Nanomaterials and nanotechnology

Property/ phenomenon
Structure and electronic configuration

Specific property
Confinement Surface area

At the macroscale microscale

No confinement Surface area of bulk materials, although important, is small compared to its volume S/V is small; becomes insignificant as objects become larger Characteristic of the bulk

At the nanoscale
Confinement in OD, 1D, and 2D Exponentially enhanced Collective surface area can be enormous Approaches 1 when all atoms are surface atoms Lattice spacing is altered. Spacing near surface contracts due to rearrangement. Ion vacancies larger Coordination under saturated at surface and in volume Quantum: HOMO and LUMO Cluster: HOCO and LUCO Magic electronic numbers in alkali metal clusters Nanomaterials exist at the quantumclassical interface Influenced by the Bohr radius

Surface-tovolume ratio Lattice spacing

Atom coordination Electron orbitals

Coordination saturated except at surface where it is negligible Continuous over the breadth of the material

Electromagnetic Properties

Quantum mechanics Radiation: absorption emission Optical response

QM applies at the bulk level: bathtub waves Blackbody radiation Absorption-emission bands broad Metals reflect with partial absorption of light. Micron-sized particles scatter light and conform to Mie theory analysis Higher order plasmon resonance and plasmon resonance is delocalized

Size-dependent absorption-emission. Environment dependent (effective medium theory) Quasi-static condition (r << 0.01 ). Dipolar plasmon resonance Localized surface plasmon resonance (i.e., transverse/longitudinal modes for prolate particles) Bulk optical constants no longer apply below 10-20 nm Bandgap is size dependent Gold resembles a semiconductor in nanoparticles <2 nm in diameter

Optical Bulk values apply and are valid in constants, , n, micron-sized particles. k Bandgap Traditional metal, semiconductor, insulator bandgaps. Bandgap independent of size

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Nanomaterials and nanotechnology

Electrical conduction Continuous and follows Ohm's law. Conductivity based on band Structure Electron mean free path not significant with respect to surface Scattering by lattice defects and thermal phonons Magnetic memory coercive force Size independent Ohm's law does not apply (classically). Formation of discrete energy levels Coulomb staircase/blockade Tunneling currents are important Ballistic conduction (electron mean free path > dimensions) Size-dependent magnetic properties. Gigantic magnetoresistance effects possible with stacked magnetic nanoparticle arrays Nanothermodynamics Nanosystems subject to environmental fluctuations. Conditions of nonequilibrium steady state in living systems N is countable. Thermodynamic limits do not apply Intensivity not always applicable as intensive properties can change with size. Serious environmental dependency Altered definition of extensivity Violations of the second law. Is the fourth law of thermodynamics required? MP drops precipitously below 20 nm Proportional to 1/r Particles <10 nm conform to Kelvin effect Surface tension and surface energy a function of size Much higher than bulk counterpart Electron affinity influenced by magic numbers in clusters Function ol size Intermolecular forces are important: H-bonds, van der Waals, hydrophobic effect, dipole interactions, etc.

Thermodynamics

Discipline Equilibria

Classical thermodynamics, statistical mechanics Macroscopic systems thermodynamic equilibrium capability Thermodynamic infinite limit: N > , V > , n/v constant Properties independent of amount of material Environment independent Properties dependent on amount of material Link between micro and macro domains

Intensive properties

Extensive properties Entropy

Melting point Kelvin effect Surface tension/ energy Specific heat Electron affinity Work function Chemical bonds

Metals relatively high melting Function of particle curvature Valid for bulk and nanomaterials Classical surface tension and surface energy Function of elemental makeup Function of elemental makeup Function of elemental makeup The big three: ionic, covalent, and metallic predominate, although all others apply

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Number of atoms

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Chemical reactivity Reaction scheme Kinetic control at higher temperatures, harsh condition; making and breaking of stronger bonds Surface adsorption by chemisorption / physisorption does not result in catalytic activity Large particles have limited solubility Thermodynamic control occurs at lower temperatures, milder conditions; making and breaking not weaker bonds Adsorption by small particles can result in catalytic activity Smaller particles have enhanced solubility. This is important in targeted drug delivery systems Occurs at lower temperatures Reactivity of nanoparticles significantly enhanced due to excess surface energy Bulk materials made of nanograins have superior properties Tensile properties can approach theoretical limit in carbon nanotubes Depends on the types of physical phenomena and size of the particle. Bulk electric functions are valid to sub100-nm particles

Adsorption

Solubility

Sintering Chemical activity Mechanical properties Tensile properties

Function of elemental makeup. Occurs at high temperatures Function of elemental makeup Reactivity takes place below the nanoscale. Bulk material made of micron-sized grains

Scaling laws Classical continuum models

Density Power Frequency Efficiency Mechanical Dielectrics

Bulk scaling laws and continuum models apply to all materials down to micron-sized particles

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