Dr.A.K.Agarwal
MPH204‐Introduction to Nanoscience & TechnologyPage 1Solar Cells and Nanotechnology
Potential advancements in nanotechnology may open the door to the production of cheaper and slightly more efficient solar cells. Conventional solar cells are called photovoltaic cells. These cells are made out of semiconducting material, usually silicon. When light hits the cells, they absorb energy though photons. This absorbed energy knocks out electrons in the silicon, allowing them to flow.
Diagram of a photovoltaic solar cell.
Conventional solar cells have two main drawbacks: they can only achieve efficiencies around 10% and they are expensive to manufacture. The first drawback, inefficiency, is almost unavoidable with silicon cells. This is because the incoming photons, or light, must have the right energy, called the band gap energy, to knock out an electron.
If the photon has less energy than the band gap energy then it will pass through. If it has more energy than the band gap, then that extra energy will be wasted as heat.
Nanotechnology might be able to increase the efficiency of solar cells, but the most promising application of nanotechnology is the reduction of manufacturing cost. The nanorods behave as wires because when they absorb light of a specific wavelength they generate electrons. These electrons flow through the nanorods until they reach the aluminum electrode where they are combined to form a current and are used as electricity. This type of cell is cheaper to manufacture than conventional ones for two main reasons. First, these plastic cells are not made from silicon, which can be very expensive. Second, manufacturing of these cells does not require expensive equipment such as clean rooms or vacuum chambers like conventional silicon based solar cells. Instead, these plastic cells can be manufactured in a beaker.
Another potential feature of these solar cells is that the nanorods could be ‘tuned’ to absorb various wavelengths of light. This could significantly increase the efficiency of the solar cell because more of the incident light could be utilized .Improvements such as this could make it possible to manufacture inexpensive solar cells with the same efficiency as current technology. Since the manufacturing cost of conventional solar cells is one of the biggest drawbacks, this new technology could have some impressive effects on our daily lives. Although this new technology is only capable of supplying low power devices with sufficient energy, its implications on society would still be tremendous. It would help preserve the environment, decrease soldiers carrying loads, provide electricity for rural areas, and have a wide array of commercial applications due to its wireless capabilities.
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Single Electron Transistor: The singleelectron transistor (SET) is a nanodevice that can control the
transport of single elementary charges on and off a metallic island. It can also function as transistor similarly to a nowadays FET. The principles of the operation of the SET is determined by the Coulomb blockade, an energy barrier that determines the current flow through the device and the charge placed on the metallic island. Regulating the gate charge of the device can modify the Coulomb blockade. The SET can also be used as an ultrasensitive electrometer in DC ad RF mode. Theoretical calculations show a charge sensitivity h values lower than 1.7106e/ Hz for the SET and experimental research gives values of 1.2105e/ Hz. The experimental value for the SET is 1000 times better than the fieldeffect transistor used as an electrometer. The SET can thus be used as ultrasensitive electrometer and will be used in the future in the study of charged nanoscale systems.Principles of the Single Electron Transistor
The Coulomb Blockade
The singleelectron transistor consists of a metallic island, placed between two tunneling junctions connected to a drain and a source and has a gate electrode as in a normal fieldeffect transistor. The tunneling junctions are simply a thin (<10 nm) oxide layer between the island and the electrodes. Quantum dots have also been used as islands for the SET. The schematics of the SET are given in figure 1. Each tunneling junction in the SET has intrinsic tunneling resistance and capacitance (parallel to each other).
Fig. 1: Left: schematic circuit representation of the singleelectron transistor. Right: a more realistic representation of what the ‘core’ of the singleelectron transistor looks like.
The island of the singleelectron transistor, even if very small (nanometric scale) still contains a very large number of electrons (@109). Yet, through tunneling, one can add or subtract electrons from the island charging it either negatively or positively. The extra electrons that charge the island are called excess electrons and their number is designed by n. The number of excess electrons can also be negative, meaning that electrons have been removed leaving a positive charge on the island (one could talk of excess holes in this case). The presence of excess electrons affects the electrostatic energy of the system, which depends on the charging energy of the SET:
C e n C
Q
E isl
ch
2 2 2
2 1 2
1
(1) where Qisl is the charge on the island, n the number of excess electrons, e the charge of one electron and CS the total capacitance of the island which is equal to: C CG CL CR (CG, CL and CR are the gate capacitance and the intrinsic capacitances of the left and right tunneling junctions respectively). The energy scale applied when working with the SET is usually defined on the charging energy itself and the unit taken is usually:
C e EC
2 2
. The energy does not only depends on Qisl, but also on the charge induced by the gate, the gate charge QG=VGCG
Dr.A.K.Agarwal
MPH204‐Introduction to Nanoscience & TechnologyPage 3where VG is the gate voltage. The electrostatic energy of the system is equal to Eel EC(nng)2, where n is the number of excess electrons of the island and ng the number of elementary gate charges. The expression for the electrostatic energy of the system then becomes:
C Q ne C
C V ne C
Q
E G G G
el
2
2 ( )
2 1 2 ) (
2 1 2
1
(2) This energy determines if tunneling through a junction is forbidden or allowed: if the adding of an extra excess electron causes the energy of the system to increase then tunneling will be energetically forbidden and the Coulomb charging energy will act as a blockade. This is known as the Coulomb blockade.
The drainsource voltage, VDS, determines the energy of the electrons before the junction. When this energy is higher than the Coulomb blockade, the electrons will overcome the blockade and tunneling will occur. The height of the blockade is determined by the number of excess electrons on the island and the gate charge.
So the adding of an excess electron on the island will be either favorable or unfavorable depending on the gate charge which on its turn depends on the gate voltage. We can see from equation (2) that if the gate charge is equal to integer values of elementary charge e the Coulomb blockade will be active and there will be no tunneling of electrons in or out the island will occur (figure 2a). The transistor will be in the conducting state (meaning that tunneling will lower the energy of the system) if the gate charge is equal to values that are half integers of the electron charge, then the system have an energy minimum which is in between two states with welldefined elementary charges. This will cause a cascade of tunnel events, involving the two junctions sequentially, giving rise to a current between the drain and the source. This can be seen graphically in figure 2b.
