Why Nano:

 A popular, understandable vision – Replicate (DNA, RNA – fundamental aim) from

templates, little submarines (Can be used in medical sciences – drug delivery in specific
points through nano technology – just a theory)
 Legitimate scientific opportunity in Nano
 Inseparable mélange of accomplishment and hyperbole – Initiated by chemists, then
afterwards picked by engineers
 Self-assembly: Can be found in biology (Ribosome) – create this types of tech
 Imitate biology – tech that can be controlled, biology cannot be controlled but nanotech
can be controlled
 High potential for technological relevance
 Unified support from the physical and biological sciences
What is Nano:
 Anything less than 100nm – can be small aggregates or single atoms
 Quantum phenomena (1 – 30 nm)
 New properties
o Ultrahigh surface area
o Low defects
o Hierarchical structures – top-down and bottom-up
 Biological/Cellular machinery – ATPase, Chloroplast, Ribosome; Sensors smaller than a
cell (A hyperbole till now)
 Large numbers of components – High density technologies and Complex Systems
What is Nanotechnology: Any man-made structure that has at least one dimension less than
100nm, designed through a process that exhibits fundamental control over the physical and
chemical attributes of the structures and can be combined to from larger structures.
What are the Sciences involved in Nano:
1. Epitaxy machine
2. AFM (atomic force microscope)
3. TEM (transmission electron microscope)
4. Single electron detection through mechanical motion - Nano Electromechanical System
(NEMS)
5. Single Photon Counting (SET)
6. Conductance is discrete in Nanoscale – Between the source and drain when the path is in
mesoscopic scale, electron acts as waveforms
7. New Chemistry – chemically synthesized quantum dots – absorption and emission depends
on size (color of the quantum dots). Semiconducting quantum dots are also possible, work
is still being done. Nano Rods, Nano Ribbons (carbon nanotube)
8. New Biology
Size Dependent Properties:
 Size matters in nanoscale, as surface area is increased, the size dependent properties are
changed. (Emission and Absorption of different wavelengths - color of same object
changes according to size of the nanoparticle)
 Quantum Dots – can be used for dyeing  medical diagnostics. Cellular activity research
– activity mapping
 Bench-top Nanoscale Experiments – Nanocrystal Synthesis  Easy to synthesize.
Chemical Synthesis – very easy bottom-up process and ready-to-do. But it cannot be used
in a semiconductor. Ultra purity is not preserved in this process, therefore, IV
characteristics cannot be done and observed from this.
Revolution or Evolution –
Evolution – Gradual change in technology
1. Ultradense Memory
2. Faster Microprocessors
3. Customized/Specialized Microprocessors
4. Portable Systems
5. Medium Performance /Low Cost Systems
Revolution – Biplob  drastic change in the topic and process
1. True Nano ICs (<10nm); Single molecule electronics
2. Cellular automata
3. Quantum Computing
4. Self-assembling/ 3D/ Bimimetic systems
5. Bio-hybirds
Revolutions in Technology –
 Microelectronics and Information Technology
 Biotechnology
 Nanotechnology
Other Targets of Nanotechnology:
 Advanced Materials
 5-minute health swab tests – painless health test and so on (MEMS and NEMS will be
required)
 Interactive glucose sensing – diabetes testing nowadays is very easy
 Human Repair
 Genomic Medicine
 Optical Computers
 Self-monitoring Food Packaging
  Fully target drug delivery - important for cancer research, drug must be applied to the
specific cells
 Heatless lights (LEDs)
 Efficient solar radiation capture – net zero  energy received = energy transmitted, carbon
emission will be reduced. Energy sector is a great application field of nanotechnology.
Nanotechnology Applications:
 Heterogeneous Catalysts – Zeolite MCM-41 for higher octane gasoline; cracking
hydrocarbons – 40% of gas produced this way
 Tennis Balls
 Oil of Olay and L’Oreal
 NanoPants
Nanoscale Patterning:
 A main topic of fabrication
 Two types of patterning –
 top-down (Engineering; conventional photolithography, chip designing; from bulk
to smaller; standardized process; cannot go into subnano region; a controlled
process) and
 bottom-up (this is biological process, self-assembling; atom by atom structure is
created – from smaller to bigger; not a standardized process; can go into subnano
region; not a controlled process)
 Nanotechnology tries to find association between these two processes
Scanning Probe Lithography: A very sharp AFM tip. There will be an aquous solution. There
will be molecules and some active matters. The tip is taken over a substrate. The molecules will
get attached into the substrate. This will be a mono layer of self-assembly. The attachment will
depend on molecular affinity. This is a bottom-up process.
Dip Pen Lithography: Many types of Si structures can be created. Tip is 65 nm and this is
nanotechnology.

The Ultimate High Density Arrays:

 More than just miniaturization with higher density
 New opportunities for biodetection and studying biorecognition
 More than 10 Million dots per (200 * 200) micro meter^2 area
Bench Top Nanoscale Patterning:
 Angle resolved Nanosphere Lithography: Reduction of in-plane nanoparticle size by a
factor of 3-4
 When a quantum dot is created for electrical purpose – its characteristics are to be observed;
IV, sensitivity
 Soft Lithography – Top-down process; creating patterns on a metal layer through some
process
 The Nanoscale
(Ramsden Chapter 2)

Size Matters in Nano – Before nano, there was Macro (Bulk realm) and Micro (Atomic Realm).
Nanoscale is 1nm-100nm. To be considered as nanotechnology, one dimension must be at least
less than 100nm.
Surface is Important –
 Surface of particle is different than bulk – it is less connected.
 Radius is inversely connected to proportion of under-connected atoms
 In a spherical aggregate of atoms, there can be 19 atoms of which only 1 has NO surface
contact
 Surface-to-volume Ratio = 3r/R  r = atom radius, R = aggregate radius. Surface area to
volume ratio is high in nanoscale. The melting point lowers of small spheres lowers than
that of the bulk by tens of degrees the energy required to break the bonds decreased, free
surface increased (less contact)  thus, lower melting point
 Nanotechnology is strongly associated with surface technology, since the nano-object is
such that almost all or most of its constituent atoms have the properties of surface atoms.
Chemical Reactivity –
 Surface atoms come in contact more prominently, chemical reactivity is pronounced in
nano-objects  Novel Catalysts, Sunscreens and powders can be designed
 Surface to Volume ratio increases and quantum nature comes into effect.
Electronic/Optical Properties at Nanoscale –
 Individual atoms have discrete energy levels which merge into bands for bulk solids
 Stacking Nano objects in 1D (Nanoplate), 2D (Nanofibers), 3D (nanoparticles) confines
carriers in 2D, 1D and 0D – creating artificial materials
 Si crystal – Only Si in the crystal. InP – Indium Phospide  group III and group V material
 Less Bandgap  More thermal generation. More Bandgap  Less thermal generation
 Quantum confinement is a size-effect – confinement occurs when a characteristic size is
less than or equal to electron coherence length. This can be realized when particle size
becomes less than Bohr radius rb = (4*pi*epsilon*hcut^2)/(me*q^2)
 This results in shifting of fundamental absorption ledge, disappearance of exciton
absorption peaks etc.
 Typical values of Bohr radii can be from a few to a few hundred nanometers, hence it is
possible to create particles with size r<rb. Thus, electron energy levels increasing, degree
of confinement increases and absorption edge shifts toward blue.
Solving one-electron 1D Schrodinger equation, it can be shown that, En =
(hcut*n*pi)^2/(8*me*r^2). Thus, as r decreases (decrease of r refers to confinement), E is
 increasing and wavelength is decreasing which denotes the absorption ledge shifting to the
blue region. This is a clear manifestation of quantum size effect.
Jellium and Superatoms –
 Jellium can be thought of as Quantum Dots. These are mainly metal clusters. This is a
chemical construct. Each metal atom contributes a characteristics number of electrons to
the free electron gas. These are dielectric nanoparticles: compounds of I-VII, II-VI, III-VI
 The electronic structure can be derived by solving Schrodinger equation.
 Triumph of Jellium model was the correct prediction of magic numbers corresponding to
clusters of exceptional stability
 Superatoms are energetically and chemically stable clusters – useful as nanoblocks for
assembly into desirable structures
Magnetic Properties –
 When particles are below a certain size (~10’s of nm), the substances show a large magnetic
susceptibility but lacks the remanent magnetism characteristic of ferromagnetism. This is
known as Super paramagnetism – below critical size (rs), the intrinsic spontaneous
magnetization of ferromagnetic material (Fe) results in a single domain. Above that size,
the material is divided into multiple domains.
 Certain critical domain size
 Kittel formula for the critical domain size (ds) is ds = 1.43*gamma_m/Js^2. Below this size,
single domain, above this size, multiple domain.
 Importance - There is a lower limit to the size (~20 nm) of magnetic elements in
nanostructured magnetic materials for data storage below which room temperature thermal
energy overcomes the magnetostatic energy resulting in zero hysteresis
Study – Section 2.8 of Ramsden book
Forces at the Nanoscale (Ramsden Chapter 3 - A different book from the one given
in the syllabus)
Walking on water – capillary action  in nanoscale, this takes a new turn. The organs of the
insects are in such dimension so that it can support them while walking on water through surface
tension.
Hydrophobic and Hydrophilic – Certain interactions happen due to surface tension and cohesive
and adhesive forces that appear in the surface. Some nanoobjects are hydrophobic and some are
hydrophilic due to this interaction.
Since surface plays an important role in the nano realm, interfacial forces become particularly
important - Casimir Force and Van der Waals Force, Capillary Forces become important in
nanoscopic regime. Concepts regarding surface tension, wetting need to be understood.
Casimir Force –
 In a very small cavity, two walls face a attractive force (~10-20nm). The force is very high
(~105 N/m) which is comparable to atmospheric pressure. The force falls off very quickly.
(proportional to 1/distance^4) where d is the distance between two walls
 Since there can ony be certain modes of vibration allowed or fit within the cavity, this
lowers the zero-point energy density between the two walls.
 Vacuum fluctuation is responsible for the Casimir Force.
Surface Tension – Surface Tension is defined as the free energy required to create and extend an
interface of area A. gamma = (delG/delA)T,P
 Unit of surface tension is N/m which is same as energy per unit area J/m2
 Work has to be done when an interface is being created, it has a higher free energy than
the bulk.
 Nanoscopic Viewpoint – Microscopic Surface Tension depends on specific chemical
interactions between surfaces
 Fowkes-Girifalco-Good Approximation – The tension at surface 1 against surface 2 is
lowered by the presence of surface 2 by an equal amount to the geometric mean of the
tensions of the two substances individually. Therefore, the work of adhesion equals the
geometric mean of the work done for cohesion.
Wcoh = 2*1*A Wadh = 2*sqrt(1*2)*A
 Corollary – the hydrophobic force is a consequence of strong cohesion of water: attraction
of suspended solids is prevented by their hydrophilicity (??)
Nanoparticles in paints – hydrophobic force causes water not to gather on the surface.
Wetting – Wetting is the spread of a liquid over a solid surface. Dewetting is withdrawal of liquid
from a surface.
 Dry means that not only water but all liquid is absent
  Spreading of a liquid (L) on a solid (S) surrounded by vapor (V) is given by Young’s
Equation – LV cos = SV - SL
 Degree of wetting is proportional to contact angle theta where theta = 0 means complete wetting,
in that case, LV = SV - SL
 Spreading Coefficient – S = ŜV - SL -LV , ŜV is the interfacial tension of a dry solid
Three cases of spreading coefficient:
1. S>0 : [ŜV > SV ] wet surface has an energy lower than unwetted one. The difference
[ŜV - SV ] can be as high as ~ 300mJ/m2 [e.g. water on metal oxides]. These systems
show enormous hysteresis.
2. S=0: happens in organic liquids on molecular solids
3. S<0: partial wetting. Thin films (~ 1mm) break up into droplets
Wetting is an important factor in MEMS and NEMS technology device and their effectiveness.
For an example, if a MEMS system is installed in blood stream (where it is necessary that the
blood wets the surface), but the blood does not wet the surface, desired results will not be found.

