# Infrared properties of exotic superconductors.

## A INTRODUCTION

The discovery of high temperature superconductivity (HTSC) by Bednorz and Müller raised the question of the relationship between these materials and other, previously known unconventional superconductors such as the organic conductors, the bismuthates and the heavy Fermion materials. Since 1987 other novel superconductors such as the borocarbides and the alkali fullerines have been discovered. The aim of this review is to examine, from the point of view of one experimental technique, infrared spectroscopy, several of these families of unconventional superconductors.

Optical spectroscopy has several advantages over other techniques for the analysis of the transport properties of a broad range of conducting systems. First, it is not surface sensitive since electromagnetic radiation penetrates a hundreds of nanometers into the crystal. Second, relatively small lateral sample dimensions of the order of 500 $`\mu `$m are enough to yield high quality spectra in the interesting 200 – 1000 cm<sup>-1</sup> frequency region, a region relevant to the excitations in most superconductors. In contrast, more powerful techniques such as angle resolved photoemission or vacuum tunneling demand ultrahigh-vacuum cleaved, virgin surfaces and as a result have been applied to only a few systems. Magnetic neutron scattering, another powerful technique, due to the weak interaction of the neutron with matter, demands large centimeter size crystals which are simply not available for most new materials. As a result, optical spectroscopy has become the spectroscopic technique of choice for the investigation of the low lying excitations of a large range of new materials and doping levels.

Reflectance spectroscopy, combined with Kramers Kronig analysis, yields the real and imaginary parts of the optical conductivity. In systems with s-wave, dirty limit superconductivity, optical methods were first used to study the energy gap and later the spectrum of excitations.. It can also be used to determine the superconducting penetration depth tensor. And unlike the dc conductivity which becomes infinite in the superconducting state and shorts out all parallel channels of conductivity, infrared techniques can be used to measure the optical conductivity of quasiparticles below $`T_c`$. Even better results are obtained with the closely related technique, microwave absorption.

In what follows we review the optical properties in the infrared of a range of unconventional superconductors as revealed by reflectance spectroscopy. We start by setting the stage with the discussion of conventional BCS superconductors and then move to several families of less and less conventional superconductors starting with materials that seem to be almost conventional but show clear signatures of deviation from familiar behaviour.

There is a grey area in all classification schemes. For unconventional superconductors it includes materials that are distinguished by high transition temperatures and where relatively little reliable infrared data exists. This includes materials such as the A15 compounds, the borocarbides, and the doped fullerines. Some of these materials are discussed by other contributors to this conference.

## B BCS SUPERCONDUCTORS IN THE INFRARED

One of the pioneering experiments in conventional superconductors was the measurement of the energy gap by far infrared reflectance spectroscopy by Tinkham and his collaborators. The gap in the excitation spectrum of magnitude $`2\mathrm{\Delta }`$ leads to a region of unit reflectance for $`h\nu <2\mathrm{\Delta }`$. Above the gap frequency absorption sets in and the reflectance drops to the normal state value. Reflectance experiments in conventional metals are difficult since, in a good metal, the normal state absorption is very weak, typically $`1R=0.005`$. To overcome the weak absorption, sensitive calorimetric techniques or multiple reflection cavities are used. The disadvantage of these methods is the difficulty of getting an absolute calibration.

The second important early contribution of infrared spectroscopy was the discovery of Joyce and Richards of phonon structure resulting from strong coupling effects, similar to the structure seen in tunnelling spectra. Fig 1. shows, from the work of Farnworth, the difference in the absorption of a lead film between the superconducting and normal states. A magnetic field was used to destroy the superconductivity. The rise in absorption at 22 cm<sup>-1</sup> is due to the onset of normal state absorption at the gap energy at $`h\nu =2\mathrm{\Delta }`$. The double-peak structure above the gap energy is due the interaction of the superconducting carriers with transverse and longitudinal acoustic phonons. The dashed curve is a theoretical calculation by Swihart and Shaw of the absorption ratio using a full Eliashberg theory including vertex corrections. The phonon spectrum of lead as determined by neutron scattering was used. It is clear from these data that it is possible to identify all the important features of a BCS superconductor with infrared reflectance spectroscopy: an infrared signature of BCS superconductivity is a region of unit reflectance that occurs below $`T_c`$ followed by phonon structure that reflects the electron phonon density of states which is directly responsible for superconducting pairing.

