MATERIALS I NANOESTRUCTURES - MEQ - 16-17

Questionnaire on Block 2
6. Introduction to nanotechnology and nanomaterials
1. Define nanotechnology.
Deals with the design, characterisation and application of structures, devices
and systems of sizes less than 100 nanometers (nm).
Nanomaterials disminueix el seu tamany i tamb el melting point. Surface
atoms require less energy to move because they are in contact with fewer
atoms of the surface.
2. Define nanomaterial.
Is a material consisting of a substance or structure which has at least one
dimension less than 100 nm.
3. Classify nanomaterials according to the number of nano-dimensions and
give examples.
1D such as: graphene
2D such as: nanotubes
3D such as: nanoparticles
According to composition: single-phase solids, multi-phase solids and multi-
phase systems.
4. Why size matters in the nano-world?
Size matters because nanoscale allows to appears new properties.
Nanostructures have new properties and behaviour that are not exhibited by
the bulk matter of the same composition and display new chemistry and
physics that lead to new properties that depend on size.
5. What is quantum confinement and how does it influence the properties of
nanomaterials?
As the particles are becoming smaller, the electrons are not free to move about
as in bulk material. Because of the restriction, the nanoparticles react
differently from that of bulk material. For example, they absorb light at
wavelengths that are strongly dependent on the particle size.
6. What kind of forces are dominant at the nanoscale and what is their
influence in the properties of nanomaterials?
Electrostatic forces dominate over gravitational force at the nanoscale.
Gravitational forces (function of mass and distance) are weak between (low-mass) nanooarticles.
Electrostatic forces (function of charge and distance) are not affected by mass, so they can be very
strong.
7. Properties at nanoscale.
1) Quantum confinement: as the particles are becoming smaller, the e are not free to move
about as in bulk material. Because of this restriction, the nanoparticles react differently
from that of bluk material. They absorb light at wavelengths that are strongly dependet
on the particle size.
2) Random molecular motion is significant: at macroscale we barely see movement and
the particle is moving wildly at nanoscale.
3) Changes in dominant forces: pregunta 6.
4) Surface area-to-volume ratio (SVR): much of the chemistry happens on the surface, so
it is very important to take in account the surface. Conforme el material s ms petit,
SVR increase by several orders of magnitude.
7. Nanoparticles and quantum dots
1. Describe the differences and similarities between metallic nanoparticles
and quantum dots.
Quantum dots are a kind of metallic nanoparticles. And the difference is that
nanoparticles have different optical and electronic properties. They are able to emit
light of specific frequencies if electricity or light is applied to them.

2. Describe the Turkevich method to prepare gold nanoparticles and explain

the color changes observed during the reaction.
https://www.youtube.com/watch?v=pMkbozvheaY

Primer es prepara una soluci aquosa de 300mL amb una concentraci de 0.5mM
de clorur d'or en un vas de precipitats. A continuaci s'escalfa amb vapor. En una
estona s'afegeix 30mL de soluci aquosa amb una concentraci de 38.8mM de
soluci de citrur de trisodi. Llavors la soluci es queda sense color, el perd i al cap
d'una estona comena a enfosquir-se. Finalment, un cop acaba la reacci s'ha de
refredar la soluci i obtenim les nanopartcules d'or suspeses en la soluci aquosa
de color vermell i a nivell de microscopi d'electrons es veuen les nanopartcules
d'or.

3. Define quantum dot.

There are semiconductors particles. Its size is about nanometers, so their optical
and electronic properties differ from those of larger particles. Emit light of specific
frequencies if electricity or light is applied to them. They are also refered as
artificial atoms.

4. Why quantum dots are fluorescent?

Because they absorb photons of light and then re-emit longer-wavelength
photons nearly instantaneously.
Los principales materiales semiconductores de los que estn hechos los
quantum dots son CdSe, CdS, CdTe, InP, ZnS y PbS, ya que stos poseen
unas propiedades electrnicas adecuadas para obtener quantum dots
fluorescentes

5. Mention two applications of quantum dots.

Laser, Leds and photovoltaics.