Figure 2: Graphical representation of the Coulomb blockade in a) blocking state and b) in conducting state for the single electron transistor. The transistor will be in the conducting state if the gate charge is equal to e(2N+1)/2 where N is an integer. If the gate charge is equal to integer values of e the Coulomb blockade will be active and there will be no conduction. In the picture N1 and N2
denote the numbers of electrons having tunneled through the junctions and p is an integer. (Source: Devoret & SchoelKopf, Nature 2000)
Dr.A.K.Agarwal
Dippen nanolithography
Dip Pen Nanolithography (DPN) allows surface patterning on scales of under sub 100 nanometers. DPN is the nanotechnology analog of the dip pen (also called the quill pen), where the tip of an atomic force microscope cantilever acts as a "pen," which is coated with a chemical compound or mixture acting as an "ink," and put in contact with a substrate, the "paper."
Molecular inks are typically composed of small molecules that are coated onto a DPN tip and are delivered to the surface through a water meniscus. The deposition rate of a molecular ink is dependent on the diffusion rate of the molecule, which is different for each molecule. The size of the feature is controlled by the tip/surface dwelltime (ranging from milliseconds to seconds) and the size of the water meniscus.
Examples: Alkane thiols written to gold Silanes written to glass or silicon
Liquid Inks: Liquid inks can be any material that is liquid at
deposition conditions. The liquid deposition properties are determined by the interactions between the liquid and the tip, the liquid and the surface, and the viscosity of the liquid itself. These interactions limit the minimum feature size of the liquid ink to about 1 micrometre, depending on the contact angle of the liquid.
Examples
Protein, peptide, and DNA patterning; Hydrogels; Sol gels; Conductive inks; Lipids
Applications
1. Nanoscale Sensor Fabrication Small, highvalue sensors that can detect multiple targets 2. Nanoscale Protein Chips Highdensity protein arrays with increased sensitivity
3. Cell engineering: DPN is emerging as a powerful research tool for manipulating cells at subcellular resolution. Stem cell differentiation, Subcellular drug delivery, Cell sorting, Surface gradients, Cell and tissue screening
4. DipPen" Nanolithography on Semiconductor Surfaces: DPN can also be apply to semiconductor
surfaces, such as silicon and gallium arsenide. Unique advantages
Directed Placement Directly print various materials onto existing nano and microstructures with nanoscale
registry
Direct Write Maskless creation of arbitrary patterns with feature resolutions from as small as 50 nm and as
large as 10 micrometres[15]
Biocompatible Subcellular to nanoscale resolution at ambient deposition conditions Scalable Force independent, allowing for parallel depositions[16]
Common misconceptions
Dr.A.K.Agarwal
MPH204‐Introduction to Nanoscience & TechnologyPage 5A quantum dot is a nanoparticle made of any semiconductor material such as silicon, cadmium selenide, cadmium sulfide, or indium arsenide. Quantum dots may be able to increase the efficiency of solar cells. In normal solar cells, a photon of light generates one electron. Experiments with both silicon quantum dots and lead sulfide quantum dots can generate two electrons for a single photon of light. Therefore, using quantum dots in solar cells could significantly increase their efficiency in producing electric power.
Researchers are also working on the use of quantum dots in displays for applications ranging from your cell phone to large screen televisions that would consume less power than current displays. By placing different size quantum dots in each pixel of a display screen, the red, green, and blue colors used to generate the full spectrum of colors would be available.
Quantum dots are semiconductor nanoparticles that glow a particular color after being illuminated by light. The color they glow depends on the size of the nanoparticle. When the quantum dots are illuminated by UV light, some of the electrons receive enough energy to break free from the atoms. This capability allows them to move around the nanoparticle, creating a conduction band in which electrons are free to move through a material and conduct electricity.
When these electrons drop back into the outer orbit around the atom (the valence band), they emit light. The color of that light depends on the energy difference between the conduction band and the valence band.
Electrons in a quantum dot generating light.
The smaller the nanoparticle, the higher the
energy difference between the valence band
and conduction band, which results in a deeper
blue color. For a larger nanoparticle, the energy
difference between the valence band and the
conduction band is lower, which shifts the glow
toward red.
Many semiconductor substances can be used as quantum dots. Nanoparticles of any other semiconductor substance have the properties of a quantum dot. The gap between the valence band and the conduction band, which is present for all semiconductor materials, causes quantum dots to fluoresce.
Dr.A.K.Agarwal
Nanowire
A nanowire is a nanostructure, with the diameter of the order of a nanometer (10−9 meters). It can also be defined as the ratio of the length to width being greater than 20. Alternatively, nanowires can be defined as structures that have a thickness or diameter constrained to tens of nanometers or less and an unconstrained length. At these scales, quantum mechanical effects are important — which coined the term "quantum wires". Many different types of nanowires exist, including metallic (e.g., Ni, Pt, Au), semiconducting (e.g., Si, InP, GaN, etc.), and insulating (e.g., SiO2, TiO2). Molecular nanowires are composed of repeating molecular units either organic (e.g. DNA) or inorganic (e.g. Mo6S9xIx).
The nanowires could be used, in the near future, to link tiny components into extremely small circuits. Synthesis of nanowires
here are two basic approaches to synthesizing nanowires: topdown and bottomup. A topdown approach reduces a large piece of material to small pieces, by various means such as lithography or electrophoresis. A bottomup approach synthesizes the nanowire by combining constituent adatoms. Most synthesis techniques use a bottomup approach.
Nanowire production uses several common laboratory techniques, including suspension, electrochemical deposition, vapor deposition, andVLS growth. Ion track technology enables growing homogeneous and segmented nanowires down to 8 nm diameter.
