Conductivity, Composition, Configuration and Production

In order to understand why carbon nanotubes conduct electricity, we must look at the atomic structure of each carbon atom. Usually, when carbon atoms bond they will bond with 4 other atoms to form a molecule without any free electrons to carry a charge. However, in a carbon nanotube, each carbon atom is only bonded to 3 other atoms. This bonding is allowed when a carbon atom is unhybridised, as the first image shows, but because the electron pairs in the 2s and 2p orbitals are unhybridised, there will be one electron left unpaired in the outer shell. Because this sort of configuration is only stable when the atom is hybridised, the carbon will react with a 4th carbon and form another carbon allotrope, or react with other elements to form other compounds. In order for a carbon nanotube to be made, something else is needed. This ‘something else’ is called hybridisation. In hybridisation, the 2s orbital and two 2p orbitals combine to create 3 sp2 orbitals, as image 3 shows. Instead of forming the structure above, where the covalent bonds are at right angles, the 3 sp2 orbitals are on approximately the same plane and at 120o to each other, as shown in the 4th and 5th images. This means the hexagons found in the walls of a carbon nanotube can form. The single electron left in the unhybridised 2p orbital is now capable of conducting electricity seeing as it can move under the influence of a potential difference. Also, sp2 orbitals have a tendency to form double bonds; this is due to the unhybridised p orbitals bonding to form a pi (π) bond if they happen to touch above or below the covalent sigma (σ) bonds. However, usually when a π and σ bond are located next to each other, a double or triple bond if created, this is not the case with carbon nanotubes due to their unique structure in which the π bond gets shared between 3

different carbons which causes general laws to break and interesting things to happen, more on this later. And yet, the above does not explain why the process for making carbon nanotubes, encourages the hybridisation of carbon, but not hybridisation to the extent that diamond is formed. As mentioned earlier, Carbon nanotubes are created in 3 main ways, arc discharge, laser ablation and chemical vapour deposition (shown on the right). The differences between these methods are irrelevant as they all produce identical nanotubes; however, they all have one thing in common – energy. Lots of energy is needed to produce carbon nanotubes and this is because energy is needed to excite an electron in order to make it form an sp2 orbital. Although the energy needed to excite an electron enough to make it form an sp2 orbital is tiny, there are millions of atoms which need energy, and so pure carbon nanotubes are very rare in nature, nanotubes can be found in the remains of normal wood fires, but due to the different compounds involved in burning wood, and the uncontrolled temperature, there are almost always either contaminated or impure. There is another allotrope of carbon that is very strong, and requires lots of heat to be made, and that is diamond. The reason the processes used to manufacture nanotubes do not produce diamonds, is that diamonds need 4 sp3 orbitals to create their superstructure, not sp2 orbitals. However, sp3 orbitals require vast amounts of energy to be formed, this is because the 2s sub-shell is emptied of all its electrons and this renders the carbon atom very unstable. The only way sp3 orbitals can stay in sp3 form is by forming a giant repeating superstructure that can hold itself together, and seeing as carbon nanotubes cannot have 4 bonds at right angles due to VSEPR causing them to form a tetrahedral structure, instead of the planar structure required for a sheet of atoms as is the case in a nanotube. During nanotube synthesis, the temperature of the reaction has a large impact on the amount of nanotubes produced. In general, the higher the temperature, the more nanotubes are produced. Nanotubes have the property of possessing a very high ballistic conductance; this is the ability of a material to conduct heat in a linear direction and to retain that heat. Because nanotubes have a very high ballistic conductance value, they can transmit heat along their length quickly and efficiently and so can keep their structure at high temperatures under which the carbon-carbon

bonds would break. This property can be put down to the fact that carbon nanotubes are so thin, they can be thought of in the quantum sense as being 1D because their diameter is almost that of the amplitude of a photon or electron, and so makes it easy for heat to pass along it and be dissipated. Exactly how and why carbon nanotubes conduct electricity is a problem with a much more complex answer than just the presence of p orbitals. As mentioned above, carbon nanotubes are held together by a series of sp2 orbitals which form a series of tessellating hexagons, with an unhybridised p orbital located above and below each carbon atom, because electrons are clouds of probability the conducting electrons are above and below the line of carbon atoms at the same time. This is shown in the image on the right, but with the p orbitals represented only above the plane of the hexagons. As explained earlier, because each carbon atom p orbital is located nearby 3 other p orbitals, a double form is not formed and instead the p orbitals combine to form a cloud of delocalised electrons which is present above and below the carbon hexagonal structure. This cloud of delocalised electrons, shown in the second image on this page, spreads along the entire length of the nanotube and due to this, lots of interesting quantum effects can be observed, for example, the nanotubes have an excellent conductivity due to the probability of an electron being anywhere within the nanotube being the same, therefore resulting in absolutely no areas of increased resistance due to every area of apparently different concentration actually being everywhere else in the nanotube at once, this shall be elaborated on later. Now, different types of nanotube are different types of conductor. Due to their structure, armchair nanotubes are similar to metallic conductors, whereas all other nanotube structures (zig-zag and chiral) are

