4G03 MIDTERM REVIEW

LECTURE ONE
Nanomaterials:

• set of substances where at least one feature is less than 100nm, looked at for the electrical, magnetic, and optical properties
that emerge at this size (quantum effects). We can engineer nanomaterials to take advantage of these properties that might
not be seen in their bulk counterparts.
• Properties of nanomaterials strongly depend on their size and shape, so a synthetic procedure, controlling the growth and
morphology of the nanoparticles is critical and appealing.
• 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 Sputtering
o Chemical etching
o Thermal/Laser ablation
o Mechanical/Ball missing
o Explosion Process
• Bottom up:
o atomic/molecular condensation
o vapour deposition
o sol-gel process
o spray pyrolysis
o chemical/electrochemical deposition
o aerosol process
o bio reduction

Synthesis:

• shape
• elemental-chemical composition
• crystal structure
• size distribution
• chemical state-oxidation state
• ligand binding/composition/density/arrangement
• Structural defect
o Imaging: visual representations
o Spectroscopy: Chemical information (how to acquire)

Challenges in NP characterization

• Surfaces and interfaces (with surrounding media) mainly control the material properties – high surface area
• Not all nanoparticles are created equal
• Very dynamic, due to their size – vary over time

Interactions of electrons with matter:

• An electron is are negatively charged and extremely light (tiny mass), located in the shells surrounded by the nucleus
(extremely small, high penetration depth, negative charge, magnetic lens via Lorentz force)
• Photons (light) is the energy and does not have mass and charge. We can use both for electron microscopy
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, therefore SLIGHTLY changing the course of the incident electron. It changes
direction due to the interaction between the electron and the nucleus of the atom it hits

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 as we need an auger
electron detector
• We use a vacuum because
otherwise the incident electron beam
will interact with gas molecules in the
chamber instead of the sample that
we want it to hit, to maximize
number of electrons that will hit the
sample
• Mean Free path is the average
distance travelled without interaction
(higher in a vacuum due to lower
pressure)

5 × 10−3
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
▪ 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
▪ If we adjust the diameter to the scale that is desired, we can focus on just the one element at a time
▪ You should absolutely not rush the scan, cause if the scan runs to fast you will not pick up anything
important
o Focus
▪ Position where electron beam cone has smallest diameter
▪ Like eyeball, 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
▪ 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
▪ Affected by relative difference of intensity zones and intensity relative to background
▪ 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
o Low energy electrons
• Applications
o Thickness of films and thin coatings
o Surface morphology and appearance
o Size and size distribution
o Shape and dispersion of particles, fibres, nanomaterials or any other additives in composites and blends
o Cell size and distribution in foam materials
o Chemical composition and elemental analysis of nano and micro materials
o Fracture and structural defect analysis

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’s
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, and higher Z means higher electron beam therefore
larger peaks
• Data Acquisition methods
o Take spectra of a fixed point or area
o Depth profile using ION gun if available
o Line profile (1D surface scan)
o Imaging (Map) (2D spectral image)
• Using a map, you just scan all of the surface and get x-ray from all of the point, 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 sensitive and gives surface information
𝑍4
• 𝑤= is the probability of a characteristic x-ray being emitted and 1-w is the probability of an auger electron being
𝑍 4 +𝑐
emitted
• Kinetic energy of the auger electron: 𝐸𝑋𝐴# 𝐵# = 𝐸𝑋 + 𝐴# + 𝐵# + 𝜑𝑠𝑝
• Φsp is the work function to account for heat lost due to accumulation and hitting the detector
• When you have a low atomic number atom- you have more KLL electrons, but denser and higher atomic number electrons
have more MNN because the inner K shell is harder to reach when more levels are there
• 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 Prode diameter for auger analysis: 8nm (at 25kV, 10pA)
o Schottky Field Electron gun
o Accelerating voltage (0.5 to 30 kV)
o Probe Current:10-11 to 2x10-7 A
o Magnification: x25-500000
• 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
o Line Profile (1D surface scan)
o Depth profile using ION gun
o Auger Image (Map)
• Because we are measuring electron energies, we see contributions from BSE and SE undergoing multiple inelastic collisions
with the sample, so we use a differential method (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 the surface with Ar+ and getting
the analysis of the auger electrons)
• 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 hav very stron coupling to matter, allowing us to excite them and create a ariety of signals, which allow us to
reveal details regarding structure-property reletionships 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 more lower gamma and therefore lower d (distance between two
distinguishable points) and you can see more
0.61𝜆
o Optical microscope: 𝑑 =
𝑛 sin 𝛼
ℎ
o TEM: 𝜆 =
(2𝑚𝐸𝑘 )1/2
• Only problem with TEM is increasing resolution means increasing accelerating voltage, which is like increasing energy, and
that requires money and space to house the energy
• 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, we are basically looking at a very
small sliver of the 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

𝑛𝜆 = 2𝑑 𝑠𝑖𝑛𝜃
𝑟
= sin 2𝜃
𝐿
𝐿
= ~2𝜃
𝑟
𝑟 𝜆
=
𝐿 𝑎𝑑
d=
√h2 +𝑘 2 +𝑙2

• 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 Polymers and biological materials
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 𝑁0 𝜎𝑎𝑡𝑜𝑚 (𝜌𝑡)
o 𝑃= =
𝜆 𝐴
• Phase contrast
o Does not indicate higher mass
o Indicates that 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, as you are looking at a more zoomed out image so you need
to account for grains in the image
o Any change in tilt, beam structure, electron wavelength, or contrast will change based off the need to satisfy Braggs
o Example: you have a sample with different grains, some grains are darker than others in the TEM due to the fact
that diffraction from one type of grain is different than diffraction from another type of grain
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