f) enlarged(e)

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