4G03 MIDTERM REVIEW

LECTURE ONE
Nanomaterials:

 set of substances where at least one feature<100nm, looked at for electrical, magnetic, and optical properties that emerge at this size
 Properties of nanomaterials strongly depend on their size and shape, so a synthetic procedure to control is good
 Nanomaterials can be found in sunscreens, cosmetics, electronics, medicine, nanocomposites and nanocoating.
 The nanomaterial classification is based on the number of a material, which are outside the nanoscale (<100nm) range

Fabrication method:

 Top Down:
o Reducing from bulk
 Bottom up:
o Synthesising with atoms

Challenges in NP characterization

 Surfaces and interfaces (with surrounding media) mainly control the material properties – high surface area
 Very dynamic, due to their size – vary over time

LECTURE TWO
Interactions of electrons with matter:

1. Secondary electron – electron beam knocks out one electron from the atom and replaces it
2. Back scattered electrons – electron beam hits and due to the force, the incident electron changes direction and is the electron also leaving
the sample the same general direction it came from.
3. Auger Electron- electron beam comes and hits the sample, knocks out an electron, and leaves a hole in the atom. This makes the sample
unstable/excited so an electron from another energy level comes down and fills the hole, relaxing the electron. The energy difference can
come out as a characteristic x-ray or as an auger electron. Which form the energy difference comes out as depends on the atomic number
(higher Z = higher chance of an auger electron).
4. Continuum X-ray- electron beam hits an atom, SLIGHTLY changing the course of the incident electron due to interaction with nucleus

Scanning electron microscopy (SEM):

 Optical microscope uses light, electron

microscope uses electrons (magnetic lens, not glass or
plastic)
 Anode adds energy to accelerate electron beam
 Electromagnetic lens creates an electron field
that the beam will go through
 Condenser lens will reduce the area of the beam
 Objective lens focuses beam on the sample
 Scan coils to focus beam away from sample after
hitting it
 Separate microscope for auger electrons
 We use a vacuum because otherwise the
incident electron beam will interact with gas molecules in
the chamber
 Mean Free path is the average distance travelled
without interaction (higher in a vacuum due to lower pressure)
−3
5 ×10
MFP=
P
 Energy of electrons and outcoming electrons/x-rays are analyzed and indicate different information about
o Morphology
 shape and size
 Secondary electron
o Topography
  surface features like scratches, smoothness, texture
 Secondary Electron
o Composition
 means elements and compounds that constitutes the material
 BSE (one phase has one shade, and another phase might be darker)
o Crystallography
 arrangement of atoms in the material
 x-ray
 colour indicates where the element is found on the sample, x-ray map

Important Parameters of SEMS:

 Electron energy (E0) – energy in units of eV coming out of the electron gun
 Working distance (W) – distance between the sample surface and the objective lens
 Landing energy (El) – energy of electrons arriving at the surface of the sample
 Spot size – diameter of the probe at the sample
 Convergence angle (α) – describes the angular range over which electron are incident at each point on the sample
 Beam current (Ib) – number of electrons impinging on specimen per unit time, usually in the range of pA – μA

How it works:

 Planar Illumination
o light hits the object, bounces back onto detector film and results in a planar array image
 Scanning Illumination
o An electron hits point A and bounces onto the detector, then moves to point B and does the same, repeats until whole process
is complete.
o Scanning strategies include:
 Raster Scanning – beam goes left to right then starts again at the left side
 Serpentine scanning – beam moves right to left, left to right, and repeats
o Magnification
 in SEM, magnification is the ratio between length measured from the SEM monitor (Lm) to the same length measured
on the sample (Ls), by increasing magnification, we decrease the scan swipe (pixilation constant). To get a broader
picture increase Ls and to get a smaller picture decrease Ls.
Lm
 M=
Ls
o Resolution – ability to separate two distinct objects, allows us to focus on one element at a time
 Probe diameter spot size should be adjusted to scale of interest
 Make sure that minimum contrast occurs between appropriate probe current and the scan rate settings.
 We can acquire a higher resolution by decreasing the spot size, focusing probe, increasing vacuum
o Focus
 Position where electron beam cone has smallest diameter
 beam should converge at the sample, otherwise the image will be blurry, and under/over focus occurs when spot size
is bigger/ has a larger diameter than it should
o Depth of field
 In focus and as sharp as possible, and so to increase depth of field we can:
 Decrease the size of the aperture in the final lens or increase the W distance between the specimen and the lens
 A smaller diameter results in a sharper image, as your sample is not perfectly flat and a smaller spot size allows you to
focus on one level then move onto the next, instead of having a larger spot size that encompasses an area with a level
change, thus we want a lower convergence angle
o Astigmatism
 Due to imperfection in lenses, non-round beam shape causes stretching in the resulting image direction changes going
through focus
o Contrast
 Ability to tell how much different a zone is from surroundings via intensity
 Important for high-res images