As we will see in what follows, the unconventional superconductors do not show this simple behavior, but even in BCS superconductors there are many complications that go beyond the simple strong coupling behavior shown in Fig 1. For example, it is not always possible to see a gap signature and a phonon spectrum in the same sample. The onset of absorption at the gap frequency is due to the presence of impurities that allow for momentum conservation. In a clean superconductor absorption does not start at $`2\mathrm{\Delta }`$ but at frequencies where inelastic processes such as phonons can take up the momentum of the photon. Lead films such as those shown in Fig. 1 have some impurities that allow for a gap to be seen but not enough to dominate the scattering processes and suppress the electron phonon scattering. A gap signature and phonons appear together in 3D metals where surface scattering processes result in apparent dirty limit behavior in pure crystals.

Furthermore, in pure 3D metals, there are surface scattering processes that result in apparent dirty limit behavior and allow a gap signature and phonons to appear in the same sample as shown in Fig. 1.

## C BKBO AN UNCONVENTIONAL OXIDE SUPERCONDUCTOR.

Ba<sub>1-x</sub>K<sub>x</sub>BiO<sub>3</sub> (BKBO), along with its cousin BaPb<sub>x</sub>Bi<sub>1-x</sub>O<sub>3</sub>, form a family of superconductors with cubic perovskite structure in the superconducting phase where $`x0.3`$. The transition temperature of BKBO is quite high (31 K) in relation to its low density of states at the Fermi level, and it has been suggested that the material is closely related to cuprate high $`T_c`$ superconductors. However the optical properties suggest that they are in fact closer to the conventional BCS superconductors than to the exotic cuprates.

Fig. 2 shows the optical conductivity at low frequency, at four temperatures, for Ba<sub>0.6</sub>K<sub>0.4</sub>BiO<sub>3</sub> with $`T_c=31`$ K from the work of Puchkov et al.  Apart from a temperature independent background, indicated by a dashed line, the temperature behavior is that of a conventional BCS, slightly dirty, superconductor. The normal state is well fit by a Drude peak with a width of $`230`$ cm<sup>-1</sup> plus some direct transverse optical phonon absorption lines at about 200 and 500 cm<sup>-1</sup>. A gap-like depression develops precisely at $`T_c`$ and a gap opens as the temperature is reduced. The superconducting gap is $`2\mathrm{\Delta }=90\pm 10`$ cm<sup>-1</sup> and as $`T_c`$ is varied with doping, the gap to $`T_c`$ ratio is constant at $`2\mathrm{\Delta }/k_BT_c=4.2\pm 0.3`$. This simple behavior should be contrasted with what is seen in the cuprates: there the gap develops already in the normal state (except in the limit of large overdoping), there is no $`2\mathrm{\Delta }`$ gap signature and the gap ratio is not constant—in the underdoped range the gap decreases as $`T_c`$ is increased with doping.

In BKBO, at 10 K, the conductivity below the gap frequency drops to a background conductivity shown as a dashed line. This background absorption level has been obtained by extrapolation from high frequencies. Puchkov et al. interpret the data in terms of two channels of conductivity, a Drude channel that undergoes a conventional superconducting transition and a second, possibly polaronic, channel that remains non-superconducting and is responsible for the broad temperature independent background. The two channel picture has also been advanced to explain the temperature dependence of the dc resistivity. Thus the infrared conductivity of BKBO is that of dirty s-wave superconductor, a behavior that is quite different from what is seen in a dirty d-wave superconductor as we will see below.

Despite the development of a conventional gap structure below $`T_c`$, the BKBO spectrum does not show all the signatures of a conventional BCS phonon coupled superconductor, which in view of the large transition temperature is expected to be a strong coupling system. A detailed calculation, based on Eliashberg theory with phonons by Marsiglio et al., bears this out yielding electron-phonons coupling $`\lambda =1`$ and a transition temperature of 31 K. As Fig. 3 shows, the imaginary part of the optical conductivity cannot be fit with this large value of $`\lambda `$ but is fit well with $`\lambda =0.2`$, a number that is clearly inconsistent with the large transition temperature and the assumed phonon spectrum taken from tunneling. Sharif et al. have found a similar low value of $`\lambda `$ based on tunneling measurements. They also conclude that BKBO is not an electron-phonon superconductor. This weak coupling to phonons is consistent with the absence of Holstein phonon structure below $`T_c`$ and as Fig. 2 shows there is no evidence of such structure in BKBO.

