superconductivity – Close Read

65 years of the BCS theory

Thanks to an arithmetic mistake, I thought 2022 was the 75th anniversary of the invention (or discovery?) of the BCS theory of superconductivity. It’s really the 65th anniversary, but since I’d worked myself up to write about it, I’m going to. 🤷🏽‍♂️ It also helps that the theory is a remarkable fact of nature that make sense of what is weirdly a macroscopic effect of microscopic causes.

There are several ways to classify superconductors – materials that conduct electricity with zero resistance under certain conditions. One of them is as conventional or unconventional. A superconductor is conventional if BCS theory can explain its superconductivity. ‘BCS’ are the initials of the theory’s three originators: John Bardeen, Leon Cooper and John Robert Schrieffer. BCS theory explains (conventional) superconductivity by explaining how the electrons in a material enter a collective superfluidic state.

At room temperature, the valence electrons flow around a material, being occasionally scattered by the grid of atomic nuclei or impurities. We know this scattering as electrical resistance.

An illustration of a lattice of sodium and chlorine atoms in a sodium chloride crystal. Credit: Benjah-bmm27, public domain

The electrons also steer clear of each other because of the repulsion of like charges (Coulomb repulsion).

When the material is cooled below a critical temperature, however, vibrations in the atomic lattice encourage the electrons to become paired. This may defy what we learnt in high school – that like charges repel – but the picture is a little more complicated, and it might make more sense if we adopt the lens of energy instead.

A system will favour a state in which it has lower energy than one in which it has more energy. When two carriers of like charges, like two electrons, approach each other, they repel each other more strongly the closer they get. This repulsion increases the system’s energy (in some form, typically kinetic energy).

In some materials, conditions can arise in which two electrons can pair up – become correlated with each other – across relatively long distances, without coming close to each other, rendering the Coulomb repulsion irrelevant. This correlation happens as a result of the electrons’ effect on their surroundings. As an electron moves through the lattice of positively charged atomic nuclei, it exerts an attractive force on the nuclei, which respond by tending towards the electron. This increases the amount of positive potential near the electron, which attracts another electron nearby to move closer as well. If the two electrons have opposite spins, they become correlated as a Cooper pair, kept that way by the attractive potential imposed by the atomic lattice.

Leon Cooper explained that neither the source of this potential nor its strength matter – as long as it is attractive, and the other conditions hold, the electrons will team up into Cooper pairs. In terms of the system’s energy, the paired state is said to be energetically favourable, meaning that the system as a whole has a lower energy than if the electrons were unpaired below the critical temperature.

Keeping the material cooled to below this critical temperature is important: while the paired state is energetically favourable, the state itself arises only below the critical temperature. Above the critical temperature, the electrons can’t access this state altogether because they have too much kinetic energy. (The temperature of a material is the average kinetic energy of its constituent particles.)

Cooper’s theory of the electron pairs fit into John Bardeen’s theory, which sought to explain changes in the energy states of a material as it goes from being non-superconducting to superconducting. Cooper had also described the formation of electron pairs one at a time, so to speak, and John Robert Schrieffer’s contribution was to work out a mathematical way to explain the formation of millions of Cooper pairs and their behaviour in the material.

The trio consequently published its now-famous paper, ‘Microscopic Theory of Superconductivity’, on April 1, 1957.

(I typo-ed this as 1947 on a calculator, which spit out the number of years since to be 75. 😑 One could have also expected me to remember that this is India’s 75th year of independence and that BCS theory was created a decade after 1947, but the independence hasn’t been registering these days.)

Anyway, electrons by themselves belong to a particle class called fermions. The other known class is that of the bosons. The difference between fermions and bosons is that the former obey Pauli’s exclusion principle while the latter do not. The exclusion principle forbids two fermions in the same system – like a metal – from simultaneously occupying the same quantum state. This means the electrons in a metal have a hierarchy of energies in normal conditions.

However, a Cooper pair, while composed of two electrons, is a boson, and doesn’t obey Pauli’s exclusion principle. The Cooper pairs of the material can all occupy the same state – i.e. the state with the lowest energy, more popularly called the ground state. This condensate of Cooper pairs behaves like a superfluid: practically flowing around the material, over, under and through the atomic lattice. Even when a Cooper pair is scattered off by an atomic nucleus or an impurity in the material, the condensate doesn’t break formation because all the other Cooper pairs continue their flow, and eventually also reintegrate the scattered Cooper pair. This flow is what we understand as electrical superconductivity.

“BCS theory was the first microscopic theory of superconductivity,” per Wikipedia. But since its advent, especially since the late 1970s, researchers have identified several superconducting materials, and behaviours, that neither BCS theory nor its extensions have been able to explain.

When a material transitions into its superconducting state, it exhibits four changes. Observing these changes is how researchers confirm that the material is now superconducting. (In no particular order:) First, the material loses all electric resistance. Second, any magnetic field inside the material’s bulk is pushed to the surface. Third, the electronic specific heat increases as the material is cooled before dropping abruptly at the critical temperature. Fourth, just as the energetically favourable state appears, some other possible states disappear.