semi-conductors (of the moving electron variety). As explained earlier, we categorise nanotubes via a (n,m) unit, n is the units (as in the number of hexagons the line passes though) along, m is the units up or down, m and n can also be thought of as gradients. If n is different to m, it will semi-conduct, as in chiral or zig-zag, and if n=m, it will metallically conduct because it will be an armchair nanotube. Unfortunately, AS level (or even A2) physics cannot explain why carbon nanotubes conduct as well as they do, so we will have to delve into the dark and murky realm of quantum mechanics. Firstly, we must confront the Hall Effect. This is where, under a magnetic field and potential difference through a conductor, another potential difference will be created going perpendicular to the electrical current and magnetic field, as the diagram shows. This applies perfectly well to all 3D conductors, but does not apply to 2D conductors. As strange as it sounds, everything in the 3D world does not need to be 3D, and this is effectively the case with carbon nanotubes. To prove this, we must look at a sheet of graphene. First, we take the plane of the graphene to be x and y, and the plane perpendicular to the graphene to be z. Intuitively, we assume that electrons can move in any way, back, or forwards, left or right, up or down, and this is normally the case. However, in the quantum world of graphene, movement up and away from the plane of graphene is quantised, this means that electrons can only be in certain distances away from the graphene at any time. This would still allow them to move away from the graphene, but for the fact that the quantum levels are almost infinitely small. This allows us to effectively ignore the z axis and so leave us with just x and y – a 2 dimensional object. Remember, 2D conductors are not as rare as you might expect, all that is required is a 2DEG (2 Dimensional Electron Gas), for example, super-cooled helium produces a 2DEG and many transistors nowadays are made from 2DEG containing semi-conductors. Now, 2D conductors do not abide by the traditional Hall Effect, instead they experience the Quantum Hall Effect. In this, the magnitude of the voltage generated by the Hall Effect takes on quantum values – you can only get certain results which are divided by the Landau energies, as series of quantum energy levels which vary according to the strength of a magnetic field. In most systems which undergo the Quantum Hall Effect, the results create a rather

lovely looking fractal, as shown on the left with the x axis as the magnitude of the p.d. and the y axis as the strength of the magnetic field. This is a trend that almost every known substance abides to, as it is determined via electrons, whose properties are constant, rather than the properties of the material itself. True for everything, that is, except for one exception - Carbon Nanotubes or Graphene, in which they are different. Normally, in order to create the Quantum Hall Effect, the material in question needs to be at a very low temperature, usually the temperature at which Helium becomes a liquid. In Graphene and CNTs, the effect can be observed at much, much higher temperatures, even room temperature. Also, the quantum values produced are half that of the normal Quantum Hall effect, which isn’t meant to be possible. So, in order to find out what is happening, we need to use the Shubnikov-de Haas Effect. This determines the harmonic oscillation of a particle (in this case the electrons) under the influence of a magnetic field and at low temperatures, and therefore the mass of said particle. This investigation results in the surprising result that, in graphene and carbon nanotubes, electrons have no mass. So, we can now explain the excellent conductivity of graphene and carbon nanotubes using special relativity. Special Relativity states that as a body approaches the speed of light, space and time become compressed and with them it’s mass. As the mass is compressed, it increases in size and so makes it harder and harder to provide enough energy to increase the speed of the object in question. This is proven by the formula above, as the energy of the object (E) increases with acceleration; m also increases in size because c remains constant. Then, as the second formula shows, when more force (F) is applied to increase the acceleration (a), it is divided by an ever increasing mass and so the acceleration produced gets smaller and smaller. So, this prevents electrons in almost all substances from being able to move very fast because huge amounts of energy are needed to speed them up (in a vacuum, electrons can get very close to the speed of light due to no resistance, but that isn’t relevant). But, as is the case with Carbon Nanotubes and Graphene, the electrons have no mass (seeing as they have no mass, they can be called luxons). This would imply that the electrons can move at the speed of light in a material. Unfortunately, that would be pushing relativity a little too far and they are slowed down by the resistivity of the graphene/carbon nanotube to a more sensible, four-hundredth of the speed of light. This is approximately:

This means nothing unless we know the speed of electrons in most other materials. In order to work this out we need to use the Drift Speed Equation as shown below, where V is drift speed, I is the current in amps, Q is the number of electrons per cubic centimetre, e is the charge of an electron and R is the Radius of the sample.