## D Sr<sub>2</sub>RuO<sub>4</sub> and URu<sub>2</sub>Si<sub>2</sub> TWO FERMI LIQUID SUPERCONDUCTORS

In this section we discuss two materials that, at first sight appear unrelated, URu<sub>2</sub>Si<sub>2</sub> a typical intermetallic compound showing heavy Fermion behavior at low temperature and Sr<sub>2</sub>RuO<sub>4</sub> an oxide of Ru that is isostructural with the high $`T_c`$ superconductor La<sub>2-x</sub>Sr<sub>x</sub>CuO<sub>4</sub> with the ruthenium replacing copper. However, a closer examination shows a surprising number of common elements of the two ruthenium containing materials. Both materials are superconductors with a rather low $`T_c`$ of the order of 1 K. Infrared spectroscopy has not been used to investigate the gap structure in these two materials since the gap is expected to occur in the difficult submillimeter region and the normal state absorption will be very weak at these frequencies at low temperature. However, infrared can be used to study the normal state transport properties.

While the inplane resistivity of Sr<sub>2</sub>RuO<sub>4</sub> is metallic, normal to the planes the resistivity (in the c-direction) shows a ”semiconducting” temperature dependence above 130 K and a metallic one at low temperatures. Similar behavior is seen in the resistivity of URu<sub>2</sub>Si<sub>2</sub> in all directions with a maximum at 80 K . Both materials become good conductors at low temperature with a $`T^2`$ dependence of the resistivity expected for a pure metal when the phonon scattering is frozen out. Superconductivity sets in at about 1 K.

The two ruthenium materials are very different in their electronic properties: URu<sub>2</sub>Si<sub>2</sub> gets its poor metallic behaviour from strong incoherent scattering which freezes out for $`k_BT<k_BT_K`$ where $`k_BT_K`$ is a Kondo energy scale characteristic of magnetic scattering. Sr<sub>2</sub>RuO<sub>4</sub> on the other hand is very anisotropic in its crystal structure with weak coupling between the current carrying RuO<sub>2</sub> planes. However at low temperature where $`k_BT<t_{}`$ the planes couple coherently and the material becomes a very anisotropic 3D conductor.

In agreement with these ideas both systems develop sharp Drude peaks at low temperature which are signatures of good metals. Fig. 4 shows the optical conductivity of URu<sub>2</sub>Si<sub>2</sub>. At 90 K, well above the coherence temperature $`T_K`$ the conductivity is flat and frequency independent. As the temperature is lowered, a Drude peak develops at low frequency, borrowing spectral weight from a frequency band that is a few times $`k_BT_K`$. As the temperature is lowered further, the peak sharpens. A detailed analysis of the spectrum in terms of a frequency dependent mass formalism shows that the carriers are massive with $`m=50m_e`$ consistent with specific heat data in this heavy Fermion system.

A similar onset of coherence is seen in the c-axis conductivity of the quasi two-dimensional material Sr<sub>2</sub>RuO<sub>4</sub>. Fig. 5 shows data of Katsufuji et al. of the c-axis conductivity. The conductivity, apart from a few strong transverse phonon peaks, consists of a flat band with a slight Drude-like peak below 0.02 eV (160 cm<sup>-1</sup>). Spectral weight is lost in the 100 to 200 cm<sup>-1</sup> region to a narrowing Drude peak. The author’s data does not extend low enough in frequency to resolve the peak but the dashed lines, fit to the increasing dc conductivity with decreasing temperature, show the expected conductivity. As in the case of URu<sub>2</sub>Si<sub>2</sub> the area under the Drude peak is a small fraction of the total infrared spectral weight suggesting a large mass for c-axis motion. This is verified by magneto oscillation experiments.

The two ruthenium containing systems behave in a very conventional way at low temperature, in that they are 3-D Fermi liquids, but at high temperature one shows effects of magnetism and the other of highly anisotropic transport properties. As we will see in the next two sections, combining both ingredients results in truly exotic behavior of the cuprates and the organic conductors.

## E THE CUPRATES

While the high superconducting transition temperature is the defining property of the HTSC cuprates, several properties set the cuprate family apart from the conventional BCS superconductors. These include the anomalous normal state resistivity as emphasized early by Anderson, the d-wave superconducting order parameter, the magnetism, the two-dimensional transport, and finally the presence of a normal state pseudogap.

