Sad Analysis Dewsdado gabriel poba baquisse BT/ME/1601/017

Intoduction Selected area (electron) diffraction (abbreviated as SAD or SAED), is a crystallographic experimental technique that can be performed inside a transmission electron microscope (TEM). In a TEM, a thin crystalline specimen is subjected to a parallel beam of high-energy electrons. As TEM specimens are typically ~100 nm thick, and the electrons typically have an energy of 100–400 kiloelectron volts, the electrons pass through the sample easily. In this case, electrons are treated as wave-like, rather than particle-like (see wave–particle duality). Because the wavelength of high-energy electrons is a few thousandths of a nanometer, [1] and the spacing between atoms in a solid is about a hundred times larger, the atoms act as a diffraction grating to the electrons, which are diffracted. That is, some fraction of them will be scattered to particular angles, determined by the crystal structure of the sample, while others continue to pass through the sample without deflection.

As a result, the image on the screen of the TEM will be a series of spots—the selected area diffraction pattern, SADP, each spot corresponding to a satisfied diffraction condition of the sample's crystal structure. If the sample is tilted, the same crystal will stay under illumination, but different diffraction conditions will be activated, and different diffraction spots will appear or disappear.

Selected area electron diffraction Parallel incoming electron beam and a selection aperture in the image plane. Diffraction from a single crystal in a polycrystalline sample if the aperture is small enough/crystal large enough. Orientation relationships between grains or different phases can be determined. ~2% accuracy of lattice parameters –Convergent electron beam better Image plane

Diffraction with large SAD aperture, ring and spot patterns Poly crystalline sample Four epitaxial phases Similar to XRD from polycrystalline samples.The orientation relationship between the phases can be determined with ED.

2θ2θ k k’ g The intensity distribution around each reciprocal lattice point is spread out in the form of spikes directed normal to the specimen k=1/λ Ewald sphere (Reflecting sphere) Higher order reflections, Laue zones 2d sinθ = nλ λ 200kV = nm Θ~1 o I(k’- k)I=(2/λ)sinθ B =g From one set of planes we only get one reflected beam -The Bragg angle increases with increasing order (n) -Tilt sample or beam to satisfy Bragg condition of higher order reflections. Zero order Laue zone (see figure 2.35 text book) First order Laue zone

Double diffraction, extinction thickness Double electron diffraction leads to oscillations in the diffracted intensity with increasing thickness of the sample –No double diffraction with XRD, kinematical intensities –Forbidden reflection may be observed t 0 : Extinction thickness –Periodicity of the oscillations –t 0 =πV c /λIF(hkl)I Incident beam Diffracted beam Doubly diffracted beam Transmitted beam Wedge shaped TEM sample t0t0

Kikuchi lines Excess Deficient Used for determination of: -crystal orientation -lattice parameter -accelerating voltage -Burgers vector Excess line Deficient line 2θB2θB θBθB θBθB Diffraction plane Objective lens 1/d

Camera constant R=L tan2θ B ~ 2Lsinθ B 2dsinθ B =λ ↓ R=Lλ/d Camera constant: K=λL Film plate

Indexing diffraction patterns The g vector to a reflection is normal to the corresponding (h k l) plane and IgI=1/d nh nk nl - Measure R i and the angles between the reflections - Calculate d i, i=1,2,3 (=K/R i ) - Compare with tabulated/theoretical calculated d-values of possible phases - Compare R i /R j with tabulated values for cubic structure. - g 1,hkl + g 2,hkl =g 3,hkl (vector sum must be ok) - Perpendicular vectors: g i ● g j = 0 - Zone axis: g i x g j =[HKL] z - All indexed g must satisfy: g ● [HKL] z =0 (h 2 k 2 l 2 ) Orientations of corresponding planes in the real space

Example: Study of unknown phase in a BiFeO 3 thin film 200 nm Si SiO 2 TiO 2 Pt BiFeO 3 Lim Goal: BiFeO 3 with space grupe: R3C and celle dimentions: a= Å c= Å Metal organic compound on Pt Heat treatment at 350 o C (10 min) to remove organic parts. Process repeated three times before final heat treatment at o C (20 min). (intermetallic phase grown)

Determination of the Bravais-lattice of an unknown crystalline phase Tilting series around common axis 0o0o 10 o 15 o 27 o 50 nm

Tilting series around a dens row of reflections in the reciprocal space 0o0o 19 o 25 o 40 o 52 o Positions of the reflections in the reciprocal space Determination of the Bravais-lattice of an unknown crystalline phase

Bravais-lattice and cell parameters From the tilt series we find that the unknown phase has a primitive orthorhombic Bravias-lattice with cell parameters: a= 6,04 Å, b= 7.94 Å og c=8.66 Å α= β= γ= 90 o 6.04 Å 7.94 Å 8.66 Å a b c [011][100] [101] d = L λ / R

Chemical analysis by use of EDS and EELS Ukjent fase BiFeO 3 BiFe 2 O 5 Ukjent fase BiFeO 3 Fe - L2,3 O - K 500 eV forskyvning, 1 eV pr. kanal

Published structure A.G. Tutov og V.N. Markin The x-ray structural analysis of the antiferromagnetic Bi 2 Fe 4 O 9 and the isotypical combinations Bi 2 Ga 4 O 9 and Bi 2 Al 4 O 9 Izvestiya Akademii Nauk SSSR, Neorganicheskie Materialy (1970), 6, Romgruppe: Pbam nr. 55, celleparametre: 7,94 Å, 8,44 Å, 6.01Å xyz Bi4g0,1760,1750 Fe4h0,3490,3330,5 Fe4f00,50,244 O4g0,140,4350 O8i0,3850,2070,242 O4h0,1330,4270,5 O2b000,5 Celle parameters found with electron diffraction (a= 6,04 Å, b= 7.94 Å and c=8.66 Å) fits reasonably well with the previously published data for the Bi 2 Fe 4 O 9 phase. The disagreement in the c-axis may be due to the fact that we have been studying a thin film grown on a crystalline substrate and is not a bulk sample. The conditions for reflections from the space group Pbam is in agreement with observations done with electron diffraction. Conclusion: The unknown phase has been identified as Bi 2 Fe 4 O 9 with space group Pbam with cell parameters a= 6,04 Å, b= 7.94 Å and c=8.66 Å.