Capillary Force – Attraction between liquid and solid will cause a liquid to rise to a height h
within a vertical tube of diameter r made from that solid; emerging from a reservoir of that liquid
until the gravity-pull on that liquid column equals the interfacial attraction. Whether the liquid will
rise in a tube or not and the height it will rise to.
Nanotechnology Straws - Various techniques are being developed to enhance the already
impressive properties of carbon nanotubes (CNTs) further by combining them with other materials.
A new model demonstrates that sufficiently small liquid metal droplets can be drawn inside a CNT
via capillary action. This could have interesting implications for scientists' understanding of the
growth of CNTs and may lead to new synthetic routes for composite nanofibers as well as
production of nanodevices from CNTs and metal nanoparticles. "We have shown that capillary
forces can result in the absorption of molten metal droplets by carbon nanotubes" Dr. Shaun Hendy
tells Nanowerk. "Capillary forces are one of the effects of surface tension and they can cause
liquids to be drawn up by small tubes, including nanotubes. However, if the liquid is molten metal,
and the nanotube is carbon, this was not expected to occur. Liquid metals generally prefer to
minimize their contact area with carbon – for instance a droplet of molten iron will remain almost
spherical when placed on a graphite sheet or piece of diamond. Because of this, it was expected
that capillary forces would not be strong enough to draw metal droplets into the carbon tubes.
However, we have shown that when the metal droplet is sufficiently small, the effects of surface
tension do in fact become large enough to cause capillary draw up by a carbon nanotube."
 Nano Tools
(Horynak et al. Chapter 3; Pradeep Chapter 2; Ref – Lindsay Chapter 4)

3 main tools of this course – Nano Tools; Nano Fabrication and Nanoelectronics (Nanofabrication
will not be covered)
Why Nano Tools –
 Characterize Nano realm - (according to Lord Kelvin) to get a proper knowledge through
measurement and observation. Measure something and explain it in terms of numbers –
means that proper knowledge is earned
 Imaging – surface roughness, diffraction pattern and so on
 Manipulation of materials
AFM - Very sensitive to pressure; always kept in the basement of an institution. The movement
of cantilever over a surface can give an idea of the surface roughness of the material.
Characterization Tools –
 Need to sort, name, categorize, catalog and detail the things, part and components of nano
world is done through Characterization Tools
 Measurement is accomplished with tools – equipment, machines, hardware and software
Imaging –
 Fundamental relationships that apply to imaging by optical wavelengths also apply to
imaging with electrons.
 The main difference is the probe and the material of the lenses: lenses in electron probe
are coordinated magnetic fields.
 Imaging the samples by optical or electronic means is dependent on the wavelength of the
source or probe: the shorter the wavelength the greater the resolving power.
 Resolving power for optical microscopes is 180 nm. (In a sense, beyond nanotechnology
limit) Oil, Glycerin can be used to increase the power
 As rule of thumb: best achievable resolution by optical microscope is half of the
illuminating beam wavelength
 Visible light wavelength range: 400 to 700 nm
 Resolving ability of electron probes is 0.2 nm depending on applied voltage. Electron
probes use electron beams as light sources. Some points about electron are to be kept in
mind – dual nature of electron, diffraction pattern of electron.
Resolution –
 Resolution is the ability/capacity to distinguish two closely spaced points in terms of
distance.
  The resolution achieved by any instrument under optimum conditions is the resolving
power. This is the measure of the clarity of the image. This is also the ability to measure
the angular separation of images that are close together.
 Abbe criterion: In 1893, Abbe showed that the smallest resolvable distance between two
points is half the wavelength of the light used.
 Rayleigh criterion: If two points are placed close enough, the closest distance at which
they appear to be separated in image is : d = 0.61 /N.A., Numerical aperture, N.A. =
n.sin, n is refractive index of the medium and  is the semi-angular aperture of the lens.
For resolving power ,  , and n or  
 Examples:
o Light microscopes: n = 1.5 [oil immersed], sin = 0.87,  = 400 nm  d = 0.2 m.
o For TEM: n = 1.0 [vacuum], sin = 0.01,   0.005 nm  d = 0.3 nm

Electron Microscopy –
 Classical microscopes consist of – an illumination source, a lens to converge the beam, an
objective lens to magnify, and a projector lens to project the image
  In electron microscopes the wave nature of the electron is used. Here electrons are used as
source of illumination and the lenses are EM lenses. Can be controlled by current flow and
voltage difference.
 The first nanoscale images were obtained with an electron microscope. These remain as of
today the most widely used general purpose nanoscale imaging tool.
 Basics: an electron when goes through a potential difference of V volts, it acquires kinetic
energy of 1/2mv2 = qV  v = [2qV/m] and since  = h/mν (de Broglie), we have  =
[h2/2mqV]. From here we can derive,  = 1.23 /(V+10-6 V2). Lower the lambda, the
lower the minimum distance possible; thus higher the resolution
SEM (Secondary/Scanning Electron Microscopy) –
Components:
 Electron gun – Primary electron source from which electron comes down, the Sample film
is very small (less than the size of fingernail). It could be a filament too. The electron that
comes out could be thermo-ionic emission. A high current is flowed through the filament
that causes the filament to heat up and the energy of the electron is greater than the work
function. LaF6 is used as filament, Tungsten has some problems. The electrons can also be
generated by Field Emission. The electrons are pushed through tunneling effect and is
thermally silent. This requires a high voltage to push the electrons to cross the boundary.
 Electron lenses – condition the electron beams so that it becomes collimated. There are
condenser lenses and focusing lenses. These are basically electromagnets so that it can
manipulate the electron beam. Electrons converge, not diverge. In electron microscope,
focal lengths can be adjusted.
 Scan coils – Controls the electron beams
 Electron detector – to detect the secondary electrons, ET detectors (which is a solid state
device). Scintillator is an avalanche detector. Photomultiplier multiplies the number of the
photons emitted based on the gain.
High energy electron beams impinge on the sample surface and there are lot of effects because of
that. There can be backscattered electrons, there can be X-rays and there can be electrons coming
out of the sample. These electrons (coming out of the surface) are known as secondary electron.
The photodetector is placed in a faraday cage to protect it from the environment. It collects the
secondary electrons. There runs a photo current in the output circuit through a photomultiplier.
There are many photodetectors available for this detection.
The sample is basically scanned in this process through raster process (reading lines
horizontally/line by line). The sample is moved. The moving of electron beam is not recommended
because focus may be lost. The thinner the focus, the better. The secondary electrons run into CRT
tube and give a 2D image showing the surface.
Height of the setup could be 1-2 meters and is to be pumped out (vacuumed down) because
otherwise the electron beams will not be collimated. The other particles (dust, ions etc.) in the
setup will cause the beam to scatter out and the image will be scattered. The current will be very
low in the output circuit. The pressure is not very high (10-6 Torr). It takes 1-2 hours to vacuum
the whole setup.
SEM is very useful for MEMS. SEM gives the image of the surface but it does not give any idea
about the structure.
(Page – 42 from T. Pradeep’s Book)
This is a JEOL SEM. The computer shows the images. There is a switch for turning on/off the
machine. This is a famous setup. The electron gun can be seen on top of the white tube. The older
models are bigger in size. The machine is to be vacuumed down before the operation.
EDX (Electron Diffraction X-rays) can be constructed from the same setup of SEM.

TEM (Transmission Electron Microscopy) – Transmission electrons create an image.

Essentially the same as SEM but from technological standpoint TEM is far more advanced and
gives higher resolution.
In SEM, the sample to be scanned is placed at one end of the setup. However, this is not the case
with TEM. The sample is place in somewhat the middle of the setup. The electron beam will go
through the sample and fall on the screen. There will be two beams then – transmitted and
diffracted beams. The grazing angle of diffracting beam is very small. The resolution is very high.

