Semiconductors

Semiconductors have an enormous impact on our society. You find semiconductors

at the heart of microprocessor chips as well as transistors. Anything that's
computerized or uses radio waves depends on semiconductors. Today, most
semiconductor chips and transistors are created with silicon.
A semiconductor is a solid material that has electrical conductivity in between that of a
conductor and that of an insulator; it can vary over that wide range either permanently or
dynamically. Semiconductors are tremendously important in technology. Semiconductor devices,
electronic components made of semiconductor materials, are essential in modern electrical
devices. Examples range from computers to cellular phones to digital audio players. Silicon is
used to create most semiconductors commercially, but dozens of other materials are used as well.

Chip

Transistor

LED

Dr. S. Paria, NIT RKL Nanotechnology 1

Carbon, silicon and germanium (germanium, like silicon, is also a semiconductor) have a
unique property in their electron structure - each has four electrons in its outer orbital.
This allows them to form nice crystals. The four electrons form perfect covalent bonds
with four neighboring atoms, creating a lattice.
Metals tend to be good conductors of electricity because they usually have “free
electrons” that can move easily between atoms, and electricity involves the flow of
electrons. While silicon crystals look metallic, they are not, in fact, metals. All of the
outer electrons in a silicon crystal are involved in perfect covalent bonds, so they can't
move around.

C: 1S2 2S22P2
Si: 1S2 2S22P6 3S23P2
Ge: 1S2 2S22P6 3S23P63d10 4S24P2

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 Energy Bands for Solids
Large energy gap between the In semiconductors, the band gap is small enough
valance and conduction bands that thermal energy can bridge the gap for a small
in an insulator says that at fraction of the electrons. In conductors, there is no
ordinary temperatures no band gap since the valance band overlaps the
electron can reach the conduction band.
conduction band.
E
Conduction Band Fermi level

Energy Gap
Conduction Band
Conduction Band
Energy Gap
Valence Band Valence Band Valence Band

Insulator Semiconductor Conductor

The Fermi level is the surface of that sea at absolute zero where no
electrons will have enough energy to rise above the surface. The
concept of the Fermi energy is a crucially important concept for the
understanding of the electrical and thermal properties of solids.

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 At T=0→ C, Si and Ge are all insulators
At T>0, → some electrons can be thermally excitedinto
the empty conduction band in Si and Ge

In the case of completely filled bands, the gap width φ between the valence band and the
conduction band can make the solid an isolator (φ φ ~ 10eV) or a semiconductor (φ φ ~ 1eV). In
fact, the thermal energy available at T ≈ 300 K, is sufficient to bring some electrons into the
conduction band if the gap is on the order of 1eV. To calculate the number of electrons with
energy above a given value E0, we must apply Boltzmann statistics, which gives the density of
electrons having energy greater than E0, i.e. E 0
−
k BT
kB = 1:3807 × 10-23 J/K; n ( E 〉 E0 ) = e

1eV = 1qJ, q = 1:60 × 10-19C,

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 Formation of a Molecule

Silicon Germanium

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 Doped Semiconductors
You can change the behavior of silicon and turn it into a conductor by doping it.
In doping, you mix a small amount of an impurity into the silicon crystal.
N-type: In N-type doping, phosphorus or arsenic is added to the silicon in small
quantities. The fifth electron has nothing to bond to, so it's free to move around.
It takes only a very small quantity of the impurity to create enough free
electrons to allow an electric current to flow through the silicon. N-type silicon
is a good conductor.
P-type: In P-type doping, boron or gallium is the dopant. Boron and gallium
each have only three outer electrons. When mixed into the silicon lattice, they
form “holes” in the lattice. The absence of an electron creates the effect of a
positive charge, hence the name P-type.
A diode is the simplest possible semiconductor device. A diode allows current to
flow in one direction but not the other.
Electron and Hole Current
Each time that an electron goes from the valence band to the
conduction band, a vacancy or hole is created. This hole behaves as
a positive charge with its own mobility, which contributes to the
current in the crystal. In general, the current in a semiconductor
will be the sum of the electron current and the hole current.
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 Quantum dots (QDs)
A quantum dot is a semiconductor nanostructure that confines the motion of conduction
band electrons, valence band holes, or excitons (bound pairs of conduction band electrons
and valence band holes) in all three spatial directions.
Quantum dots are important in transistors, solar cells, LEDs, and diode lasers, agents for
medical imaging.
Quantum dots (QDs) are nanometer-scale semiconductor crystals composed of groups I–VII
(such as CuCl or CuBr), II–VI or III–V elements (CdS, CdSe, Si, GaAs, CdTe, InP, and
InAs), and are defined as particles with physical dimensions smaller than the exciton Bohr
radius.
Exciton Bohr radius is the distance in an electron hole-pair

