What is self assembly?

Simply put, we're talking about collections of objects that put themselves together. Imagine holding a box containing a jigsaw puzzle, giving the box a shake, and peeking inside to find that the puzzle had assembled itself! While such behavior would be shocking in a jigsaw puzzle, a little reflection reveals that it's not so surprising to find self assembling systems in the natural world. After all, no one put you together did they? Biological systems as well as a variety of inorganic physical systems exhibit self assembling or self ordering behavior. Drawing on these systems for inspiration, scientists have begun to investigate the self assembly process in hopes of learning to design and control the behavior of self assembling systems.

Self-assembly
Under controlled evaporation
particles self-assemble...... into regular 2D (or 3D) arrays.

Co-nanocrystal.Diam. 3-12 nm.

Ligand: Oleic acid,2 nm. TEM of self-assembled array of 5 nm diameter Co particles with 2nm Oleic

Why the sudden interest in NPs? Monodisperse particles. Self-assembly:

Can get defect free perfect lattices.

Can deposit films 1 monolayer thick

and monolayer by monolayer on top of that! Can even grow 2 element 3D crystals!

Much of this work is motivated by recent advances in micro- and nanoscale science. On one hand, fabrication methods in micro- and nanoscience allow for batch processing. That is, we have the ability to make many copies of the same device simultaneously.
How do we design these devices so that they spontaneously assemble themselves into a useful working structure?

On the other hand, traditional fabrication methods are limited in resolution. To make smaller structures, i.e., true nanoscale structures, requires the development of new methods.
Taking their cue from nature, coaxing nanostructures into self assembling is an avenue many scientists are exploring. Ultimately, a deeper understanding of self assembly may shed light on the nature of life itself.

Self assembly in the kitchen (and other parts of the house)

Simple systems exhibit self assembling behavior.

Assembly by capillary forces

It is based on the so-called "capillary bond." This "bond" exploits two properties of objects in water.

First, small objects resting on the surface of water attract one another. In this way, interacting particles feel a force of attraction.
Second, when two hydrophobic surfaces come into contact they remain in contact. In other words, they bond. In an experiment the polymer polydimethylsiloxane (PDMS) was used to fabricate their self assembling shapes. PDMS is naturally hydrophobic and its surface properties can be easily changed from hydrophobic to hydrophilic by treating with an oxygen plasma. In this way interacting particles with varying surface properties can be fabricated.

Others have exploited the capillary bond using more prosaic materials to construct the interacting particles. Soda straws as a self assembling system. Like PDMS, soda straws are made of a hydrophobic polymer. They float easily on the surface of water and can be induced by light shaking to self assemble. The soda straw system demonstrates another important aspect of assembly by capillary forces - by controlling the "height" of interacting particles the capillary force can be made repulsive.

Assembly by electrostatic forces

Assembly by capillary forces relies upon particle-particle interaction and interaction between particles and their environment. The particles have surface properties (hydrophobic or hydrophilic) and the environment is water. Place the particles in oil or alcohol and assembly stops. Make the particles entirely hydrophilic and assembly stops. Thinking of the capillary self assembly process in these terms naturally leads to the question of whether or not a different set of particle-particle and particleenvironment interactions can be used to create a self assembling system.

One natural alternative is to use electrostatic forces to induce self assembly. Anyone who's ever opened a package full of packing "peanuts" knows they hold a charge quite well. Toss a bunch of packing peanuts at a Van de Graff generator and some will self assemble into long chains. A more refined version of this demonstration using rice and corn oil is often used to illustrate the principle behind electrorheological fluids: dielectric particles in a fluid assemble into chains upon the application of an electric field.

The particles float freely in a fluid, the particle and fluid have different dielectric properties. the top and bottom boundaries are electrodes. A voltage difference is applied between the electrodes, the particles begin to move back and forth between the plates transferring charge and assembling themselves into chain-like structures.

In a laboratory, we can conducted this experiment using pieces of resistance paper as the particles. The fluid is vegetable oil and the applied voltage is about 15kV. The system starts in a disordered state like so: particles are free to move in three dimensions.

The field is applied between parallel aluminum electrodes residing on the left and right of the container. A short time after applying the field, the system becomes ordered:

How does changing particle shape change the assembled structures?

What happens if you make different parts of the particles from different materials?
What happens if you change from the parallel plate geometry?

Assembly by magnetic forces A simple to construct, yet interesting, self assembling system involves magnets. In its simplest incarnation, the system is no more than a collection of disk shaped magnets randomly strewn about a inside a container. Here, simple shaking is enough to cause formation of a more highly ordered state: What do we mean by "more highly ordered"? Well, in the animation above, the ordering is clear.

Initially, the magnets are randomly placed in some closed region of the plane.
Upon shaking, they form a chain-like structure.

How should we make this notion of ordering or of complexity precise?

One idea is to use the Kolmogorov definition - the complexity is the length of the shortest computer program needed to produce the pattern we see.
Above, before shaking, our program would need to specify the location of every particle. After shaking, we need only specify the location of one magnet and the fact that all others are arrayed in a chain behind it. This system is more "ordered." It is worth observing that even after assembly is completed in the system above, a good deal of disorder remains. We can visualize the disorder by painting a colored stripe on the side of our magnets: Upon repeated the experiment we see that rotational orientation is not preserved, there is still rotational "disorder" in the system:

Further, if we numbered each disk, we would see that there was no preferred order for the position of disks in the chain.