Nanotechnology and the Structure of Materials

Five different levels of structure of materials may be examined and described

Atomic structure
Short-and long-range arrangements Nanostructure

Microstructure, and
Macrostructure
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Structure of materials
Atomic Structure Atomic or ionic arrangements up to ~ 0.1 nm (10-10 meters) Bonding type leads to different atomic or ionic arrangements in materials Diamond from C-C covalent bonds used as thin films for wear-resistant edge in cutting tools
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Structure of materials
Short-range atomic arrangement
Atomic or ionic arrangements from 0.1 1nm (10-10 - 10-9 meters) Atoms or ions show order in their arrangement over relatively short distances; arrangement of atoms or ions extends only to their nearest neighbors Ions in silica (SiO2) glass is amorphous due to short-range arrangement and forms basis of the fiber-optics industry
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Structure of materials
Long-range atomic arrangement
Repetitive three-dimensional patterns or arrangements of atoms or ions in crystalline materials They range from ~ 10nm (10-8 meters) up to cm; include Lead-zirconiumtitanate-ions (PZT) arranged in tetragonal and/or rhombohedral crystal structures These crystalline materials are piezoelectric, that is, they develop a voltage and a spark on applying pressure

Structure of materials
Nanostructure
Structure of materials from 1 - 100nm (10-9 - 10-7 meters) Nano-sized particles of iron oxide (~ 5 10 nm) typical example Nano-sized iron oxide particles used in liquid magnets as cooling (heat transfer) medium for loadspeakers

Structure of materials
Microstructure
Structure of materials from ~>102 105nm (10-7 - 10-4 meters) or 0.1 100m Fine grain of crystalline structure In general, finer grain size leads to higher strength at room temperature

Structure of materials
Macrostructure Structure of materials ~>105 nm (~10-4 m or 100m) Relatively thick coatings such as paints on automobiles Used for aesthetics and also to provide corrosion resistance

Nanotechnology
What is nanotechnology?
Nano is 10-9 and a nano meter 10-9 meters (or 1nm

about the size of ten atom one carbon atom is ~0.15nm) Technology is is the building of useful things from scientific principles Nanotechnology means building useful things at the 10-9 meters level Nanotechnology may therefore, be defined as the study, development and processing of materials, devices and systems at atomic, molecular or macromolecular scale

Nanostructure:

A nanometer (nm) is 10-9 meter (1 m = 3.28 ft).

Nanotech: from1 nm to ~100 nm
Argon 0.3 nm Albumin 6.5 nm Ribosome 25 nm

CH4
H2O

0.4 nm
0.3 nm

Red Blood Cell 2000x7000 nm

Dimensions at the nanoscale

Argon 0.3 nm CH4 H 2O 0.4 nm 0.3 nm

~1 nm ~100 nm
Albumin 6.5 nm Ribosome 25 nm

HIV 125 nm Red Blood Cell 2000x7000 nm

Nanotechnology

What is nanotechnology (cont..)?

Nanotechnology involves the controlled creation and use of structures, devices and

systems with a length scale of 1 100 nm It covers the design, behavior and modeling nanostructures, nano-metrology and characterization

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Nanotechnology
What is nanotechnology (cont..)?
Nanoscale materials and devices may be

fabricate/created using two different approaches Bottom-up approach or methods where nanomaterials or structures are fabricated from buildup of atoms or molecules in a controlled manner Top-down methods where nano-fabrication and micro-technologies used to fabricate nano-scale structures and devices from a block of the material. The size limit of smallest features created depending on the technology
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Nanotechnology and materials science and engineering

Some nanotechnology areas of interest
Nano-structured materials Self organizing and self assembling

molecular structures Biological and biomedical systems Scanning probe microscopy

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Polymorphism
Allotropy is ability of a substance to exist in more than one physical form e.g., Carbon has four allotropes that include diamond and graphite Polymorphism is allotropy of solids which relies solely on differences in crystal structure, that is two or more distinct crystal structures for the same material e.g., -Fe has BCC structure and -Fe FCC

iron system Allotropes of carbon: diamond, graphite, Buckminsterfullerene C60 , carbon nanotubes liquid BCC FCC 1538C -Fe 1394C -Fe