QDs ranges from 2-10 nm (10 – 50 atoms) in diameter and a

total of 100 to 100,000 atoms within the quantum dot volume .
A quantum dot contains a small finite number (of the order of
1-100) of conduction band electrons, valence band holes, or
excitons, i.e., a finite number of elementary electric charges.
Band gap energies of nanoscopic semiconductors are strongly
size dependent. As the radius of the nanocrystal decreases,
the band gap increases.

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 Solid
(many atoms)

Particle
(13 atoms)

Particle
(4 atoms)

Sub level
1 atom E

The spacing between energy states gets larger as the volume gets smaller

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 Quantum Confinement
When we reduced the volume of a solid to such an extent that the energy levels inside
becomes discrete, we have achieved quantum confinement. In doing so we can create small
“droplets” of isolated electrons. In fact, that we can often count them.
How many electrons are there in a gold particle made from 10 atoms?
Electronic configuration of gold atom: 1S22P63S23P63d104S24P64d104f145S25P65d106S1
Total 79 electrons are there. With 10 atoms 790 electrons. One electron left partially un
filled in 6S sublevel. There will be ten or so free electron in conduction level at T = 0.

How small is small enough for confinement?

The electrons behave like waves we trap them according to the rules of waves.

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 Optical properties of QDs
Quantum confinement effects give rise to unique optical and electronic properties in
QDs, giving them numerous advantages over current fluorophores, such as organic
dyes, fluorescent proteins and lanthanide chelates.
Properties that particularly influence fluorophore behaviour, and therefore applicability to
different situations, include the width of the excitation spectrum, the width of the emission
spectrum, photostability, and the decay lifetime.
Conventional dyes: (i) Narrow excitation spectra, requiring excitation by light of a specific
wavelength, which varies between particular dyes. (ii) Broad emission spectra, meaning the
spectra of different dyes may overlap to a large extent.
QDs: (i) QDs have broad absorption spectra, allowing excitation by a wide range of
wavelengths, a property which may be exploited to simultaneously excite multiple different
coloured QDs using a single wavelength. (ii) In contrast, QDs have narrow emission spectra,
which can be controlled in a relatively simple manner by variation of core size and composition,
and through variation of surface coatings. They can be engineered to emit light at a variety of
precise wavelengths from ultraviolet (UV) to infrared (IR).
The narrow emission and broad absorption spectra of QDs makes them well suited to
multiplexed imaging, in which multiple colours and intensities are combined to
encode genes, proteins and small-molecule.

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 Excitation spectra Emission
spectra

Rhodamine 6G and CdSe QDs. The QD emission spectrum is nearly symmetrical and much
narrower in peak width while its excitation profile is broad and continuous, meaning that QDs
can be efficiently excited at any wavelength shorter than 530 nm. By contrast, the organic dye
rhodamine 6G has a narrow excitation profile and broad emission spectrum.
Advantages: (i) Photostability is a critical feature in most fluorescence applications, and is an
area in which QDs have singular advantage. Unlike organic fluorophores which bleach after
only a few minutes on exposure to light, QDs are extremely stable and can undergo repeated
cycles of excitation and fluorescence for hours with a high level of brightness and
photobleaching threshold
QDs have been shown to be more photostable than a number of organic dyes, including
Alexa488, reported to be the most stable organic dye.
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Dihydrolipoic acid (DHLA)-capped cadmium selenide-zinc sulfide (CdSe-ZnS) QDs
showed no loss in intensity after 14 h, and were nearly 100 times as stable as, and also 20
times as bright as, rhodamine 6G.
Time dependence of the fluorescence intensity of silanised
nanocrystals and rhodamine 6G at 488 nm. The
nanocrystals exhibit a stable emission for at least 4 h,
while the dye bleaches after 10 min, colours correspond to
nanocrystal emission.R6G is in black
R6G