Components –
 FEG (Field Emission Gun) – placed inside a casing which will emit the electron beam.
This is a very high voltage setup (100-400 keV energy to see the diffraction pattern) The
wavelength of the of the beam is in picometer range (2-6 pm) which gives a very high
energy. The electron beam is accelerated by Anode plate.
90-120kV Low End; 300-400kV High Power
 Condenser Lenses - The electron beam passes through the condenser lenses
 Apertures – to control the beams so that they are collimated. Either the transmitted (bright
field) or the diffracted beam (dark field) can be observed. Observing both gives a better
contrast.
 Viewing Screen – Phosphor plates on the screen
 CCD Camera – Captures the image of the image of the specimen depending of the density
of various components in the sample. CCD is integrated circuit made of closed back diodes.
It is able to interact with electronic charges via the photoelectric effect.
Sample Preparation –
 The sample in TEM must be very thin and specially processed. Thin sample gives better
transmission.
 It takes at least 3 months of training to learn how to create a sample. The creation of sample
takes about 1 week. This is completely manual process.
 The better the sample, the better image.
  The sample is to be grinded and a hole is to be made to observe the cross section of the
sample. The cross section is made prominent through grinding. Chemical/Mechanical
Polishing can be used to get the required smoothness. One must be careful not to break the
sample while preparing it.
The resolution of TEM image is typically 0.2 nm. Carl Zeiss has achieved 0.07nm resolution with
ultrahigh vacuum TEM (10-9 Torr)  HRTEM.
In order to observe cells and cellular activity, semiconductor images, 10nm gold particles, bacteria
and virus, TEM can be used.
(The image creation is not necessary at this stage, taught in post-graduation level)
(Materials can be found in T Pradeep’s book)

SEM + TEM – A hybrid tool

Scanning/Tunneling Probes –
 Atomic scale imaging had been possible (using electron microscopes) for some time before
the STM was invented, but the ease of operation and construction of STMs popularized
Nanotechnology.
 The STM has largely been superseded by its close relation, the atomic force microscope
(AFM), because the AFM is capable of imaging insulating surfaces and therefore has a
more general set of applications. STM did not have an insulating surface, rather a
conducting one. Thus, substantial amount of tunneling current flows. AFM is versatile
and it can image many samples. The AFM also enabled the measurement of the mechanical
properties of individual molecules. Despite these enormous advances in scanning probe
microscopy, the electron microscope still offers the most accurate measurement of many
nanoscale structures.
 AFM is ultrasensitive to vibrations, thus, AFM machines are placed in the basement.
 At around the same time, the optics community began to develop techniques and dyes
for fluorescent imaging of single molecules. These methods broke the classical limits on
optical resolution, allowing particles to be located with nanometer accuracy in optical
images. The new optical methods also enabled new approaches to measuring motion
at a single molecule level.
 The discovery that small particles could be manipulated with a light beam also
occurred in this time frame (the mid-1980s), leading to the development of devices
that manipulate single molecules attached to small particles. High power laser beams
are used. Methods for the direct imaging of nanostructures and the measurement of their
mechanical properties and their fluctuations have undergone a dramatic revolution in the
past 20 years. This technology is still in development, has not reached matured stage yet.
Scanning Probe Microscopes –
 In such a microscope, a nano-sized probe investigates a material and/or structure through
electron tunneling current
 They investigate mostly the surface
 Two types - Scanning Tunneling Microscopy (STM – older model) and Atomic Force
Microscope (AFM – modern version)
 "Nanoscience and nanotechnology burst onto the scene as a result of the invention of the
scanning tunneling microscope by Gerd Binning and Heine Rohrer at IBM labs in
Switzerland in 1979" – S. M. Lindsay
STM (Scanning Tunneling Microscope) –
Piezoelectric – Voltage/Dimension change causes Dimension/Voltage change.
A metal probe was attached to a tripod consisting of three piezoelectric elements (shown in the
figure as PX, PY, and PZ). A piezoelectric material is one that changes its dimensions when a
voltage is applied across it. One of the elements, PZ, is used to control the height of the probe
above the surface. The other two (PX and PY) are used together to scan the probe across the surface
in a raster pattern.

The probe is advanced toward the surface until a preset level of tunnel current is detected. At this
point, the advance is terminated and the x−y scan of the surface begins. During this scan, a
feedback circuit is used to control the height of the probe above the surface so that the tunnel
current remains constant. Changes in the height of the probe reflect either changes in the height of
the surface (A in Fig) or a change of the local work function (B in Fig). The signal that is used to
correct the height of the probe is also sent to a computer display where the display intensity is used
as a measure of height at a particular point on the raster scan.

This is comparatively a newer model. A sample with fine surface and an atomically sharp tip (one
or two atoms dangling at the tip). This sharp tip produces a very sharp image (resolution of 3-5
Angstroms). Raster scanning to get the image.
 A remarkable surprise emerged from the first application of the STM to study the surface
of a gold crystal.
 Atomic scale steps (3 Å) were seen quite clearly in the scans across the gold surface.
Clearly, the microscope was capable of imaging at a resolution much greater than the
predicted 45 Å. •
 This surprising result came about because, at the nanoscale, the probe is not really a sphere.
It has an atomic scale structure, and if this includes one atom dangling from the very tip,
then atomic scale resolution is possible.
 This remarkable effect only occurs if the surface being imaged is extremely flat. A rough
surface will sample tunneling signal from around the edges of the tip, so resolution is
indeed ultimately limited by the radius of the probe. However, many surfaces of interest
can be prepared so as to be extremely flat and atomic resolution is regularly obtained on
surfaces like this.
 This unexpected atomic scale resolution was put to use to obtain images of the rather
complex surface that results from annealing the silicon (111) surface at high temperature
in ultrahigh vacuum. The reconstructed silicon surface is called the silicon “7 ×7” surface
 because of the symmetry of the pattern obtained when low-energy electrons are diffracted
from it.
(For materials of STM, see the book of Lindsay)
AFM (Atomic Force Microscopy –
The AFM was invented by Binnig, Quate, and Gerber in 1986 with the goal of addressing the
limitation of STM to imaging conducting samples.
This is basically a development and extension of STM. AFM has become one of the most powerful
tools of nanotechnology as it does not require any special environment (except for vibration free
environment). It can be placed in ambient condition. It also does not require High Vacuum or High
Voltage.
AFM is placed on optical tabletop which to overcome the issues of vibration. The tabletop is very
heavy so that the effect of the vibration is mitigated. The tabletop floats because of air pressure
from the supporting legs of the table making it immune to the vibration from the ground. The
components are to bolted on the tabletop, otherwise they will not be in place.

Much like the STM, the flexible cantilever (equipped with a sharp diamond point) was scanned
over a surface while the height of the cantilever above the surface was adjusted so as to keep the
tunnel current between the cantilever and a tunnel probe, placed above the cantilever, constant.
The cantilever can move (usually vertically) within its stiffness limitations. There is an atomically
sharp tip with it. A very intense laser is projected on the sample and the photodiode checks the
intensity of the laser. And creates the contrast image of the surface. Surface roughness can be
detected by vertical movement of the cantilever.

AFM technique relies on attractive Van der Waals and repulsive electrostatic forces between the
probe tip and the surface. Theoretical magnification 109. The tunneling current that flows between
the tip and the surface gives the image.
AFM works in 3 modes –
1. contact mode - Most AFMs work with contact mode. Contact mode gives higher resolution.
The radius of curvature in contact mode is in the order of 50nm. Typical lateral resolution
is 1.5nm and vertical resolution is 0.05 nm. It has a disadvantage that includes the damage
of the tip. It is to be replenished after some time.
The sample is placed on a glue type surface that is conducting. This will give the tunneling
current. The cantilever and probe placed is in the holder. The holder is called cartridge.
The image as the cantilever hovers over the sample is visible in a nearby CRT screen.
Spring constant of the cantilever is 10-3 to 100 N/m. The force range working on the tip
0.01-100 nano Newton.
The resonant frequency of a cantilever is given by the square root of the ratio of its spring
constant, k, to its mass, m, f0 = 1/2π*(k/m)
2. tapping mode and
3. non-contact mode.
From slide –
 The inventors initially selected the arbitrary distance of 0.16 Å and estimated that the force
required to stretch an ionic bond by this amount is ∼10−8 N while stretching a weak van
der Waals bond by the same amount would produce a force of ∼10−11 N. These are forces
 that are easily detectable using the cantilever spring and detection scheme that they
proposed. This is because the bonds that hold atoms together have, near their equilibrium
position, a spring constant that is quite similar to that of a macroscopic cantilever.
 The AFM has flourished, turning into a tool with many uses. It has several distinct imaging
modes. It “feels” the surface, and has become the ultimate nano-manipulation tool, capable
of pulling apart individual molecules or scratching or painting nanoscale structures.
Comparison of Various Nanotools –
Manipulation, Imaging, Sensing and Control in the Nanoscopic world has impacted the flourishing
of nanotechnology. Technology precedes theory sometimes. Technology evolves at a high pace.

Characterization Tools –
Characterization tools enables the measurement of various properties (length, density etc.) of a
sample.
 Optical (Imaging) Probe Characterization Methods
o Microscope – Binocular microscopes and Compound microscopes (imaging –
gross and fine morphology); a certain limit of magnification (micrometer range)
o Optical Microscopy – Ultrafine morphology
o Spectroscopy – precise particle sizing
o BAM (Brewster Angle Microscopy) – Gas-liquid interface imaging
 Electron Probe Characterization Methods –
o SEM, TEM
 o RHEED (Reflection High-Energy Electron Diffraction) – shows surface structre,
gives crystallographic information  RHEED gun emits electron high grazing
angle (very small angle) with the sample  a diffraction pattern is created which
is viewed on a screen (under proper conditions). The patterns provide many
information
o LEED
o EELS (Electron Energy Loss Spectroscopy)
 Scanning Probe Characterization Methods
o AFM, STM
 Photon (Spectroscopic) Probe Characterization Methods
o UPS (UV Photoemission Spectroscopy) - Surface Analysis
o AAS (Atomic Absorption Spectroscopy), ICP (Fluorescence Spectroscopy) –
Element analysis
o PLS (Photoluminescence Spectroscopy) – A laser is passed through FT-IR and
scans the sample. When high energy light is emitted on the sample, the electrons
jump to higher energy states. The jumps will occur to particular levels and will
return to their original energy states after some time. The energy is released as
radiative energy (as a photon). FT-IR scanning gives peaks in corresponding energy
levels  energy levels correspond to wavelength. Thus, quantum state bandgap can
be determined from PLS. This is a low cost test.
o XRD (X-ray Diffraction) – The collimated beam of x-ray is incident on the sample.
The reflected x-rays will give a range of spectral lines (spectroscopy) which will
have some peaks. Lattice constant can be measured through this technique.
o EDX (Energy Dispersive X-ray Spectroscopy), XRF (X-ray Fluorescence), XPS –
all are of the same family
 Ion Particle Probe Characterization Methods
o SIMS (Secondary Ion Mass Spectroscopy – gives idea about the material
composition), RBS (Rutherford Back Scattering) – Destructive method, the sample
is destroyed
o Depth Profiling
 Thermodynamic Characterization Methods

(There is a chart on Characterization Tools in the NanoCourseware pdf; these materials

were taken from Hornyak’s book chapter – 3)
 Fabrication and Processing (Top-Down)
This is a microelectronics process and has become very matured. All chips are made through
Fabrication which is a top down process.
Si and Semiconductor:
Chips are made of Si which is very widely and cheaply available. The matrix of Si crystal is mono
element crystal. The valence electrons of Si take part in creating covalent bond with other Si atoms
to form Si crystal.

