1.

Introduction
Análisis de la
UNIT 1 BULK ANALYSIS
COMPOSICION GLOBAL

1. Introduction.

2. General characteristics of techniques for solid and

surface analysis

Analysis with
LATERAL &/or DEPTH
RESOLUTION

Bio-imaging techniques(e.g. metals distribution)

63Cu+

- Biological Tissues.
Metal distribution Metals are receiving ever-increasing recognition for their roles in
in a plant leaf
biomedical and biological processes.

Abnormal metal levels may be indicative for some neurodegenerative

- Geology disorders*, such as Alzheimer’s (Al, Zn), Parkinson’s (Fe), Wilson’s (Cu), breast

Ca distribution cancer, age-related eye macula degeneration (Zn, Fe), glaucoma, etc. To
in a Garnet. know the distribution of these metals in the target organs (e.g. brain, eyes) will
help to understand the biological processes.

The measurement of metal distribution in leaves and seeds will allow to search
- Materials Science. Galvanized for the proper way of plant feeding or for the search of proper genetic modifications.
steel.

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 IMMUNOHISTOCHEMISTRY
Mapping of proteins can be carried out by bioconjugation of the proper 63Cu+

antibody to e.g.: - Biological Tissues.

Metal distribution
- Rare-earth metals
in a plant leaf.
- Metal nanoparticles (signal amplification)

Advantages versus
conventional detection: - Geology
• Absence of autofluorescence. Ca distribution
in a Garnet.
• High multiplexing capabilities (less
risk of spectral overlapping).

• Quantification. Metal-tagged
- Materials Science. Galvanized
• Analysis of metalloproteins: immunoprobes steel.
simultaneous distribution of the
protein and the coordinated metals.

Study of the variation of the compositional

distribution of stalagmites, which may be used for
information of the environmental conditions that
prevailed during the process of formation of the
stalagmite, including floods.

Map of the distribution of Calcium in a garnet from the Ordovician Moretown Formation, Massachusetts.

The change in elemental composition from the center (also known as core) to the edge (or rim) of a
crystal in a mineral can yield information about the history of the crystal’s formation, including
temperature, pressure and chemistry of the surrounding medium

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 The timeline of human
63Cu+ Stone Age evolution
- Biological Tissues. is usually divided according
Metal distribution Bronze Age to the main material used and
in a plant leaf. dominated by humans.

- Geology
Ca distribution
in a Garnet.
Arrow
Iron Age

- Materials Science. Galvanized

steel.
The timeline of human evolution outlines the
Iron helmet
major events in the development of human
species, and the evolution of humans' ancestors.

Classification of materials
INTRODUCTION
Classification according to chemical composition and atomic structure
Nowadays, the production of new materials and their proper processing Materials Characteristics
to convert them into finished products constitute a key part
of the economy of our society Most of their properties can be attributed to the existence of
Metals and
delocalized electrons: they can conduct electricity and heat; they
alloys
are opaque to visible light; they are resistant, though can be
distorted.
They are constituted by metals and non-metals (e.g. oxides,
Ceramics
nitrides and carbides). Generally, they are thermal and electric
and glasses
insulators, resistant to high temperatures and to aggressive
environments, hard and fragile.

Polymers Organic compounds characterized by the high length of the

molecular structures. They have low density and high flexibility.

Materials with electrical conductivity due to electron flow

Semiconductors (as opposed to ionic conductivity) intermediate in magnitude
between that of a conductor and an insulator.
.
Engineered or naturally occurring materials made from two or
Composites more materials with significantly different physical or chemical
properties which remain separate and distinct at the
macroscopic or microscopic scale within the finished structure.

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Classification according to particular characteristics and applications
- BIOMATERIALS.
- BIOMATERIALS, which relate to any material designed
to be implanted into living organisms. The driving force for the - MATERIALS FOR CATALYSIS. The
high development which is being achieved by this sector is the development of new materials oriented to catalysis has
possibility to increase the life length and the life quality. permitted the creation of new or improved chemical and
physical processes.

- BIOMATERIALS. - BIOMATERIALS.

- MATERIALS FOR CATALYSIS. - MATERIALS FOR CATALYSIS.

- MAGNETIC MATERIALS. Used in many different - MAGNETIC MATERIALS.

aspects of our lives, allowing for example, for information
encoding (e.g. credit cards, hard disks, code bars). - NANOMATERIALS.
Nanotechnology deals with structures sized between 1 to 100 nm in at
least one dimension, and involves developing materials or devices
possessing at least one dimension within that size.