Physicists experimentally observed the fourth change only in January this year – based on the transition of a material called Bi-2212 (bismuth strontium calcium copper oxide, a.k.a. BSCCO, a.k.a. bisko). Bi-2212 is, however, an unconventional superconductor. BCS theory can’t explain its superconducting transition, which, among other things, happens at a higher temperature than is associated with conventional materials.

In the January 2022 study, physicists also reported that Bi-2212 transitions to its superconducting state in two steps: Cooper pairs form at 120 K – related to the fourth sign of superconductivity – while the first sign appears at around 77 K. To compare, elemental rhenium, a conventional superconductor, becomes superconducting in a single step at 2.4 K.

A cogent explanation of the nature of high-temperature superconductivity in cuprate superconductors like Bi-2212 is one of the most important open problems in condensed-matter physics today. It is why we still await further updates on the IISc team’s room-temperature superconductivity claim.

Physicists observe long-expected helium superfluid phase

Physicists have reported that they have finally observed helium 3 existing in a long-predicted type of superfluid, called the ß phase.

This is an important discovery, if it’s borne out, for reasons that partly have to do with its isotope, helium 4. Helium 4 is a fascinating substance because the helium 4 atom is a boson – a type of particle whose quantum properties and behaviour are explained by rules called Bose-Einstein statistics. Helium 3, on the other hand, is a fermion, and fermions are governed by Fermi-Dirac statistics.

Bosons and fermions have one important difference: bosons are allowed to disobey Pauli’s exclusion principle, and by doing so they can assume exotic states of matter rarely found in nature, with many unusual properties.

For example, when helium 4 is cooled below a certain temperature, it becomes a superfluid: a liquid that flows without experiencing any resistance. If you poured a superfluid into a bowl, it will be able to climb the walls of the bowl and spill out without any help. But helium 3 atoms are fermions, so they are bound to obey Pauli’s exclusion principle and can’t become a superfluid.

At least this is what physicists believed for a long time, until the early 1970s, when two independent groups of physicists found – one in theory and the other in experiments – that helium 3 could indeed enter a superfluid phase, but at a temperature 1,000-times lower than the critical temperature of helium 4. The theory group, led by Anthony Leggett at the University of Sussex, had in fact made a significant discovery.

Today, we know that the flow of superfluid helium 4 is analogous to the flow of electrons in a conventional superconductor, which also move around as if they face no resistance from the surrounding atoms. Leggett and co. found that the theory used to explain these superconductors could also be used to explain helium 3 superfluidity. This theory is called Bardeen-Cooper-Schrieffer (BCS) theory, and the materials whose superconductivity it can explain are called BCS superconductors.

Electrons are fermions and cannot ‘super-flow’. But in a BCS superconductor that has been cooled below its critical temperature, some forces in the material cause the electrons to overcome their mutual repulsion (“like charges repel”) and pair up. These electron pairs, while being made of two individual fermions, actually behave like bosons. Similarly, Leggett and co. found that helium 3 atoms could pair up to form a bosonic composite and super-flow.

Over many years, physicists used what they had learnt through these discoveries to expand our understanding of this substance. They found, among other things, that superfluid helium 3 can exist in many phases. The superfluidity would persist in each phase but with different characteristics.

Superfluid helium 3 was first thought to have two phases, called A and B. The temperature-pressure plot below clearly shows the conditions in which each phase emerges.

Credit: E.V. Thuneberg, *Encyclopedia of Condensed Matter Physics*, 2005

When physicists subjected superfluid helium 3 in its A phase to a strong magnetic field, they found another phase that they called A1, whose atom-pairs had different spin characteristics.

In 2015, a group of researchers led by Vladimir Dmitriev, at the P.L. Kapitza Institute for Physical Problems, Moscow, discovered a fourth phase, which they called the polar, or P, phase. Here, they confined helium 3 in a nematic aerogel and exposed the setup to a low magnetic field. Aerogels are ultra-light materials that are extremely porous; nematic means its molecules were arranged in parallel. The aeorogel in the Dmitriev and co. experiment was 98% porous, and whose pores “were much longer than they were wide” (source). That is, the team had found that the shape of the container in which helium 3 was confined also affected the phase of its superfluidity.

In August 2021 (preprint), the same team reported that it had observed a long-expected-to-exist fifth phase called the ß phase.

They reported that they took the setup they used to force superfluid helium 3 into the P phase, but this time exposed it to a high magnetic field. According to their paper, they found that while the superfluid earlier moved into the P phase through a single transition, as the temperature was brought down, this time it did so in two steps. First, it moved into an intermediate phase and then into the P phase. The intermediate is the ß phase.

(If this sounds simple, it wasn’t: the discoveries were each limited by the availability of specially designed instruments capable of picking up on very small-scale changes unavailable to the naked eye. Second, researchers also have had to know in advance what changes they should expect to happen in each phase, and this requires the corresponding theoretical clarity.)

The temperatures at which the phase transition between the two polar phases differ as the magnetic field strength increases. The gap between the two phases is bridged by the ß phase. Source: https://doi.org/10.1103/PhysRevLett.127.265301

I have considerably simplified helium 3’s transition from the ‘normal’ to the superfluid phase in this post. To describe it accurately, physicists use advanced mathematics and associated concepts in high-energy physics. One such concept is symmetry-breaking. When a helium 3 atom pairs up with another to form a bosonic composite, the pair must have a ‘new’ spin and orbital momentum; and their combined wavefunction will also have a ‘new’ phase. All these steps break different symmetries.