Suspension[edit]
A suspended nanowire is a wire produced in a highvacuum chamber held at the longitudinal extremities. Suspended nanowires can be produced by:
The chemical etching of a larger wire
The bombardment of a larger wire, typically with highly energetic ions
Indenting the tip of a STM in the surface of a metal near its melting point, and then retracting it VLS Growth[edit]
A common technique for creating a nanowire is VaporLiquidSolid (VLS) synthesis. This process can produce crystalline nanowires of some semiconductor materials. It uses as source material either laser ablated particles or a feed gas such as silane.
VLS synthesis requires a catalyst. For nanowires, the best catalysts are liquid metal (such as gold) nanoclusters, which can either be selfassembled from a thin film by dewetting, or purchased in colloidal form and deposited on a substrate.
Solutionphase synthesis[edit]
Solutionphase synthesis refers to techniques that grow nanowires in solution. They can produce nanowires of many types of materials. Solutionphase synthesis has the advantage that it can produce very large quantities, compared to other methods. In one technique, the polyol synthesis, ethylene glycol is both solvent and reducing agent. This technique is particularly versatile at producing nanowires of lead, platinum, and silver.
Physics of nanowires Conductivity of nanowires
Nanowires also show other peculiar electrical properties due to their size. Unlike single wall carbon nanotubes, whose motion of electrons can fall under the regime of ballistic transport (meaning the electrons can travel freely from one electrode to the other), nanowire conductivity is strongly influenced by edge effects. The edge effects come from atoms that lay at the nanowire surface and are not fully bonded to neighboring atoms like the atoms within the bulk of the nanowire. The unbonded atoms are often a source of defects within the nanowire,
Dr.A.K.Agarwal
MPH204‐Introduction to Nanoscience & TechnologyPage 7and may cause the nanowire to conduct electricity more poorly than the bulk material. As a nanowire shrinks in size, the surface atoms become more numerous compared to the atoms within the nanowire, and edge effects become more important.
Welding nanowires[edit]
For nanowires with diameters less than 10 nm, existing welding techniques, which require precise control of the heating mechanism and which may introduce the possibility of damage, will not be practical. Recently scientists discovered that singlecrystalline ultrathin gold nanowires with diameters ~310 nm can be "coldwelded" together within seconds by mechanical contact alone, and under remarkably low applied pressures (unlike macro and microscale cold welding process). Nanowire welds were also demonstrated between gold and silver, and silver nanowires (with diameters ~515 nm) at near room temperature, indicating that this technique may be generally applicable for ultrathin metallic nanowires.
Electronic devices
Nanowires still belong to the experimental world of laboratories. However, they may complement or replace carbon nanotubes in some applications. Some early experiments have shown how they can be used to build the next generation of computing devices.
To create active electronic elements, the first key step was to chemically dope a semiconductor nanowire. This has already been done to individual nanowires to create ptype and ntype, pn junction semiconductors.
Conducting nanowires offer the possibility of connecting molecularscale entities in a molecular computer. Dispersions of conducting nanowires in different polymers are being investigated for use as transparent electrodes for flexible flatscreen displays.
Sensing of proteins and chemicals using semiconductor nanowires[edit]
In an analogous way to FET devices in which the modulation of conductance (flow of electrons/holes) in the semiconductor, between the input (source) and the output (drain) terminals, is controlled by electrostatic potential variation (gateelectrode) of the charge carriers in the device conduction channel, the methodology of a Bio/ChemFET is based on the detection of the local change in charge density, or socalled “field effect”, that characterizes the recognition event between a target molecule and the surface receptor.
While several inorganic semiconducting materials such as Si, Ge, or metal oxides (e.g. In2O3, SnO2, ZnO, etc.) have been used for the preparation of nanowires. Silicon nanowires are usually the material of choice when fabricating nanowire FETbased chemo/biosensors.
Dr.A.K.Agarwal
Nanorodnanorods have dimensions range from 1–100 nm. They may be synthesized from metals or semiconducting materials. Standard aspect ratios (length divided by width) are 35. Nanorods are produced by direct chemical synthesis. A combination of ligands act as shape control agents and bond to different facets of the nanorod with different strengths. This allows different faces of the nanorod to grow at different rates, producing an elongated object.
One potential application of nanorods is in display technologies, because the reflectivity of the rods can be changed by changing their orientation with an applied electric field. Another application is for microelectromechanical systems (MEMS). Nanorods, along with other noble metal nanoparticles, also function as theragnostic agents. Nanorods absorb in the near IR, and generate heat when excited with IR light. This property has led to the use of nanorods as cancer therapeutics. Nanorods can be conjugated with tumor targeting motifs and ingested. When a patient is exposed to IR light (which passes through body tissue), nanorods selectively takenup by tumor cells are locally heated, destroying only the cancerous tissue while leaving healthy cells intact.
Nanorods based on semiconducting materials have also been investigated for application as energy harvesting and light emitting devices. In 2006, Ramanathan et al. demonstrated1 electricfield mediated tunable photoluminescence from ZnO nanorods, with potential for application as novel sources of nearultraviolet radiation.
Synthesis
ZnO nanorods :Zinc oxide (ZnO) nanorod, also known as nanowire, has a direct bandgap energy of 3.37 eV and it has an excitation binding energy of 60 meV. Recent years, ZnO nanorods have been intensely used to fabricate nanoscale electronic devices, including field effect transistor, ultraviolet photodetector, Schottky diode, and ultrabright lightemitting diode (LED). Among various methods for fabrication, growing from vapor phase is the most developed approach. In a typical growth process, ZnO vapor is condensed onto a solid substrate. ZnO vapor can be generated by three methods: thermal evaporation, chemical reduction, and Vapor LiquidSolid (VLS) method. In the thermal evaporation method, commercial ZnO powder is mixed with SnO2 and evaporated by heating the mixture at elevated temperature. In the chemical reduction method, zinc vapor, generated by the reduction of ZnO, is transferred to the growth zone, followed by reoxidation to ZnO. Metalorganic chemical vapor deposition (MOCVD) has also been recently developed. No catalyst is involved in this process and the growth temperature is at 400 ~500 °C, i.e. considerably milder conditions compared to the traditional vapor growth method.