Materials with morphological features on the nanoscale are called

Nanomaterials, especially those that have special properties arising
from their nanoscale dimensions.

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 Coatings and Thin Films. General aspects.
- BIOMATERIALS.

- MATERIALS FOR CATALYSIS. The objective of a coating or a thin film is to have a

final material with improved performance:
- MAGNETIC MATERIALS.
it is impressive to see how in many applications
the small mass amount in the coating is enough
- NANOMATERIALS.
to modify the properties of a bulk material
- COATINGS AND THIN FILMS.
The presence of coatings with thicknesses in
the micrometer range or even thinner coatings
(below 100 nanometres) can give rise to a
dramatic change of the properties of the
material as a whole.

Galvanized steel Tinplate

Coatings and Thin Films. General aspects.

Examples of technological sectors using coatings Thin Film Solar Cells (TFSC):
- Trim coatings for automotive components.
Automotive sector - Hard coatings for mobile parts of engines.

- Hard coatings for cutting tools.

Machinery - Tribological coatings for mobile gears.

Domestic - Tap coatings, pipes, knobs, etc.

Architecture - Heat-insulating coatings for glass panels used in modern buildings.

Many different photovoltaic materials are deposited with various deposition
methods on a variety of substrates. Thin-film solar cells are usually categorized
Microelectronics, - Magnetic layers for hard discs, magnetic tags, etc. according to the photovoltaic material used, e.g.:
Magnetism - Active layers in optical discs.
- Anti-reflective, anti-moisture, etc. in mirrors, glasses, lenses, etc.
- Amorphous silicon (a-Si) and other thin-film silicon (TF-Si)
& Optics
- Cadmium telluride (CdTe)
Toys & Imitation jewellery - Protective and decorative coatings. - Copper indium gallium selenide (CIS or CIGS)
- Protective coatings for food packaging (e.g. to avoid problems - Dye-sensitized solar cells and other organic solar cells
Food related to humidity and light).

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 Thin Film Batteries:
Final remarks for the Introduction…….
Thin film lithium ion batteries are
similar to lithium-ion batteries, but they Human beings are exposed to the harmful effects of
are composed of thin materials, some some materials, particularly of some new materials
only nanometers or micrometers thick, produced along the last century. An example is the
which allow for the finished battery to production of plastics, which are used for example for
be just a few millimeters thick. food packaging.

A few years ago, it has been noticed that harmful

These batteries have the ability to be an integral part of
implantable medical devices (such as defibrillators and
neural stimulators), “smart” cards, radiofrequency
identification, and wireless sensors.
They can also serve as a way to store energy collected
from solar cells or other harvesting devices.
migrations from the plastic towards the food can take
place, particularly under some circumstances (for
example, at high temperatures), producing health
problems.
Such a discovery has given rise
to mandatory security norms
and to the search for improved food
packaging materials.

2. General characteristics of the techniques

for solid and surface analysis.
3 D information
Less time.
Lower cost.
Less contamination. It can be obtained:
DIRECT Less sample destruction.
SOLID
ANALYSIS More information *speciation (oxidation states,
bonds, etc).
*analysis with lateral resolution.
*in-depth profile analysis.

Analysis with lateral resolution

In-depth profile analysis

- By sequentially removing the or - By advanced image analysis
layers (with ions or by laser
of optical sections
ablation)

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 PROPERTIES OF THE IDEAL TECHNIQUE X Ray Fluorescence
FOR DIRECT SOLID ANALYSIS
Análisis de la Arc and Spark Spectroscopy
BULK ANALYSIS
COMPOSICION GLOBAL
1. Applicability to any sample type (conductors, insulators, particles,
blocks, etc). THERMAL ANALYSIS
Group of techniques where a given physical or
2. Non destructive. chemical property of a sample (a few mg) is
measured as it changes with temperature
3. High sensitivity and precision.
4. Linear range from 1 atom up to 100%.
5. Without matrix interferences.
6. Lateral and depth information.
7. Elemental and molecular information.