There’s a theory called Grand Unification in particle physics, in which physicists expect that at higher and higher energies, the three fundamental forces that affect subatomic particles – the strong-nuclear, the weak-nuclear and the electromagnetic – will combine into a single unified force. Physicists have found in their mathematical calculations that the symmetries that will break in this super-transition resemble those broken by helium 3 during its transition to superfluidity.

Understanding helium 3 can also be rewarding for insights into the insides of neutron stars. Neutron stars are extreme objects – surpassed in their extremeness only by black holes, which exist at the point where known theories of gravitational physics collapse into meaninglessness. A few lakh years after a neutron star is born, it is expected to have cooled sufficiently for its interiors to be composed of superfluids and superconductors.

We may never be able to directly observe these materials in their natural environment. But by studying helium 3’s various phases of superfluidity, we can get a sense of what a neutron star’s innards could be like, and whether their interactions among themselves and the neutrons on the surface could explain these objects’ still-mysterious characteristics.

Featured image: The liquid helium is in the superfluid phase. A thin invisible film creeps up the inside wall of the cup and down on the outside. A drop forms. It will fall off into the liquid helium below. This will repeat until the cup is empty – provided the liquid remains superfluid. Caption and credit: Alfred Leitner, public domain.

The imperfection of strontium titanate

When you squeeze some crystals, you distort their lattice of atoms just enough to separate a pair of charged particles and that in turn gives rise to a voltage. Such materials are called piezoelectric crystals. Not all crystals are piezoelectric because the property depends on what the arrangement of atoms in the lattice is.

For example, the atoms of strontium, titanium and oxygen are arranged in a cubic structure to form strontium titanate (SrTiO3) such that each molecule displays a mirror symmetry through its centre. That is, if you placed a mirror passing through the molecule’s centre, the object plus its reflection would show the molecule as it actually is. Such molecules are said to be centrosymmetric, and centrosymmetric crystals aren’t piezoelectric.

In fact, strontium titanate isn’t ferroelectric or pyroelectric either – an external electric field can’t reverse their polarisation nor do they produce a voltage when they’re heated or cooled – for the same reason. Its crystal lattice is just too symmetrical.

The strontium titanate lattice. Oxygen atoms are red, titanium cations are blue and strontium cations are green.

However, scientists haven’t been deterred by this limitation (such as it is) because its perfect symmetry indicates that messing with the symmetry can introduce new properties in the material. There are also natural limits to the lattice itself. A cut and polished diamond looks beautiful because, at its surface, the crystal lattice ends and the air begins – arbitrarily stopping the repetitive pattern of carbon atoms.

An infinite diamond that occupies all points in the universe might look good on paper but it wouldn’t be nearly as resplendent because only the symmetry-breaking at the surface allows light to enter the crystal and bounce around. Similarly, centrosymmetric strontium titanate might be a natural wonder, so to speak, but the centrosymmetry also keeps it from being useful (despite its various unusual properties; e.g. it was the first insulator found to be a superconductor at low temperatures, in 1967).

Tausonite, a naturally occurring mineral form of strontium titanate. Credit: Materialscientist/Wikimedia Commons, CC BY-SA 3.0

So does strontium titanate exhibit pyro- or piezoelectricity on its surface? Surprisingly, while this seems like a fairly straightforward question to ask, it hasn’t been straightforward to answer.

A part of the problem is the definition of a surface. Obviously, the surface of any object refers to the object’s topmost or outermost layer. But when you’re talking about, say, a small electric current originating from the material, it’s difficult to imagine how you could check if the current originated from the bulk of the material or just the surface.

Researchers from the US, Denmark and Israel recently reported resolving this problem using concepts from thermodynamics 101. If the surface of strontium titanate is pyroelectric, the presence of electric currents should co-exist with heat. So if a bit of heat is applied and taken away, the material should begin cooling (or thermalising) and the electric currents should also dissipate. The faster the material cools, the faster the currents dissipate, and the faster the currents dissipate, the lower the depth to which the material is pyroelectric.

In effect, the researchers induced pyroelectricity and then tracked how quickly it vanished to infer how deeply inside the material it existed.

Both the bulk and the surface are composed of the same atoms, but the atomic lattice on the surface also has a bit of surface tension. Materials scientists have already calculated how deeply this tension penetrates the surface of strontium titanate, so the question was also whether the pyroelectric behaviour was contained in this region or went beyond, into the rest of the bulk.

The team sandwiched a slab of strontium titanate between two electrodes, at room temperature. At the crystal-electrode interface, which is a meeting of two surfaces, opposing charged particles on either side gather and neutralise themselves. But when an infrared laser is shined on the ensemble (as shown above), the surface of strontium titanate heats up and develops a voltage, which in turn draws the charges at its surface away from the interface. The charges in the electrode are then left without a partner so they flow through a wire connected to the other electrode and create a current.

