Unit 3
Characterization Techniques for
Nanostructures
Characterization Techniques for Nanostructures:
1. XRD: X-Ray Diffraction
2. SEM: Scanning electron microscope
3. TEM: Transmission electron microscope
4. STM: Scanning tunnelling microscope
5. AFM: Atomic force microscope
6. XPS: X-ray photoelectron spectroscope
7. BET: N-adsorption-desorption analysis
8. TGA: Thermogravimetric analysis
XRD: BASICS (Sample) Lattice parameters:
BASICS (Instrument)
1. a (edge length)
BASICS (Sample): Crystalline solids (Soli State Chemistry) 2. d-space
3. (h, k, l) – planes
o
d
XRD: BASICS (Instrument)
Working principle:
1. X-ray
2. X-ray/sample interaction
3. Bragg’s equation
XRD: BASICS (Instrument)
XRD : Instrumentation
(h, k, l) plane
θ
XRD : Instrumentation
XRD (X-Ray Diffraction)
KEY 4-Steps to understand XRD:
1. The X-ray beam is directed to the powdered sample (collimated to ensure that it hits the
sample at a specific angle)
2. X-rays are diffracted at specific angles when the condition of Bragg's Law is
satisfied.
3. The intensity of the diffracted X-rays is measured as a function of the angle θ, creating a
diffraction pattern.
4. The positions of these peaks (in terms of 2θ) relate to the lattice spacings in the crystals,
while the intensity of the peaks is related to the number of planes contributing to the
reflection and their arrangement.
XRD : Principle
Sin θ = AB/BZ
Concise key points:
[Link] Wavelength: The wavelength of the X-ray is typically fixed (e.g., around 1.54 Å for copper Kα
radiation).
[Link] Angle: During an X-ray diffraction (XRD) experiment, the angle of incidence (θ) can be varied.
[Link] d-spacing: As you change θ, the equation from Bragg's law:
nλ = 2dsinθ allows for different interplanar spacings (d) to satisfy the condition for constructive
interference.
[Link] Interference: At specific angles (θ), constructive interference occurs for various sets of
crystal planes that correspond to different d spacings.
Therefore, by adjusting θ, you effectively “find” the appropriate d value that matches the
fixed wavelength of the X-ray, leading to the observation of diffraction peaks.
XRD Interpretation → Lattice parameter for NaCl
XRD : Interpretation
(h, k, l)
plane?
International Centre for Diffraction Data (ICDD)
Example 1: Simple cubic system
‘a’ calculation
d-space calculation 2. Use Braggs law
(h, k, l) calculation
Tetragonal crystal system
TiO2: Anatase, Rutile, Brookite
Crystallite Size calculations
TEM: Significant Features
TEM can reveal stunning detail at the atomic
scale by magnifying nanometer structures
up to 50 million times. This is because
electrons can have a significantly shorter
wavelength (about 100,000 times smaller)
than that of visible light when accelerated
through a strong electromagnetic field, thus
increasing the microscope resolution by
several orders of magnitude.
TEM: Significant Application
in Research
Structure
•Cobalt catalysts are commonly used for Fischer-
Property Tropsch synthesis.
•The (001) basal plane of hexagonal close-packed (hcp)
cobalt is more selective for producing long-chain
Performance hydrocarbons (e.g., waxes) because it favors CO
dissociation and chain growth.
•In contrast, the (101) plane tends to favor methane
TEM: Identify the structural features (CH₄) formation due to differences in CO adsorption
and dissociation behavior.
Design catalysts accordingly
TEM: Identifying the Structural Characteristics of Solids
❖ Surface Topography: Details of surface features (Texture and roughness at the nanoscale).
❖ Morphology: Shape (1D, 2D, 3D), particle size and distribution, layer thickness, stacking, porosity,
and agglomeration.
❖ Lattice Structure: Arrangement of atoms in the crystalline material.
