Three Techniques related to my

PhD thesis
João Paulo de Freitas Grilo
Professor: Augusto Lopes
 Summary

• Brief topic of PhD thesis

• Impedance Spectroscopy
• Transmission Electron Microscopy
• Electron Energy Loss Spectroscopy
• Articles related to my PhD thesis

João Paulo Grilo 2

• Project of my Ph.D thesis
– Development of multifunctional composite
electrolytes
– Materials based on ceria (gadolinium doped ceria –
GDC) and eutectic mixtures of alkaline carbonates
– Compositions (percentages of phases),
microstructures (oxide particle size ranging from the
nano to the micrometer scale) and operating
environments (temperatures and atmospheres)
– Analyse electrical properties with microstructure and
environments
– nature and concentration of the charge carriers
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 Impedance
Spectroscopy
• IS is an used analytical technique for the
characterization of electrochemical systems.
• Electrical impedance is the measure of the
opposition that a circuit presents to a current
when a voltage is applied. It is the algebraic sum
of
• |Z| = 𝑍′2 + 𝑍′′2 Contribution of current resistance
of the capacitor and inductor: Vary
with frequency.

Contribution of current resistance

of the resistor: Does not vary with
frequency
João Paulo Grilo 4
 Impedance
Spectroscopy
• The technique consists in disturbing the
equilibrium position of an electrochemical
system, by applying a sinusoidal alternating
voltage of low amplitude, usually between
100 and 500 mV, and recording the real and
imaginary parts of the impedance versus
Furnace
frequency. Current collector: Au
or Pt

Sample
impedance analyzer João Paulo Grilo 5
 Impedance
Spectroscopy
• Measurements are performed in a frequency range from 0.1
mHz to 30MHz.
• IS permits the separation of the various individual contributions
associated with the polarization processes in a material which
has different responses in a range of frequencies.

In ceramic electrolytes, as GDC it is

common to attribute the
phenomenon at high frequencies
the bulk conducting process, and the
phenomenon at intermediate
frequencies the grain boundaries
conducting process.
João Paulo Grilo 6
 IS related to PhD
M. Benamira et al ECS T. v. 7, p. 2261-2268, 2007. thesis
Reported electrical analyses of composite
materials based on mixtures of gadolinium-
doped ceria (GDC) and Li2CO3-K2CO3. Li2CO3-
K2CO3

• A) And B) spectra shape depends on

measurement temperature.
• A)two semi-circles are observed, the first in
the high frequency range is well-defined and
a larger one, not fully defined, at low
frequency range.
• B) The first semicircle, in the high frequency
range, becomes very small and difficult to
describe; whereas, the second one is
predominant at medium and low frequencies.
João Paulo Grilo 7
 Transmission
Electron Microscopy
• 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 it. 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 or to be
detected by a sensor such as a CCD camera.
• Electrons can easily pass through or electrons can scatter
by the presence of the different structures of the
specimens
João Paulo Grilo 8
 Transmission Electron
Microscopy
• Show iternal structures of specimens with magnification up to
1,000,000 X, revealing structures in atomic resolution, up to
0.5 Angstroms
Electrons are fast emmited by
a source that is inside that a
vacum chamber. The final
image is reflected.

Transmission electron
micrograph of dislocations in a
metal, which are faults in the
structure of the crystal lattice at
the atomic scale

João Paulo Grilo 9

 Transmission Electron
Microscopy
Electron gun (thermionic and field emission), use
Tungsten wire or LaB6. The filament releases electrons.

Electrons continues into vacuum tube and there are

magnetic lens.
Condenser lens gather the electrons of the first
crossover image and focus them onto the specimen
to illuminate only the area being examined.

Objective lens is used primarily to focus and

initially magnify the image. The specimen
stage is inserted into the objective lens for
imaging purposes.

Projector lenses further magnify the image

coming from the intermediate lens and
projects it on to the phosphorescent screen.

João Paulo Grilo 10

 TEM related to PhD
thesis
X. Wang et al Elect. Commun. v. 10, p. 1617–1620, 2008.
core-shell SDC (Ce0.8Sm0.2O1.9)/amorphous Na2CO3
nanopowders
a) nanoparticle with core-shell
structure, this is clear due the large
contrast difference between the
inner and the outer

b) is possible to see the dominant lattice fringes in the core; the distance
between parallel fringes is equal to the spacing of the {111} planes in SDC.
No lattice fringe can be observed in Na2CO3 shell layer which further
confirms that Na2CO3 is amorphous.

João Paulo Grilo 11

 Electron Energy Loss
Spectroscopy
• Electron energy-loss spectroscopy (EELS) is an analytical
technique that measures the change in kinetic energy of
electrons after they have interacted with a specimen.
• A material is exposed to a beam of electrons with a known,
narrow range of kinetics energy. Some of the electrons will
undergo inelastic scattering, which means that they lose
energy and have their paths slightly and randomly deflected.

EELS involve measurement of the energy

distribution of electrons that have interacted
with a specimen and lost energy due to
inelastic scattering.

João Paulo Grilo 12

 Summary
EELS system is attached to TEM. A) The simplest form of energy-loss system
A TEM provides ideal conditions for consists of a conventional TEM fitted with a
performing inelastic scattering magnetic prism below its image-viewing
experiments. chamber
electrons are allowed to enter the
spectrometer, where they are dispersed
according to their kinetic energy.

An alternative strategy is to incorporate a

spectrometer into the TEM imaging column B).

An energy-loss spectrum is produced just

below the omega filter and subsequent TEM
lenses project it onto the viewing screen or
onto an electronic detector, usually employing
a CCD camera.

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João Paulo Grilo
 Electron Energy Loss
Spectroscopy
Zero loss: this peak represents the electrons which Low-loss region: from a few
passed through the specimen with loss negligible, or hundreds of meV up to around one
with no energy loss. These electrons are elastically hundred eV. It involves intrabands
scattering electrons. (metals) or interbands (valence to
conduction bands in semi-
conductors). It contains all the
information on optical phenomena
(plasmons, but also band gaps,
excitons, interband
transitions, etc.).

Core-loss region: from one hundred eV

to thousands. corresponding to
transitions from a core electron level to
an empty band level. Spectral
signatures in this range are related to
Typical EELS spectrum (carbon nanotube filled the elemental composition and
with manganese). electronic structure of the sample
under the electron beam.
João Paulo Grilo 14
 Electron Energy Loss
Spectroscopy
Y. Ma “Ceria-based Nanocomposite Electrolyte for Low-Temperature
Solid Oxide Fuel cells” Licentiate Thesis, Stockholm, 2009.

In his work Ying Ma reported the manufacturing of SDC

nanowires. To confirm the presence of the elements in the
nanowires, he performed EELS analyses on the TEM picture
region.
A) TEM micrograph taken from
inner zone of the nanowire
shows the texture of a single
nanowire as poly-crystalline
with recognizable boundaries
or voids.

B) confirms that the nanowires are comprised of only Sm (N4,5),

Ce (N1, M4,5) and O (K). The intensity of Ce (M4) line is observed
to be higher than that of Ce (M5), indicating that the oxidation
state of cerium in the SDC nanowires is mainly +4
João Paulo Grilo 15
 Thank you

João Paulo de Freitas Grilo

Professor: Augusto Lopes