Gold nanorods: The seedmediated growth method is the most common and achieved method for synthesizing highquality gold nanorods. A typical growth protocol involves the addition of citratecapped gold nanospheres, served as seeds, to the bulk HAuCl4 growth solution. The growth solution is obtained by the reduction of HAuCl4 with ascorbic acid in the presence of cetyltrimethylammonium bromide (CTAB) surfactant and silver ions. Longer nanorods (up to an aspect ratio of 25) can be obtained in the absence of silver nitrate by use of a threestep addition procedure.
Dr.A.K.Agarwal
MPH204‐Introduction to Nanoscience & TechnologyPage 9Cation Exchange: Cation exchange is a conventional but promising technique for new nanorod synthesis. Cation exchange transformations in nanorods are kineticallyfavorable and often shapeconserving. Compared to bulk crystal systems, the cation exchange of nanorods is milliontimes faster due to high surface area. Existing nanorods serve as templates to make a variety of nanorods that are not accessible in traditional wet chemical synthesis. Furthermore, complexity can be added by partial transformation, making nanorod heterostructures.
Exciton: An exciton is a bound state of an electron and an electron hole which are attracted to each other by the electrostatic Coulomb force. It is an electrically neutral quasiparticle that exists in insulators, semiconductors and in some liquids. The exciton is regarded as an elementary excitation of condensed matter that can transport energy without transporting net electric charge.[2] The distance between
the electron and the hole within an exciton is called Bohr radius of the exciton.
An exciton can form when a photon is absorbed by a semiconductor. This excites an electron from the valence band into the conduction band. In turn, this leaves behind a positivelycharged electron hole (an abstraction for the location from which an electron was moved). The electron in the conduction band is then effectively attracted to this localized hole by the repulsive Coulomb forces from large numbers of electrons surrounding the hole and excited electron. This attraction provides a stabilizing energy balance. Consequently, the exciton has slightly less energy than the unbound electron and hole. However, the binding energy is much smaller and the particle's size much larger than a hydrogen atom.
Quantum confinement in a semiconductor
Typical exciton Bohr radius of semiconductors is of a few nanometers. In bulk semiconductors, the exciton can move freely in all directions. When the length of a semiconductor is reduced
to the same order as the exciton radius, i.e., to a few nanometers, quantum confinement effect
occurs and the exciton properties are modified. Depending on the dimension of the confinement, confinement, three kinds of confined structures are defined: quantum well (sometimes termed QW), quantum wire (QWR) and quantum dot (QD). In a QW, the material size is reduced only in one direction and the exciton can move freely in other two directions. In a QWR, the material size is reduced in two directions and the exciton can move freely in one direction only. In a
QD, the material size is reduced in all directions and the exciton can not move freely in any direction.
Quantum dots are said to be in the 'weak confinement regime' if their radii are on the order of the exciton Bohr radius; quantum dots are said to be in the 'strong confinement regime' if their radii are smaller than the exciton Bohr radius. If the size of the quantum dot is small enough that the quantum confinement effects dominate (typically less than 10 nm), the electronic and optical properties are highly tunable.
Band gap energy
The band gap can become larger in the strong confinement regime where the size of the quantum dot is smaller than the Exciton Bohr radius ab* as the energy levels split up.
where ab is the Bohr radius=0.053 nm, m is the mass, μ is the reduced mass, and εr is the sizedependent dielectric constant
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This results in the increase in the total emission energy (the sum of the energy levels in the smaller band gaps in the strong confinement regime is larger than the energy levels in the band gaps of the original levels in the weak confinement regime) and the emission at various wavelengths; which is precisely what happens in the sun, where the quantum confinement effects are completely dominant and the energy levels split up to the degree that the energy spectrum is almost continuous, thus emitting white light.
Confinement energy
The exciton entity can be modeled using the particle in the box. The electron and the hole can be seen as hydrogen in the Bohr model with the hydrogen nucleus replaced by the hole of positive charge and negative electron mass. Then the energy levels of the exciton can be represented as the solution to the particle in a box at the ground level (n = 1) with the mass replaced by the reduced mass. Thus by varying the size of the quantum dot, the confinement energy of the exciton can be controlled.
Bound exciton energy
There is Coulomb attraction between the negatively charged electron and the positively charged hole. The negative energy involved in the attraction is proportional to Rydberg's energy and inversely proportional to square of the sizedependent dielectric constant[6] of the semiconductor. When the size of the semiconductor crystal is smaller than the Exciton Bohr radius, the Coulomb interaction must be modified to fit the situation. Therefore, the sum of these energies can be represented as:
where μ is the reduced mass, a is the radius, me is the free electron mass, mh is the hole mass, and εr is the size
dependent dielectric constant.
Although the above equations were derived using simplifying assumptions, the implications are clear; the energy of the quantum dots are dependent on their size due to the quantum confinement effects, which dominate below the critical size leading to changes in the optical properties. This effect of quantum confinement on the quantum dots have been experimentally verified[7] and is a key feature of many emerging electronic structures.[8][9]
Besides confinement in all three dimensions (i.e., a quantum dot), other quantum confined semiconductors include:
Colloidal Synthesis
Colloidal semiconductor nanocrystals are synthesized from precursor compounds dissolved in solutions, much like traditional chemical processes. The synthesis of colloidal quantum dots is done by using precursors, organic surfactants, and solvents.
Heating the solution at high temperature, the precursors decompose forming monomers which then nucleate and generate nanocrystals. The temperature during the synthetic process is a critical factors in determining optimal conditions for the nanocrystal growth. It must be high enough to allow for rearrangement and annealing of atoms during the synthesis process while being low enough to promote crystal growth.