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 Bioimaging using quantum dots
The unique photophysical properties of inorganic nanomaterials provides a new
class of biological labels that could overcome the limitations of conventional
organic fluorophores. QDs show size-tunable fluorescence emission and have a
narrow and symmetric spectral line profile compared with organic dyes, making
QDs ideal for simultaneous detection of multiple fluorophores by excitation of a
single light source.
Photoluminescence lifetimes are long (~20-50 ns), which allows imaging of living
cells without interference from background autofluorescence
Stability against photobleaching, large molar extinction coefficients, high quantum
yield, and large surface-to-volume ratios make QDs superior.
Spherical QDs are the most widely used for biological applications.
One of the most intriguing features of QDs is that the particle size determines many of the
QD properties, most importantly the wavelength of fluorescence emission.By altering the QD
size and its chemical composition, fluorescence emission may be tuned from the near
ultraviolet, throughout the visible, and into the near-infrared spectrum, spanning a broad
wavelength range of 400–2000 nm

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When the fluorophore is excited by quanta of specific
energy, it excites electrons from the ground state to a
higher energy singlet state (S1, S2).

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Core/shell QDs: In most of the cases, “naked” QDs are susceptible to photooxidation and, thus,
they need to be capped by a protective shell of an insulating material or wide-bandgap
semiconductor structurally matched with the core material. The shell of QDs plays an
important role. The shell should be transparent, be of nonemissive/higher band gap, and
structurally similar to the core material so as to efficiently confine the excitation to the core.
For instance, encapsulation of CdSe core by ZnS shell reduces the photochemical bleaching
and dramatically increases its quantum yield.
Suitability for bioimaging: Initially, chemically synthesized QDs could not be employed for
biochemical applications because they did not disperse well in water, e.g., ZnS or TOPO
(trioctylphosphine oxide)-coated QDs are hydrophobic in nature. It is, thus, necessary to make
them “water soluble” to facilitate their conjugation to biomolecules and make them useful for
biological imaging.
Some of the methods to make the QDs water-dispersible are (i) derivatizing their surface with
mercaptoacetic acid; (ii) encapsulating them in phospholipid micelles (iii) derivatizing their
surface with silica overcoat; and (iv) coating them with an amine-modified poly(acrylic acid).

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 Design of nanoparticles for bioimaging application
The main parameters for the synthesis of nanoparticles for bioimaging applications are:
(i) Synthesis of optical core: The first step is the synthesis of the core, which encapsulates
the fluorochrome, e.g., the dyes or the QDs.
(ii) Synthesis of shell: The shell serves the purposes of protecting the optical core from the
external environment thus improving its photostability (e.g., for organic dyes),
enhancing the optical properties (by providing a lattice mismatch, e.g., for QDs) and
providing further ability to bind/adhere to molecules for surface stability and
bioconjugation.
(iii) Surface modification: There is a natural tendency for the particles to coagulate and
aggregate. However, it is important that the nanoparticles remain suitably dispersed,
preferably, in an aqueous environment for any application. This may be achieved by
modifying the surface of the metal nanoparticles by employing various dispersing
agents, e.g., surfactants, polymers, chelating groups, etc.
(iv) Bioconjugation and targeting: For targeted delivery of the nanoparticles to the desired
site of action and binding, it is necessary to attach suitable biomolecules on the surface
of the nanoparticles such as antibodies, peptides, enzymes, etc. These molecules can also
act to promote or maintain their dispersion. The conjugation of nanoparticles and drugs,
by passive (accumulation of drug or drug carrier system at a particular site) and active
targeting (specific modification of a nanosystems carrier with “agents” having selective
affinity for recognition and interaction with specific cell, tissue etc.)
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 mercaptoacetic acid

Ligands surrounding a
TOPO-coated QD

amphiphilic polymer like

octylamine-modified polyacrylic
acid.

