MM-407: NANOSTRUCTURED MATERIALS

NANOTECHNOLOGY Nanotechnology deals with small structures or smallsized materials Prefix of nanotechnology i.e. nanos comes from the Greek word for dwarf Nanometer (nm) is one billionth of a meter, or l0-9 m One nanometer is approximately the length equivalent to 10 hydrogen or 5 silicon atoms aligned in a line Small features permit more functionality

Physical Properties of Nanomaterials Copper which is an opaque substance become transparent. Platinum which is an inert material become catalyst. Aluminum which combustible. is a stable material turns

Silicon insulators become conductors. Gold which is solid, inert and yellow on room temperature at micro scale becomes liquid and red in color at nano scale on room temperature. It also gets unusual catalytic properties not seen at macro scale.

Nanotechnology Definitions The development and use of devices that have a size of only a few nanometres www.physics.about.com Research and technology development at the atomic, molecular or macromolecular level in the length scale of approximately 1 - 100 nm range, to provide a fundamental understanding of phenomena and materials at the nanoscale and to create and use structures, devices and systems that have novel properties and functions because of their small and/or intermediate size. www.nano.gov Branch of engineering that deals with things smaller than 100 nm (especially with the manipulation of individual molecules). www.hyperdictionary.com The art of manipulating materials on an atomic or molecular scale especially to build microscopic devices. Miriam Webster Dictionary

Nanotechnology, or, as it is sometimes called, molecular manufacturing, is a branch of engineering that deals with the design and manufacture of extremely small electronic circuits and mechanical devices built at the molecular level of matter. www.whatis.com

OLD NANOTECHNOLOGY Stained-glass windows Silver-Halide Photography AR-coated lenses

(anti-reflecting)

Viruses are nanomachines NEW NANOTECHNOLOGY Vastly improved catalysts enhance surface area to volume ratios Designer drugs Cheap, sensitive medical diagnostics Transparent Sunblock Nanotube-strengthened cables Difference:
Designing and manipulating at the molecular level whereas before it was either evolution that did it for us or results

happened which we never really understood and so couldnt optimize

HISTORY OF SCIENTIFIC REVOLUTIONS

Discovery type Industrial Industrial Industrial Automation Automation Health Industrial Automation Health, industrial, automation Tools

Name

Age Stone Bronze Industrial Consumer Information Genetic Nano age Assembler age? Life age

Metallurgy Steam power Mass production Computing Genetic Engineering Nanotechnology Molecular assemblers Life assemblers

Start date 2,200,000 BC 3500BC 1764 1906 1946 1953 1991 2020? 2050?

Wilson et al. 2002. Nanotechnology: basic science and emerging technologies. Chapman & Hall/CRC. New York.

PERSPECTIVE OF SIZE Water molecules 3 atoms

DNA molecules millions of atoms Carbon nanotubes millions of atoms

Molecule of DNA

Carbon nanotubes

Examples of zero-dimensional nanostructures or nanomaterials with their typical ranges of dimension

SURFACE VS. VOLUME a

Diamond unit cell

Si has a diamond structure with a = 5.43 A Si nanocube 10 nm on a side is composed of: ~6250 unit cells ~50,000 atoms Each nanocube face is composed of: ~340 unit cells per face ~680 surface atoms per face Total surface area is: ~4080 atoms (~10% surface atoms) A bulk Si film 1 m thick on a 10 cm square: ~6.3 X 1019 unit cells ~5 X 1020 atoms ~1.4 X 1017 surface atoms (~0.03% surface atoms)

MORE THAN SIZE.

Interesting phenomena:

Chemical Take advantage of large surface to volume ratio, interfacial and surface chemistry important, systems too small for statistical analysis Electronic Quantum confinement, bandgap engineering, change in density of states, electron tunneling Magnetic Giant magneto-resistance by nanoscale multilayers, change in magnetic susceptibility Mechanical Improved strength hardness in light-weight nanocomposites and nanomaterials, altered bending, compression properties, nanomechanics of molecular structures

Optical Absorption and fluorescence of nanocrystals, single photon phenomena, photonic band gap engineering Fluidic Enhanced flow properties with nanoparticles, nanoscale adsorbed films important Thermal Increased thermoelectric performance of nanoscale materials, interfacial thermal resistance important