Dr.A.K.Agarwal
MPH204‐Introduction to Nanoscience & TechnologyPage 11The concentration of monomers is another critical factor that has to be stringently controlled during nanocrystal growth. The growth process of nanocrystals can occur in two different regimes, "focusing" and "defocusing". At high monomer concentrations, the critical size (the size where nanocrystals neither grow nor shrink) is relatively small, resulting in growth of nearly all particles. In this regime, smaller particles grow faster than large ones (since larger crystals need more atoms to grow than small crystals) resulting in "focusing" of the size distribution to yield nearly monodisperse particles. The size focusing is optimal when the monomer concentration is kept such that the average nanocrystal size present is always slightly larger than the critical size. Over time, the monomer concentration diminishes, the critical size becomes larger than the average size present, and the distribution "defocuses".
Typical dots are made of binary alloys such as cadmium selenide, cadmium sulfide, indium arsenide, andindium phosphide. Dots may also be made from ternary alloys such as cadmium selenide sulfide. These quantum dots can contain as few as 100 to 100,000 atoms within the quantum dot volume, with a diameter of 10 to 50 atoms. This corresponds to about 2 to 10 nanometers, and at 10 nm in diameter, nearly 3 million quantum dots could be lined up end to end and fit within the width of a human thumb.
Large batches of quantum dots may be synthesized via colloidal synthesis. Due to this scalability and the convenience of benchtop conditions, colloidal synthetic methods are promising for commercial applications.
Auger Electron Spectroscopy (AES)
The Auger Process: Xray and high energy electron bombardment of atom can create core hole Core hole will eventually decay via either
(i) photon emission (xray fluorescence XRF) more likely for deep core hole (high BE) high Z elements (ii) radiationless internal rearrangement (Auger process) more likely for shallow core hole (low BE) low
Z elements (almost exclusively for Z<15) Auger process is a three electron process and leaves atom doublyionized occurs independently of incident excitation (doesn't "compete" with photoemission)
• Photon not much use for surface analysis since propagates large distances in solid (but is used for xray microprobe analysis in SEM/TEM)
• Auger electrons produced with similar kinetic energies to photoelectrons so similar surface sensitivity • Initial core hole can be generated by xrays see Auger peaks in XPS or electrons (most common in AES) spectrum contains Auger, incident and inelastically scattered electrons but no photoemission peaks!
In simple, oneelectron picture (ignoring relaxation or final state effects), X ray photon h ≈ EA EB
Auger electron KE ≈ EA EB EC
Dr.A.K.Agarwal
by core –hole to overcomeBEDr.A.K.Agarwal
MPH204‐Introduction to Nanoscience & TechnologyPage 13Nanorobotics
Nanorobotics is the emerging technology field creating machines or robots whose components are at or close to the scale of a nanometer (10−9meters). More specifically, nanorobotics refers to the nanotechnology engineering discipline of designing and building nanorobots, with devices ranging in size from 0.1–10 micrometers and constructed of nanoscale or molecular components.
Nanomachines are largely in the researchanddevelopment phase, but some primitive molecular machines have been tested. An example is a sensor having a switch approximately 1.5 nanometers across, capable of counting specific molecules in a chemical sample. The first useful applications of nanomachines might be in medical technology, which could be used to identify and destroy cancer cells. Another potential application is the detection of toxic chemicals, and the measurement of their concentrations.
Another definition is a robot that allows precision interactions with nanoscale objects, or can manipulate with nanoscale resolution. Such devices are more related to microscopy or scanning probe microscopy, instead of the description of nanorobots as molecular machine. Following the microscopy definition even a large apparatus such as an atomic force microscope can be considered a nanorobotic instrument when configured to perform nanomanipulation. For this perspective, macroscale robots or microrobots that can move with nanoscale precision can also be considered nanorobots.
Since nanorobots would be microscopic in size, it would probably be necessary for very large numbers of them to work together to perform microscopic and macroscopic tasks.
Approaches
Biochip : The joint use of nanoelectronics, photolithography, and new biomaterials provides a possible approach to manufacturing nanorobots for common medical applications, such as for surgical instrumentation, diagnosis and drug delivery. This method for manufacturing on nanotechnology scale is currently in use in the electronics industry.
Nubots : Nubot is an abbreviation for "nucleic acid robot." Nubots are organic molecular machines at the nanoscale. DNA structure can provide means to assemble 2D and 3D nanomechanical devices. DNA based machines can be activated using small molecules, proteins and other molecules of DNA. Biological circuit gates based on DNA materials have been engineered as molecular machines to allow invitro drug delivery for
targeted health problems. Such material based systems would work most closely to smart biomaterial drug system delivery, while not allowing precise in vivo teleoperation of such engineered prototypes.
Positional nanoassembly:Nanofactory Collaboration, founded by Robert Freitas and Ralph
Merkle , specifically aimed at developing positionallycontrolled diamond mechanosynthesis and a diamondoid nanofactory that would have the capability of building diamondoid medical nanorobots.
Bacteriabased :This approach proposes the use of biological microorganisms, like the bacterium Escherichia coli. Thus the model uses a flagellum for propulsion purposes. Electromagnetic fields normally control the motion of this kind of biological integrated device.
Open technology: A document with a proposal on nanobiotech development using open technology
approaches has been addressed to the United Nations General Assembly.[31] According to the document , the use of nanobiotechnology should be established as a human heritage for the coming generations, and developed as
Dr.A.K.Agarwal
an open technology based on ethical practices for peaceful purposes. Open technology is stated as a fundamental key for such an aim.Nanorobot Race :In the same ways that technology development had the space race and nuclear arms race, a race for nanorobots is occurring There is plenty of ground allowing nanorobots to be included among
the emerging technologies. Some of the reasons are that large corporations, such as General Electric, Hewlett Packard and Northrop Grumman have been recently working in the development and research of nanorobots.
Potential applications
Nanomedicine :Potential applications for nanorobotics in medicine include early diagnosis and targeted drug delivery for cancer, biomedical instrumentation, surgery, pharmacokinetics monitoring of diabetes, and health care. In such plans, future medical nanotechnology is expected to employ nanorobots injected into the patient to perform work at a cellular level. Such nanorobots intended for use in medicine should be nonreplicating, as replication would needlessly increase device complexity, reduce reliability, and interfere with the medical mission.