The laser is turned off and the strontium titanate’s surface begins to cool. Its voltage drops and allows the charged particles to move away from each other, and some of them move towards the surface to once again neutralise oppositely charged particles from the other side. This process stops the current. So measuring how quickly the current drops off gives away how quickly the voltage vanishes, which gives away how much of the material’s volume developed a voltage due to the pyroelectric effect.

The penetration depth the group measured was in line with the calculations based on surface tension: about 1.2 nm. To be sure the effect didn’t involve the bulk, the researchers repeated the experiment with a thin layer of silica (the major component of sand) on top of the strontium titanate surface, and there was no electric current when the laser was on or off.

In fact, according to a report in Nature, the team also took various precautions to ensure any electric effects originated only from the surface, and due to effects intrinsic to the material itself.

… they checked that the direction of the heat-induced current does not depend on the orientation of the crystal, ruling out a bulk effect; and that the local heating produced by the laser is very small…, which means that the strain gradients induced by thermal expansion are insignificant. Other experiments and data analysis were carried out to exclude the possibility that the induced current is due to molecules … adsorbed to the surface, charges trapped by lattice defects, excitation of free electrons induced by light, or the thermoelectric Seebeck effect (which generates currents in semiconductors that contain temperature gradients).

Now we know strontium titanate is pyroelectric, and piezoelectric, on its surface at room temperature – but this is not all we know. During their experiments (with different samples of the crystal), the researchers spotted something odd:

The pyroelectric coefficient – a measure of the strength of the material’s pyroelectricity – was constant between 193 K and 225 K (–80.15º C to –48.15º C) but dropped sharply above 225 K and vanished above 380 K. The researchers note in their paper, published on September 18, that others have previously reported that the strontium titanate lattice near the surface changes from a cubic to a tetragonal structure at around 150 K, and that a similar transformation could be happening at 225 K.

In other words, the surface pyroelectric effect wasn’t just producing a voltage but could in fact be altering the relative arrangement of atoms itself. What the precise mechanism of action could be we don’t know – nor any other features that might arise in the material as a result. The researchers hope future studies can resolve these questions.

The science in Netflix’s ‘Spectral’

I watched Spectral, the movie that released on Netflix on December 9, 2016, after Universal Studios got cold feet about releasing it on the big screen – the same place where a previous offering, Warcraft, had been gutted. Spectral is sci-fi and has a few great moments but mostly it’s bland and begging for some tabasco. The premise: an elite group of American soldiers deployed in Moldova come upon some belligerent ghost-like creatures in a city they’re fighting in. They’ve no clue how to stop them, so they fly in an engineer to consult from DARPA, the same guy who built the goggles that detected the creatures in the first place. Together, they do things. Now, I’d like to talk about the science in the film and not the plot itself, though the former feeds the latter.

SPOILERS AHEAD

A scene from the film 'Spectral' (2016). Source: Netflix — A scene from the film ‘Spectral’ (2016). Source: Netflix

Towards the middle of the movie, the engineer realises that the ghost-like creatures have the same limitations as – wait for it – a Bose-Einstein condensate (BEC). They can pass through walls but not ceramic or heavy metal (not the music), they rapidly freeze objects in their path, and conventional weapons, typically projectiles of some kind, can’t stop them. Frankly, it’s fabulous that Ian Fried, the film’s writer, thought to use creatures made of BECs as villains.

A BEC is an exotic state of matter in which a group of ultra-cold particles condense into a superfluid (i.e., it flows without viscosity). Once a BEC forms, a subsection of a BEC can’t be removed from it without breaking the whole BEC state down. You’d think this makes the BEC especially fragile – because it’s susceptible to so many ‘liabilities’ – but it’s the exact opposite. In a BEC, the energy required to ‘kick’ a single particle out of its special state is equal to the energy that’s required to ‘kick’ all the particles out, making BECs as a whole that much more durable.

This property is apparently beneficial for the creatures of Spectral, and that’s where the similarity ends because BECs have other properties that are inimical to the portrayal of the creatures. Two immediately came to mind: first, BECs are attainable only at ultra-cold temperatures; and second, the creatures can’t be seen by the naked eye but are revealed by UV light. There’s a third and relevant property but which we’ll come to later: that BECs have to be composed of bosons or bosonic particles.

It’s not clear why Spectral‘s creatures are visible only when exposed to light of a certain kind. Clyne, the DARPA engineer, says in a scene, “If I can turn it inside out, by reversing the polarity of some of the components, I might be able to turn it from a camera [that, he earlier says, is one that “projects the right wavelength of UV light”] into a searchlight. We’ll [then] be able to see them with our own eyes.” However, the documented ability of BECs to slow down light to a great extent (5.7-million times more than lead can, in certain conditions) should make them appear extremely opaque. More specifically, while a BEC can be created that is transparent to a very narrow range of frequencies of electromagnetic radiation, it will stonewall all frequencies outside of this range on the flipside. That the BECs in Spectral are opaque to a single frequency and transparent to all others is weird.