The control of impurities in the Si crystal makes it conducting or insulating.

The bandgap structure –

 Very large in Insulator – very few electrons in the conduction band, not possible to jump
 Overlap of Valence band and Conduction band in Conductor – large amount of electrons
in the conduction band
 Manageable bandgap in Semiconductor – the bandgap can be engineered to be made
smaller or larger – amount of electrons in the conduction band can be controlled –
conductivity can be controlled
The bools can be cut to make the wafers on which the chips are made (the small circles are the
wafers). This process is very mature.
Surface Leakage – Surface leakage is a very important property of a semiconductor and it is to
be reduced. If surface leakage exists in a considerable amount, the diodes will be leaky in nature
i.e. certain amount of current will keep flowing.
Semiconductor Business and Silicon Valley:
 The semiconductor industry is the aggregate collection of companies engaged in the design
and fabrication of semiconductor devices.
 It formed around 1960, once the fabrication of semiconductors became a viable business.
It has since grown to be the $249 billion industry it is today.
Overview of Fabrication Process:

1. Start with the Si (or any semiconductor) Ingot/Bool

2. Slice it up and polish it to make wafers
3. Put a SiO2 masking layer on top of that and do photo-masking
4. Then lithography is done  UV Light is shined through a master mask (the design of the
circuit is contained in it). In the master mask, there are all the important marks. The light
then goes through a lens and the image is imprinted on the wafer.
Developing, Etching and Stripping and many other processing are done to get the final product.
The complete process is repeated multiple times in today’s technology. The pattern is curved into
the structure.
1. Material Preparation – Sand to polycrystalline Si
Sand  Si containing gas (from Oxide to Hydride)  Si reactor  polycrystalline Si
2. Crystal Growth and Wafer preparation – Polycrystalline Si to Wafers (dopant is added in
this stage)
3. Wafer Fabrication and Wafer Sort – Circuit/Devices formed in and on wafer surface.
Individual chips electronically tested (wafer sort)  the Dies in the wafer are individual
devices which are cut from the wafer and put in the integrated circuit
4. Packaging – Functioning Die placed in a protective package (packaging is to follow some
certain standard so that it can be used in a variety of applications – IEEE standards)
5. Final and Electrical test
Integrated Chip: A chip containing resistor, transistor, capacitor etc.
Moore’s Law (shrinking chips) – Amount of transistors in a chip doubles within 18 months and
cost becomes half.
State of the Art technology –
 As the size of technology is decreased, the wave nature of electron becomes prominent 
scattering-less transport/ ballistic transport  very high mobility of electron in room temp
 heat may increase due to other reasons which cannot be reduced  heat transfer
becomes quantized in this scale  heat density very high (as high as the nozzle of a rocket)
 may melt down the chip
 Reliability and Repeatability
 MEMS (not less than 50 micron)
Wafer Processing:
 Wafer processing
 Automated control of processing
 Characterization and Probe
 Growth Machines
Crystal Growth Technique:
Two methods –
1. Czocharalski Crystal Growth – A chamber containing a quartz crucible. Polysilicon ingots
are put here and melted. The temperature is 1400 degree celcius. The seed crystal is used
to pull out the melted material/bool which is to be cut to create the wafers
2. Float Zone Technique – Polysilicon (amorphous) is held between to rods and heated suing
RF heating method. The RF coils moves up and down along the rod.
Etch Pit Density: When the wafer is kept into HF acid, the acid eats into the impurities which will
be apparent in the microscope. They will be visible as black dots. The density is considered to be
etch pit density. The orientation of crystal affects the size and shape of the etch pits.
Greater density of Etch Pit  Greater Leakage current in diodes
Cleaning:
Cleaning is important because of the nanoscale. The metal lines are very thin (about 1/10 th of the
width of a hair) and a dirt sitting between the two metal lines will short it out. The dirt can come
from the surrounding environment (air, dust, spit/saliva etc.). These particles sit on the wafer and
disrupts the ideal performance. Therefore, to get proper performance, cleaning is very important.

Whenever the wafer is taken out of the growth chamber, there will be 20nm thickness of oxide
layer on the wafer coming from the ambient. The molecules in the surface interface have dangling
bonds. Three arms of Si will make covalent bonds and the other arm will be available to be bonded
with the contaminations form the air. Thus, surface states will be created which means there will
be states in the forbidden bandgap. This will assist in band-band tunneling and create leakage
current. For further processing, RCA cleaning is to be done to remove this layer.
The HF is buffered with Ammonium Hydroxide to reduce its strength.
DI Water – Deionized Water  The ions removed from the tap water. The ions are to be removed
if the water is to be used in microelectronics processing.
Basic Processes:
 Layering – SiO2 layers are grown or deposited into various processors
 Patterning – Same mask can be used to make either an island or a hole
 Doping
o Ion Implantation – non-uniform and highly directional process
o Diffusion of dopants – uniform process
 Heat Treatments
Thermal Processes:
Thermal processes are the processes operate at high temperature, which is usually higher than
melting point of aluminum.
 Oxidation – Growing a layer of oxide, oxide is very important because SiO2 is a very stable
and versatile oxide.
 Diffusion – Put oxide layers, dopant atoms through diffusion
 High Temp CVD
o Epi
o Poly
 Silicon Nitride
 RTP
o RTA
o RTP
Thermal Process can work in two ways –
 Horizontal Furnace – there are glass/quartz tubes. Heating will be done by RF coils. The
wafer will be sitting in the furnace. The gas goes into the chamber and comes out from the
other end. The gas must go through some processing before being released into the
environment.

 Vertical Furnace – Vertical arrangement for saving of space.

o Place the process tube in vertical direction
o Smaller footprint
o Better contamination control – the gas gets depleted when it reaches the end of the
chamber in the horizontal process, does not happen in vertical process
o Better wafer handling
o Lower maintenance cost
Gas manifolds are used to control the gas flow because they are electrically operated.

Oxidation Process:
Oxidation is an important process in fabrication of semiconductor chips.
• Oxygen comes from gas
• Silicon comes from substrate
• Oxygen diffuse across existing Silicon dioxide layer and react with silicon
• The thicker of the film, the lower of the growth rate

Applications –
• Diffusion Masking Layer – ultra pure O2 not needed
• Surface Passivation – Screen oxide, pad oxide, barrier oxide
• Isolation – Field oxide and LOCOS
• Gate oxide – ultra pure O2 needed
Oxidation Rate depends on –
• Temperature
• Chemistry, wet or dry oxidation
• Thickness
• Pressure
• Wafer orientation (<100> vs.<111>)
• Silicon dopant

Wet oxidation is easier because the OH molecule aids with the diffusion process. However, the
oxide produced by wet oxidation is not highly pure.
Local Oxidation of Silicon:

 Compare with blanket field oxide

o Better isolation
o Lower step height
o Less steep sidewall
 Disadvantage
o rough surface topography
o Bird’s beak
Device Dielectric:
CMOS Gate oxide – thinnest and most critical layer (1.6nm/ 1.6Angstrom). Only 1V applied in
the gate terminal will create a field of 6.25*10^6 V/cm  almost on the order of six, which is huge
for a small thickness. This thin layer must withstand that voltage. There will be some leakages if
there are impurities in the Gate Oxide.

Diffusion:
Diffusion is a isotropic/uniform process. Unwanted diffusion can cause leakage in the channel and
current will flow with the application of very small voltages which cannot be controlled (2nd
figure).
Diffusion as doping process is very cheap.

Greater the temperature, greater the depth. The values depend on the chamber geometry.
Ion Implantation:
 Anisotropic process
 Highly controllable and highly directional – can be stopped at any moment
 Can be used for abrupt boundary
 However, high energy ions will make the surface very rough.
Ion implantation requires a costly setup. The ion path has to be pumped out completely.

Thermal Annealing Improves Crystal Quality After Implantation Damage:

Acceptors such as Mg or Zn form complexes with hydrogen and thus become passive. Electron
beams dissociate these complexes and activate the acceptors. 2014 Nobel Laureate Nakamura
showed that even a simple thermal treatment (annealing) leads to efficient activation of Mg
acceptors.

The resistivity improves after the thermal annealing process.

Wet Etching: Etching means selective material removal. These are basically different chemical
reactions. For example – if buffered HF solution is used, it will remove the oxides from SiO2 and
Si if kept in it (almost 6nm/minute). Buffered HF can attack SiO2 but does not affect Si very quickly
like SiO2.
Etching Rate also depends on crystallographic axis.  Also called preferential etching
Wet Etching is basically reaction in aquous solution. Most acids and some alkaline solutions are
etchants. The wafer can be placed in the solution and reaction will take place. Or, in modern days
and labs, applicators are used to inject etchants on the wafers.
 Reactant transport to surface
 Selective and controlled reaction of etchant with the film to be etched
 Transport of by-products away from surface
Drawbacks –
 Anisotropic (Directional) Etching is desired. Lack of anisotropy
 Poor process control
 Excessive particulate contamination

Wet etching is used for non-critical feature sizes.

Dry Etching:
Dry etchings are basically plasma etching. In plasma etching, plasma is created in high electric
field. The plasmas (ions) are highly directional  will have a momentum. The ions are heavy and
when they hit the substrate, there will be physical sputtering. If there is reactive gas flow, it will
conduct chemical reactions.
Physical Sputtering + Chemical Gas  Reactive Ion Etching (RIE)
This is done in a reactor. The wafer is placed in the reactor and plasma is fired on the wafer.
Dry Etching advantages –
 Perfect etching – highly anisotropic
 Highly controllable – if RF field is turned off, etching is off immediately
 Limited particulate contamination
 Used in critical feature size
Drawbacks – expensive, apparatus has to be pumped out
Deposition Techniques:
Deposition of thin films.
 Evaporation Deposition – There is a substrate in room temperature and the source is in high
temperature (just above its melting point). The vapor from the melted source will be
deposited on the substrate. This is called Physical Vapor Deposition (PVD).

The high temperature  very problematic. Switching off doesn’t instantly stop the vapor
from being deposited.
 Sputtering Deposition – High energy Ions (Ar atoms) are fired on the Al target and the
pieces from the Al target gets deposited on the Si Substrate. (not a high temp process 
greater controllability)
 An electron beam is used to heat the source. This is also a physical deposition technique.
The high field filament will emit electrons and the magnetic field will cause the electrons
to fall on the source. The source will be melted somehow. And it will be deposited on the
substrate.