Today, harmful side effects of treatments such as chemotherapy are commonly a result of drug delivery methods that don't pinpoint their intended target cells accurately. Researchers at Harvard and MIT, however, have been able to attach special RNA strands, measuring nearly 10 nm in diameter, to nanoparticles, filling them with a chemotherapy drug. These RNA strands are attracted to cancer cells. When the nanoparticle encounters a cancer cell, it adheres to it, and releases the drug into the cancer cell. This directed method of drug delivery has great potential for treating cancer patients while avoiding negative effects (commonly associated with improper drug delivery).
Another useful application of nanorobots is assisting in the repair of tissue cells alongside white blood cells. The recruitment of inflammatory cells or white blood cells (which includeneutrophils, lymphocytes, monocytes and mast cells) to the affected area is the first response of tissues to injury. Because of their small size nanorobots could attach themselves to the surface of recruited white cells, to squeeze their way out through the walls of blood vessels and arrive at the injury site, where they can assist in the tissue repair process. Certain substances could possibly be utilized to accelerate the recovery.
Drug delivery
Nanotechnology has provided the possibility of delivering drugs to specific cells using nanoparticles. The overall drug consumption and sideeffects may be lowered significantly by depositing the active agent in the morbid region only and in no higher dose than needed. This highly selective approach would reduce costs and human suffering. An example can be found in dendrimers and nanoporous materials. Another example is to use block copolymers, which form micelles for drug encapsulation. They could hold small drug molecules transporting them to the desired location. Another vision is based on small electromechanical systems; nanoelectromechanical systems are being investigated for the active release of drugs. Some potentially important applications include cancer treatment with iron nanoparticles or gold shells. A targeted or personalized medicine is intended to reduce the drug consumption and treatment expenses resulting in an overall societal benefit by reducing the costs to the public health system.
Nanomedical approaches to drug delivery center on developing nanoscale particles or molecules to improve drug bioavailability. Bioavailability refers to the presence of drug molecules where they are needed in the body
Dr.A.K.Agarwal
MPH204‐Introduction to Nanoscience & TechnologyPage 15and where they will do the most good. Drug delivery focuses on maximizing bioavailability both at specific places in the body and over a period of time. This can potentially be achieved by molecular targeting by nanoengineered devices. In vivo imaging is another area where tools and devices are being developed. Using nanoparticle contrast agents, images such as ultrasound and MRI have a favorable distribution and improved contrast. The new methods of nanoengineered materials that are being developed might be effective in treating illnesses and diseases such as cancer. What nanoscientists will be able to achieve in the future is beyond current imagination. This might be accomplished by self assembled biocompatible nanodevices that will detect, evaluate, treat and report to the clinical doctor automatically.
Drug delivery systems, lipid or polymerbased nanoparticles, can be designed to improve the pharmacological and therapeutic properties of drugs. The strength of drug delivery systems is their ability to alter the pharmacokinetics and biodistribution of the drug. When designed to avoid the body's defence mechanisms, nanoparticles have beneficial properties that can be used to improve drug delivery. Where larger particles would have been cleared from the body, cells take up these nanoparticles because of their size. Complex drug delivery mechanisms are being developed, including the ability to get drugs through cell membranes and into cell cytoplasm. Drugs are placed in the body and only activate on encountering a particular signal. Potential nanodrugs will work by very specific and wellunderstood mechanisms; one of the major impacts of nanotechnology and nanoscience will be in leading development of completely new drugs with more useful behavior and less side effects.
It is greatly observed that nanoparticles are promising tools for the advancement of drug delivery, medical imaging, and as diagnostic sensors. However, the biodistribution of these nanoparticles is still imperfect due to the complex host's reactions to nano and microsized materials and the difficulty in targeting specific organs in the body. While advancement of research proves that targeting and distribution can be augmented by nanoparticles, the dangers of nanotoxicity become an important next step in further understanding of their medical uses.
Applications and reported research studies
Abraxane, approved by the U.S. Food and Drug Administration (FDA) to treat breast cancer and nonsmall cell lung cancer (NSCLC), is the nanoparticle albumin bound paclitaxel.
In a mice study, scientists from Rice University reported enhanced effectiveness and reduced toxicity of an existing treatment for head and neck cancer when using the nanoparticles to deliver the drug. The hydrophilic carbonic clusters functionalized with polyethylene glycol or PEGHCC are mixed with the chemotherapeutic drug paclitaxel (Taxol) and the epidermal growth factor receptor (EGFR) targeted Cetuximab and injected intravenously. They found the tumors were killed more effectively with radiation and the healthy tissue suffered less toxicity than without the nanotechnology drug delivery.
Researchers at Case Western Reserve University reported using nanoparticle chain to deliver doxorubicin to breast cancer cells in a mice study. Three magnetic, ironoxide nanospheres were chemically linked to one doxorubicinloaded liposome and formed a 100 nm long nanoparticle chain. After the nanochains penetrated the tumor, radiofrequency field was generated that caused the magnetic nanoparticles to vibrate and rupture the liposome, dispersing the drug in its free form throughout the tumor. The result showed that the nano treatment was more effective in halting tumor growth than the standard treatment with doxorubicin. It is also less harmful to healthy cells since only 5% to 10% of the standard dose of doxorubicin were used.
Nanoparticles made of polyethylene glycol (PEG) carrying payload of antibiotics at its core could swift charge thus allowing them to target bacterial infection more precisely inside the body, a group
Dr.A.K.Agarwal
of MIT researchers reported. The nanoparticles, containing a sublayer of pH sensitive chains of the amino acid histidine, carry a slightly negative charge when circulating in the blood stream, can evade detection and clearing by the immune system. When they encounter an infection site the particles gain a positive charge provoked by the slightly acidic environment at the infection sites, allowing them to bind to the negatively charged bacterial cell walls and release antibiotics at locally high concentration. This nano delivery system can potentially destroy bacteria even it has developed resistance to antibiotics because of the targeted high dose and prolonged release of the drug.