There is an extensive literature on the optical conductivity of the cuprates which has been reviewed recently by Basov and Timusk. Here we focus on those features of the optical conductivity that make the cuprates unique: the lack of the $`2\mathrm{\Delta }`$ gap signature in the optical conductivity, the crucial role played by the two-dimensional nature of the transport and finally the the normal state pseudogap.

The absorption and the optical conductivity of a typical HTSC cuprate, YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7-δ</sub>, is shown in Fig. 6. The normal state shows a Drude-like peak. Below $`T_c`$ the spectral weight of the peak is transferred to the condensate delta function at $`\omega =0`$ but there is no signature of a superconducting gap as seen in BKBO. Instead, there remains a weak continuous conductivity at all frequencies including in the region where one expects to see the superconducting gap. Careful study of the optical conductivity by various techniques shows that the width of the Drude peak diminishes by several orders of magnitude just below $`T_c`$ which suggests that a gap is formed in the spectrum of excitations responsible for the scattering of the carriers. This behaviour is in striking contrast to electron-phonon superconductors where there are no major changes to the phonon spectrum at the superconducting transition. In the cuprates the excitations are electronic and as a gap develops in these excitations a dramatic decrease in scattering takes place. The optical properties of the cuprates are those of a clean limit superconductor where the $`2\mathrm{\Delta }`$ transitions are forbidden because of momentum conservation. In this respect the cuprates behave exactly the same as the BCS superconductors. An obvious experiment to try would be to introduce impurities to approach the dirty limit.

Fig 7 shows the effect of defects on the optical conductivity of radiation damaged YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7-δ</sub> from the work of Basov et al. As the defect concentration rises, a Drude-like peak, displaced slightly from zero frequency, grows. There is no sign of a peak at $`2\mathrm{\Delta }`$, expected to be in the neighborhood of 600 cm<sup>-1</sup>. This behavior is seen in a number of cuprate systems containing either doped impurities or other forms of disorder such as partial occupancy at oxygen sites or radiation damage. Recent work of Basov et al. shows similar effects in Zn doped YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7-δ</sub>: there is no $`2\mathrm{\Delta }`$ gap signature and, in the superconducting state there is a Drude-like conductivity peak, shifted slightly from zero to finite frequencies. A BCS s-wave superconductor is relatively insensitive to disorder where the main result of strong impurity scattering is the erasure of any gap anisotropy and the removal of the clean limit restriction on momentum conservation resulting in the familiar $`2\mathrm{\Delta }`$ gap signature. In contrast, in a d-wave superconductor impurity scattering has the effect of restoring part of the Fermi surface near the nodes and the optical conductivity acquires a low frequency component, very similar to a Drude peak.

The second fundamental property of the cuprates is an intrinsic anisotropy of electronic transport that goes beyond the simple anisotropic effective mass seen for example in doped semiconductors or in the Sr<sub>2</sub>RuO<sub>4</sub> system discussed above. Here we have a qualitative difference in the properties along the planes where the conductivity is coherent and metallic and perpendicular to the planes, in the c-direction, where the conductivity is incoherent down to the lowest temperatures and frequencies. Fig 8 shows the c-axis conductivity of a YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7-δ</sub> crystal that is slightly underdoped. Like the Sr<sub>2</sub>RuO<sub>4</sub> discussed in the last section, at high temperature there is a broad, essentially frequency independent, absorption band and no coherent Drude peak. Since the material shown is underdoped it shows a depressed conductivity below 300 cm<sup>-1</sup> due to the normal state pseudogap at low temperature that will be discussed below. But down to the lowest frequency and temperature, there is no evidence of a Drude peak. The arrows denote the values of the dc resistivity and it clear that, at least above 70 K, there is no coherent conduction in this system. It is not possible to measure the dc resistivity below this temperature since the material becomes superconducting. Recent microwave measurements show that the conductivity remains incoherent down to 22 GHz and 1.2 K.

Recent work using a variety of experimental probes, most strikingly angle resolved photoemission, shows that the normal state of the high temperature superconductors is dominated by a partial gap, or a pseudogap. The experimental evidence has been reviewed recently by Timusk and Statt. The pseudogap forms at a temperature $`T^{}`$ which is substantially above the superconducting transition temperature in most underdoped samples. $`T^{}`$ approaches $`T_c`$ in YBCO near optimal doping. Just as infrared spectroscopy can show the collapse of scattering associated with the development of superconductivity, it also shows the loss of electron-electron scattering on formation of the pseudogap. As shown first by Basov et al. and illustrated in Fig. 9, from a recent paper of Homes et al. there is a loss of ab plane scattering associated with the formation of the pseudogap for frequencies below about 660 cm<sup>-1</sup>.