912C BCC
-Fe

Allotropy of Carbon and Carbon Nanotubes

The four allotropes of carbon
a) Diamond b) Graphite c) Buckminsterfullerene (C60), third allotrope of carbon

Consists of 60 carbon atoms of 12 regular pentagons and 20 regular hexagons that fit together perfectly as a soccer ball The soccer ball shape has 60 corners where each carbon atom at the corner has two single bonds and one double bond (d) Carbon nanotubes, the fourth allotrope of carbon Envisioned as sheets of graphite rolled into tubes with hemispherical fullerene (C60) caps on the ends Typically 1 25 nm in diameter and a few microns (103 nm) long

Nanotechnology and materials science and engineering Nano-structured materials

Nano-sized iron oxide particles, cerium oxide, CeO2 and zinc

oxide, ZnO nanocrystals, and quantum dots (which are florescent semiconductor nanocrystals)
Buckminsterfullerene (C60), third allotrope of carbon

Carbon nanotubes, the fourth allotrope of carbon

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Types of Carbon Nanotubes:

1. rm chai A r.

2. Zi gzag.

3. C hi ral

Nanostructure: Zeolites Silicate-Aluminate

Nanotechnology and materials science and engineering Some useful properties of nanostructured materials
The small (nano-) size of the materials

results in:
Higher active surfaces per unit of volume and mass Increased catalytic activity and water solubility Increased hardness, ductility, magnetic coupling and selective absorption
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Catalysts and Surface Defects

A catalyst increases the rate of a chemical reaction without being consumed Active sites on catalysts are normally surface defects
.

Single crystals of (Ce0.5Zr0.5)O2 used in an automotive catalytic converter

Nanotechnology and materials science and engineering

Applications of nano structured materials
Nano-sized iron oxide particles used in liquid magnets as

cooling (heat transfer) medium for loudspeakers Quantum dots may be used for high resolution cellular imaging Gold nanorods ~200 times smaller than red blood cells used for ultra-sensitive medical imaging technique for cells Carbon nanotubes which can accumulate in tumors absorb near-infrared light that is harmless to human tissue leads to the absorbed light releasing excess energy as heat to destroy the tumor Polymer-based nanoparticles used to improve drug delivery
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Gas absorbed in carbon nanotubes

Inclusion in zeolites

Nanotechnology and materials science and engineering

Self-organizing and self-assembling molecular structures
A Bottom-up method where nano-materials or structures

are fabricated by molecular self-assembly Atoms, molecules, and molecular aggregates organize and arrange themselves without human intervention Inorganic and organic monolayers 1 5 nm in thickness that are ~ only one molecule or even one atom thick with a wide range of excellent properties including being chemically active, as well as being dense and hard for wear resistance Monolayers deposited on semiconducting substrates as basis of solar energy cells, and sensors

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Nanotechnology and materials science and engineering

Self-organizing and self-assembling molecular structures
Monolayers of different materials forming multilayers with

specific magnetic properties for magnetic recording , and high corrosion resistance Self organizing and self-assembly molecular systems that mimic the self assembly of molecules in biology as in the addition of water to lipids which leads to self-assembly into ordered structures with hydrocarbon tails on the inside and the head group projecting into the water. The self-assembly ordered structures may be used for incorporating protein namomachines e.g. ATPase a nanoturbine that is embedded in a lipid membrane that converts ADP to ATP the energy currency of the cell. Nanosized biosensors formed by self-assembly based on biology
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Nanotechnology and materials science and engineering