 Chemical Vapor Deposition (CVD) – There is a substrate and on the substrate gases are
flowing. The vapor gas comes down on the wafer and high temperature aids the reaction.
Thus, Silicon Nitride will grow on top the thin film and the byproducts will flow away.

 Epitaxial Growth – Atom by atom growth, processing temperature high. This gives ultra
pure process.
  MOCVD (Metallo Organic Chemical Vapor Deposition) – the products are volatile gases
and can be easily removed. Epitaxial GaAs layer grown on Ge(100) substrate by MOCVD-
DG(1). MOCVD is used to scale up the process (to increase the size of wafer)
Molecular Beam Epitaxy:
Oxide layer deposited on Si layer with a very abrupt interface. The sample is entered into the
chamber and placed in the sample holder which can rotate. RHEED gun/ electron gun is incident
on the phosphor plate at a grazing angle and creates a pattern.
The chamber is filled with liquid nitrogen and the pressure is very low (10-9 - 10-12 torrs). The
effusion cells are used to seal the PBNs. The control shutters can open and close to control the
flow of gas. RF coils are controlled by PID controllers. The temperature is to be controlled because
the process depends on the exponent of change in temperature.

Standard Lithography:
Standard lithography is a part and parcel of nanotechnology because it can still produce workable
chips.
 Start with Si wafer (thin film) into which the devices will be developed. There is a spin
coating on the wafer with photoresist. The rpm is given by the photoresist maker. If the
speed is high, the wafer will be uniform
 The photomask has the final pattern that will be imprinted. In the photomask, there can be
many designs (1-8 patterns). There are also alignment masks in the photomasks so that the
devices can be aligned (repeatedly use different photomask on the same chip so that you
can have a large scale production). Minimum feature size on the wafer is not the device.
Chrome metal is opaque (light cannot pass through it). The light passes through the holes.
(A complementary structure can be used – chrome metal in hole’s position and vice versa;
the masking process will then also be complementary). Photomask is used in a photo
aligner.
 Minimum feature size depends on Photomask, Exposure and Development process.
 Exposure – pass UV light through the photomask on to the wafer (wafer and photomask
placed in very close proximity). The light will expose the photoresist and chemical reaction
will take place. A certain amount of time has be allowed for exposure to get a proper
thickness of device (passing of photo energy)
 Development – Chemical process where the reaction from the previous step is visible. The
wafer is put in the KOH in the developer solution. After some time, the selective removal
of photoresist (where chemical reaction took placed) will occur – holes and islands on the
wafers.
 If there is a problem, the resist is to be removed. The easiest way to remove resist is
Acetone  Methanol  DI water
 If everything is okay, then etching, deposition and liftoff can be done.
Conventional Lithography:
Hundreds of chips in one go. E-beam is used to produce the mask.

After repeated use of the mask, the chrome lines may be broken and the resolution may become
low and it will be unsuitable for use.
The 10 Step Process: Peter Vansen (I guess) – 2 chapters (just the relevant parts)
1. Surface Preparation – Clean and dry wafer surface  SiO2 layer is deposited into the Si
surface. It will be removed later. No need to maintain too much purity. RCA or buffer
etching can be done to clean the surface. To dry the surface, dry N2 is used.
2. Photoresist Apply – Spin coat a thin layer of photoresist on surface  the wafer is to be
rotated so that the photoresist is uniformly distributed. The wafer is primed before applying
photoresist.
3. Softbake – Partial evaporation of photoresist solvents by heating  wafer kept in 110
degree celcius for 5 minutes so that the unwanted water vapors in priming solution and
photoresist is evaporated
4. Alignment and Exposure – Precise alignment of mask/reticle to wafer and exposure of
photoresist. Negative resist is polymerized.  One of the most crucial steps. Aligner
machine aligns the mask with the wafer. In close proximity, the UV light is shined. The
exposure is to be timed so that the photoresist receives enough photo energy.
5. Development – Removal of unpolymerized resist  Another crucial step. If negative
photoresist is used, the portion of the resist that receives the light becomes stiff
(polymerized). If the wafer is kept into developer solution, then the unpolymerized resist
is removed.
6. Hardbake – Additional evaporation of solvents  130 degree celcius to make the resist
harder. Also evaporates the remaining solvents.
7. Develop Inspect – Inspect surface for alignment and defects
8. Etch – Top layer of wafer is removed through opening in resist layer  Etching will
selectively remove oxide layer
9. Photoresist Removal (Stripping) – Remove photoresist layer from the wafer  the stripper
solution (Toluene) can remove the photoresist.
10. Final Inspection – Surface inspection for etch irregularities and other problems
Mask:
Photoresist can be of two types – Positive and Negative.
 Light Field – Light will pass through the mask except for the spots where chrome metal is
placed (the patterns have the metals).
  Dark Field – There are metals everywhere except along the patterns

Bonding and Packaging:

Bonding and packaging is required because
 the die that is used is very small in size and very fragile. It cannot be used as the way it is
 the wirings are not done in the die
Also –
1. A substantial lead system
2. Physical protection
3. Environmental protection
4. Heat dissipation
Cleanroom:
Semiconductor devices are very vulnerable to many types of contaminants. They fall into five
major classes.
1. Particles
2. Metallic ions
3. Chemicals
4. Bacteria
5. Airborne molecular contaminants (AMCs)
The major contamination sources are: 1. Air 2. The production facility 3. Cleanroom personnel 4.
Process water 5. Process chemicals 6. Process gases 7. Static charge
Class 1 is the best possible environment.

Sources –
Example of 10 step process:

The grey portion is the wafer onto which SiO2 has been deposited. Photoresist has also been
applied.

A dark field mask is applied (on the positive photoresist, UV is passed through the open space in
the mask). Thus, the photoresist will be removed from the other points after keeping it in the
developer solution.

The etching time needs to calculated so that the unexposed SiO2 is removed completely. The
photoresist is to be removed. Then there will remain an island of SiO2 on the wafer.
It needs to etched now. Dry etching method can be used (buffer HF not always preferable as it can
attack the SiO2 as well). ECR RIE can be used for this process. The exposed wafer is processed
by the etching process. A mesa layer is created afterwards.

The thickness depends on the application. CVD and Spin coating is done. The thickness to be used
properly because if thin layer is used, the mesa will not be covered completely which will be
vulnerable to acid.

Now, a bright field mask is used over the positive photoresist. Now, application of acid will remove
the exposed (without photoresist) SiO2 while keeping the unexposed area (with the photoresist)
unaffected.
Now the remaining photoresist is to be removed through proper process (acetone). Thus, the device
will look like the following.

This is the top view of the device.

Now a negative photoresist is used. A dark field mask is used. Thus, the photoresist will be
removed from everywhere except the area that was exposed to the UV light.
The SiO2 layer is passivating the mesa layer. Now, uniform metal is applied through PVD process.
Metal alloy will be deposited and it has to go through the small openings (the two small areas
beside the photoresist).

Then, liftoff is done. The negative photoresist is overdeveloped. Stripper solution is used to remove
the photoresist under the metal. Then, if mechanical pressure is applied on the metal layer, the
metal layer will be removed (broken) as there is no support in that region. Thus, a junction is
created.
In this way, a PIN photodiode is created. (Initial product will be very bad but with practice and
trial and error, it can be better)
(Slide can be found in the Files section – Fabrication VanZant – whole pdf not needed; just
the relevant parts)
Chapter 7 – some theory needed
Chapter 8 – a bit more thorough
 Bottom Up Process
(Pradeep Chapter 5, Lindsay Chapter 6, Review Paper – Progress in Surface)

Aspects of Bottom Up Process:

 Opposite of top down/ conventional Lithography.
 Self-assembly occurs in bottom up processes. Entropy plays a central role in self-
assembling systems made by equilibrium methods. The final structure must be reasonably
stable at room temperature, but it also must be weakly enough bound so that erroneous
structures dissociate (some mutations are possible due to this structure), allowing the
system to explore the large number of configurations needed to find the desired
configuration of lowest free energy.
 Bottom-up assembly generally means making complex nanostructures starting from the
random collisions of the components dissolved in a solvent. (Biology provides the most
striking example of this process; complex macroscopic organisms emerge from the chaotic
soup of the fertilized egg, and it is this self- assembly of living systems that provides much
of the inspiration for current research in this field.)
 Self-assembly of complex structures requires achieving just the right balance between
entropy at a given temperature and the binding enthalpies of the various components.
 Kinetic methods, relying on trapping the system in some non-equilibrium configuration by
rapidly changing the concentration of a reactant, changing the solvent, or changing the
temperature of the system.
 There can be “equilibrium” nanostructures that spontaneously assemble, as well as
nanostructures that are made by kinetically trapping metastable intermediate structures.
 Traditional chemical synthesis is an important route for assembling nanostructures.
 The goal is to produce the desired product through strong and very specific interactions.
 Even with highly specific chemical reactions that form stable bonds, entropy can still
complicate the picture, and few chemical synthesis procedures result in a pure product.
Thus, characterization and purification of the resulting compounds are as much a part of
organic synthesis as the carrying out of reactions.
Surface Action important for Bottom-Up Processes:
 Some knowledge of synthetic chemistry is essential for budding nano scientists.
 Small structures have large surface to volume ratios and the surfaces are covered with
atoms, atoms that cannot satisfy chemical bonding requirements with the neighboring atom
of the same material.
 For this reason, surface chemistry considerations can dominate the properties of small
particles.
 As another example, experiments frequently require that nanoparticles, whether they be
biological molecules or solid- state particles, be placed at specific locations on a solid
surface.
 This linking together of components of the system requires chemistry.
Self-assembly: (Pradeep Chapter 5)
 Bottom up approach of manufacturing nano devices has been demonstrated
 Most celebrated example: Iron Corrals and molecular abacus by IBM researchers.
 Functional nanostructures must involve self-assembly: in this process, once the process
begins, the structures form without external interference.
 The structure forms through self-organization: The necessary information is coded within
the molecules using weak forces, e.g. hydrogen bond, van der Waals forces etc.

