Unit 4

Characterization of Nanomaterials
and Nanostructures
 Scanning Probe Microscopy
Diffraction of light or electron waves associated with far-field interactions limit their resolution to
wavelength scales. The near-field interactions in a SPM, however, enable us to obtain a true
image of surface atoms. Images of atoms can be obtained by an SPM because it can accurately
measure the surface atom profiles in the vertical and lateral directions.

SPM started with the scanning tunneling microscope (STM) invented in 1982

An STM uses a tunneling current, a phenomenon of quantum mechanics, to examine material

surfaces. The tunneling current flows through an atomic-scale gap between a sharp metallic tip
and conducting surface atoms.

Atomic Force Microscopy (AFM) uses near-field forces between atoms of the probe tip apex and
the surface to generate signals of surface topography.

The AFM is more widely used than the STM because it is not restricted to electrically conducting
surfaces.
 Instrumentation
The STM and AFM differ in probe material and in how the sensor works. In an STM, the probe is commonly
made from tungsten wire.

The tungsten wire conducts the tunneling current flowing between surface atoms and tip atoms.

In the AFM, the probe tip is commonly made from SiO2 or Si3N4 and mounted onto a cantilever spring.

A probe motion sensor senses the spacing between the tip apex and the sample and provides a correction signal
to control the piezoelectric scanner movement. In the STM, the tunneling current is used to sense the spacing
between the probe and the sample surface. In the AFM, near-field forces between tip and sample detected by a
beam deflection system are used to sense the spacing.

The scanner controls the probe that moves over the sample in three dimensions in a precise way. The scanning
probe needs to be positioned with an accuracy of 1 pm (10−12 m) if atomic resolution is required. To achieve this
level of precision, a scanner is made from piezoelectric materials. Piezoelectric materials change shape in an
electric field or generate an electric field due to shape change. The relative length of the change is proportional
to applied voltage (E).
Comparison with diffraction limited techniques
Instrumentation
 Instrumentation
A scanning probe microscope is a computer-based instrument, unlike light and electron
microscopes that can operate without computers. The computer controls the scanner
and probe through an electronic interface. The interface supplies the voltages that
control the piezoelectric scanner, accepts the signal from the position sensing unit and
contains the feedback control system for keeping the spacing between sample and tip
constant.

scanning probe microscope must be isolated from any vibrations in its surroundings in
order to achieve high resolution because its performance relies on precise control of the
distance between the mechanical probe and sample surface. To maintain a constant
near-atomic spacing during operation, any vibration from the environment must be
eliminated. Common interference includes floor vibrations and acoustic vibration.
Isolation from floor vibration is achieved by mounting the SPM on springs, rubber feet or
air-damped feet. Isolation from acoustic vibration is achieved by operating the
instrument in a solid box.
Forces when two atoms come close
Modes in AFM
The feedback loop adjusts the sample
height (z-piezo) to keep the oscillation
amplitude constant.
• If the surface goes “up,” the amplitude
reduces: feedback raises the cantilever
• If the surface goes “down,” the
amplitude increases → feedback lowers
the cantilever.
AFM
AFM
AFM
Modes in AFM
AFM tips
 AFM tips
A single-beam cantilever beam is usually made from silicon with dimensions of
about 100–500 μm long and 0.5–5 μm wide. The triangular beam is commonly
made from silicon nitride. Most cantilevers are produced with integrated tips in a
micro-fabrication process, similar to the process for manufacturing integrated
circuits in the electronics industry.

A tip radius of about 20 nm has been achieved. The open angle, however, is often
limited by etching characteristics of crystalline materials. Etched surfaces of
crystalline materials are often comprised of certain crystallographic planes. For
example, the silicon tip pointing to the <100> direction has a cone angle of about
54.7◦, which is the angle between {100} and {111} planes, because {111} planes are
the etched surface of crystalline silicon.
Sources of error
Sources of error
 Sources of error

Vibration
 Error Elimination

• Repeat the scan for the same area;

• Change the scanning direction;
• Change the scanned area size;
• Rotate the sample and conduct a second scan; and
• Change the scanning speed.
Resolution
Ability to distinguish between 2 points.
Higher resolution means more detail and clarity.