For this, I shall use the example of copper. In reality, I and R don’t make a difference when you are comparing samples, so I will set them as 1 and 0.1. This gives us:

This gives us the answer:

From this, we can conclude that the electrons in graphene and carbon nanotubes move 32,000,000,000 times faster than those in pretty much any other material. We must note that the speed of flow of electricity is not the same as the above figures seeing as the charge is passed from electron to electron, rather than the actual movement of the electrons themselves. The speed of electricity in a copper cable is about 96% of the speed of light. In order to find the speed of electricity in a carbon nanotube or graphene sheet, we do not multiply this by 32,000,000,000 because that would mean electricity would go faster than the speed of light,

instead, the electricity in carbon nanotubes travels 32,000,000,000 times closer to the speed of light than electricity in copper. This means it travels at approximately 99.999999999875% of the speed of light. Seeing as copper is only slightly less conductive than silver, the best metallic conductor, it is easy to see why carbon nanotubes are much, much more conductive than anything else at room temperature. This property, combined with their extraordinarily low mass of the nanotubes makes them ideal electrical conductors. Another property which might make carbon nanotubes quite appealing for electrical cables is their 2D-ness. In effect, the prevents the electrons from escaping very far from the surface (not the end of the nanotube) even under very high voltages and so would make them very, very safe as electrical cables. If the insulation (which wouldn’t be needed) was split, electricity would not jump to anything near it. It would jump if they cable itself was broken, but in most circumstances the nanotube would remain safe. But, as mentioned before, this property relies on the nanotubes being practically perfect in every way. At the moment, we can manufacture perfect nanotubes, but this faces a few vital problems. Firstly, we cannot make very long carbon nanotubes and still keep them perfect, it is just too difficult. Secondly, the price of carbon nanotubes can reach up to $47,500 per kilogram, a price which does not yet justify their potential assets to electrical power supplies. Finally, methods of manufacturing pure nanotubes are limited by our current technology. Until other methods of nanotube production are developed, it will not be possible to manufacture long and pure carbon nanotubes on an industrial scale. A highly unusual use of the unusual properties of carbon nanotubes would be as inexpensive sources of lighting. This is due to Cherenkov radiation. This is a peculiar effect produced when electrons travelling near to the speed of light enter a medium, such as water, in which light travels slower than the electron. The electrons entering the water will polarize the atoms in the water molecules (seeing as the electrons

carry and negative charge). This means some of the electrons in the energy levels in each atom will be given enough energy to move up to a higher energy shell. However, electrons always want to occupy the lowest energy state and so jump back down to a lower shell (It must be noted that electrons only ‘jump’ up energy levels because those electron energies are quantised, they can only occupy discrete energy levels). As the electrons jump down a shell they need to lose this energy, so they emit a photon. This produces an effect similar to a sonic boom; the electrons out-pace the photons produced by other electron’s entry and so cause them to stack up. This results in a much more concentrated ‘wave’ or ‘cone’ of light in front of the electrons and this is seen as an intense blue light. The light is blue because photons are not particles, they are waves (as proved by Thomas Young’s Double-Slit experiment), as the photons ‘stack up’ the waves are compressed together. The photons produced by the electrons entry usually have a frequency which encompasses the visible light spectra. So, normally the light produced should be white (white light is produced when all the colours in the visible light spectrum mix together), but because they are compressed, we can fit more waves in any given space, this gives the light a higher frequency which effectively shifts the spectra produced towards the blue end of the electromagnetic spectrum, hence the blue light. This phenomenon is usually only observed in nuclear reactor cores, as this image on the previous page shows, and in certain particle physics experiments. Seeing as electrons in a carbon nanotube travel much faster than light in water, an open-ended nanotube cable in even a small amount of water could produce enormous quantities of photons which would become visible as blue light. Seeing as a very little amount of electricity is needed (this is only the case with carbon nanotubes, usually lots of energy is needed), this could act as a reliable and cheap light source. Of course, as usual, some people would object to such lights claiming they are dangerous because they have the word ‘radiation’ in them, but they are not really any more dangerous than a normal light bulb or lighting strip. Of course, nanotubes cannot yet be produced on such a scale to make such usage viable, but seeing as it can make use of imperfect nanotubes, once production on a large scale becomes possible, this light source will surely flourish.

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