Nenotechnalogy . 1959 - Richard Feynman - Nobel Prize in Physics “There’s plenty of room at the bottom” - an invitation to enter a new field of physics Offered two $1000 prizes: « Build an electric motor in a 1/64 inch cube « Reduce a page of a book by a factor of 25,000; read using an electron microscope 1960 - engineer claimed the first prize 1985 - graduate student wrote a page from A Tale of Two Cities 1/160 millimeter in length using Ebeam lithography redicted the nse af nano ‘echology na lanemarn 1959 tk at Clteen ‘The prneipies ef price” he #39. 0 net peak opninet tne ponaibilty ef marwevenng Mange atemby atom “But he aaa antespated hat unaque lars would preva they are finaly. ce eee | Richard Feynman's Predictions There's Plenty ©! f Roomat the Bottom - December 29th 1959 s ona small scale Manipulating and controlling things Write the Encyclopedia Brittanicaon the head ofa pin . How do we write small? « Information ona small scale . Betterelectron microscopes ‘The marvelous biological system Miniaturizing the computer Miniaturization by evaporation Problems of lubrication A hundred tiny hands Rearranging the atoms Atoms ina small world ©2003 by Glenn FishbineCategory of nanomaterials example ‘One-dimensional nanomaterials: layers, multilayers, thin films, platelets and surface coatings. They have been developed and used for decades, particularly in the electronics industry. Two-dimensional nanomaterials nanowires, nanofibres made froma variety of elements other than carbon, nanotubes and, a ‘Subset of this group, carbon nanotubes. Three-dimensional nanomaterials are known as nanoparticles and include precipitates, colloids and quantum dots (tiny Particles of semiconductor materials), and Nanocrystalline materiatsBased on the size and shape, the Nano materials are Classified as » Nanoparticles > Nanotubes > Nanocapsules >Nanosprings & > Nanofibers > Nanobelts > Nanowires > Quantum dots >Fullerenes >NanofluidsNanomaterials can have one, two or in the nanoscale e three dimensions Category of nanomaterials example layers, multilayers, thin fil One-dimensional nanomaterials Surface coatings. They have been developed and used for decades, particularly in the electronics industry. Two-dim 1 ‘al Nanowires, nanofibres made from a variety of wo-dimensional nanomaterials elements other than carbon, nanotubes and, a subset of this group, carbon nanotubes. are known as nanoparticles and include Precipitates, colloids and quantum dots (tiny Three-dimensional nanomaterials Particles of semiconductor materials), and Nanocrystalline materialsBased on the size and shape, the Nano materials are classified as > Nanoparticles »Nanocapsules >Nanofibers > Nanowires >Fullerenes > Nanotubes »Nanosprings > Nanobelts > Quantum dots >Nanofluids—_ What is Fullerene? A Fullerene is any molecule composed entirely of Carbon, in the form of a hollow sphere, ellipsoid, or tube. Spherical fullerenes are also called buckyballs, and cylindrical ones are Called carbon nanotubes or buckytubes. =3=On8- Buckminster fullerene Cgo (left) and carbon nanotubes (right) are two examples of structures in the fullerene family. Ceo in solution| Allotropes of carbon Allotropes : / ; different structural modifications of an element: the atoms of the element are bonded together in a different manner. Allotropes of carbon: «Diamond (hardest natural mineral) Diamond and graphite are two allot fF i «Amorphous carbon (coal and soot) pure Torre Bi Pee *Fullerene family (Coo,carbon nanotubes element that differ in . he structure. *Graphite(dry lubricant, graphene) etc)oN laming--Fullerene © The substance of the Fullerene was named after the American, inventor architects and plulosophers Richard Buckminster Fuller (1895 till 1983). As an architect, R.B Fuller designed the ns which exist of 5-corners and 6- constructiot an pavilion to the corners, for example, the Americ Expo in '67 in Montréal(-od. Son's).oN laming--Fullerene © The substance of the Fullerene was named after the American, inventor architects and plulosophers Richard Buckminster Fuller (1895 till 1983). As an architect, R.B Fuller designed the ns which exist of 5-corners and 6- constructiot an pavilion to the corners, for example, the Americ Expo in '67 in Montréal(-od. Son's).a FULLERENE MOLECULAR MODELS C56-C76 C56 (Td) Rotating Animation LIEN iillies C60(C2,) GS eS %S J tA aes J ere.) C72 (Dea) C60(C2,)~~ Eyllerene Reactions « Possible reactions Coo and C7. (toa “QD @® lesser extent) may * % j undergo . & an ym gs + Additions —_— & © Polymerization * Substitutionsalso possible (doping with boron) Taylor, Roger, and David. Walton. . 