8. Low acquisition and maintenance costs.

9. Easy operation.
10. Fast and without sample preparation requirements.

Applications of Thermal Analysis in various industries X Ray Fluorescence

Análisis de la Arc and Spark Spectroscopy
BULK ANALYSIS
COMPOSICION GLOBAL
THERMAL ANALYSIS

Analysis
Análisis with
con EPXMAelectrónica
Microsonda , GD-OES.
LATERAL &/or
RESOLUCION DEPTH y/o
LATERAL Ablación
XPS or con láser
ESCA . -
ENRESOLUTION
PROFUNDIDAD ICP-OES o ICP-MS
AES .
SIMS y SNMS
Auger y Esca SNMS,
GD-MS, SIMS,
LMMS, LA-ICP-MS.
GD-OES y GD-MS

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 Main elemental spectroscopic techniques
for direct analysis with spatial resolution
hν XRF: X Ray Fluorescence.
B+ hν LIBS: Laser Induced Breawdown
Detected particles Spectroscopy.
A+
EPXMA: Electron Probe X-ray
Photons Electrons Ions
- Micro Analysis.
e e-
XRF GD-OES: Glow Discharge –

Excitation source
B0 Photons XPS LMMS Optical Emission Spectrometry.
LIBS

XPS: X-ray Photoelectron Spectroscopy.

Electrons EPXMA AES AES: Auger Electron Spectroscopy.

LMMS: Laser Microprobe – Mass

GD-MS Spectrometry.
Ions GD-OES SIMS
SNMS GD-MS: Glow Discharge – MS.
• The most important techniques for direct solid analysis are Spectroscopic. SIMS: Secondary Ions Mass
Spectrometry.
• Most of them are based on the interaction between the material of interest with SNMS: Sputtered Neutrals Mass
photons, electrons, neutral particles, ions, heat, electric fields, etc. and the subsequent Spectrometry.

detection of photons or secondary emitted particles (or sputtered) in response to Optical Electron Mass
spectrometry Spectrometry Spectrometry
such interaction

Laser Ablation + ICP-OES / ICP-MS

EXCITATION SOURCE
Removal of material from the surface
of an object by vaporization
Penetration Depth

Ions Electrons
- 1. The sample surface is volatilized by a high energy Photons
highly focussed photon beam from a laser source.
1 nm
2 nm
- 2. The volatilized sample is transported as aerosol towards
the ICP, where it is excited and ionized.
1000 nm
SOLID

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 INFORMATION DEPTH INFORMATION AREA
Over the past three decades, the interest in X-ray microscopy has
been fostered by advances in X-ray sources, X-ray optics and X-ray
detector technology.
Incident Emitted
beam ELECTRONS
particles PHOTONS * X-ray scanning microscopy techniques largely benefit from the
high brilliance and high collimation of X-ray beams produced by
synchrotron sources.
SAMPLE SAMPLE
SURFACE Information depth * Smaller µXRF instrumentation uses polycapillary and doubly
SURFACE
curved crystal focusing X-ray optics, offering an alternative means to
Penetration
depth “excited” generate small focal spots with high X-ray flux on the sample surface
volumne for µXRF applications

A synchrotron is a particular type of cyclic particle accelerator in which the

guiding magnetic field (bending the particles into a closed path) is time-
dependent, being synchronized to a particle beam of increasing kinetic
energy

When high-energy particles are in rapid motion, including electrons forced to

travel in a curved path by a magnetic field, synchrotron radiation is produced

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 Thin Films Analysis by SPUTTERING DEPTH PROFILING TECHNIQUES
• Removed Matter Techniques.- The analysis of the sputtered matter as a function of the sputtering time
allows the determination of the compositional distribution of a thin film vs the distance from the original
surface (depth of the layer)
• Remaining Surface Techniques.- The surface remaining after sputtering is analyzed

-Analysis time & costs of analyses

-Results interpretation
-Matrix effects

-Elemental or molecular info
-Major, minor, trace.. components
-Qualitative or Quantitative.
-Precision & Accuracy
-Depth resolution
-Imaging
-“Ideal” samples (crystalline substrate, clean & polished surfaces, well
defined layers) or Technical processing samples
LIBS, LMMS & LA-ICP-MS
-Stability (vacuum conditions)
-Conductivity (conducting vs insulators)
-Dimensions

**To summarize, we can conclude that:

i) It is important to know the capabilities and

limitations of each technique. This will allow to
select the best one depending on the sample and the
required information.

ii) A single technique can not provide all the

information and, therefore, the different techniques
available should be considered as complementary.

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