Using the biomimetic strategy, researchers in the Harvard University Wyss Institute demonstrated in a mouse model that the drug coated nanoparticles can dissolve blood clots by selectively binding to the narrowed regions in the blood vessels – just like the platelets do. By précised targeting and concentrating drug at the location of obstruction, the dose used is less than 1/50th of the normal dose.
The Xshaped RNA nanoparticles capable of carrying four functional modules were created by researchers in the University of Kentucky. These RNA molecules are chemically and thermodynamically stable, able to remain intact in the mouse body for more than 8 hours and to resist degradation by RNase in the blood stream. The Xshaped RNA can achieve therapeutic and diagnostic functions by regulating gene expression and cellular function, and binding to cancer cells with precision.
An early phase clinical trial using the platform of ‘Minicell’ nanoparticle for drug delivery Researchers at The Methodist Hospital Research Institute in Houston have created ‘LeukoLike Vectors’ or LLVs. LLVs are the drugcarrying silicon nanoparticles coated with the lipoproteinremoved from the membranes of the white blood cells, leukocytes. The ‘cloaked’ nanoparticles were found to behave like leukocytes, are able to evade the body immune system and survive much longer in vivo when studied in mice.
Protein and peptide delivery
Protein and peptides exert multiple biological actions in human body and they have been identified as showing great promise for treatment of various diseases and disorders. These macromolecules are called biopharmaceuticals. Targeted and/or controlled delivery of these biopharmaceuticals using nanomaterials like nanoparticles and Dendrimers is an emerging field callednanobiopharmaceutics, and these products are called nanobiopharmaceuticals.
Applications and reported research studies
Nanoparticles delivering the myelin antigens were found to induce immune tolerance in a mouse model with relapsing multiple sclerosis. Biodegradable polystyrene microparticles coated with the myelin sheath peptides reset the mouse’s immune system and prevent the disease from recurring or reduce the symptoms by halting the attack of the immune system to the protective myelin sheath coating the nerve fibers of the central nervous system. Team of researchers in Northwestern University indicated that this treatment method can potentially be used in otherautoimmune diseases.[31][32]
Researchers at UCLA developed a nanoparticle system with watersoluble shell encapsulated a protein derived from bird anemia virus, apoptin. Apoptin selectively sends ‘selfdestruct’ signal to tumor cells and trigger the programmed cell death (apoptosis) as it builds up in the nucleus, while leaving healthy cells unharmed. In the mouse model of human breast cancer, the treatment was found to significantly reduce the tumors’ growth. This new form of treatment resembles chemotherapy and gene therapy but without the risk of harming healthy cells, a common pitfall of chemotherapy, and no probability of genetic mutation that usually accompanies gene therapy.[33][34]
Dr.A.K.Agarwal
MPH204‐Introduction to Nanoscience & TechnologyPage 17A schematic illustration showing how nanoparticles or other cancer drugs might be used to treat cancer. The small size of nanoparticles endows them with properties that can be very useful in oncology, particularly in imaging. Quantum dots (nanoparticles with quantum confinement properties, such as sizetunable light
emission), when used in conjunction with MRI (magnetic resonance imaging), can produce exceptional images
of tumor sites. These nanoparticles are much
brighter than organic dyes and only need one light
source for excitation. This means that the use of
fluorescent quantum dots could produce a higher
contrast image and at a lower cost than today's
organic dyes used as contrast media. The downside,
however, is that quantum dots are usually made of
quite toxic elements.
Another nanoproperty, high surface area to volume
ratio, allows many functional groups to be attached to a
nanoparticle, which can seek out and bind to
certain tumor cells. Additionally, the small size of
nanoparticles (10 to 100 nanometers), allows them to preferentially accumulate at tumor sites (because tumors lack an effective lymphatic drainage system). A very exciting research question is how to make these imaging nanoparticles do more things for cancer. For instance, is it possible to manufacture multifunctional nanoparticles that would detect, image, and then proceed to treat a tumor? This question is under vigorous investigation; the answer to which could shape the future of cancer treatment. A promising new cancer treatment that may one day replace radiation and chemotherapy is edging closer to human trials.Kanzius RF therapy attaches microscopic nanoparticles to cancer cells and then "cooks" tumors inside the body with radio waves that heat only the nanoparticles and the adjacent (cancerous) cells.
Sensor test chips containing thousands of nanowires, able to detect proteins and other biomarkers left behind by cancer cells, could enable the detection and diagnosis of cancer in the early stages from a few drops of a patient's blood.
The basic point to use drug delivery is based upon three facts: a) efficient encapsulation of the drugs, b) successful delivery of said drugs to the targeted region of the body, and c) successful release of that drug there. Researchers at Rice University , have demonstrated the use of 120 nm diameter nanoshells coated with gold to kill cancer tumors in mice. The nanoshells can be targeted to bond to cancerous cells by conjugating antibodies or peptides to the nanoshell surface. By irradiating the area of the tumor with an infrared laser, which passes through flesh without heating it, the gold is heated sufficiently to cause death to the cancer cells.[37]
Nanoparticles of cadmium selenide (quantum dots) glow when exposed to ultraviolet light. When injected, they seep into cancer tumors. The surgeon can see the glowing tumor, and use it as a guide for more accurate tumor removal.
In photodynamic therapy, a particle is placed within the body and is illuminated with light from the outside. The light gets absorbed by the particle and if the particle is metal, energy from the light will heat the particle and surrounding tissue. Light may also be used to produce high energy oxygen molecules which will chemically react with and destroy most organic molecules that are next to them (like tumors). This therapy is appealing for many reasons. It does not leave a “toxic trail” of reactive molecules throughout the body (chemotherapy) because it is directed where only the light is shined and the particles exist. Photodynamic therapy has potential for a noninvasive procedure for dealing with diseases, growth and tumors.
