Scanning Electron Microscope (SEM)

A scanning electron microscope (SEM) is a type of electron microscope that produces images of a sample
by scanning it with a focused beam of electrons.

The electrons interact with atoms in the sample, producing various signals that can be detected and that
contain information about the sample's surface topography and composition.

Advantage
• High resolution
• Relatively easy to operate
• Reasonable cost

Disadvantage
• It needs coating for non-conductive sample.
• It does not provide no depth(height) information
• You can try to get cross-sectional image.
• AFM or STM
Scanning Electron Microscope (SEM)

secondary electrons

transmitted electrons
Scanning Electron Microscope (SEM)

Secondary Electrons

• Secondary electrons (SEs) come from the inelastic scattering between the SEM electron gun
and the atoms in the sample.
• Inelastic scattering is when the collisions do not conserve kinetic energy, and as such the
internal states of one or both of the particles has changed. Energy can be converted into
breaking the chemical bonds between components.
• Detecting SEs provides information about the sample surface.

Back Scattered Electrons

• Backscattered electrons (BSEs) come from the elastic scattering between the SEM electron gun
and the atoms in the sample.
• Elastic scattering is when the collisions between target and incident particles have total
conservation of kinetic energy. The internal states of each of the particles remains
unchanged.
• Detecting BSEs provides information about the sample atomic weight. Heavy elements will
appear brighter because they are more likely to generate BSEs.
Scanning Electron Microscope (SEM)

SE image BSE image

Scanning Electron Microscope (SEM)
Transmission Electron Microscopy (TEM)

• Transmission electron microscopy (TEM) is a microscopy

technique in which a beam of electrons is transmitted
through an ultra-thin specimen, interacting with the
specimen as it passes through.

• An image is formed from the interaction of the electrons

transmitted through the specimen; the image is magnified
and focused onto an imaging device, such as a
fluorescent screen, on a layer of photographic film, or to
be detected by a sensor such as a Charge-coupled device
(CCD) camera.
 Transmission Electron Microscopy (TEM)

The selected area electron diffraction (SAED) pattern each spot corresponding to a satisfied diffraction
condition of the sample's crystal structure.
Transmission Electron Microscopy (TEM)

SnO2 nanowire grown by VLS method.

 Transmission Electron Microscopy (TEM)
Focused Ion Beam (FIB)

Advantage
• Very high resolution (atomic level)

Disadvantage
• Expensive
• Sample has to be thin so that electron beam
can penetrate.
• typically ~100 nanometers or less.
• Sample preparation can take long time.
• It does not provide no depth (height)
information
 Scanning Probe Microscope (SPM)
Two major members of Scanning Probe Microscope (SPM) family are
• Atomic Force Microscopy (AFM)
• Scanning Tunneling Microscopy (STM)

They have demonstrated resolution on the order of fractions of a nanometer, more than 1000 times better than
the optical diffraction limit.

STM & AFM are surface image techniques & can produce
• Topographic Images of surface
• Atomic resolution in all three dimensions
• Combining with appropriately designed attachments

STM & AFM have several advantages over SEM/TEM for characterizing nanoparticles.
• Images from STM & AFM represent data in three dimensions, so that it is possible to measure the height
of the nanoparticles quantitatively.
• With an SEM/TEM, the images measured are only twodimensional.
Scanning Tunneling Microscope (STM)

• To form image, tip is raster-scanned across surface and tunneling

current is measured.

Quantum tunneling
Fe atoms on Cu (1 1 1) surface
Scanning Tunneling Microscope (STM)

• Constant current mode

• Measure Z-location for topography imaging.
• Low speed
• Irregular surfaces with high precision

• Constant Height Mode

• Measure tunneling current for imaging
• Fast speed
• Relatively smooth surfaces
 Atomic Force Microscope (AFM)

• AFM offers the capability of 3D visualization and both qualitative and quantitative information on many
physical properties including size, morphology, surface texture and roughness.

• Statistical information, including size, surface area, and volume distributions, can be determined as well.

• AFM can characterize nanoparticles in multiple mediums including ambient air, controlled environments, and
even liquid dispersions.