Una de estas aplicaciones son los quantum dots LEDs (QLEDs), ya que los
quantum dots tambin poseen propiedades electroluminiscentes, pueden emitir luz
tras aplicarles un voltaje elctrico. Una de sus ventajas es que pueden utilizarse
en sustratos flexibles, algo que no es posible con los materiales convencionales.
Podran emplearse para alumbrado eficiente o pantallas de dispositivos
electrnicos ya que consumen poca energa.

Su alta capacidad de absorcin de luz puede usarse para mejorar la eficiencia

de placas fotovoltaicas y reducir su coste. Quizs los quantum dots jueguen un
importante papel en el futuro de las energas renovables.
8. Carbon nanomaterials.
1. Give three examples of carbon nanomaterials. Indicate their similitudes
and differences.
- Fullerenes: also known as Buckminsterfullerenes. Are similar in structure to
graphene. They're carbon molecules which can have spherical, ellipsoid or tube
shapes.
- Carbon nanotubes: They are of the allotropes of the carbon (is the property of
some single substances of having different molecular structures. Molecules
formed by only one element and poses different molecular structure). They are
cylindrical. They have thermal conductivity, mechanical and electrical properties.
Have applications as additives to various structural materials.
- Graphene: They are other allotropes of carbon in the form of a two dimensional
atomic scale. They are the basic structural element of other allotropes such as
graphite, carbon nanotubes and fullerenes. It is considered also as an aromatic
molecule. It is 100 times stronger than steel. Conducts heat and electricity
efficiently and it is nearly transparent.
2. What are carbon nanotubes? Describe their properties and give two
examples if potential applications.
They are of the allotropes of the carbon (is the property of some single substances
of having different molecular structures. Molecules formed by only one element
and poses different molecular structure). They are cylindrical. They have thermal
conductivity, mechanical and electrical properties. Have applications as additives to
various structural materials.
Fiel emmiters, cnt-based ink, transistors and hydrogen storage on CNTS.
3. What the main functionalization methods for carbon nanotubes?
SWNT: ost single-walled nanotubes (SWNTs) have a diameter of close to
1 nanometer, and can be many millions of times longer. The structure of a SWNT
can be conceptualized by wrapping a one-atom-thick layer of graphite called
graphene into a seamless cylinder. The way the graphene sheet is wrapped is
represented by a pair of indices (n,m). The integers n and m denote the number of
unit vectors along two directions in the honeycomb crystal lattice of graphene.
If m = 0, the nanotubes are called zigzag nanotubes, and if n = m, the nanotubes
are called armchair nanotubes. Otherwise, they are called chiral. SWNTs are an
important variety of carbon nanotube because most of their properties change
significantly with the (n,m) values, and this dependence is non-monotonic
(see Kataura plot). In particular, their band gap can vary from zero to about 2 eV
and their electrical conductivity can show metallic or semiconducting behavior.
Single-walled nanotubes are likely candidates for miniaturizing electronics. The
most basic building block of these systems is the electric wire, and SWNTs with
diameters of an order of a nanometer can be excellent conductors.

MWNT: Multi-walled nanotubes (MWNTs) consist of multiple rolled layers

(concentric tubes) of graphene. There are two models that can be used to describe
the structures of multi-walled nanotubes. In the Russian Doll model, sheets of
graphite are arranged in concentric cylinders, e.g., a (0,8) single-walled nanotube
(SWNT) within a larger (0,17) single-walled nanotube. In the Parchment model, a
single sheet of graphite is rolled in around itself, resembling a scroll of parchment
or a rolled newspaper. The interlayer distance in multi-walled nanotubes is close to
the distance between graphene layers in graphite, approximately 3.4 . The
Russian Doll structure is observed more commonly. Its individual shells can be
described as SWNTs, which can be metallic or semiconducting. Because of
statistical probability and restrictions on the relative diameters of the individual
tubes, one of the shells, and thus the whole MWNT, is usually a zero-gap
metal[citation needed].
Double-walled carbon nanotubes (DWNTs) form a special class of nanotubes
because their morphology and properties are similar to those of SWNTs but they
are more resistant to chemicals. This is especially important when it is necessary
to graft chemical functions to the surface of the nanotubes (functionalization) to
add properties to the CNT. Covalent functionalization of SWNTs will break some
C=C double bonds, leaving "holes" in the structure on the nanotube, and thus
modifying both its mechanical and electrical properties. In the case of DWNTs, only
the outer wall is modified.