❖ Crystallinity: Degree of order in the material, distinguishing between crystalline and amorphous
regions.
❖ D-space: Distance between atomic planes in the crystal structure.
❖ Crystal Planes: Orientation and spacing of various crystallographic planes, aiding in understanding
material properties.
❖ Phase Identification: Differentiation of various phases in multiphase materials based on diffraction
patterns.
❖ Defects: Presence of dislocations, vacancies, and interstitials.
❖ Strain: Localized variations in lattice parameters indicating mechanical deformation.
❖ Grain Boundaries: Regions where crystals of different orientations meet, including their structure
and characteristics.
❖ Phase Contrast: Variations in electron density and thickness leading to differences in contrast in the
images.
TEM (Advanced features): Understanding Advanced Characteristics of Solids Structures
Elemental Composition: Energy-dispersive X-ray spectroscopy (EDX) attached to TEM (Qualitative and
quantitative analysis of elements).
Single or polycrystalline nature: Selective area electron diffraction (SAED pattern).
Chemical Bonding: Electron energy loss spectroscopy (EELS)- Insights into the types of bonding at the
atomic level.
Local Electronic Structure: High-angle annular dark field (HAADF) imaging -Probing electronic
properties.
EELS works by measuring the energy lost by electrons as they interact with a material. By analyzing these
energy losses, we can determine the material's elemental composition, chemical bonding, and electronic
structure.
The shape and position of core-loss peaks in Electron Energy Loss Spectroscopy (EELS) are highly
sensitive to the chemical environment of the atoms in a material.
Example:
❖ In carbon, the 1s core electron in graphite (sp² hybridized) has a slightly different binding energy
compared to the 1s electron in diamond (sp³ hybridized).
❖ Similarly, the core-loss peak for oxygen in a metal oxide (e.g., TiO₂) will be different from that in a
covalent molecule (e.g., H₂O).
How Chemical Environment Affects Core-Loss Peaks: Examples
Example 1: Carbon in Different Bonding Environments
•Graphite (sp² bonding):
• The carbon K-edge shows a sharp peak at ~285 eV, corresponding to the transition of 1s electrons to π*
antibonding states.
• A broader feature at higher energy (~290 eV) corresponds to transitions to σ* states.
•Diamond (sp³ bonding):
• The carbon K-edge lacks the sharp π* peak because there are no π bonds in diamond.
• Instead, it shows a broader feature corresponding to transitions to σ* states.
•Graphene:
• Similar to graphite but with subtle differences due to its single-layer structure.
Example 2: Transition Metal Oxides
•Titanium in TiO₂ (Ti⁴⁺):
• The Ti L-edge shows distinct peaks corresponding to transitions from 2p to 3d states.
• The splitting and intensity of these peaks depend on the crystal field splitting and oxidation state of titanium.
•Titanium in Ti₂O₃ (Ti³⁺):
• The Ti L-edge looks different because the oxidation state and local coordination environment have changed.
Example 3: Nitrogen in Different Compounds
•Nitrogen in N₂ (molecular nitrogen):
• The nitrogen K-edge shows a sharp peak corresponding to the transition of 1s electrons to π* molecular orbitals.
•Nitrogen in NH₃ (ammonia):
• The nitrogen K-edge looks different because the bonding environment is now sp³ hybridized, and the electronic states
are altered.
Transmission Electron Microscope (TEM)
Instrumentation
TEM: Instrumentation
1 2
3
TEM: Working Principle
Electron/Sample Interaction
Different scattering
1
Two types of interactions with isolated atoms render
elastic scattering (No energy transfer):
(i) Interaction with the electron cloud results in low-angle
scattering.
(ii) Coulombic attraction to the positively charged nucleus
results in high-angle (Rutherford) scattering.
Different Techniques in TEM
❖ When the electron beam enters the crystal, elastic scattering will occur at characteristic angles
(Bragg angles) corresponding to the unique lattice spacings (also called d spacings) in that
material.