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Conjugation of QDs to biomolecules: (a) Use of a bifunctional ligand such as mercaptoacetic
acid for linking QDs to biomolecules. (b) TOPO-capped QDs bound to a modified acrylic acid
polymer by hydrophobic forces. (c) QD solubilisation and bioconjugation using a
mercaptosilane compound. (d) Positively charged biomolecules linked to negatively charged
QDs by electrostatic attraction. (e) Incorporation of QDs into microbeads and nanobeads

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 Detection of microbial cells
Cryptosporidium parvum and Giardia lamblia are parasites that exist in rivers and lakes. These
parasites can cause intestinal illnesses.
This novel fluorescence system exhibited superior
photostability, gave 1.5- to 9-fold-higher signal-to-
noise ratios than traditional organic dyes in detecting,
and allowed dual color detection.
Semiconductor quantum dot-conjugated antibodies
are used to label.
Lebeling: The target cells were first bound with biotinylated
antibodies before conjugation of QDs to the cell-attached
antibodies.
A dual-color image of QD 605-
labeled C. parvum (red) and
QD 565-labeled G. lamblia
(green)

Appl. Environ. Microbiol. 70, 597-598, 2004.

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5 µl of C. parvum or G. lamblia preparation (concentration, 107 cells/ ml) was spotted on
a poly-L-lysine-coated glass slide and was air dried. The fixed cells were combined with
20 µl of blocking buffer and were incubated for 20 min in a humidified chamber. After
being washed with phosphate-buffered saline (PBS) (pH 7.4) three times for 5 min, the
cells were combined with 20 µl of 1× × biotinylated antibodies (anti-C. parvum or anti-G.
lamblia) and were incubated for 30 min at 37°C. The cells were further washed with PBS
three times for 5 min and were incubated with 20 µl of diluted QD (two
streptavidincoated) solution for 30 min at 37°C. After a final wash with PBS (three times
for 5 min), the slide was mounted with mounting solutions and was observed under a
microscope.

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Gao and coworkers have combined CdSe QD targeting and imaging in live animals. QD
probes encapsulated in a triblock copolymer could be delivered to tumors by both passive
and active targeting mechanisms. In passive mode, macromolecules around the particles and
the nanocrystals accumulated preferentially at the tumor sites through an enhanced
permeability and retention effect.
This effect is believed to arise from two factors: (i)
angiogenic tumors produce vascular endothelial growth
factors that hyperpermeabilize the tumor-associated
neovasculatures and cause leakage of circulating
macromolecules and small particles; and (ii) tumors lack an
effective lymphatic drainage system, which leads to
macromolecule or nanoparticle accumulation.
In active tumor targeting, antibody (Ab)-conjugated QDs
targeted due to rapid QD-antibody binding to tumor-specific
antigens. For active tumor targeting, they used antibody-
conjugated QDs to target a prostate-specific membrane
antigen (PSMA).

Nature Biotechnology 22, 969 - 976 (2004)

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 Schematic illustration of biconjugated QDs for in vivo cancer targeting and imaging

(a) Structure of a multifunctional QD probe, showing the capping ligand TOPO (tri-n-octylphosphine
oxide), an encapsulating copolymer layer, tumor-targeting ligands (such as peptides, antibodies or
smallmolecule inhibitors) and polyethylene glycol (PEG)

(b) Chemical modification of a triblock copolymer (ABC) with an 8-carbon side chain. This hydrophobic side
chain is directly attached to the hydrophilic acrylic acid segment and interacts strongly with the hydrophobic
tails of TOPO. Dynamic light scattering shows a compact QD-polymer structure, indicating that QDs are
tightly wrapped by the hydrophobic segments and hydrocarbon side chains.
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Permeation and retention of QD probes via leaky tumor vasculatures (passive
targeting) and high affinity binding of QD-antibody conjugates to tumor antigens
(active targeting).