Dr.A.K.Agarwal
SurgeryAt Rice University, a flesh welder is used to fuse two pieces of chicken meat into a single piece. The two pieces of chicken are placed together touching. A greenish liquid containing goldcoatednanoshells is dribbled along the seam. An infrared laser is traced along the seam, causing the two sides to weld together. This could solve the difficulties and blood leaks caused when the surgeon tries to restitch the arteries that have been cut during a kidney or heart transplant. The flesh welder could weld the artery perfectly.[38]
Visualization
Tracking movement can help determine how well drugs are being distributed or how substances are metabolized. It is difficult to track a small group of cells throughout the body, so scientists used to dye the cells. These dyes needed to be excited by light of a certain wavelength in order for them to light up. While different color dyes absorb different frequencies of light, there was a need for as many light sources as cells. A way around this problem is with luminescent tags. These tags are quantum dots attached to proteins that penetrate cell membranes. The dots can be random in size, can be made of bioinert material, and they demonstrate the nanoscale property that color is sizedependent. As a result, sizes are selected so that the frequency of light used to make a group of quantum dots fluoresce is an even multiple of the frequency required to make another group incandesce. Then both groups can be lit with a single light source.
Tissue engineering
Nanotechnology may be able to help reproduce or repair damaged tissue. “Tissue engineering” makes use of artificially stimulated cell proliferation by using suitable nanomaterialbased scaffolds and growth factors. For example, bones could be regrown on carbon nanotube scaffolds. Tissue engineering might replace today's conventional treatments like organ transplants or artificial implants. Advanced forms of tissue engineering may lead to life extension.
Antibiotic resistance
Nanoparicles can be used in combination therapy for decreasing antibiotic resistance. It has been shown that Zinc Oxide nanoparticles can decrease the antibiotic resistance and enhance the antibacterial activity of Ciprofloxacin against microorganism in Vitro. Nanoparticles can interfere with the different proteins which are interacting in the antibiotic resistance or pharmacologic mechanisms of drugs.[40]
Immune response
Buckyballs have been investigated for the ability to "interrupt" the allergy/immune response by preventing mast cells (which cause allergic response) from releasing histamine into the blood and tissues, by binding to free radicals "dramatically better than any antioxidant currently available, such as vitamin E.
Diagnostic and medical devices
Nanotechnologyonachip is one more dimension of labonachip technology. Magnetic nanoparticles, bound to a suitable antibody, are used to label specific molecules, structures or microorganisms. Gold nanoparticles tagged with short segments of DNA can be used for detection of genetic sequence in a sample. Multicolor optical coding for biological assays has been achieved by embedding differentsized quantum dots into polymeric microbeads. Nanopore technology for analysis of nucleic acids converts strings of nucleotides directly into electronic signatures.Nanotechnology is also opening up new opportunities in implantable delivery systems, which are often preferable to the use of injectable drugs, because the latter frequently display first order kinetics (the blood concentration goes up rapidly, but drops exponentially over time). This rapid rise may
Dr.A.K.Agarwal
MPH204‐Introduction to Nanoscience & TechnologyPage 19cause difficulties with toxicity, and drug efficacy can diminish as the drug concentration falls below the targeted range.
Neuroelectronic interfaces
Neuroelectronic interfacing is a visionary goal dealing with the construction of nanodevices that will permit computers to be joined and linked to the nervous system. This idea requires the building of a molecular structure that will permit control and detection of nerve impulses by an external computer. The computers will be able to interpret, register, and respond to signals the body gives off when it feels sensations. The demand for such structures is huge because many diseases involve the decay of the nervous system (ALS and multiple sclerosis). Also, many injuries and accidents may impair the nervous system resulting in dysfunctional systems and paraplegia. If computers could control the nervous system through neuroelectronic interface, problems that impair the system could be controlled so that effects of diseases and injuries could be overcome. Two considerations must be made when selecting the power source for such applications. They are refuelable and nonrefuelable strategies. A refuelable strategy implies energy is refilled continuously or periodically with external sonic, chemical, tethered, magnetic, or electrical sources. A nonrefuelable strategy implies that all power is drawn from internal energy storage which would stop when all energy is drained.
One limitation to this innovation is the fact that electrical interference is a possibility. Electric fields, electromagnetic pulses (EMP), and stray fields from other in vivo electrical devices can all cause interference. Also, thick insulators are required to prevent electron leakage, and if high conductivity of the in vivo medium occurs there is a risk of sudden power loss and “shorting out.” Finally, thick wires are also needed to conduct substantial power levels without overheating. Little practical progress has been made even though research is happening.
Medical applications of molecular nanotechnology
Molecular nanotechnology is a speculative subfield of nanotechnology regarding the possibility of engineering molecular assemblers, machines which could reorder matter at a molecular or atomic scale. Molecular nanotechnology is highly theoretical, seeking to anticipate what inventions nanotechnology might yield and to propose an agenda for future inquiry. The proposed elements of molecular nanotechnology, such as molecular assemblers and nanorobots are far beyond current capabilities.
Nanorobots
The somewhat speculative claims about the possibility of using nanorobots[43] in medicine, advocates say, would totally change the world of medicine once it is realized. Nanomedicine would make use of these nanorobots (e.g., Computational Genes), introduced into the body, to repair or detect damages and infections. According to Robert Freitas of the Institute for Molecular Manufacturing, a typical blood borne medical nanorobot would be between 0.53 micrometres in size, because that is the maximum size possible due to capillary passage requirement. Carboncould be the primary element used to build these nanorobots due to the inherent strength and other characteristics of some forms of carbon (diamond/fullerene composites), and nanorobots would be fabricated in desktop nanofactories specialized for this purpose.
Nanodevices could be observed at work inside the body using MRI, especially if their components were manufactured using mostly 13C atoms rather than the natural 12C isotope of carbon, since13C has a nonzero nuclear magnetic moment. Medical nanodevices would first be injected into a human body, and would then go to work in a specific organ or tissue mass. The doctor will monitor the progress, and make certain that the nanodevices have gotten to the correct target treatment region. The doctor will also be able to scan a section of