SEM components

 Electron gun
o Function is to provide a large and stable current in a small beam
 Thermionic emitter produces electrons when heated and uses W filament or LaB6, Used in SEM
  Field emitter produces electrons by applying a large electric potential and has increased chromaticity (more uniform
energies) which results in more consistent imaging (Schottky uses heat fields, Cold uses just the voltage), Used in
FESEM
 Lens
o Electromagnetic lens contains a copper wire coil within an iron pole piece which create a magnetic field when applying current
through the coils, and this magnetic field converge the electron beam via a force parallel to the z-axis, which will force the
electrons to spiral through the lens, which causes the electron to experience another force parallel to the radius of the lens,
which compresses the beam towards the z-axis
o The condenser lends converges the cone of electron beams to a spot below it, then flares out again and reconverges by
objective lens down onto sample. Condenser lens controls initial spot size (spot size-control)
o Objective lens is lowest which focuses probe onto the sample and used to focus beam on specimen.
o Scanning coil are used to scan surface, current is increases to get higher magnification
 Aperture
o For refinement of beam, different size apertures are utilized (circular holes in metal discs at micron scale)
o Small objective aperture sizes will produce better resolution and good depth of field
 Sample Holder and Detector
o Specific holder with holes where sample mount is mounted onto
o Carbon, copper, silver tape used for sticking on non-conductive samples so you don’t fuck data with accumulation

LECTURE THREE
SEM:

 Inelastic deformation is when energy is lost in a collision (SE)

 Elastic deformation is when no energy is lost during a collision (BSE)
 Interaction volume is the volume of the sample that the electron interacts with
o Accelerating voltage – adds energy to electron beam so it penetrates deeper into the sample
o Atomic number – atom is denser and more to penetrate through, so the interaction volume lowers
o Tilt – you add a slant so one electron enters and exits the sample is a longer way than just straight on (BSE)
 When I have a high voltage and interaction volume the SE leaving the sample have low energy
 SE don’t change with atomic number as electron leaving the sample is near the surface anyways
¿ SE
o SE coefficient (δ)= −¿
¿ total e ¿
o δ insensitive to atomic number and increases with decreases in beam energy
o SE’s have very low escape depth due to low energies (usually 2-5eV, mostly <50eV)
o Collision among primary electrons and the weakly bonded outer shell therefore Low energy electrons

Energy dispersive X-ray spectroscopy:

 EDX is a bulk analysis technique as the information is coming from deep withing the sample (1-4 micrometeres)
 You then get the spectra/ characteristic x-rays shown, which you can compare with the size of known peaks to determine the
compositions and elements in the sample
 In EDS it is the same idea but an electron is expelled instead, and is described and characterized by the electron movements
o Electron expelled from X energy layer is called X (K, L, M, N)
o Electron that replaces it and filled the hole is called A# (K, L, M, N) where A is the layer and # is the specifics on what sublayer if
necessary
o Electron that is expelled to account for the energy difference is called B# where B is the energy layer and # is the sub layer from
which it was expelled
 You can then look at the peaks and decide what energies of the peaks corresponds with the graph
 Acquisition time is the time the EDS door is open to get the x-ray, a longer acquisition time might result in stronger peaks
 Spectral Noise
o Decrease accelerating voltage therefore decrease frequency and therefore spectral noise
o Decrease atomic number to decrease electron beam and sample interaction volume to reduce noise
o Intensity of background noise is proportional to current Z, higher Z means higher electron beam = larger peaks
 Data Acquisition methods
o Take spectra of a fixed point or area, Depth profile using ION gun if available, Line profile (1D surface scan), Imaging (Map) (2D
spectral image)
 Using a map, you just scan all of the surface and get x-ray and get data from the whole surface of the sample
 E0/Ec
Auger Spectroscopy:

 Similar to x- ray, we are measuring kinetic energy of the electron

 Electron hits sample, knocks out an electron and leaves a hole for an electron from another energy level to come down and fill the space,
the energy difference is expelled as another electron called the auger electron (SURFACE INFORMATION)
4
Z
 w= 4
is the probability of a characteristic x-ray being emitted and 1-w is the probability of an auger electron being emitted
Z +c
 Kinetic energy of the auger electron: E X A B =E X + A¿ + B ¿ +φ sp
¿ ¿