Obviating the need for special filters or torches to be able to see the creatures simplifies Spectral by removing one entire layer of complexity. However, it would remove the need for the DARPA engineer also, who comes up with the hyperspectral camera and, its inside-out version, the “right wavelength of UV” searchlight. Additionally, the complexity serves another purpose. Ahead of the climax, Clyne builds an energy-discharging gun whose plasma-bullets of heat can rip through the BECs (fair enough). This tech is also slightly futuristic. If the sci-fi/futurism of the rest of Spectral leading up to that moment (when he invents the gun) was absent, then the second-half of the movie would’ve become way more sci-fi than the first-half, effectively leaving Spectral split between two genres: sci-fi and wtf. Thus the need for the “right wavelength of UV” condition?

Now, to the third property. Not all particles can be used to make BECs. Its two predictors, Satyendra Nath Bose and Albert Einstein, were working (on paper) with kinds of particles since called bosons. In nature, bosons are force-carriers, acting against matter-maker particles called fermions. A more technical distinction between them is that the behaviour of bosons is explained using Bose-Einstein statistics while the behaviour of fermions is explained using Fermi-Dirac statistics. And only Bose-Einstein statistics predicts the existence of states of matter called condensates, not Femi-Dirac statistics.

(Aside: Clyne, when explaining what BECs are in Spectral, says its predictors are “Nath Bose and Albert Einstein”. Both ‘Nath’ and ‘Bose’ are surnames in India, so “Nath Bose” is both anyone and no one at all. Ugh. Another thing is I’ve never heard anyone refer to S.N. Bose as “Nath Bose”, only ‘Satyendranath Bose’ or, simply, ‘Satyen Bose’. Why do Clyne/Fried stick to “Nath Bose”? Was “Satyendra” too hard to pronounce?)

All particles constitute a certain amount of energy, which under some circumstances can increase or decrease. However, the increments of energy in which this happens are well-defined and fixed (hence the ‘quantum’ of quantum mechanics). So, for an oversimplified example, a particle can be said to occupy energy levels constituting 2, 4 or 6 units but never of 1, 2.5 or 3 units. Now, when a very-low-density collection of bosons is cooled to an ultra-cold temperature (a few hundredths of kelvins or cooler), the bosons increasingly prefer occupying fewer and fewer energy levels. At one point, they will all occupy a single and common level – flouting a fundamental rule that there’s a maximum limit for the number of particles that can be in the same level at once. (In technical parlance, the wavefunctions of all the bosons will merge.)

When this condition is achieved, a BEC will have been formed. And in this condition, even if a new boson is added to the condensate, it will be forced into occupying the same level as every other boson in the condensate. This condition is also out of limits for all fermions – except in very special circumstances, and circumstances whose exceptionalism perhaps makes way for Spectral‘s more fantastic condensate-creatures. We known one such as superconductivity.

In a superconducting material, electrons flow without any resistance whatsoever at very low temperatures. The most widely applied theory of superconductivity interprets this flow as being that of a superfluid, and the ‘sea’ of electrons flowing as such to be a BEC. However, electrons are fermions. To overcome this barrier, Leon Cooper proposed in 1956 that the electrons didn’t form a condensate straight away but that there was an intervening state called a Cooper pair. A Cooper pair is a pair of electrons that had become bound, overcoming their like-charges repulsion because of the vibration of atoms of the superconducting metal surrounding them. The electrons in a Cooper pair also can’t easily quit their embrace because, once they become bound, the total energy they constitute as a pair is lower than the energy that would be destabilising in any other circumstances.

Could Spectral‘s creatures have represented such superconducting states of matter? It’s definitely science fiction because it’s not too far beyond the bounds of what we know about BEC today (at least in terms of a concept). And in being science fiction, Spectral assumes the liberty to make certain leaps of reasoning – one being, for example, how a BEC-creature is able to ram against an M1 Abrams and still not dissipate. Or how a BEC-creature is able to sit on an electric transformer without blowing up. I get that these in fact are the sort of liberties a sci-fi script is indeed allowed to take, so there’s little point harping on them. However, that Clyne figured the creatures ought to be BECs prompted way more disbelief than anything else because BECs are in the here and the now – and they haven’t been known to behave anything like the creatures in Spectral do.

For some, this information might even help decide if a movie is sci-fi or fantasy. To me, it’s sci-fi.

SPOILERS END

On the more imaginative side of things, Spectral also dwells for a bit on how these creatures might have been created in the first place and how they’re conscious. Any answers to these questions, I’m pretty sure, would be closer to fantasy than to sci-fi. For example, I wonder how the computing capabilities of a very large neural network seen at the end of the movie (not a spoiler, trust me) were available to the creatures wirelessly, or where the power source was that the soldiers were actually after. Spectral does try to skip the whys and hows by having Clyne declare, “I guess science doesn’t have the answer to everything” – but you’re just going “No shit, Sherlock.”

His character is, as this Verge review puts it, exemplarily shallow while the movie never suggests before the climax that science might indeed have all the answers. In fact, the movie as such, throughout its 108 minutes, wasn’t that great for me; it doesn’t ever live up to its billing as a “supernatural Black Hawk Down“. You think about BHD and you remember it being so emotional – Spectral has none of that. It was just obviously more fun to think about the implications of its antagonists being modelled after a phenomenon I’ve often read/written about but never thought about that way.

Superconductivity: From Feshbach to Fermi

(This post is continued from this one.)