Biological and biomedical systems
Both Bottom-up and Top-down methods of nanotechnology approaches to drug delivery Bottom-up approach of using nanoparticles from biodegradable polymers or liposomes (special lipid bilayer) that encapsulate the drug with targeting molecules such as antibodies or proteins on the surface of the nanoparticle that targets specific cell types for controlled delivery of drug Top-up micro-fabricated drug delivery chip with reservoirs that contain the drug and as the cap of each reservoir is removed the drug is released Bottom-up molecular self-assembly of small building blocks used to generate tissue engineering scaffolds

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Microscopy
Optical resolution ca. 10-7 m = 0.1 m = 100 nm For higher resolution need higher frequency X-Rays? Difficult to focus. Electrons
wavelengths ca. 3 pm (0.003 nm)
(Magnification - 1,000,000X)

Atomic resolution possible Electron beam focused by magnetic lenses.

Scanning Probe Microscopy of Nanomaterials

Scanning Probe Microscopy
Ultra-precision instruments with accuracies in the order of 1 nm or even 0.1 nm needed for research and development and manufacturing in the nanoregime Transmission electron microscope (TEM) was the first tool that allowed us to see and count atoms Scanning electron microscope (SEM) followed the TEM and produces a sharp, three dimensional view of a specimen TEM however, produces images of greater magnification

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Scanning Probe Microscopy of Nanomaterials

Scanning Probe Microscopy
Scanning probe microscopy (SPM) is a general

term that includes scanning tunneling microscopy (STM) and atomic force microscopy (AFM) as typical examples Scanning probe microscopy (SPM) used to image surfaces at the nanometer scale

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Scanning Probe Microscopy of Nanomaterials

Scanning Probe Microscopy
Scanning probe microscopy (SPM) uses a fine

probe that is either scanned over a surface or the surface is scanned under the probe, instead of using a bean of elections as in TEM and SEM The use of a probe eliminates the constraint imposed by the wavelength of a beam of electrons Resolutions obtained using SPM range from resolving atoms to giving true 3-D maps of surfaces of samples with 0.1 1 nm resolution possible

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Scanning Probe Microscopy of Nanomaterials

Scanning Tunneling Microscopy
A scanning tunneling microscope (STM) scans a sharp tip

over the surface of a sample, and a voltage applied to the tip Electrons from the tip tunnel or leak to the sample or vice versa depending on the bias voltage when the tip is ~1 nm from the sample The resulting current is a function of the tip to the sample distance, and measurements of current used to map the sample surface The sample surface can be imaged at an extremely small scale down to resolving individual atoms

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Scanning Tunneling Microscopy (STM)

Atoms can be arranged and imaged!
Photos produced from the work of C.P. Lutz, Zeppenfeld, and D.M. Eigler. Reprinted with permission from International Business Machines Corporation, copyright 1995.

Carbon monoxide molecules arranged on a platinum (111) surface.

Iron atoms arranged on a copper (111) surface. These Kanji characters represent the word atom.

Scanning Probe Microscopy of Nanomaterials

Atomic Force Microscopy
Atomic force microscope (AFM) developed to overcome the

basic drawback of STM requiring conducting or semiconducting surfaces for imaging AFM therefore, images surfaces including polymers, ceramics, composites, glass and biological samples The AFM scans a sharp tip (nano-sized of about 500 nm long and 100 nm wide) held at the apex of a cantilever over the surface of a sample The extension of a crystal called a piezo on the cantilever is responsible for the movement of the tip across the surface

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Scanning Probe Microscopy of Nanomaterials

Atomic Force Microscopy
The force between the tip and the surface of the sample

causes the cantilever to bend A device called an optical lever measures the deflection of the cantilever The optical lever consists of a laser beam and a positionsensitive photodetector The position-sensitive photodetector can measure changes in position of the incident laser beam as small as 1 nm, thus giving sub-nanometer resolution In contact mode AFM, an actuator moves the sample with respect to the tip in order to maintain a constant deflection and the surface of the sample is thus mapped as a function of height
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