Fig 8 shows a depression in the conductivity associated with the pseudogap that develops in this underdoped sample. There is a gaplike region of flat conductivity that fills in as the temperature is increased but there appears to be no change in the overall frequency scale of the conductivity as the temperature is raised – the gap fills in rather than closing. These measurements of the c-axis pseudogap by Homes et al. were the first to yield spectroscopic evidence of the pseudogap. The c-axis pseudogap has since been observed in several other HTSC systems where samples of sufficient thickness are available as well as in the ladder cuprates.

In summary, infrared spectroscopy has revealed several exotic properties of the cuprates, the electronic coupling mechanism, possibly associated with magnetism, the intrinsic anisotropy and finally the presence of a pseudogap in the normal state. In what follows we will see that organic low-dimensional superconductors share some of these properties and that they are the properties that can be used to define exotic superconductivity.

## F THE ORGANIC SUPERCONDUCTORS

There are two main families of organic superconductors: conductors based on the two-dimensional (BEDT-TTF) organic molecule with a $`T_c`$ in the neighborhood of 10 K, and the family of one-dimensional materials, the Bechgaard salts, based on the TMTSF molecule with a $`T_c`$ just over 1 K.

There is surprisingly little known about the electronic properties of organic conductors largely because of the small size and fragility of the available crystals. Thus magnetic neutron scattering and angle resolved photoemission, powerful, momentum sensitive techniques, have not proven to be as useful here as they have been in the cuprates. While there is a considerable body of infrared spectroscopy, the strong mid-infrared absorption seen in the organics by all investigators is in clear contradiction with the extensive low temperature magnetic transport data. These contradictions in the interpretation of the experiments have lead to two completely opposing views of the normal state transport particularly in the Bechgaard materials where most of the work has been done.

Magnetic transport measurements have generally been interpreted in terms of Fermi liquid models with extraordinarily long scattering times. In agreement with this picture it is found that Kohler’s rule holds except for the conductivity component along the conducting chains. Various oscillatory phenomena have been seen in high fields and these have been interpreted in terms of electrons moving in quasi two-dimensional orbits. This interpretation of the data has been summarized by Greene and Chaikin. Specific heat data also suggest a superconducting transition from a normal metallic state.

The infrared community takes a diametrically opposed stand on the transport properties. Measurements of the frequency dependent conductivity at low temperature shows that the very large dc conductivity of $`200,000`$ ($`\mathrm{\Omega }`$cm)<sup>-1</sup> retains its large value well into the microwave region but then drops dramatically in the 300 GHz range to a low value of $`1000`$ ($`\mathrm{\Omega }`$cm)<sup>-1</sup>. The reflectance of such a system is expected to show a prominent plasma edge in the 300 GHz region, a difficult experimental region to work in with small needle like samples. Nevertheless, early far infrared work of Tanner’s group as well as recent backward wave oscillator data from Grüner’s group has shown evidence of this edge experimentally. A clear observation of this edge confirms the picture of two component conductivity, a narrow Drude peak, presumably caused by a density wave followed by a very broad incoherent band due to a strongly correlated Luttinger liquid.

Fig. 10 shows recent conductivity data of (TMTSF)<sub>2</sub>ClO<sub>4</sub> from Cao et al. for light polarized along the conducting chains. We see, at room temperature, a broad incoherent band very similar to what is seen in the c-direction of the cuprates where the carriers are confined to the planes. The dc conductivity is not much larger than the infrared conductivity although there appears to be an incipient pseudogap already at room temperature.

As the temperature is lowered the dc conductivity increases and spectral weight is shifted to lower frequencies. A clear, gap-like depression, can be seen below 300 cm<sup>-1</sup>. This behavior has also been seen in the charge density wave system TTF-TCNQ.

These data have been interpreted in terms of transport by charge density wave fluctuations. Several characteristics point to this picture. First, there is a growth in the intensity of phonon lines as the temperature is lowered, behavior that is usually associated with sliding density waves interacting with the lattice. Secondly, estimates of the spectral weight associated with the narrow low frequency mode of $`500m_e`$ suggest that phonons are involved as well. In this picture the peak in the far-infrared would correspond to direct transitions across the charge density wave gap.