❖ As a result, the diffraction pattern captures an imprint of the Bragg angles and conveys
information about the crystalline structure of the material such as symmetry, lattice spacings,
strain, and defects. For polycrystalline or amorphous materials, the diffraction pattern becomes a
series of diffuse rings wherein the ring radii correspond to the lattice spacings, and the magnitude
of diffuseness increases with decreasing average crystallite size.
In BF imaging, the electron beam passes through the sample. The areas that let electrons pass
through appear bright, while areas that scatter the electrons appear darker: provide information about
the overall structure and composition of the sample.
In DF imaging, only the scattered electrons—specifically from certain angles—are used to form the
image, making the background dark and highlighting specific features. A special device (called an
objective aperture) is used to only allow scattered electrons to reach the detector: DF images highlight
specific features, such as defects or phase boundaries, that might not be as visible in BF images.
STEM (Scanning Transmission Electron Microscopy) is a powerful imaging technique in electron microscopy
where a focused electron beam is scanned across a thin sample, and transmitted electrons are collected to form
high-resolution images. It provides atomic-scale resolution and compositional information, often using detectors
like HAADF (High-Angle Annular Dark-Field) for Z-contrast imaging.
HAADF (High-Angle Annular Dark-Field) is an imaging mode in STEM where electrons scattered at high
angles are collected by an annular detector. These high-angle scattered electrons are primarily due to
Rutherford scattering (thermal), which strongly depends on the atomic number (Z) of the atoms in the
sample. As a result, HAADF provides Z-contrast imaging, where heavier atoms appear brighter, enabling
precise mapping of atomic composition and structure. This technique is especially useful for visualizing
atomic columns in materials and identifying defects or interfaces at the atomic scale.
EELS (Electron Energy Loss Spectroscopy) is an analytical technique used in Transmission
Electron Microscopy (TEM) to measure the energy lost by electrons as they pass through a thin
sample.
Elemental Analysis: EELS detects core-loss edges in the energy spectrum, allowing identification of elements
present in the sample, including light elements like carbon and oxygen.
Chemical Bonding Information: The fine structure near core-loss edges (ELNES) provides insights into the
chemical environment, oxidation states, and bonding of atoms.
Electronic Properties: The low-loss region of the spectrum reveals information about band gaps, plasmon
excitations, and the density of states in materials.
High Spatial Resolution: When combined with STEM (Scanning Transmission Electron Microscopy), EELS can
achieve atomic-scale resolution, enabling mapping of chemical and electronic properties at the nanoscale.
Versatile Applications: EELS is widely used in materials science, nanotechnology, and biology to study catalysts,
semiconductors, nanoparticles, and biological molecules.
Scanning Electron Microscope (SEM)
Cambridge University: Mr. Oatley and his
students assembled their first SEM in
1948.
SEM: Working Principle
The sample itself is mounted on a stage in the chamber area and both the column and the chamber are
maintained under vacuum by a combination of pumps.
The samples are mounted and coated with thin layer of heavy metal elements to allow spatial scattering
of electric charges on the surface of the specimen allowing better image production, with high clarity.
SEM: Types of Detectors
Amplitude - refers to the varying intensity of electrons
[Link] Aberration: This occurs when the lens fails to focus all electron beams to the same convergence point,
causing a loss in resolution.
[Link] Aberration: This arises from differences in focus for electrons of different energies, resulting in color
mismatches in the image.
XPS: Spectrum
XPS: Principle
1) X-ray Irradiation: A sample is exposed to monochromatic X-rays, which eject core electrons from atoms in the
sample due to the photoelectric effect.
2) Electron Ejection: The energy of the X-rays is transferred to core electrons, causing them to overcome their
binding energy and be emitted as photoelectrons.
3) Energy Analysis: The kinetic energy of the emitted photoelectrons is measured using an electron energy
analyzer.
4) Binding Energy Calculation: The binding energy of the electrons is determined using the equation:
Ernest Rutherford Eqn.