4. What is graphene? Describe their properties and give two examples if

potential applications.
They are other allotropes of carbon in the form of a two dimensional atomic scale.
They are the basic structural element of other allotropes such as graphite, carbon
nanotubes and fullerenes. It is considered also as an aromatic molecule. I ti s 100
times stronger than steel. Conducts heat and electricity efficiently and it is nearly
transparent.
Bendability of graphene: LCD screens with graphene, bendable watches and
smartphones, sensors in textile (smart clothing), etc.
 9. Characterization techniques
1. Mention similarities and differences between the optical and the electron
microscope.
Both light microscopes and electron microscopes use radiation (light or electron beams) to
form larger and more detailed images of objects (e.g. biological specimens, materials, crystal
structures, etc.) than the human eye can produce unaided. (See also: What is eyesight ?)
An electron microscope is a microscope that uses beams of electrons instead of rays of visible
light to form highly magnified images of tiny areas materials or biological specimens.
Comparing light vs electron microscopes is made more complicated by the fact that there are
different types of electron microscopes. The two main types of electron microscope are
the Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM). Other
types of electron microscope include the Scanning Tunneling Microscope (STM) and Field
Emission Transmission Microscope (FE-TEM).
Brief notes, see the tables lower down this page for figures, explanations and comments:

Similarities: Form larger (magnified) and more detailed (highly resolved) images of
small objects or small areas of larger objects e.g. a leaf, part of a bone,
etc. than can be formed by the human eye.
Used in study and research in biology and medical sciences (more
about histology), material sciences e.g. metallurgy and other aspects of
science.
Specimens must be carefully prepared using techniques appropriate for
both the equipment and the sample e.g. slicing, staining, mounting, etc.
(e.g. how to prepare histology slides).

Differences: Size: Light microscopes are smaller and lighter, so are easier to move
and set-up.
Cost / Availability: Light microscopes are less expensive than electron
microscopes.
Radiation Type: Light microscopes use light (approx wavelength 400-700
nm), electron microscopes use beams of electrons (approx equivalent
wavelength 1 nm).
Control of image formation : Light via glass lenses, beams of electrons
can be focused using electromagnets due to negative charge on
electrons.
Resolution*: Electron microscopes have much higher resolution than light
microscopes
Magnification*: Electron microscopes have much higher magnification
than light microscopes
Colour Images: Light microscopes form images including the range of
wavelengths (colours) provided by the light source - but remember that
the colours seen are often due to stains rather than the actual colours
present in nature). Electron microscopes produce greyscale (sometimes
called "black and white") images. However, "false-colour" electron
micrographs are common - and can be very beautiful!
Preparation of specimens : Generally involves harsher processes, e.g.
using corrosive chemicals, for viewing via electron microscope than
preparation of slides for viewing using a light microscope. Therefore more
skill required - both to prepare specimens and to interpret EM images
(due to "artefacts" in images, artefacts = features in images that are not
present in the specimen but rather are due to the processes used to
prepare the specimen and produce the image)
Image Formation : Light microscope images can be viewed directly.
Electron microscopes require use of a fluorescent screen, photographic
plate or electronic display because electrons cannot be observed directly
 by the human eye.
Usage Limitations : Living specimens cannot be viewed using electron
microscopes because electron microscopes require there to be a vacuum
in the tube - otherwise the electrons would be absorbed by air molecules.

2. Which are the main modes of interaction of electrons with matter that are
used in electron microscopy?
- TEM: Transmitted electrons, structure and composition. Illuminates the whole
sample. Pots veure el que hi ha dins la mostra. Els electrons que traspassen el
specimen. Un microscopio electrnico de transmisin (TEM, por sus siglas en ingls,
o MET, en espaol) es un microscopio que utiliza un haz de electrones para visualizar un
objeto, debido a que la potencia amplificadora de un microscopio ptico est limitada por
la longitud de onda de la luz visible. Lo caracterstico de este microscopio es el uso de una
muestra ultrafina y que la imagen se obtenga de los electrones que atraviesan la muestra.