Monolayers: (Pradeep Chapter 5, Lindsay Chapter 6,7)

 A very useful type of self-assembly occurs when molecules attach to a surface to which
they are chemically attracted. The chemical attraction will eventually lead to a dense layer
of molecules on the surface.
 Monolayers are single-molecule thin layers prepared on surfaces – an ultra-thin layer of
molecules of infinite breadth.
 These self-assembled monolayers have great utility as a way of modifying the chemical
properties of a surface.
 Examples: –
o A surface covered with methyl terminated alkanes is extremely hydrophobic,
whereas a surface covered in carboxylate groups (–COOH) is extremely
hydrophilic.
o Alkanethiols (- SH) are available with a wide variety of different end groups and
these can be used to change the characteristics of the surface.
 The simplicity of the design and molecular structure and the user's ability to manipulate
with ease make these attractive for many applications.
 Crystal Monolayers are half of Lattice Constant (If lattice constant is a, monolayer will be
a/2). In chemical sense, monolayer is a single molecule.
The black portion at the end is the Thyol Group (- SH).
SAM Potentials:
 SAMs are of prime technological interest, as the presence of molecules chemically
bound to the surface renders the properties of the modified interface (i.e., wetting,
conductivity, adhesion, and chemistry) to be entirely different than those of the bare
substrate.
 The exposed terminal functional group(s) of the SAM can be further modified so as to
enhance or to alter the film properties. Changing the groups exposed at the air–film
surface is critical for determining and designing the interaction strengths of proximal
molecules or analytes (i.e., sensing, electron transfer, cell adhesion, polymer adsorption)
or for post-assembly modification of the film. Molecules that are confined to the air–film
interface can undergo selective chemistry, as they are confined to two dimensions; unlike
(three-dimensional) solution-phase chemistry, the molecules are held in fixed
conformations.
 The incorporation of functional moieties such as chromophores, electroactive groups, or
molecules that can bond within the SAM (i.e., covalent cross-linking between adjacent
molecules or non-covalent hydrogen bonding) enable capabilities in sensing, electron
transfer, molecular recognition, and other areas.
 Many technologically relevant materials possess well-defined surface chemistries,
including metals, semiconductors, oxides, and other complex materials such as
 superconductors; a variety of hetero-atom containing molecules have been shown to self-
assemble on such substrates.
 The nature of interactions between molecules and substrates range from hard acid–base
interactions to soft donor– acceptor charge transfer interactions. However, there are a
number of materials that possess complex and varied surface chemistries. Complex
materials (e.g., some oxides, ferroelectric materials such as LiNbO3 and others) possess
crystal structures with a number of atomic constituents; often times, their surfaces are
enriched in a particular element due to processing and the chemical environment (e.g.,
exposure of lead zirconate titanate (PbZrTiO3) to acidic conditions leads to a surface that
is lead-depleted). Certain areas of a material can be selectively protected so as to create a
distribution of chemical compositions within the same material, or for the purpose of
further growth or etching.
 The physical and chemical properties of SAMs leave them amenable to further
manipulation, thus creating patterns within the film.
 As SAMs are of such exceptional technological importance, there is a great desire to
control their features, or the features of the substrates supporting them, down to the
nanometer scale as technology continues to shrink in size and dimension.
 Self-assembly has been a useful method with which to isolate and to study molecules and
assemblies at the nanoscale. The invention and development of scanning probe
microscopes have greatly enhanced our ability to understand and to optimize the patterning
of SAMs, as the spatial distributions of individual adsorbates can be directly measured.
The concept of self-assembled monolayers was first introduced by Irving Langmuir in 1917 during
his study on amphiphiles in water.

While spreading the amphiphiles [a chemical compound possessing both hydrophilic (water-
loving, polar) and lipophilic (fat-loving) properties] on water, Langmuir found that the film formed
had the thickness of one molecule. K. Blodgett was able to transfer the monolayer, onto a solid
support. Spontaneous formation of a monolayer was first reported by Zisman in 1946 by observing
the spontaneous formation of alkyl amines on a platinum surface.
The field observed a tremendous growth when in 1983 researchers found that ordererd mopnolayer
of thiols (-SH) can be prepared on a gold surface by adsorption.
Adsorption:
Adsorption is the process that occurs when a gas or liquid solute accumulates on the surface of a
solid or a liquid (adsorbent) forming a molecular or atomic film (adsorbate).
Monolayers on Gold:

Alkanethiolate monolayers grown on coin metals (Ag, Au, Pt) are structurally simple and easy to
construct. The molecular sheet is made of thiolate species with long alkyl chains and the substrate
is one of the above metals. This is why a large no. of studies have been conducted on these systems.
 One of the most studied and readily assembled molecular monolayers consists of alkane chains
(–CH2– repeats) modified at one end with a thiol (–SH) group that attaches chemically to a
gold surface.
 Monolayers can be formed by alkane chains that vary in length from just a few carbon atoms
up to chains that are so long that they are difficult to dissolve (>20 methylene groups).
 Longer chains (12 or more methylene units) pack together with stronger van der Waals
interactions and therefore tend to form more ordered films, though reasonably well-ordered
films can be formed by chains with as few as six or eight methylene units.
 Typically, an ethanol solution of a few mM concentration of alkanethiol is kept in contact with
a clean gold surface for several hours. If the head group is not reactive, the film remains stable
after the sample is pulled out of the solution and rinsed.
Langmuir-Blodgett Methodology:

Langmuir Revisited:

Photograph of the Langmuir trough setup for the particle deposition experiments. The silicon wafer
is visible in the center of trough and it is connected to the dipper arm with a support at 301 relative
to the water/ n-hexane interface. The trough was machined out of Teflon and has a slot in the back
where the dipper arm can move without disturbing the interface.
Langmuir’s Growth Law:
𝑑𝜃
 Growth of the monolayer can be explained by Langmuir’s Growth Law which is =
𝑑𝑡
𝑘(1 − 𝜃).
  The rate of growth is proportional to the number of the sites available [k is the rate constant,
𝜃 is a fraction of sites.]
Why Gold:
Gold is the chosen substrate for various reasons:
• It is easy to make a thin gold film by thermal evaporation
• For gold, there is no stable oxide at room temperature [Au2O3 can be made through ozone
exposure]
• None of the commonly present gases of atmosphere undergoes chemisorption on gold
surface
• Repeated solvent washes are adequate to make gold surface atomically clean
• Removal of carbonaceous deposits on gold can be done through oxidizing with a ‘piranha’
solution [30% of H2O2: conc. H2SO4 = 1:3 @ 100C].
Growth of SAMs:
 Michael Faraday showed the synthesis of solid nanoparticles by a precipitation reaction in
a mixed solvent (CS2/Water).
 The reduction of an aqueous gold salt with phosphorus in carbon disulfide to produce a
ruby colored aqueous solution of dispersed gold particles.
 Carried out in a mixed solvent, the reduction reaction that produces gold particles from the
gold salt stops shorts of producing large solid precipitates because the gold nanoparticles
become suspended as colloids in the second component in the solution.
 This strategy is still used to produce nanoparticles and quantum dots.
o A typical example: a solution of lead nitrate to another solution of potassium iodide,
a brilliant yellow precipitate of insoluble lead iodide is formed.
2KI (aq) + Pb(NO3)2 (aq)  PbI2 (s) + 2KNO3 (aq)
o The synthesis of quantum dots of Cd compounds (CdSe) : A cold solution od one
of the components is injected into a hot solution of the other component. A
precipitation reaction begins and because of the rapid cooling caused by the
injection of the cold solution, further growth of crystallites is halted. The solution
is subsequently reheated, causing small crystallite (which have a larger surface to
volume ration and are therefore less stable) to dissolve and recrystallize onto more
stable existing crystallites to produce a much more uniform distribution of
crystallites. This process is called Oswald Ripening.
 Kinetic Control of Growth – the vapor phase deposition of Si that grows as a nanowire
underneath a liquid formed from a Gold-Silicon eutectic (low melting point at the Gold-
Silicon interface).
Patterning of SAMs: "Patterning self-assembled monolayers" by Rachel K. Smith, Penelope A.
Lewis, Paul S. Weiss. A review published in Progress in Surface Science, 75 (2004) 1–68

Dip pen lithography is to be

studied properly
Comparison of SAM Patterning Techniques:

SAMs and Applications: Pradeep Chapter 5 (Section 7)