1) Chemical Information: The binding energy is unique to each element and its chemical state, providing
information about the sample’s elemental composition and chemical bonding.
XPS: Principle
XPS: Instrument
XPS is used to measure:
❖ Elemental composition of the surface (top 1– 10 nm usually)
❖ Empirical formula of pure materials
❖ Elements that contaminate a surface
❖ Chemical or electronic state of each element in the surface
❖ Uniformity of elemental composition across the top surface (or line profiling or mapping)
❖ Uniformity of elemental composition as a function of ion beam etching (or depth profiling)
Capabilities of advanced systems in XPS
1. Measure uniformity of elemental composition across the top the surface (or line profiling or mapping)
2. Measure uniformity of elemental composition as a function of depth by ion beam etching
(or depth profiling)
3. Measure uniformity of elemental composition as a function of depth by tilting the sample
(or angle resolved XPS)
Interesting Features of
XPS
Chemical States from XPS analyses
1. The ability to produce Chemical State information from the topmost 1-12 nm of any surface makes XPS a
unique and invaluable tool for understanding the chemistry of any surface
2. Chemical state analysis of the surface of polymers readily reveals the presence or absence of the chemical
states of carbon known as: carbide (C 2-), hydrocarbon (C-C), alcohol (C-OH), ketone (C=O), organic ester
(COOR), carbonate (CO3), fluoro-hydrocarbon (CF2-CH2), trifluorocarbon (CF3).
3. Chemical state analysis of the surface of a silicon wafer readily reveals the presence or absence of the
chemical states of silicon known as: n-doped silicon, p-doped silicon, silicon suboxide (Si2O), silicon
monoxide (SiO), Si2O3, silicon dioxide (SiO2).
Degradation during analysis
Non-monochromatic X-ray sources produce a significant amount of high energy Bremsstrahlung X-rays (1– 15 keV of
energy) which directly degrade the surface chemistry of various materials. Non-monochromatic X-ray sources also produce a
significant amount of heat (100 to 200 °C) on the surface of the sample because the anode that produces the X-rays is
typically only 1 to 5 cm (2 in) away from the sample. This level of heat, when combined with the Bremsstrahlung X-rays, acts
synergistically to increase the amount and rate of degradation for certain materials.
Monochromatic X-ray for example: 1.486 keV if aluminium K-alpha X-rays are used.
Because the vacuum removes various gases (e.g. O2, CO) and liquids (e.g. water, alcohol, solvents) that were initially trapped
within or on the surface of the sample, the chemistry and morphology of the surface will continue to change until the surface
achieves a steady state.
Quantitative Accuracy
1. XPS is widely used to generate empirical formula because it readily yields excellent quantitative accuracy
from homogeneous solid state materials.
2. Quantitative accuracy depends on several parameters such as: signal-to-noise ratio, peak intensity, accuracy
of relative sensitivity factors, correction for electron transmission function, surface volume homogeneity,
correction for energy dependency of electron mean free path, and degree of sample degradation due to
analysis.
3. Under optimum conditions, the quantitative accuracy of the atomic percent (at%) values calculated from the
Major XPS Peaks is 90-95% for each major peak. If a high level quality control protocol is used, the
accuracy can be further improved.
4. Under routine work conditions, where the surface is a mixture of contamination and expected material, the
accuracy ranges from 80-90% of the value reported in atomic percent values.
5. The quantitative accuracy for the weaker XPS signals, that have peak intensities 10-20% of the strongest
signal, are 60-80% of the true value.
Analysis time
1–10 minutes for a survey scan that measures the amount of all elements, 1– 10 minutes for high energy
resolution scans that reveal chemical state differences, 1– 4 hours for a depth profile that measures 4– 5
elements as a function of etched depth (usual final depth is 1,000 nm)
Detection limits
0.1–1.0 at% (0.1 at% = 1 part per thousand = 1000 ppm). (Ultimate detection limit for most elements is
approximately 100 ppm, which requires 8–16 hours.)