- SEM: Scans with a focused point. Noms et permet veure la superfcie de la

mostra. Backscattered electrons and secondary electrons, topography and
compositionA 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 contain information about the
sample's surface topography and composition. The electron beam is generally scanned in
a raster scan pattern, and the beam's position is combined with the detected signal to produce
an image. SEM can achieve resolution better than 1 nanometer. Specimens can be observed
in high vacuum, in low vacuum, in wet conditions (in environmental SEM), and at a wide range
of cryogenic or elevated temperatures.
The most common SEM mode is detection of secondary electrons emitted by atoms excited by
the electron beam. The number of secondary electrons that can be detected depends, among
other things, on specimen topography. By scanning the sample and collecting the secondary
electrons that are emitted using a special detector, an image displaying the topography of the
surface is created.

- EDS: X-rays, composition. 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 a unique set of peaks on its electromagnetic emission spectrum[2] (which
is the main principle of spectroscopy).
IMAGE METHODS:
1) SCANNING PROBE MICROSCOPY: creates images of surfaces using a probe. Probe is
moved (scanned) over the sample. Sample-probe interaction is monitored as function of
location. s una tcnica lenta I milited maximum image size.
2)TUNNELING MICROSCOPY: SCANNING TUNNELING MICROSCOPY
3) ATOMIC FORCE MICROSCOPY: (pregunta 4)
3.1- Contact: Atomic-force-microscopy: at short probe sample distances the forces are
repulsive. Opera amb la corba de van der waals
3.2-non contact: atomic force microscopy: at large probe samples distances the forces are
attractive. Opera sense corba van der waals.
3.3- intermittent contact: atomic force microscopy
3. Mention similarities and differences between the transmission and
scanning electron microscopy.
Similarities: the source of radiation are electrons, medium is high vacuum.
Differencies:
SEM: used to produce excellent images of the surfaces of cells and small
organisms. Excellent for studying surface morphology of the organisms, cells or
any suitable material under study, electron beam scans over the surface of the
sample, based on scattered electrons or produces images by detecting
secondary electrons which are emitted from the surface due to excitation by the
primary electron beam and SEM scans with a focused point.

TEM: used to study the ultra structure of the cell and its components. It can see
objects as small as a protein molecule or even at nano level. Provides details
about internal composition of cells or any suitable material under study, electron
beam pass through the sample, based on transmitted electrons or produces
images by detecting primary electrons transmitted from the sample and TEM
illuminates the whole sample.

4. Describe how the atomic force microscope works.

With this technique it is possible to detect nano newton or even smaller forces.
To improve it they use a laser beam. The AFM brings a probe in close proximity
to the surface, then the force is detected by the deflection of a spring, usually a
cantilever (diving bard) and the forces between the probe tip and the sample are
sensed to control the distance between the tip and the sample.

5. How x-ray diffraction can be used to characterize nanomaterials?

It is a non destructive technique for probing the structure of nanomaterials.
When a X-RAY photon falls on an intrinsic semiconductor, charge carriers are
created, the electrons and holes.
The x-ray photon is slowed down by colliding inleastically with other electrons in
the semiconductor, and thus creating many charge carriers.
The number of charges created will count as pulses, this pulses then are
converted to voltage, representing the energy of the x-ray photons.
Different atoms would emit different energies of x-ray since every atom has
different atomic sizes and electron configuration.
 10. Nanomaterial applications
1. What is nanolithography and can it be used to manufacture nanomaterials.
It is the art and science of fabricating nanoelectronic and nanophotonic devices
and systems.
Substrate-resist spinning-exposure to UV light or X-rays or ions beams.
Development (hi ha un buit al mig part adalt del quadrat):
1) metal deposition-liftt off
2) etching-lift off
3) electrolytic growth-lift off
2. Give three examples of potential applications of nanomaterials.
- Nanotubes
- Graphene
- Nanocomposites
- Nanofibers
- Nanowires
3. Nanoimprint lithography: with thi technique is possible to create picures like nanofabrication
techniques. Primer saplica P and heat (imprint), desprs es refreda (release) I per ltim sibt el
RIE of residual layer.
4. scanning probe lithography: STM manipulation of atoms, allow us to move atoms and create
structures like cercle.
5. dip pen nanolithography: wwiting on substrates with molecular inks. Hi ha un substrate I a sobre
la AFM tip (bola del boli) que permet molecular transport cap al substrate I llavors en direccin
horitzonal surt wirting direction. Ink transfer using a coated afm tip by capillary effect.