i) Sensors
ii) Affinity Biosensors
iii) Chemical Sensors
iv) pH sensing
v) Corrosion prevention
 Nanoelectronics (Nanoelectronic Devices)
(Overview of Nanoelectronic Devices)
Two broad classes of alternative nanoelectronic switches and amplifiers:
1. Solid-State Quantum-Effect and Single-Electron Devices (Fabricating quantum-effect
and single-electron devices in solids is the approach taken by most research groups
exploring new-technology nanoelectronic devices. It makes novel devices out of the same
semiconductors used for transistors.)
2. Molecular Electronic Devices. (Molecular electronics is a relatively new approach that
would change both the operating principles and the materials used in electronic device)
Typical FET:
 The metal-oxide semiconductor FET (MOSFET) has been by far the most common type
of transistor in modern microelectronic digital circuits, since Shockley’s explanation of the
device in 1952.
 Properly designed MOSFET circuits use very little power and are economical to
fabricate (the same mask can be used made a great amount of devices from the same wafer
and it can be used multiple times).
 Pure silicon is a very poor conductor, so dopant impurities, such as boron or arsenic, are
introduced into the silicon to create an excess of mobile positive or negative charges.
Negatively doped (N-doped) silicon contains free electrons that are able to move through
the bulk semiconductor. Positively doped (P-doped) silicon contains electron vacancies,
commonly known as “holes,” which act as positive charges that move freely through the
bulk material.
 A metal electrode separated from the semiconductor below by an insulating oxide barrier
serves as the gate of the MOSFET, whose voltage and associated electric field controls the
flow of current from the source to the drain. This is why the device is called a “field effect”
transistor.
 When the voltage on the gate is low, the region between source and drain contains few
mobile negative charges, and very little current can flow. Increasing this voltage
sufficiently attracts electrons to the region under the gate, opening the channel and allowing
masses of electrons to flow from the source to the drain. This corresponds to a dramatic
rise in current.
Popularity of FETs:
 The change in conductivity makes the MOSFET a two-state device. Since small changes
of gate voltage result in large changes in conductivity, the MOSFET also can be used as an
amplifier.
 Nanoelectronic devices for use in computers must function in these same two roles of two-
state device and amplifier.
 In the past, the most common way to make smaller circuits has been simply to shrink the
dimensions of all of the circuit components by a constant factor, a process called “scaling.”
 This scaling has proceeded at an exponential rate, doubling the number of transistors on a
chip approximately every 18 months since the invention of the integrated circuit by Kilby
 in 1958. This has produced today’s commercial, massproduced integrated circuits, such as
Intel’s Pentium chip, which contains over 3.2 million transistors with a minimum feature
size of approximately 350 nm [1994].
 The MOSFET has remained popular because its operation changes very little and it
maintains very favorable cost-to-performance ratios as it is scaled down. However, as
MOSFET’s reach minimum feature sizes of 100 nm and less, this rapid, cost-effective
scaling of dense circuitry may not persist.
Obstacles to Further Miniaturization of FETs:
 In the past, the most common way to make smaller electronic circuits has been simply to
shrink the dimensions of all of the circuit components by a constant factor, a process called
“scaling.”
 The MOSFET has remained popular because its operation changes very little and it
maintains very favorable cost-to-performance ratios as it is scaled down to much smaller
sizes. This scaling has proceeded at an exponential rate, doubling the number of transistors
on a chip approximately every 18 months since the invention of the integrated circuit by
Kilby in 1958.
As MOSFET’s reach minimum feature sizes of 100 nm and less, this rapid, cost-effective scaling
of dense circuitry may not persist.
The National Technology Roadmap for Semiconductors, published by the Semiconductor Industry
Association, projects that chips will be made from transistors with major features (gate lengths) of
70 nm in the year 2010 [1994]. Individual working transistors with 40 nm gate lengths have already
been demonstrated in silicon [1995]. Transistors with gate lengths as small as 25 nm have been
made using gallium arsenide [1990].
It is unclear, though, whether such transistors can be made sufficiently uniform and reliable to
build a densely integrated computer containing a billion or more of them. Additionally, a dense
network of such transistors could be slowed down by the flow of current through extremely narrow
wires from one device to the next.
A few of the obstacles to FET scaling are simply enumerated below, in increasing order of their
intractability.
– High electric fields, due to a bias voltage being applied over very short distances, can
cause “avalanche breakdown” by knocking large numbers of electrons out of the
semiconductor at high energies.
– Heat dissipation of transistors (and other switching devices), due to their necessarily
limited thermodynamic efficiency, limits their density in circuits, since overheating can
cause them to malfunction.
– Vanishing bulk properties and nonuniformity of doped semiconductors on small scales.
This can only be overcome either by not doping at all (accumulating electrons purely using
gates, as has been demonstrated in a GaAs heterostructure) or by making the dopant atoms
form a regular array. Molecular nanoelectronics is one path to the latter option.
– Shrinkage of depletion regions until they are too thin to prevent quantum mechanical
tunneling of electrons from source to drain when the device supposedly is turned off. The
 function of nanoelectronic devices is not similarly impaired, because it depends on such
tunneling of electrons through barriers.
– Shrinkage and unevenness of the thin oxide layer beneath the gate that prevents electrons
from leaking out of the gate to the drain. This leakage through thin spots in the oxide also
involves electron tunneling.
The thermodynamic obstacle to FET scaling, heat dissipation, suggests that it would be desirable
to find replacements for FET’s that might permit the construction of circuits that require fewer
switching devices in order to perform the same functions.
 All but one of the other obstacles to scaling result from the simultaneous decrease in the
effectiveness of doping and the increase in the significance of quantum mechanical effects.
 Once electronic devices approach the nanometer and the molecular scale, the bulk
properties of solids are replaced by the quantum mechanical properties of a relatively few
atoms.
 Properties associated with uniformly doped semiconductors will become less evident and
influential in the operation of an electronic device. Quantum mechanical effects, such as
energy quantization and tunneling, become much more significant.
 In order for a transistor-like device to operate on the nanometer scale and, ultimately, on
the molecular scale, it would be advantageous if it did not depend upon doped materials
and if it operated based on quantum mechanical effects, rather than in spite of them
Quantum Effects:
 Once electronic devices approach the nanometer and the molecular scale, the bulk
properties of solids are replaced by the quantum mechanical properties of a relatively few
atoms. Properties associated with uniformly doped semiconductors will become less
evident and influential in the operation of an electronic device.
 Quantum mechanical effects, such as energy quantization and tunneling, become much
more significant in devices in order to perform the same functions.
 The thermodynamic obstacle to FET scaling, heat dissipation, suggests that it would be
desirable to find replacements for FET’s that might permit the construction of circuits that
require fewer switching.
Islands of e- Confinement:
 A number of nanometer-scale solid-state replacements for the bulk- effect
semiconductor transistor have been suggested.
 All of these devices function by taking advantage of effects that occur on the
nanometer-scale due to quantum mechanics.
 The essential structural feature that all of these devices have in common is a small
“island” composed of semiconductor or metal in which electrons may be confined. This
island of a nanoelectronic device assumes a role analogous to that of the channel in an
FET.
 The extent of confinement of the electrons in the island defines three basic categories
of solid-state nanoelectronic devices.
o Quantum Dots (QDs or “artificial atoms”): Island confines electrons with zero
classical degrees of freedom remaining.
 o Resonant Tunneling Devices (RTDs): Island confines electrons with one or two
classical degrees of freedom.
o Single-Electron Transistors (SETs): Island confines electrons with three
classical degrees of freedom.
The composition, shape, and size of the island gives the different types of solid-state
nanoelectronic devices their distinct properties. Controlling these factors (this is a crucial factor
but gaining control over these factors is very difficult) permits the designer of the device to employ
quantum effects in different ways to control the passage of electrons on to and off of the island.
 For example, the mean free path of mobile electrons can be much greater in semiconductors
than in metals. Thus a mobile electron might travel coherently all the way across a
semiconductor island, without severe collisions. This means that conductivity of a device
can be strongly enhanced or suppressed by quantum mechanical interference between
separate paths an electron might take through the device.
Islands, Potential Wells, and Quantum Effects:
 The smallest dimension of the island in a solid-state nanoelectronic device ranges from
approximately 5–100 nm. (Highest value may have changed nowadays)
 Quantum well is 1D confinement, Electron gas is 2D confinement
 The island may consist of a small region or layer different from the surrounding material.
Otherwise, edges of the island may be defined by electric fields from small electrodes
patterned in the shape of the desired island boundary. Often, the island is embedded
between two narrow walls of some other material, or an insulating oxide of the island
material, or an insulating defect zone in the substrate (Most of the crystals are inherently
defective). The island is surrounded by potential energy barriers, which impede the
movement of electrons in and out of the island region.
 Two essential quantum mechanical effects are exhibited by electrons confined to
nanometer-scale islands between closely spaced potential energy barriers.
o First, quantum mechanics restricts each electron’s energy to one of a finite number
of one-electron energy levels (quantum states with discrete, “quantized” energies).
The smaller the distance between the barriers (i.e., the smaller the island), the more
widely spaced in energy are the levels for the electrons in the potential well between
the barriers. The symbol Δε is used to represent the energy spacing between two
energy levels in such a potential well.
o Second, if the potential barriers are thin enough (approximately 5–10 nm or less,
depending on the height of the barriers), electrons occupying energy levels lower
than the height of the barrier have a finite probability of “tunneling” through the
barrier to get on or off the island. However, for an electron of a given energy to
tunnel through a barrier, there must be an empty state with that same energy waiting
on the other side.
 The two effects, energy quantization and tunneling, strongly influence the flow of electrons
through a nanoelectronic device. If an electron is confined in a well, its energy becomes
quantized/discrete.
 When a bias voltage is applied across the island, it induces mobile electrons in the
conduction band of the source region to attempt to move through the potential well in the
island region to get to the region of lower potential in the drain region. The only way for
 electrons to pass through the device is to tunnel on to and off of the island through the two
high potential barriers that define the island and separate it from the source and the drain.
But tunneling can occur and charge can flow toward the drain only if there is an unoccupied
quantum energy level in the well at an energy that matches one of the occupied energy
levels in the source band.

RTD and RTT:

RTD –
In the figure below (left), if proper biasing voltage is applied, the energy states in the potential
energy well is aligned with the occupied conduction band and when it is aligned, there is a
tunneling current. This is the operation of RTD (resonant tunneling diode).
It is crucial to the operation of resonant tunneling devices (and the other categories of
nanoelectronic devices) that the energy of the quantum states in the potential well on the island
can be adjusted relative to the energy of the bands in the source and drain. When the bias potential
is sufficient to lower the energy of an unoccupied one-electron quantum state inside the well to be
within the range of energies for the source conduction band, the quantum well is said to be “in
resonance” or “on,” and current can flow onto the island and out to the drain. This is shown
schematically in Fig. 3(c). Otherwise, current through the device is blocked—the device is “out of
resonance” or switched “off,” as in Fig. 3(b). This use of a variable applied bias to switch a
tunneling current on and off characterizes the operation of a two terminal resonant-tunneling
device called a resonant-tunneling diode or RTD.
RTT-
Similar adjustment of the energy levels in the potential well relative to those in the source also can
be achieved by varying the voltage on a third (gate) terminal, rather than the voltage on the source.
In this three-terminal configuration, shown in Fig. 4(a) and termed a resonant tunneling transistor
(RTT), a small gate voltage can control a large current across the device [Fig. 4(b) and (c)]. Thus,
an RTT can perform as both switch and amplifier.
A resonant-tunneling device usually has a long and narrow island (i.e., a “quantum wire” or
“pancake”) with shortest dimension 5–10 nm. The short dimension(s) make Δε large, while the
large dimension(s) keep U small. (That is Δε >> U) . This means that the spacings between allowed
energies of collections of electrons on the island are determined solely by Δε, because U is a
negligible term in calculating the total energy U+ Δε for adding an electron to the island.
Quantum Dots:
QD’s are constructed with islands that are short in all three dimensions, confining the electrons
with zero classical degrees of freedom—electronic states are quantized in all three dimensions.
The dot-like island may be made of either metal or semiconductor. It can consist of small deposited
or lithographically defined regions; small, self-organized droplets or nanocrystallites grown in situ
or deposited in a film.
Using the physical ideas outlined above, we observe that making an island short in all three
dimensions leads to widely spaced quantum energy levels for an electron on the island—i.e. Δεx,
Δεy and Δεz are all large. The charging energy U is also large, because there is no way for a pair
of electrons to get far from each other. As a result, both the interaction among the electrons on a
QD and the energy levels for each individual electron influence the flow of current through the
dot.
Drawbacks and Obstacles to Solid State Nanoelectronic Device:
(Self-study from the paper)
Molecular Electronics:
Molecular electronics uses primarily covalently bonded molecular structures, electrically isolated
from a bulk substrate.
Devices of this description, wires and switches composed of individual molecules and nanometer-
scale supramolecular structures, sometimes are said to form the basis for an “intramolecular
electronics”
Solids have the significant disadvantage that it is relatively difficult and expensive to fabricate or
“sculpt” in them the many millions or billions of nearly identical nanometer-scale structures that
will be needed in each ultra-dense computer chip. Individual molecules, natural nanometer-scale
structures, easily can be made exactly the same by the trillions of billions. The great power and
variety of organic chemistry also should offer more options for designing and fabricating
nanometer-scale devices than are available in silicon.
Molecular Electronic Switching Devices:
At least four broad classes of molecular electronic switching devices can be distinguished in the
research literature:
1. Electric-Field Controlled Molecular Electronic Switching devices, including molecular
quantum-effect devices
2. Electromechanical Molecular Electronic Devices, employing electrically or mechanically
applied forces to change the conformation or to move a switching molecule or group of
atoms to turn a current on and off;
3. Photoactive/Photochromic Molecular Switching Devices which use light to change the
shape, orientation, or electron configuration of a molecule in order to switch a current;
4. Electrochemical Molecular Devices which use electrochemical reactions to change the
shape, orientation, or electron configuration of a molecule and hence to switch a current
Molecular Wires:
The figure below depicts the structure of a molecular wire invented by Tour that was used recently
to demonstrate conductance in a single molecule. In that experiment, one end of the conducting
molecule was adsorbed to a gold surface, but an STM tip was used as the other electrode in the
circuit.