Measured area
Measured area depends on instrument design. The minimum analysis area ranges from 10 to 200 micrometres.
Largest size for a monochromatic beam of X-rays is 1–5 mm. Non-monochromatic beams are 10–50 mm in
diameter. Spectroscopic image resolution levels of 200 nm or below has been achieved on latest imaging XPS
instruments using synchrotron radiation as X-ray source.
❖ XPS detects all elements with an atomic number (Z) of 3 (lithium) and above. It cannot detect
hydrogen (Z = 1) or helium (Z = 2) because the diameter of these orbitals is so small, reducing the
catch probability to almost zero.
❖ Detection limits for most of the elements are in the parts per thousand range. Detections limits of
parts per million (ppm) are possible but require special conditions: concentration at top surface or
very long collection time (overnight).
TGA: Thermogravimetric analysis
TG Curve. Note the plateau of constant weight (region A), the mass loss
portion (region B), and another plateau of constant mass (region C)
TGA: Thermogravimetric analysis: Instrumentation
INTERPRETATION OF TG CURVES
Using TG curve we can relate the mass changes to the stoichiometry involved. This can often lead us
directly to the quantitative analysis of samples whose quantitative composition is known
let’s consider the example of TGA curve of CaCO3,
(Fig.) This curve indicates that CaCO3 decomposes
to form stable oxide CaO and the gas carbon dioxide.
This can be explained by the chemistry of CaCO3
when it is heated.
BET Surface Area Analysis
Nano scale particles – High Surface Area – Magic Results
BET
Equation
(Vm)
(16.2 Ų for N2)
N2-adsorption-desorption analysis: BET Surface area Analysis (Brunauer, Emmett, and Teller)
Directly measures surface area & pore size distribution
Another technique evolved from it is Barrett-Joyner-Halenda (BJH) analysis which are used to
determine pore area and specific pore volume using adsorption and desorption techniques.
Why is Liquid N2 Used In BET Analysis?
At liquid nitrogen temperatures, the kinetic energy of the nitrogen molecules is significantly reduced. This
leads to greater adsorption efficiency, as the molecules are more likely to condense onto the surface of
the adsorbent (sample).
BET Analyzer: Instrumentation
Step 1: Sample Preparation
[Link] Selection: Choose the material to be analyzed, ensuring it is clean and dry.
[Link]: Place the sample in the BET instrument and degas it at a high temperature under a
vacuum or inert gas to remove any adsorbed water and other contaminants. This ensures that the
surface area measurement reflects the true surface area of the material.
Step 2: Adsorption Process
i. Conditioning: After degassing, the sample typically needs to be cooled to a controlled
temperature, often using liquid nitrogen (-196°C) for gas adsorption studies.
ii. Gas Introduction: A gas (commonly nitrogen) is introduced into the chamber containing the
sample. The gas molecules interact with the surface of the material, adsorbing onto it.
Step 3: Measurement of Adsorption
i. Pressure Variation: The instrument gradually increases the pressure of the gas in a controlled
manner. As the pressure rises, more gas molecules are adsorbed onto the surface of the sample.
ii. Isotherm Construction: The amount of gas adsorbed at each pressure is measured, allowing for
the construction of an adsorption isotherm—a plot of the amount of gas adsorbed (Y-axis) versus
the relative pressure (X-axis P/P₀, where P is the equilibrium pressure and P₀ is the saturation
pressure). Desorption isotherm will be done by evacuation. This phase can also be recorded to analyze
hysteresis.
Step 4: BET Equation Application:
BET Analyzer: Principle
1
2
3
C = enthalpy of adsorption.
•For gases, the molar volume is approximately 22.4
ea liters/mole at standard temperature and pressure
(STP: 0°C, 1 atm).
16.2 Ų for N2
4
Pore width can make a big difference in the shape of isotherm