8-603 2 Mar 2007" “The Chemistry of Fullerenes Nature 363 (1993)Quantum Dots (QD) e nanoparticles/structures that exhibit finement, which leads to many & © Quantum dots (QD) ar 3 dimensional quantum con unique optical and transport properties. Lin. Wang Wang, National Energy Research Scentific Computing Center at Lawrence Berkeley Naonal Laboratory. GaAs Quantum dot containing just 465 atoms,Quantum Dots (QD) e nanoparticles/structures that exhibit finement, which leads to many & © Quantum dots (QD) ar 3 dimensional quantum con unique optical and transport properties. Lin. Wang Wang, National Energy Research Scentific Computing Center at Lawrence Berkeley Naonal Laboratory. GaAs Quantum dot containing just 465 atoms,- Quantum dots ally regarded as semiconductors by © Quantum dots are usu x definition. » Similar behavior is obse some cases it may be acceptable to spe quantum dots. © Typically, quantum dots are composed of gr V, and IV-VI materials. © QDsare bandgap tunable by size which means their optical and electrical properties can be engineered to meet specific applications. ved in some metals. Therefore, in ak about metal oups II-VI, III-= Quant onfinement © Quantum Confinement is the spatial confinement of k electron-hole Pairs (excitons) within a material. * 1D confinement: Quantum Wells * 2D confinement: Quantum Wire * 3D confinement: Quantum Dot * Quantumconfinement is more prominent in semiconductors because they have an energy gap in their electronic band structure. ° Metals do not have a bandgap, so quantum size effects are less prevalent. Quantum confinement is only observed at dimensions below 2 nm. in one or more dimensionsBulle (Quantum Well Quantum Wire ‘Quantum Dot ‘Source: Nanoscale Materials in Chemistry, Wiley, 2001 * Ifa bulk metal is made thinnerand thinner, until theelectronscan —_ moveonly in two dimensions (instead of 3), then it is “2D quantum confinement” Next level is ‘quantum wire * Ultimately ‘quantum dot’ 35| What do You mean ERane™ Nano Particles are the particles of size between 1 nm to 100 nm + 1 nmis only three to five atoms wide. + ~40,000 times smaller than the width of an average human hair Nanometer - One billionth (10-°) of a meter + The size of Hydrogen atom 0.04 nm + The size of Proteins ~ 1-20nm + Feature size of computer chips 180 nm + Diameter of human hair ~ 10 pm At the nanoscale, the physical, chemical, and biological properties of materials differ in fundamental and valuable ways from the properties of individual atoms and molecules or bulk matterWhy Nano Particles ? Nanoparticles are of interest because of the new Properties (such as chemical reactivity and optical behavior) that they exhibit compared with larger particles of the same materials. For example, titanium dioxide and zinc oxide become transparent at the nanoscale and have found application in sunscreens, Nanoparticles have a range of potential applications: In the short-term application such as in cosmetics, textiles and paints, In the longer term applications such as drug delivery where they could be to used deliver drugs to a specific site in the body. | Nanoparticles can also be arranged into layers on surfaces, providing a large surface area and hence enhanced activity, relevant to a range of | Potential applications such as catalysts.Nano-scale Elects on Froperlles Properties Examples - : Catalytic Better catalytic efficiency through higher surface-to-volume k| ratio _ _ | Electrical Increased electrical conductivity in ceramics and magnetic nanocomposites, increased electric resistance in metals Magnetic Increased magnetic coercivity up to a critical grain size. superparamagnetic behaviour Mechanical Improved hardness and toughness of metals and alloys, ductility and superplasticity of ceramic Optical Spectral shift of optical absorbtion and fluorescence properties, increased quantum efficiency of semiconductor crystals Sterical Increased selectivity, hollow spheres for specific drug transportation and controlled release Biological Increased permeability through biological _ barriers (membranes, blood-brain barrier, etc.), improved biocom- patibility- Size Range of Nanoparticles” p, Thesize range that holds so much interestis typically from 100 nm down to atomic level ( 8 0.2 nm) » Because it isin thisrange (particularly at lower end) that materialscan have different or enhanced propertiescompared with the same materialsat a larger size. “Two main reasons for this change in behavior are : 40- Size Range of Nanoparticles” te Thesize range that holds so much interest is typically from 100 nm down toatomic level ( ¥ 0.2 nm) > Because it is in this range (particularly at lower end) thar materialscan. have different or enhanced propertiescompared with the same materialsat a larger size. “Two main reasons for this change in behavior are : + Anincreased relativesurface area (results in corresponding increase in chemical reactivity; useful as catalysts to improve the efficiency) + Dominance of Quantum Confinement Effects { significantly changea material's optical, magnetic or electrical properties)Nanomaterials have a relatively larger surface area when compared to the same Volume of the material produced in a larger form. & Let us considera sphere of radiusr Then its surface area=4nx? Its volume = (4/3) nr Surface area to its volume ratio = 3/r Thus when the radius of the sphere decreases, its surface area to volume Ratio