Depth of Field (DoF)

Range of distance over which the image appears in focus
A shallow DoF keeps only a small area in focus, while a deep DoF keeps more of the scene
sharp

Brightness
Controls how light or dark an image appears.
Increasing brightness makes the whole image lighter, while decreasing it darkens the image.

Contrast
The difference between the lightest and darkest parts of an image.
High contrast creates a more dramatic effect with vivid differences, while low contrast makes the
image appear more flat or muted.
SEM
BSE provides information on surface SE provides detailed information on
topology and atomic number surface topology. Image is pseudo 3D
Figure 2 presents the secondary (SE) and backscattered electrons (BSE) image of the sample
where it is possible to observe that the material consists of two distinct phases; the bright grains
being composed by a phase with average atomic number higher than the dark triangular
precipitates.

DOI: [Link]
 SE BSE

SE image with a much higher depth of field than BSE

EDS and WDS
 Charging in SEM

Solution

Deposit conducting
coating of Au/Cu
using sputtering

[Link]
TEM
 Sample preparation
Solid sample Powder sample

Thickness less than 100 nm

X-ray Diffraction: Principles and Practice

• Materials Characterization
• Importance of X-ray Diffraction
• Basics
• Diffraction
• X-ray Diffraction
• Crystal Structure and X-ray Diffraction
• Different Methods
• Phase Analysis
• Texture Analysis
• Stress Analysis
• Particles Size Analysis
Generation of X-rays
Generation of X Rays
X-ray tube X-rays
Be window

W cathode Metal anode

Electrons

Rotating anode
 Diffractometer

➢ Source

➢ Optics

➢ Detector

Incident Beam Part Diffracted Beam Part

Sample Diffracted Beam

Optics
Source Incident Beam Detector
Optics
 Detectors

➢ Single photon detector (Point or 0D)

▪ scintillation detector NaI
▪ proportional counter, Xenon gas
▪ semiconductor
➢ Position sensitive detector (Linear or 1D)
▪ gas filled wire detectors, Xenon gas
▪ charge coupled devices (CCD)
➢ Area detectors (2D)
▪ wire
▪ CCD
➢ 3D detector

Photoelectron or Photomultiplier tube or

X-ray photon Electrical signal
Electron-hole pair amplifier
Use of Filter

• Ni filter for Cu Target

Crystal Systems and Bravais Lattices
Structure of Common Materials
• Metals
• Copper: FCC
• -Iron: BCC
• Zinc: HCP
• Silver: FCC
• Aluminium: FCC
• Ceramics
• SiC: Diamond Cubic
• Al2O3: Hexagonal
• MgO: NaCl type
Diffraction
• A diffracted beam may be defined as a beam composed of a large
number of scattered rays mutually reinforcing each other

Scattering
Interaction with a single particle

Diffraction
Interaction with a crystal
Scattering Modes
• Random arrangement of atoms in space gives rise to scattering in all
directions: weak effect and intensities add
• By atoms arranged periodically in space
• In a few specific directions satisfying Bragg’s law: strong intensities of the
scattered beam :Diffraction
• No scattering along directions not satisfying Bragg’s law
Geometry of Bragg’s law
➢The incident beam, the normal to the reflection plane,
and the diffracted beam are always co-planar.

➢The angle between the diffracted beam and the

transmitted beam is always 2 (usually measured).