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Figure compares the in vivo imaging results from three types
of surface modifications: COOH groups, PEG groups and
PEG plus PSMAAb. In agreement with histological
examinations, no tumor signals were detected with the
COOH probe, only weak tumor signals were observed with
the PEG probe (passive targeting) and intense signals were
detected in the PEGPSMA Ab conjugated probe (active
targeting). This comparison provides evidence for the
conclusion that active tumor targeting by using a tumor-
specific ligand is much faster and more efficient than passive
targeting based on tumor permeation, uptake and retention.

The amounts of injected QDs and the lengths of circulation

were: 6 nmol and 6 h for the COOH probe; 6 nmol and 24 h
for the PEG probe; and 0.4 nmol and 2 h for the PSMA
probe.

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Single-quantum-dot-based DNA nanosensor
Rapid and highly sensitive detection of DNA is critical in diagnosing genetic diseases.

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Ultrasensitive nanosensor based on fluorescence resonance energy transfer (FRET)
capable of detecting low concentrations of DNA in a separation-free format. This system
uses quantum dots (QDs) linked to DNA probes to capture DNA targets. The target strand
binds to a dye-labelled (Cy5, cyanine) reporter strand thus forming a FRET donor–
acceptor ensemble. The QD also functions as a concentrator that amplifies the target
signal by confining several targets in a nanoscale domain. Unbound nanosensors produce
near-zero background fluorescence, but on binding to even a small amount of target DNA
(~50 copies or less) they generate a very distinct FRET signal. A nanosensor-based
oligonucleotide ligation assay has been demonstrated to successfully detect a point
mutation typical of some ovarian tumours in clinical samples.

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 Comparison of different microscope
Microscope (radiation/ interaction used) Magnification Resolution

Human eye (Visible light) - 100 µm

Optical Microscope (UV-vis-IR) 103 0.1 µm
Scanning Electron Microscope (electrons) 105-106 3 nm
Transmition Electron Microscope > 106 0.1 nm
(electrons)
Scanning Tunnelling Microscope (electron > 106 0.1 nm
current)
Atomic Force Microscope > 106 0.1 nm
Scanning Near-Field Optical Microscope > 105 20-30 nm
(Vis light)

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 Scanning Tunneling Microscope (STM)
The governing principle of scanning tunneling microscopy (STM) is the quantum
tunneling of electrons through a thin potential barrier separating two electrodes. The
instrument basically consists of a very sharp tip which position is controlled by
piezoelectric elements (converting voltage in mechanical deformation). By applying a
volatge (Vt) between the tip and a metallic or semiconducting sample, a current can flow
(It) between these electrodes when their distance is reduced to a few atomic diameters.
The amplitude of the current strongly depends on the distance between the tip and the
sample, and of course also on the potential difference Vt.
The STM operates in the regime of extremely
small distances between the tip and the surface of
only 0.5 to 1.0 nm, i.e. 2 to 4 atomic diameters. At
these distances, the electrons can ‘jump’ from the
tip to the surface or vice versa. This ‘jumping’ is a
quantum mechanical process, known as
‘tunneling’. Hence the name of this microscope:
tunneling microscope. The tunneling process is
very difficult, which implies that the tunneling
current is always very low. STMs usually operate
at tunneling currents between a few picoAmperes
(pA) and a few nanoAmperes (nA).
http://dpmc.unige.ch/gr_fischer/localprobe.html
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http://www.physics.leidenuniv.nl/sections/cm/ip/group/Principle_of_SPM.htm
 Transmission Electron Microscopy (TEM)
Similarity of Optical and Electron Microscope
Optical Electron
Electron gun
Anode
Essential difference:
Condenser lenses
wavelength of
Sample electrons: 3.7⋅10-3 nm
Objective lens at 100 keV
wavelength of light:
400 - 700 nm
Intermediate image
Projector lens
Consequently:
resolution of electron
microscope higher
Final image

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 Operating voltages : 20-200kv
TEM images are formed using transmitted eletrons (instead of the visible light) which
can produce magnificationdetails up to 10,00,000x with resolution better than 1 nm.
Furthermore, the analysis of the X-ray porduced by the interraction between the
acclerated eletrons with the sample allows detemining the elemental composistion of the
smaple with high spatial resolution.

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