WHAT ARE NANOSTRUCTURES? At least one dimension is between 1 - 100 nm 2-D structures (1-D confinement): Thin films Planar quantum wells Superlattices 1-D structures (2-D confinement): Nanowires Quantum wires Nanorods Nanotubes 0-D structures (3-D confinement): Nanoparticles Quantum dots Dimensionality, confinement depends on structure: Bulk nanocrystalline films Nanocomposites

THIN FILMS Nanoscale Thin Film Single two dimensional film, thickness < ~100 nm Electrons can be confined in one dimension; affects wavefunction, density of states Phonons can confined in one dimension; affects thermal transport Boundaries, interfaces affect transport

FABRICATION OF NANOSTRUCTURES AND NANOMATERIALS Group according to the growth media: (1) Vapor phase growth, including laser reaction pyrolysis for nanoparticle synthesis and atomic layer deposition (ALD) for thin film deposition. (2) Liquid phase growth, including colloidal processing for the formation of nanoparticles and self assembly of monolayers. (3) Solid phase formation, including phase segregation to make metallic particles in glass matrix and two-photon induced polymerization for the fabrication of three-dimensional photonic crystals . 4) Hybrid growth, including vapor-liquid-solid (VLS) growth of nanowires.

Group the techniques according to the form of products: (1) Nanoparticles by means of colloidal processing, flame combustion and phase segregation. (2) Nanorods or nanowires by template-based electroplating, solution liquid solid growth(SLS), and spontaneous anisotropic growth. (3) Thin films by molecular beam epitaxy (MBE) and atomic layer deposition (ALD). (4) Nanostructured bulk materials, for example, photonic bandgap crystals

CHALLENGES IN NANOTECHNOLOGY Integration of nanostructures/nanomaterials into or with macroscopic systems that can interface with people Building & demonstration of novel tools to study at the nanometer level what is being manifested at the macro level The small size and complexity of nanoscale structures make the development of new measurement technologies New measurement techniques need to be developed at the nanometer scale and may require new innovations in metrological technology.
Measurements nanomaterials of physical properties of require extremely sensitive

instrumentation, while the noise level must be kept very low.

FABRICATION AND PROCESSING OF NANOMATERIALS THE FOLLOWING CHALLENGES MUST BE MET: (1) Overcome the huge surface energy, a result of enormous surface area or large surface to volume ratio. (2) Nanomaterials with desired size, uniform size distribution, morphology, crystallinity, chemical composition, and microstructure (3) Prevent nanomaterials and nanostructures from coarsening through either Ostwald ripening or agglomeration as time evolutes. For the fabrication of nanoparticles, a small size is not the only requirement.

PRACTICAL APPLICATION & PROCESSING CONDITIONS FOR NANOMATERIALS

(i)

Identical size of all particles (also called monosized or with uniform size distribution) Identical shape or morphology, Identical chemical composition and crystal structure that are desired among different particles and within individual particles, such as core and surface composition must be the same

(ii)

(iii)

(iv)

EXCITING APPLICATIONS OF NANOTECHNOLOGY INCLUDE:

Individually dispersed or monodispersed, i.e. no agglomeration. If agglomeration does occur, nanoparticles should be readily redispersible.

Nanopowders the unusual properties of particles less than 100 nm allow a range of new and improved materials with a breadth of applications, such as plastics that behave like ceramics or metals; new catalysts for environmental remediation; improved food shelf-life and packaging; and novel drug delivery devices. Carbon nanotubes graphite can be rolled into a cylinder with a diameter of about 1 nm. These strong but light carbon nanotubes are being developed for a raft of uses, such as sensors, fuel cells, computers nd televisions. Nanomembrane filtration systems these have the potential to address one of the most pressing issues of the 21st Century safe, clean, affordable water.

 Molecular electronic cross bar latches Hewlett-Packard believes that silicon computer chips will probably reach a technical dead end in about a decade, to be replaced by tiny nanodevices described as cross bar latches. Quantum dots these are small devices that contain a tiny droplet of free electrons essentially artificial atoms. The potential applications are enormous, such as counterfeit-resistant inks, new biosensors, quantum electronics, photonics and the possibility of tamper-proof data transmission. New technologies for clean and efficient energy generation.

