Tag Archives: metals

Plasmons, Shiny Metals, and Stained Glass

Remember plasmas, the phase of matter where atoms are ripped apart into electrons and nuclei? Plasmas are primed for strong electromagnetic interactions with the world around them, because of all the loose charged particles. They can be used to etch down into surfaces and catalyze chemical reactions, though the ions in a plasma won’t necessarily react with every form of matter they come across. And you can actually use an electromagnetic field on its own to contain a plasma, because of the plasma’s sensitivity to electromagnetic force. The most common design for a fusion reactor, the tokamak, uses a doughnut-shaped field to contain a plasma.

That’s how plasmas work at the macroscale, but it’s the individual charged ions in the plasma which react to electromagnetic force. Their interactions sum to a larger observable phenomena, which emerges from nanoscale interactions. But interestingly, the collective interactions of these ions can actually be approximated as discrete entities, called quasiparticles. We’ve talked about quasiparticles before, when we talked about holes which are quasiparticles defined by the absence of an electron. But in plasmas, the collective motion of the ions can also be considered as a quasiparticle, called a plasmon. Each individual ion is responding to its local electromagnetic field, but the plasmon is what we see at a larger scale when everything appears to be responding in unison. A plasmon isn’t actually a particle, just a convenient way to think about collective phenomena.

Plasmons can be excited by an external electromagnetic stimulus, such as light. And actually, anyone who has looked up at a stained glass window has witnessed plasmonic absorption of light! Adding small amounts of an impurity like gold to glass results in a mixture of phases, with tiny gold nanoparticles effectively suspended in the amorphous silica that makes up glass. Gold, like many metals, has a high electron density, and the electrons effectively comprise a plasma within each nanoparticle. When light shines through the colored glass, some wavelengths are plasmonically absorbed and others pass through. Adding a different metal to the glass can change the color, and so can different preparations of the glass that modify the size of the included nanoparticles. So all the colors in the window shown below are due to differing nanoparticles that plasmonically absorb light as it passes through!

Now you might ask, what determines which wavelengths of light pass through and which don’t? In the case of stained glass, it has to do with the size of the nanoparticles and the metal. But more generally, plasmas have a characteristic frequency at which they oscillate most easily, called the plasma frequency. The plasma frequency depends on several fundamental physical constants, including the mass and charge of an electron, but notably it also depends on the density of electrons in the plasma. For nanoparticles, the size of the particle also affects the response frequency. The practical upshot of the plasma frequency, though, is that if incident light has a frequency higher than the plasma frequency, the electrons in the plasma can’t respond fast enough to couple to the light, and it passes through the material. So the material properties that dictate the plasma frequency also determine whether light will be absorbed or transmitted.

For most metals that aren’t nanoscale, the plasma frequency is somewhere in the ultraviolet range of the electromagnetic spectrum.  Thus, incident visible light is reflected by the free electron plasma in the metal, right at the surface of the material. And that’s why metals appear shiny!

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I’m With The Band Theory

We have already talked about the mechanical aspects of how a solid is assembled from individual atoms, when the atoms are in a repeating periodic structure called a crystal lattice. The lattice type can determine many of the material properties, but one of the most interesting and useful properties to think about is electrical conduction. One of the simplest ways to measure conduction is by creating a potential difference, so that one side of the material is more energetically favorable to charged particles than the other. This is called applying a voltage, named after Alessandro Volta who invented the battery, a device that uses chemical differences to create a voltage. When there is a voltage applied, electrons are drawn through the material, but how many electrons flow (which determines how large the measured electrical current is) varies widely by material. In some solids where electrons move freely, it’s easy to pass a lot of electrons through, creating an electrical current. This is characteristic of a metal, where electrical conduction is easy. But in other solids, it takes a lot of energy to move electrons through so electrical conduction is difficult, and we say these materials are insulators. And there is a third class of material, a semiconductor, which can be switched between conducting and non-conducting states.

To understand what causes the different electrical behaviors, we can think about how the atomic energy states available to electrons scale up to a bulk material. Each individual atom has a set of available electron states, that can be mathematically described using quantum mechanics. Some of these states are occupied by electrons, and some are not. A collection of atoms will have a collection of states, some occupied and some free, and an electron has to have available states that it can move between in order to traverse a solid. If there are no available states, it doesn’t matter how energetically favorable it is for the electron to go somewhere else, it has no way of getting there.

For a solid made up of only one kind of atom, the electronic states in each atom will be similar but may vary slightly due to varying conditions throughout a non-perfect crystal. This means that if we sum up all the states, instead of the precisely delineated states we found in a single atom, we’ll have smeared out bands of available states and forbidden regions which give a rough approximation of what energies electrons can have. As usual, the lowest energy states will be mostly occupied, and the highest energy states will be mostly empty. It’s the states right at the top of the electron occupancy which turn out to be the most useful for conduction, because of the minimal energy cost involved in moving electrons. (The line demarcating this is called the Fermi energy or Fermi level.) And how these available electron states look when we depict them as a function of energy can be very different, as shown below:

The various bands of allowed electronic states can overlap with each other, can have a small separation in energy, or can have a large separation in energy. Overlapping bands mean that in both bands, electrons have many available states to transition to, and that is why materials with overlapping bands have high electrical conductivity. These are metals, like gold or copper. For materials with a large separation between bands, the lower energy band is completely full and the higher energy band is completely empty. If an electron in the full band is tempted to move through the material, it must first scrounge up the energy to jump up to an available state, which is so considerable a task that most electrons can’t manage it. These are insulators, which may only pass one electron for every 1030 (a billion billion billion, or more electrons than stars in the universe) that pass through a metal at the same potential.

But the most interesting case, at least as far as modern electronics is concerned, is the material with a small separation between bands, the semiconductor. Only a small energy is needed to boost an electron from the full band to the empty band, and if the energy required is provided by thermal energy at room temperature, semiconductors can have significant electrical conduction at room temperature. But the most useful semiconductors are not quite conductive under normal conditions, but can easily be turned on by applying an electric field. That means they can operate as an electrical switch, acting as a metal or an insulator depending on what’s required. Silicon is the most widely used semiconductor in the present day,

Where the bands of available states fall exactly is determined by the crystal lattice type and the interatomic spacing, two factors which are themselves determined by the outer electrons of the atoms themselves. And for amorphous solids without a periodic structure, like glass, we still get energy bands. In fact, one way to think of the transparency of glass is that visible photons entering the material do not have enough energy to excite electrons from a filled band into an empty band, so they pass through the material without interacting with it. And that’s why you can see through glass!

All the justification for band theory involves a lot of math, of course. But just the basic idea, that bulk materials have bands of available states for electrons and the energy and grouping of these states determines electrical behavior, is pretty amazing because it puts a framework around the broad variety of electrical behaviors that we see in materials in nature. And, if you want to understand how electronics work, band theory is the first big piece of that puzzle.