After a bit of searching on Wikipedia, I found that the fundamental philosophical underpinnings of superconductivity were to be found in a statistical concept called the Feshbach resonance. If I had to teach superconductivity to those who only knew of the phenomenon superfluously, that’s where I’d begin. So.

Imagine a group of students who have gathered in a room to study together for a paper the next day. Usually, there is that one guy among them who will be hell-bent on gossiping more than studying, affecting the performance of the rest of the group. In fact, given sufficient time, the entire group’s interest will gradually shift in the direction of the gossip and away from its syllabus. The way to get the entire group back on track is to introduce a Feshbach resonance: cut the bond between the group’s interest and the entity causing the disruption. If done properly, the group will turn coherent in its interest and to focusing on studying for the paper.

In multi-body systems, such as a conductor harboring electrons, the presence of a Feshbach resonance renders an internal degree of freedom independent of those coordinates “along” which dissociation is most like to occur. And in a superconductor, a Feshbach resonance results in each electron pairing up with another (i.e., electron-vibrations are quelled by eliminating thermal excitation) owing to both being influenced by an attractive potential that arises out of the electron’s interaction with the vibrating lattice.

Feshbach resonance & BCS theory

For particulate considerations, the lattice-vibrations are quantized in the form of hypothetical particles called phonons. As for why the Feshbach resonance must occur the way it does in a superconductor: that is the conclusion, rather implication, of the BCS theory formulated in 1957 by John Bardeen, Leon Neil Cooper, and John Robert Schrieffer.

The BCS theory essentially treats electrons like rebellious, teenage kids (I must be getting old). As negatively charged electrons pass through the crystal lattice, they draw the positively charged nuclei toward themselves, creating an increase in the positive charge density in their vicinity that attracts more electrons in turn. The resulting electrostatic pull is stronger near nuclei and very weak at larger distances. The BCS theory states that two electrons that would otherwise repel each other will pair up in the face of such a unifying electrostatic potential, howsoever weak it is.

This is something like rebellious teens who, in the face of a common enemy, will unite with each other no matter what the differences between them earlier were.

Since electrons are fermions, they bow down to Pauli’s exclusion principle, which states that no two fermions may occupy the same quantum state. As each quantum state is defined by some specific combination of state variables called quantum numbers, at least one quantum number must differ between the two co-paired electrons.

prof_wolfgang_pauli — Prof. Wolfgang Pauli (1900-1958)

In the case of superconductors, this is particle spin: the electrons in the member-pair will have opposite spins. Further, once such unions have been achieved between different pairs of electrons, each pair becomes indistinguishable from the other, even in principle. Imagine: they are all electron-pairs with two opposing spins but with the same values for all other quantum numbers. Each pair, called a Cooper pair, is just the same as the next!

Bose-Einstein condensates

This unification results in the sea of electrons displaying many properties normally associated with Bose-Einstein condensates (BECs). In a BEC, the particles that attain the state of indistinguishability are bosons (particles with integer spin), not fermions (particles with half-integer spin). The phenomenon occurs at temperatures close to absolute zero and in the presence of an external confining potential, such as an electric field.

Since bosons don’t follow Pauli’s exclusion principle, a major fraction of the indistinguishable entities in the condensate may and do occupy the same quantum state. This causes quantum mechanical effects to become apparent on a macroscopic scale.

By extension, the formulation and conclusions of the BCS theory, alongside its success in supporting associated phenomena, imply that superconductivity may be a quantum phenomenon manifesting in a macroscopic scale.

Note: If even one Cooper pair is “broken”, the superconducting state will be lost as the passage of electric current will be disrupted, and the condensate will dissolve into individual electrons, which means the energy required to break one Cooper pair is the same as the energy required to break the composition of the condensate. So thermal vibrations of the crystal lattice, usually weak, become insufficient to interrupt the flow of Cooper pairs, which is the flow of electrons.

The Meissner effect

In this context, the Meissner effect is simply an extrapolation of Lenz’s law but with zero electrical resistance.

Lenz’s law states that the electromotive force (EMF) because of a current in a conductor acts in a direction that always resists a change in the magnetic flux that causes the EMF. In the absence of resistance, the magnetic fields due to electric currents at the surface of a superconductor cancel all magnetic fields inside the bulk of the material, effectively pushing magnetic field lines of an external magnetic potential outward. However, the Meissner effect manifests only when the externally applied field is weaker than a certain critical threshold: if it is stronger, then the superconductor returns to its conducting state.

Now, there are a class of materials called Type II superconductors – as opposed to the Type I class described earlier – that only push some of the magnetic field outward, the rest remaining conserved inside the material in filaments while being surrounded by supercurrents. This state is called the vortex state, and its occurrence means the material can withstand much stronger magnetic fields and continue to remain superconducting while also exhibiting the hybrid Meissner effect.

Temperature & superconductivity

There are also a host of other effects that only superconductors can exhibit, including Cooper-pair tunneling, flux quantization, and the isotope effect, and it was by studying them that a strong relationship was observed between temperature and superconductivity in various forms.