The picture of transport along the chain axis by charge density wave fluctuations rests mainly on the assumption that strong infrared absorption is due to intrinsic bulk effects. It has been suggested that surface defects such as cracks may be responsible for the absorption and there is indeed scatter in the infrared data from various laboratories suggesting that sample quality may be a problem. However it should be noted that the simple picture of cracks predicts that the absorption should continue well into the microwave range as long as the penetration depth is smaller than the crack depth.

There are several ways of investigating this problem. One of course is the use of samples with better controlled surfaces to see if the strong mid-infrared absorption is intrinsic. Assuming that it is, then reflectance measurements in high magnetic fields should be made to determine if sufficiently strong fields will break up the density waves and turn the materials into quasi one dimensional metals. There is preliminary evidence that this might be the case.

Because of the low transition temperature and the low frequency range of the expected superconducting gap, little is known about the optical properties of the organic conductors in the superconducting state. It is hoped however, that when larger crystals become available, far infrared and microwave techniques will be used to investigate the issue of the superconducting gap as well as the transition region between the high dc and microwave conductivity and the strongly absorbing pseudogap range.

We finally touch briefly on the question of transport normal to the conducting chains. Fig 11 shows the infrared conductivity of (TMTSF)<sub>2</sub>ClO<sub>4</sub> in the b direction where there is considerable overlap between the chains (the third direction has even lower coupling between the chains). We again see a flat conductivity, similar to the case of the c-axis cuprates. There is some evidence of a collective mode since the dc conductivity is considerably higher than the infrared conductivity. However, the discrepancy is much smaller than what is observed in the chain direction. If one were to assign a scattering rate to this flat conductivity it would be of the order of 500 cm-1 (40 meV). This is to be compared with the estimated $`t_{}=40`$ meV, the transfer matrix element normal to the chains. In terms of a Fermi liquid picture, one would then expect that below a crossover temperature of $`T=40`$ meV $`=460`$ K coherence would develop and the material would become a 2D Fermi liquid. It is clear that down to 2 K there is completely incoherent transport between the chains.

In summary the organic superconductors display very anomalous properties in the infrared. There is no evidence of simple metallic transport in any direction. Along the chains the currents are carried by collective modes, possibly sliding charge density waves while normal to the chains there is complete incoherence similar to what is seen in interplane transport in the cuprates.

## G CONCLUSIONS

We have discussed in this review an infrared view of the transport properties of a variety of superconductors, from the conventional BCS strong coupling superconductor lead, to the exotic cuprates and organic charge transfer materials. The focus has been on several markers of deviation from classic phonon-coupled systems: 1) the collapse of scattering at $`T_c`$, a signature of an electronic mechanism since phonon scattering is unaffected, to first order, by the formation of a gap in the electronic system, 2) the growth of a Drude peak in the superconducting state of dirty samples and absence of a $`2\mathrm{\Delta }`$ gap feature, both signatures of an order parameter with nodes 3) the role of intrinsic dimensionality that goes beyond simple anisotropy where we find that the carriers are confined to planes and chains and interplane/chain conductivity is incoherent down to the lowest temperatures and frequencies, 4) the presence of a pseudogap in the normal state associated with charge transport by complex objects.

For a true classification of all superconductors into anomalous and exotic varieties, as opposed to conventional ones, one needs data from all experimental techniques. Nevertheless the infrared is a good initial tool for this task since it can be applied to a wide range of materials being relatively modest in the demands it places on the crystal growers, who are of course responsible for much of the past progress in our understanding of unconventional superconductivity.

Acknowledgements.

I would first like to acknowledge Georgorgios Varelogiannis for the suggestion to undertake this survey of the infrared properties of unconventional superconductors and Jules Carbotte for valuable discussions on all aspects of superconductivity. The results described in this paper come in most part from the work of D.N. Basov, D.B. Bonn, N. Cao, B.F. Farnworth, C.C. Homes, H.K. Ng, R. Hughes, J.J. McGuire, A. Puchkov, M. Reedyk, T. Rõõm T. Strach and T. Startseva at McMaster. I thank Y. Tokura for permission to use Fig. 5. The crystal growers responsible for these results are K. Bechgaard, D. Colson, B. Dabrowski, S. Doyle, P. Fournier, J.D. Garrett, P.D. Han, A.M. Hermann, N. T. Kimura, K. Kishio, N.N. Koleshnikov, H.A. Mook, M. Okuya, R. Liang, W.D. Mosley and D.A. Payne. To them the experimentalists owe much.