Nanostructures Definition: A nanostructure is an object of intermediate size between molecular and microscopic (micrometersized) structures. Number of dimensions on the nanoscale Nanotextured surfaces one dimension on nanoscale i.e., only the thickness of the surface of an object is between 0.1 and 100 nm. Nanotubes have two dimensions on the nanoscale, i.e., the diameter of the tube is between 0.1 and 100 nm; its length could be much greater. Spherical nanoparticles have three dimensions on the nanoscale,

i.e., the particle is between 0.1 and 100 nm in each spatial dimension. The terms nanoparticles and ultrafine particles (UFP) often are used synonymously although UFP can reach into the micrometer range.

Two approaches to the synthesis nanomaterials and the fabrication nanostructures:

1)

of of

Top-down Bottom-up

2)

Attrition or milling is a typical top-down method in making nanoparticles.

Colloidal dispersion is a good example of bottom-up approach in the synthesis of nanoparticles. Lithography may be considered as a hybrid approach, since the growth of thin films is bottom-up whereas etching is top-down, while nanolithography and

nanomanipulation approach.

are

commonly

bottom-up

BOTTOM-UP APPROACH
Build-up of a material from the bottom: atom-by-atom molecule-by-molecule

In organic chemistry and/or polymer science, we know polymers are synthesized by connecting individual monomers together. In crystal growth, growth species, such as atoms, ions and molecules, after impinging onto the growth surface, assemble into crystal structure one after another.

Advantages Less defects, Homogeneous chemical composition, Better short and long range ordering

Reason
Driven mainly by the reduction of Gibbs free energy,, therefore closer to a thermodynamic equilibrium state

Examples: Production of salt and nitrate in chemical industry, Growth of single crystals and deposition of films in electronic industry. For most materials, there is no difference in physical properties of materials regardless of the synthesis routes, provided that chemical composition, crystallinity, and microstructure of the material in question are identical.

Top-down Approach Disadvantages Introduces internal stress, Surface defects (i.e. imperfections) Contaminations

SOLID SURFACES PHYSICAL CHEMISTRY Nanomaterials possess a large fraction of surface atoms per unit volume. The ratio of surface atoms to interior atoms changes on dividing macroscopic object into smaller parts. The total surface energy increases with the overall surface area. Large surface energy therefore thermodynamically unstable or metastable

The percentage of surface atoms changes with the palladium cluster diameter.

SURFACE ENERGY REDUCTION (i) Surface Relaxation

The surface atoms or ions shift inward

(ii) Surface Restructuring

Combining surface dangling bonds into new bonds

Original

Restructured

(iii) Surface adsorption Chemical or physical adsorption of terminal chemical species onto the surface by forming chemical bonds or weak attraction forces such as electrostatic or van der Waals forces (iv) Composition segregation or impurity enrichment Through solid-state diffusion. AGGLOMERATION OF INDIVIDUAL NANOSTRUCTURES (1) Sintering
Individual structures merge together Polycrystalline material

(2) Ostwald ripening Large structures grow at the cost of smaller ones
Appreciable solubility in a solvent

Single uniform structure

(a) Sintering (b) Ostwald ripening

Sintering Solid-state diffusion

(i)

Surface diffusion Requires the smallest activation energy Start at relatively low temperature Volume diffusion Require moderate temperatures, Volume diffusion dominates Cross grain-boundary diffusion Requires highest activation energy Significant only at high temperatures

(ii)

(iii)

Evaporation-condensation Nanomaterials have an appreciable vapor pressure at

the processing temperature.

Dissolution-precipitation Solid is dispersed in a liquid in which the solid is

partially soluble

Vapor pressure of a number of liquids as a function of droplet radius

Variation in solubility of silica with radius of curvature of surface

OSTWALD RIPENING

Can have either positive or negative influence on the resulting materials, depends on process & application Can either widen or narrow the size distribution, depending on the control of the process conditions Abnormal grain growth, leading to inhomogeneous microstructure and inferior mechanical properties Specifically, it has been used to narrow the size distribution of nanoparticles by eliminating small one