• AFM consists of a cantilever with a sharp tip (probe) at its end that is used to scan the specimen surface. When
the tip is brought into proximity of a sample surface, forces between the tip and the sample lead to a
deflection of the cantilever.
Atomic Force Microscope (AFM)
 Atomic Force Microscope (AFM)

Contact Mode Non-contact Mode

• Repulsive force • Attractive force
• Use soft Cantilever to prevent sample damage • Use hard Cantilever to prevent sample damage
• Relatively high resolution • Relatively low resolution
• Relatively slow scan speed • Relatively fast scan speed
Atomic Force Microscope (AFM)

Advantage
• Direct height measurements and Clear views of surface features (no coating is necessary)
• Three dimensional AFM images
• Conductors and insulators
• Images can be measured in all environments; ambient air, liquids and vacuums.
• SEM, TEM, STM must be done under vacuum.

Disadvantage
• It is slow in scanning an image, unlike an electron microscope which does it in almost real-time.
Scanning Tunneling Microscope (STM) VS Atomic Force Microscope (AFM)

• Resolution of STM is better than AFM because of the exponential dependence of the
tunneling current on distance.

• STM is generally applicable only to conducting samples while AFM is applied to both
conductors and insulators.
Summary
 Spectroscopy

Branch of analysis devoted to identifying elements and compounds and elucidating atomic and molecular
structure by measuring the radiant energy absorbed or emitted by a substance at characteristic wavelengths of
the electromagnetic spectrum (including gamma ray, X ray, ultraviolet, visible light, infrared, microwave, and
radio-frequency radiation) on excitation by an external energy source.

Probe Response

• Electrons • Electrons
Sample
• Radiation • Radiation
• Atoms • Atoms
• Ions • Ions
 X-ray photoelectron spectroscopy (XPS)

• X-ray photoelectron spectroscopy (XPS) is a surface-sensitive quantitative spectroscopic technique

based on the photoelectric effect that can identify the elements that exist within a material (elemental
composition) or are covering its surface, as well as their chemical state.

• XPS spectra are obtained by irradiating a material with a beam of X-rays while simultaneously
measuring the kinetic energy and number of electrons
X-ray photoelectron spectroscopy (XPS)

• The energy states of atoms or molecular ions in the valence band region have characteristic
ionization energies that reflect perturbations by the surrounding lattice environment.

XPS is used to measure:

• elemental composition of the surface
• 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)

From Handbook of X-ray Photoelectron Spectroscopy

X-ray photoelectron spectroscopy (XPS)
 Energy Dispersive X-ray Spectroscopy (EDS or EDX)

• Energy-dispersive X-ray spectroscopy (EDS, or EDX), is an analytical technique used for the elemental
analysis or chemical characterization of a sample.

• It relies on an interaction of some source of X-ray excitation and a sample.

• Its characterization capabilities are due in large part to the fundamental principle that each element
has a unique atomic structure allowing unique set of peaks on its X-ray emission spectrum.

• EDS detector can be attached to SEM or TEM.

 Energy Dispersive X-ray Spectroscopy (EDS or EDX)

• Probes samples with electron beam and results in emission of X-rays with energies characteristic of the
elements present in the sample.

• Composition of particles in nm (combine with TEM, <1 μm if with SEM) range can be examined due to
the use of electron beam. Probe depth is about 1 μm.

• Maps (composition as a function of position) of a particle -> quantify chemical homogeneity of

multicomponent particles.
 Energy Dispersive X-ray Spectroscopy (EDS or EDX)

Quantification analysis

Limitation of EDS: it’s not easy to detect light element. Hydrogen, Helium and lithium are not detectable at all.
• ICP-MS (Inductively Coupled Plasma-Mass Spectrometry)
• GDOES (Glow-discharge optical emission spectroscopy)
 X-ray Absorption Spectroscopy (XAS)

X-ray absorption spectroscopy (XAS) is a widely used technique for determining the local geometric
and/or electronic structure of matter. The experiment is usually performed at synchrotron radiation
facilities, which provide intense and tunable X-ray beams. Samples can be in the gas phase, solutions,
or solids

Pohang Light Source-II (PLS-II)

 X-ray Absorption Spectroscopy (XAS)

µ = ln (I0 / I ) I0 : intensity of incident beam, I : intensity

Principle of XAS of transmitted beam

This interference at the absorbing

atom will vary with energy, causing
the oscillations in µ(E )

XANES : up to ~ 60 eV above the edge

EXAFS : from ~ 60 eV to 1200 eV above the edge
X-ray absorption near edge structure (XANES)
X-ray absorption near edge structure (XANES)

The edges of many elements show significant edge

shifts (binding energy shifts) with oxidation state
X-ray absorption near edge structure (XANES)
Extended X-ray Absorption Fine Structure (EXAFS)

Based on β-Fe2O3
Extended X-ray Absorption Fine Structure (EXAFS)