Bardeen_Cooper_Schrieffer — (L to R) John Bardeen, Leon Cooper, and John Schrieffer

In fact, Bardeen, Cooper, and Schrieffer hit upon their eponymous theory after observing a band gap in the electronic spectra of superconductors. The electrons in any conductor can exist at specific energies, each well-defined. Electrons above a certain energy, usually in the valence band, become free to pass through the entire material instead of staying in motion around the nuclei, and are responsible for conduction.

The trio observed that upon cooling the material to closer and closer to absolute zero, there was a curious gap in the energies at which electrons could be found in the material at a particular temperature. This meant that, at that temperature, the electrons were jumping from existing at one energy to existing at some other lower energy. The observation indicated that some form of condensation was occurring. However, a BEC was ruled out because of Pauli’s exclusion principle. At the same time, a BEC-like state had to have been achieved by the electrons.

This temperature is called the transition temperature, and is the temperature below which a conductor transitions into its superconducting state, and Cooper pairs form, leading to the drop in the energy of each electron. Also, the differences in various properties of the material on either side of this threshold are also attributed to this temperature, including an important notion called the Fermi energy: it is the potential energy that any system possesses when all its thermal energy has been removed from it. This is a significant idea because it defines both the kind and amount of energy that a superconductor has to offer for an externally applied electric current.

enrico_fermi — Enrico Fermi, along with Paul Dirac, defined the Fermi-Dirac statistics that governs the behavior all identical particles that obey Pauli’s exclusion principle (i.e., fermions). Fermi level and Fermi energy are concepts named for him; however, as long as we’re discussing eponymy, Fermilab overshadows them all.

In simple terms, the density of various energy states of the electrons at the Fermi energy of a given material dictates the “breadth” of the band gap if the electron-phonon interaction energy were to be held fixed at some value: a direct proportionality. Thus, the value of the energy gap at absolute zero should be a fixed multiple of the value of the energy gap at the superconducting transition temperature (the multiplication factor was found to be 3.5 universally, irrespective of the material).

Similarly, because of the suppression of thermal excitation (because of the low temperature), the heat capacity of the material reduces drastically at low temperatures, and vanishes below the transition temperature. However, just before hitting zero at the threshold, the heat capacity balloons up to beyond its original value, and then pops. It was found that the ballooned value was always 2.5 times the material’s normal heat capacity value… again, universally, irrespective of the material!

The temperature-dependence of superconductors gains further importance with respect to applications and industrial deployment in the context of its possible occurring at higher temperatures. The low temperatures currently necessary eliminate thermal excitations, in the form of vibrations, of nuclei and almost entirely counter the possibility of electrons, or Cooper pairs, colliding into them.The low temperatures also assist in the flow of Cooper pairs as a superfluid apart from allowing for the energy of the superfluid being higher than the phononic energy of the lattice.

However, to achieve all these states in order to turn a conductor into a superconductor at a higher temperature, a more definitive theory of superconductivity is required. One that allows for the conception of superconductivity that requires only certain internal conditions to prevail while the ambient temperature soars. The 1986-discovery of high-temperature superconductors in ceramics by Bednorz and Muller was the turning point. It started to displace the BCS theory which, physicists realized, doesn’t contain the necessary mechanisms for superconductivity to manifest itself in ceramics – insulators at room temperature – at temperatures as high as 125 K.

A firmer description of superconductivity, therefore, still remains elusive. Its construction should not only pave the for one of the few phenomena that hardly appears in nature and natural processes to be fully understood, but also for its substitution against standard conductors that are responsible for lossy transmission and other such undesirable effects. After all, superconductors are the creation of humankind, and only by its hand while they ever be fully worked.

Stages of superconductivity: Researchers’ insight on ‘pseudogap’ an important advance (phys.org)

Getting started on superconductivity

After the hoopla surrounding and attention on particle physics subsided, I realized that I’d been riding a speeding wagon all the time. All I’d done is used the lead-up to (the search for the Higgs boson) and the climax itself to teach myself something. Now, it’s left me really excited! Learning about particle physics, I’ve come to understand, is not a single-track course: all the way from making theoretical predictions to having them experimentally verified, particle physics is an amalgamation of far-reaching advancements in a host of other subjects.

One such is superconductivity. Philosophically, it’s a state of existence so far removed from its naturally occurring one that it’s a veritable “freak”. It is common knowledge that everything that’s naturally occurring is equipped to resist change that energizes, to return whenever possible to a state of lower energy. Symmetry and surface tension are great examples of this tendency. Superconductivity, on the other hand, is the desistence of a system to resist the passage of an electric current through it. As a phenomenon that as yet doesn’t manifest in naturally occurring substances, I can’t really opine on its phenomenological “naturalness”.

In particle physics, superconductivity plays a significant role in building powerful particle accelerators. In the presence of a magnetic field, a charged particle moves in a curved trajectory through it because of the Lorentz force acting on it; this fact is used to guide the protons in the Large Hadron Collider (LHC) at CERN through a ring 27 km long. Because moving in a curved path involves acceleration, each “swing” around the ring happens faster than the last, eventually resulting in the particle traveling at close to the speed of light.

superconducting_quardupole_electromagnetic_LHC — A set of superconducting quadrupole-electromagnets installed at the LHC with the cryogenic cooling system visible in the background

In order to generate these extremely powerful magnetic fields – powerful because of the minuteness of each charge and the velocity required to be achieved – superconducting magnets are used that generate fields of the order of 20 T (to compare: the earth’s magnetic field is 25-60 μT, or close to 500,000-times weaker)! Furthermore, the direction of the magnetic field is also switched accordingly to achieve circular motion, to keep the particle from being swung off into the inner wall of the collider at any point!