 Φsp is the work function to account for heat lost due to accumulation and hitting the detector
 H and He are basically impossible to detect with auger spectroscopy as the barely have electrons to begin with
 Electron Illumination system:
o SE image resolution: 3nm (at 25kV, 10 pA)
o Schottky Field Electron gun
 Auger analysis system:
o Analyzer: electrostatic hemispherical analyzer (HAS)
o Energy resolution (ΔE/E): 0.05%-0.6%
 Data Acquisition:
o Take spectra of a fixed point or area, Line Profile (1D surface
scan), Depth profile using ION gun, Auger Image
 Because we are measuring electron energies, we see contributions from
BSE and SE undergoing multiple inelastic collisions with the sample, so (not
N(E) – E, but instead dN(E) – E plot)
 You can use an argon gun to scan surface and get a depth profile (simultaneously etching surface with Ar+ & getting data)
 Cryofracture: fracture in a vacuum to eliminate oxidation
 Advantages: reproducible data, standard surface analysis techniques, non-destructive, high spatial resolution
 Disadvantages: only surface, ultra high vacuum needed, needs standards for data analysis, no H and He detection

LECTURE FOUR
Why use a TEM:

 One of highest spatial resolution imaging techniques

 Electrons have very strong coupling to matter, allowing us to excite them and create a variety of signals & reveal details regarding
structure-property relationships in materials
 Spatial resolution is the ability to tell the difference between two close object or one big object
o A higher spatial resolution means a lower gamma and therefore lower d (distance between two distinguishable points) and you
can see more
0.61 λ h
o Optical microscope: d= TEM: λ=
n sin α ¿¿
 Only problem with TEM is increasing resolution means increasing accelerating voltage, and that requires money
 To get a higher resolution you can also use a higher index of refraction and get a higher alpha
 Some problems you might run into:
o Spherical aberration:
o Chromatic aberration:
o Astigmatism:
 Samples should be thinner than 500nm and thinner than 20nm for higher quality images, (small sliver sample)
 TEM’s are good for investigating thin foils and nanoparticles
 In a TEM the sample is actually between the condenser and objective lens
 How does a TEM obtain diffraction patterns:

 Some electrons pass through the sample and hit the image plane, but some get diffracted back and hit the back focal plane
 On the back focal plane, energies of the same wavelength hit the plane in the sample place
 On the first image plane, the variety of energies/wavelengths converge at the same point

r L
nλ=2 d sinθ =sin 2θ = 2θ
L r
r λ a
= d=
L d √ h + k 2 +l2
2

 r= distance between sample plane and the path of the diffracted electron
 L= distance between sample and plane where you see a diffraction pattern aka camera length

Major diffraction techniques:

 Selected Area diffraction

o Illuminate large area of the specimen with a parallel beam
o Insert an aperture in the first image plane to select an area of the image
o Focus the first image plane on the OL back focal plane
o Advantages – can observe large area of the sample with a bright beam, and due to it being a magnified image, you can easily
select an area with an aperture. Used for thin films, bulk samples, and in-situ phase transformation
o Disadvantage – cannot select an area less than 1 μm due to spherical aberrations and precision in aperture positioning
 Nano Beam (electron) Diffraction (NBD)
o Focus beam (CL) on the front focal plane (FP) of the objective lens (OL) and use a small condenser aperture
o A parallel beam without selection errors can form a 10-50nm probe size
o Useful for investigating individual nanocrystals and superlattices
o More complex alignments than TEM, and high-resolution images are difficult to obtain so (need to switch between NAED and
TEM modes)
 Convergent Beam Electron Diffraction (CBED)
o Point and space group
o Lattice parameter 3-D space group
o Thickness
o Defects

Major imaging Techniques/ contrast mechanisms:

 Mass-Thickness contrast
o If there is little contrast in an image you can go in and add a dense material like uranium or lead
o Higher masses mean more scattering therefore they are darker on the image
1 N σ ( ρt )
o P= = 0 atom
λ A
 Phase contrast
o when the electrons hit the sample, they do so at different WAVE phases, so the higher the energy of the electron that hits the
sample, the darker the area will appear on the image
 Diffraction Contrast
o Different orientation causes diffraction by Braggs law; looking at a more zoomed out image, you need to account for grains
o Any change in tilt, beam structure, electron wavelength, or contrast will change based off the need to satisfy Braggs
o Bright field
 Occurs when you are obtaining an image from the first image focal plane, will result in a TEM like image
 Put the aperture hole on back focal plane and transmitted electron (straight beam) is produced
o Dark Field
 Occurs when trying to obtain an image from the back focal plane and results in a diffraction pattern
 Place the aperture hole on back focal plane, but emit the electron beam as diffracted electrons (at an angle) to have
them diffract back off the back focal plane and get a dark field image
o Lattice beam image
 By using both dark and bright field imaging you can then see the lattice structure of the sample
 Use two beam condition when you want just to see the lattice of your sample and particles
 Use many beam condition if
you want information about phases
and lattice parameter