However, in more recent work by Reed and Tour, each end of a conducting molecule was adsorbed
to a different gold electrode mounted on a surface in order to complete a circuit and even to
demonstrate quantum-device effects. Wires of this general type also were used in the Purdue self-
assembled molecular electronic circuit array mentioned above, in which the characteristic
“staircase” pattern of Coulomb blockade was observed at room temperature in the plot of current
versus bias voltage.
Wires like the one illustrated in Fig. 7 are characterized by extended repeating structures—here a
sequence of benzene-like rings connected by acetylene linkages—each part of which is linked to
the next by bonds including many π -electrons above and below the plane of the structure. These
orbitals or clouds of π-electrons conjugate with each other, or interact, to form a single large orbital
throughout the length of the wire to permit mobile electrons to flow.
Buckyballs – C60; very stable structures.
Electromechanical Molecular Electronic Devices:
(Didn’t talk much about this part)
 Quantum Tunneling
(Quantum Mechanics – An Introduction for Device Physicists and Electrical
Engineers – Chapter 3)

The wave function penetrated into the barriers. When we treat the particle as a wave, then the wave
nature of barrier penetration can occur. This is familiar in electromagnetic waves, where the
decaying wave (as opposed to a propagating wave) is termed an evanescent wave.
For energies below the top of the barrier, the wave is attenuated, and it decays exponentially. Yet,
it takes a significant distance for this decay to eliminate the wave completely. If the barrier is
thinner than this critical distance, the evanescent wave can excite a propagating wave in the region
beyond the barrier. In optics, this effect is termed frustrated total internal reflection. The wave can
penetrate the barrier, and continue to propagate, with an attenuated amplitude, in the trans-barrier
region. For particles, this process is termed tunneling, with analogy to the miners who burrow
through a mountain in order to get to the other side!
Tunneling is important in degenerately doped p–n junction diodes. Nevertheless, tunneling arises
when the particle is treated as a wave.
Since Esaki’s discovery of the tunnel diode, tunneling has become important in a variety of
situations. In reverse biased p–n junctions, Zener breakdown occurs when electrons in the valence
band can tunnel across the gap into the conduction band if a sufficiently high electric field is
applied to bring these two bands to the same energy levels (on opposite sides of the junction).
Similarly, resonant tunneling diodes have been fabricated in heterostructures such as GaAs–
AlGaAs, and we will discuss these in some detail in a later section. Finally, as semiconductor
devices become smaller, particularly the metal–oxide–semiconductor field-effect transistor
(mosfet), where a thin layer of insulator (usually SiO2 of HfO2) is used as the gate insulator, this
thin oxide becomes susceptible to leakage currents via tunneling through the oxide.
Simple Tunnel Barrier:
The simple barrier is shown in Figure 3.1. Here the potential is defined to exist only between -a
and a, and the zero of potential for the propagating waves on either side is the same. We can
therefore define the wave vector k in the region |x| > a, and the decaying wave vector γ in the
region |x| < a.

(See the derivation from the book)

The transmission probability is the ratio of the currents on the two sides of the barrier, directed in
the same direction of course.
It is important to note that the result (3.10) is valid only for a weak potential for which the energy
is actually below the top of the barrier. If we consider an incident energy above the barrier, we
expect the barrier region to act as a thin dielectric and cause interference fringes. We can see this
by making the simple substitution suggested by (3.1) through γ → −ik′. This changes (3.10) into

(Derivation to be seen from the paper/chapter)

Complex Tunnel Barrier:
Different potentials at each side (different k values on two sides). The actual transmission
coefficient relates the currents

(Derivation to be seen from the paper/chapter)

Double Barrier:
We now want to put together two tunnel barriers separated by a quantum well. The quantum well
(that is, the region between the two barriers) will have discrete energy levels because of the
confinement quantization.

We will find that, when the incident wave energy corresponds to one of these resonant energy
states of the quantum well, the transmission through the double barrier will rise to a value that is
unity (for equal barriers). This resonant tunneling, in which the transmission is unity, is quite useful
as an energy filter.
The well is situated between 0 and b. Following the derivation from the previous ones; the
following can be found,
We note that both E and A′ describe a wave propagating to the right. Denoting the definition of
the thickness of the well region as b, we can simply relate these two coefficients via
A′ = Eeikb
where k is the propagation constant in the well region. Similarly, F and B′ relate the same wave
propagating in the opposite direction. These two can thus be related by
B′ = Fe-ikb
These definitions now allow us to write the connection as a matrix in the following manner
Equation (3.21) now defines a matrix MW, where the subscript indicates the well region. This
means that we can now take the matrices defined in previous sections for the left-hand and right-
hand regions and write the overall tunneling matrix as;

From this, it is easy to now write the composite M11 as

and it is apparent that the resonance behavior arises from the inclusion of the off diagonal
elements of each transmission matrix, weighted by the propagation factors.
Simple, Equal Barriers:
assume that the two barriers are exactly equal, so the same propagation wave vector k exists in the
well and in the regions to the left and right of the composite structure. By the same token, each of
the two barriers has the same potential height and therefore the same γ. We note that this leads to
a magnitude squared factor in the second term of (3.23), but not in the first term with one notable
exception. The factor of ei2ka does cancel since we are to the left of the right-hand barrier (-a-
direction) but to the right of the left-hand barrier (+a-direction). Thus, the right-hand barrier
contributes a factor of e−i2ka, and the left-hand barrier contributes a factor of ei2ka, so the two cancel
each other.
While this latter form shows the explicit elements in the total transmission, it is easier both to
understand and to manipulate, if we leave the explicit terms out for the present. To do the bit a
little better, let us write the terms as a phasor; that is, let us write each of the various matrix
elements as M11 = m11 eiϑ
Unequal-Barrier Case:
(Self-read)
Shape of the Resonance:
It is apparent from the shape of the transmission curve in Figure 3.8 that there is a very sharp
resonance that coincides with the resonant energy level in the quantum well.
When the energy E is swept through the resonance energy E0, the phase angle arg(P) is swept
through an amount approaching π. Price (1999) has pointed out that this has an analogy with formal
wave propagation theory, so that one can assign a transit time for passage of an electron through
the double barrier structure as

Tunneling Devices:
One of the attractions of tunneling devices is that it is possible to apply textbook quantum
mechanics to gain an understanding of their operation, and still achieve a reasonable degree of
success in actually getting quantitative agreement with experimental results.
The Landauer Formulation:

Left side is the conduction band and the right side is the valence band with a barrier in between.
The general barrier can be a simple square barrier, or a multitude of individual barriers, just so
long as the total tunneling probability through the entire structure is coherent. The properties of
the barrier are completely described by the quantity T(k). The potentials are not equal (k’s are not
equal).
In equilibrium, where there is no applied bias, the left-going and right-going waves are equivalent
and there is no net current. By requiring that the energy be con served during the process, we can
write the z-component of energy as (we take the z-direction as that of the tunneling current)

where the constant accounts for the bias and is negative for a positive potential applied to the right
of the barrier. The two wave vectors are easily related to one another by this equation, and we note
that the derivative of this equation allows us to relate the velocities on the two sides. In particular,
we note that

The current flow through the barrier is related to the tunneling probability and to the total number
of electrons that are available for tunneling. Thus, the flow from the left to the right is given by
where the factor of 2 is for spin degeneracy of the electron states, the (2π)3 is the normalization on
the number of k states (related to the density of states in k space), and f(EL)is the electron
distribution function at the barrier. Similarly, the current flow from the right to the left is given by

These two equations can be combined to give total current density as follows
Ballistic Transport:
(Sir mentioned this quite a few times)
Ballistic conduction (ballistic transport) is the unimpeded flow (or transport) of charge carriers
(usually electrons), or energy-carrying particles, over relatively long distances in a material. In
general, the resistivity of a material exists because an electron, while moving inside a medium, is
scattered by impurities, defects, thermal fluctuations of ions in a crystalline solid, or, generally, by
any freely-moving atom/molecule composing a gas or liquid. Without scattering, electrons simply
obey Newton's second law of motion at non-relativistic speeds.
Ballistic conduction is typically observed in quasi-1D structures, such as carbon nanotubes or
silicon nanowires, because of extreme size quantization effects in these materials. Ballistic
conduction is not limited to electrons (or holes) but can also apply to phonons. It is theoretically
possible for ballistic conduction to be extended to other quasi-particles, but this has not been
experimentally verified. For a specific example, ballistic transport can be observed in a metal
nanowire: due to the small size of the wire (nanometer-scale or 10−9 meters scale) and the mean
free path which can be longer than that in a metal.
Ballistic conduction differs from superconductivity due to the absence of the Meissner effect in
the material. A ballistic conductor would stop conducting if the driving force is turned off, whereas
in a superconductor current would continue to flow after the driving supply is disconnected.
Esaki Diode:
(Self-study)
Single Electron Tunneling:
(Have to go through this)
Josephson Tunneling:
(Have to go through this)