To understand the role the phenomenon of superconductivity plays in building these magnets, let’s understand how electromagnets work. In a standard iron-core electromagnet, insulated wire is wound around an iron cylinder, and when a current is passed through the wire, a magnetic field is generated around the cross-section of the wire. Because of the coiling, though, the centre of the magnetic field passes through the axis of the cylinder, whose magnetic permeability magnifies the field by a factor of thousands, itself becoming magnetic.

When the current is turned off, the magnetic field instantaneously disappears. When the number of coils is increased, the strength of the magnetic field increases. When the strength of the current is increased, the strength of the magnetic field increases. However, beyond a point, the heat dissipated due to the wire’s electric resistance reduces the amount of current flowing through it, consequently resulting in a weakening of the core’s magnetic field over time.

It is Ohm’s law that establishes proportionality between voltage (V) and electric current (I), calling the proportionality-constant the material’s electrical resistance: R = V/I. To overcome heating due to resistance, resistance itself must be brought down to zero. According to Ohm’s law, this can be done either by passing a ridiculously large current through the wire or bringing the voltage across its ends down to zero. However, performing either of these changes on conventional conductors is impossible: how does one quickly pass a large volume of water through any pipe across which the pressure difference is miniscule?!

The solution to this unique problem, therefore, lay in a new class of materials that humankind had to prepare, a class of materials that could “instigate” an alternate form of electrical conduction such that an electrical current could pass through it in the absence of a voltage difference. In other words, the material should be able to carry large amounts of current without offering up any resistance to it. This class of materials came to be known as superconductors – after Heike Kamerlingh Onnes discovered the phenomenon in 1911.

In a conducting material, the electrons that essentially effect the flow of electric current could be thought of as a charged fluid flowing through and around an ionic 3D grid, an arrangement of positively charged nuclei that all together make up the crystal lattice. When a voltage-drop is established, the fluid begins to get excited and moves around, an action called conducting. However, the electrons constantly collide with the ions. The ions, then, absorb some of the energy of the current, start vibrating, and gradually dissipate it as heat. This manifests as the resistance. In a superconductor, however, the fluid exists as a superfluid, and flows such that the electrons never collide into the ions.

In (a classical understanding of) the superfluid state, each electron repels every other electron because of their charge likeness, and attracts the positively charged nuclei. As a result, the nucleus moves very slightly toward the electron, causing an equally slight distortion of the crystal lattice. Because of the newly increased positive-charge density in the vicinity, some more electrons are attracted by the nucleus.

This attraction, which, across the entirety of the lattice, can cause a long-range but weak “draw” of electrons, results in pairs of electrons overcoming their mutual hatred of each other and tending toward one nucleus (or the resultant charge-centre of some nuclei). Effectively, this is a pairing of electrons whose total energy was shown by Leon Cooper in 1956 to be lesser than the energy of the most energetic electron if it had existed unpaired in the material. Subsequently, these pairs came to be called Cooper pairs, and a fluid composed of Cooper pairs, a superfluid (thermodynamically, a superfluid is defined as a fluid that can flow without dissipating any energy).

Although the sea of electrons in the new superconducting class of materials could condense into a superfluid, the fluid itself can’t be expected to flow naturally. Earlier, the application of an electric current imparted enough energy to all the electrons in the metal (via a voltage difference) to move around and to scatter against nuclei to yield resistance. Now, however, upon Cooper-pairing, the superfluid had to be given an environment in which there’d be no vibrating nuclei. And so: enter cryogenics.

ILCTA_cryo — The International Linear Collider – Test Area’s (ILCTA) cryogenic refrigerator room

The thermal energy of a crystal lattice is given by E = kT, where ‘k’ is Boltzmann’s constant and T, the temperature. Demonstrably, to reduce the kinetic energy of all nuclei in the lattice to zero, the crystal itself had to be cooled to absolute zero (0 kelvin). This could be achieved by cryogenic cooling techniques. For instance, at the LHC, the superconducting magnets are electromagnets wherein the coiled wire is made of a superconducting material. When cooled to a really low temperature using a two-stage heat-exchanger composed of liquid helium jacketed with liquid nitrogen, the wires can carry extremely large amounts of current to generate very intense magnetic fields.

At the same time, however, if the energy of the superfluid itself surpassed the thermal energy of the lattice, then it could flow without the lattice having to be cooled down. Because the thermal energy is different for different crystals at different ambient temperatures, the challenge now lies in identifying materials that could permit superconductivity at temperatures approaching room-temperature. Now that would be (even more) exciting!

Graphene the Ubiquitous (astrohep.wordpress.com)

P.S. A lot of the related topics have not been covered in this post, such as the Meissner effect, electron-phonon interactions, properties of cuprates and lanthanides, and Mott insulators. They will be taken up in the future as they’re topics that require in-depth detailing, quite unlike this post which has been constructed as a superfluous introduction only.

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