increases. Consider one cubic volume , its surface area is 6m? When it divided into eight pieces its surface area becomes 12m? When the same is divided into 27 pieces its surface area becomes 18m? Thus we find that when the given volume is divided into smaller pieces, the Surface area increases. Hence particle size decreases a greater proportion Of atoms are found at the surface compared to those inside.l Fora cube: oa area =6 Breaking the large cube into smaller cubes keeps the ‘Total volume the same but Increasethe total surfacearea Notice the difference in powers of thelineardimension inthe ratioof surfaceareatovolume (SA/V) Cellsizes “Surface tension +Nanotex pantsSurface area increases while total volume remains constantRadius (cm) 1.00 2.00 3.00 r - | Surface Area (cm?) 12.6 50.3 113 an | Volume (cm3} 419 | 33.5 113 4 a9 | ze | Surface Area/Volume (em™!) | 3.0 | 18 10 3 r_ Quantum confinement effects When atoms are isolated the energy levels are discrete. When very large number of atoms are closely packed to form a solid, the energy levels split and form bands. Nanomaterials represent intermediate stage. Consider the problems of particles in a potential well as well as in a potential Box, the dimensions such wells or boxes are of the order of de-Broglie Wavelength of electrons or mean free path of electrons energy levels change. This effect is called Quantum Confinement. When the material is in sufficiently small size typically 10 nanometers or less, Organization of energy levels into which electrons can climb or fall change. Specifically, the phenomenon results from electrons and holes being squeezed Into a dimension that approaches a critical quantum measurement called the “excitation Bohr Radius". These can effect the optical, electrical and magnetic Behavior of materials.i ._ == = = ore Size Dependence of properties Q Mechanical, optical, magnetic, electrical and chemical characteristics oF Nanosized materials depend not only on type of material but very much also on their size and shape. “By nanotechnology the light yield of semiconductors can be increased drastically sLight is to be produced efficiently andtin a pleasant color from semiconductor material which has the benefits of conventional light sources. 46In materials where strong chemical bonding is present, delocalization of valence electrons can be extensive. ‘The extent of delocalization can vary with the size of the system. + Structurealso changes with size. + The above two changes can lead to different physical and chemical properties, depending on size - Optical properties - Bandgap - Specific heat h - Surface reactivity + Even when such nano particles are consolidated into macro scale solids, new propertiesof bulk materials are possible. - Example: enhanced plasticityOs Ina classical sense, color is caused b in matter, resulting in the visibility of t} y the partial absorption of light by electrons he complementary part of | the light Q+ On most smooth metal surfaces, lightis totally; reflected by the high density of electrons => no color, justa mirror-like appea ance, O+ Small particles absorb, leading to some color. Thisisa size: dependent property, Example: Gold, which readily forms nano particles but not easily oxidized, exhibits different colors depending on particlasize. - _ Goldcolloids have been used to color glassessince early days of glass making, Ruby-glass contains finely dispersed gold-colloids. - Silverand copper also give attractive colors 49OFor semiconductors with size such as ZnO, CdS, and Si, the band gap changes Q When the band gaps lie in the visible } wi pectrum, a change in band gap withsize means a change in color QFor magnetic materials such as Fe, Co, Ni, Fe,O,, etc., magnetic Propertiesare size dependent OThe ‘coercive force’ (or magnetic memory) needed to reverse an internal magnetic field within the particle is size dependent Othe strength of a particle's internal magnetic field can be size dependent 8A carbon nanotube between electrodes spaced 500 nm apart C~1aF (10-8F) A Ceo molecule between electrodes spaced 1.4 nm apart (C ~ 0.3 aF)© 100 micrometers (io3m) The fly's eye is made of hundreds of tiny resembling honeycomb.Electron Microscope Size Bk ql 10 micrometers (ao“4m) . a, fly'seye is made of = undreds of smaller eyes. Each facet is a small lens with light sensitive cells underneath. Image necessitates an electron microscope.Micro Size 1 micrometer (o-4m) In between the facets are bristles which give sensory input from the surface o! the eye.10 nanometers (l0~mM) Atthe centre of the cell isa Hightly coiled molecule called DNA. It contains the genetic material needed to duplicate the fly.1 nm Size 1 nanometerA Perspective Atomoinm DNA (width) 2 nm Protein5 -50nm Virus 75 - 100 nm Materials internalized by cells < 100 nm Bacteria 1,000 — 10,000 nm White Blood Cell 10,000 nm & 59waa Size Matters Fluorescence at different wavelengths tr a single l TV light due to quantum Confinement in semiconductor quantum dotsSynthesis of Nanomaterials