➢Sin  cannot be more than unity; this requires

nλ < 2d, for n=1, λ < 2d

λ should be less than twice the d spacing we want to study

Order of reflection

➢Rewrite Bragg’s law λ=2 sin d/n

➢A reflection of any order as a first order reflection from planes, real or fictitious,
spaced at a distance 1/n of the previous spacing

➢Set d’ = d/n λ=2d’ sin

➢An nth order reflection from (hkl) planes of spacing d may be considered as a first
order reflection from the (nh nk nl) plane of spacing d’ = d/n

*The term reflection is only notional due to symmetry between incoming and
outgoing beam w.r.t. plane normal, otherwise we are only talking of diffraction.
Two Circle Diffractometer
• For polycrystalline Materials
NaCl crystals in a tube facing X-ray beam
Ɵ Sin2Ɵ Sin2Ɵ/Sin2Ɵ1
Systematic Absences

Permitted Reflections

Simple Cubic (100), (110), (111), (200), (210), (211),

(220), (300), (221) ………
BCC (110), (200), (211), (220), (310), (222)….
FCC (111), (200), (220), (311)…..
Powder Diffractometer
Diffraction from a variety of materials

(From “Elements of X-ray

Diffraction”, B.D. Cullity,
Addison Wesley)
Name and formula
Reference code: 00-001-1260
Stick pattern from JCPDS
PDF index name: Nickel
Empirical formula: Ni
Chemical formula: Ni
Crystallographic parameters
Crystal system: Cubic
Space group: Fm-3m
Space group number: 225
a (Å): 3.5175
b (Å): 3.5175
c (Å): 3.5175
Alpha (°): 90.0000
Beta (°): 90.0000
Gamma (°): 90.0000
Measured density (g/cm^3): 8.90
Volume of cell (10^6 pm^3): 43.52
Z: 4.00
RIR: -
Status, subfiles and quality
Status: Marked as deleted by ICDD
Subfiles: Inorganic
Quality: Blank (B)
References
Primary reference: Hanawalt et al., Anal. Chem., 10, 475,
(1938)
Optical data: Data on Chem. for Cer. Use, Natl. Res.
Council Bull. 107
Unit cell: The Structure of Crystals, 1st Ed. [Link]
Information in a Diffraction Pattern

• Phase Identification
• Crystal Size
• Crystal Quality
• Texture (to some extent)
• Crystal Structure
 Analysis of Single Phase
2(˚) d (Å) (I/I1)*100
27.42 3.25 10
31.70 2.82 100
45.54 1.99 60
53.55 1.71 5
56.40 1.63 30
Intensity (a.u.)

65.70 1.42 20
76.08 1.25 30
84.11 1.15 30
89.94 1.09 5
I1: Intensity of the strongest peak
➢ Resolution: ability to distinguish between energies

➢ Energy proportionality: ability to produce signal proportioanl to

energy of x-ray photon detected

➢ Sensitivity: ability to detect low intensity levels

➢ Speed: to capture dynamic phenomenon

➢ Range: better view of the reciprocal space

 Data collection and analysis

➢ Choose 2θ range

➢ Step size and time per step

➢ Hardware: slit size, filter, sample alignment

➢ Fast scan followed with a slower scan

➢ Look for fluorescence

➢ Collected data: Background subtraction, Kα2 stripping

➢ Normalize data for comparison I/Imax
Summary
• X-ray Diffraction is a very useful to characterize materials for following
information
• Phase analysis
• Lattice parameter determination
• Strain determination
• Texture and orientation analysis
• Order-disorder transformation
• and many more things
• Choice of correct type of method is critical for the kind of work one intends to do.
• Powerful technique for thin film characterization
UV vis NIR setup

Broad band
UV–Vis–NIR transmittance spectra of
antireflective (AR) coatings from porous silica,
containing 10, 17, and 25 mol % CeO2, on low-
iron soda-lime glass in comparison to uncoated
glass. Curing conditions were 60 min at 350 °C.
DLS
AFM 3D imaging

SEM + EDX (surface topology + elemental information)

TEM (surface topology + Phase information)

XRD (Phase information)

UV vis (Optical characterization)

DLS (Size of nanoparticles)

[Link]