Organic superconductor

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An organic superconductor is a synthetic organic compound that exhibits superconductivity at low temperatures.

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As of 2007 the highest achieved critical temperature for an organic superconductor at standard pressure is 33 K (−240 °C; −400 °F), observed in the alkali-doped fullerene RbCs2C60. [1] [2]

In 1979 Klaus Bechgaard synthesized the first organic superconductor (TMTSF)2PF6 (the corresponding material class was named after him later) with a transition temperature of TC = 0.9 K, at an external pressure of 11 kbar. [3]

Many materials may be characterized as organic superconductors. These include the Bechgaard salts and Fabre salts which are both quasi-one-dimensional, and quasi-two-dimensional materials such as k-BEDT-TTF2X charge-transfer complex, λ-BETS2X compounds, graphite intercalation compounds and three-dimensional materials such as the alkali-doped fullerenes.

Organic superconductors are of special interest not only for scientists, looking for room-temperature superconductivity and for model systems explaining the origin of superconductivity but also for daily life issues as organic compounds are mainly built of carbon and hydrogen which belong to the most common elements on earth in contrast to copper or osmium.

One-dimensional Fabre and Bechgaard salts

Fabre-salts are composed of tetramethyltetrathiafulvalene (TMTTF) and Bechgaard salts of tetramethyltetraselenafulvalene (TMTSF). These two organic molecules are similar except for the sulfur-atoms of TMTTF being replaced by selenium-atoms in TMTSF. The molecules are stacked in columns (with a tendency to dimerization) which are separated by anions. Typical anions are, for example, octahedral PF6, AsF6 or tetrahedral ClO4 or ReO4.

Both material classes are quasi-one-dimensional at room-temperature, only conducting along the molecule stacks, and share a very rich phase diagram containing antiferromagnetic ordering, charge order, spin-density wave state, dimensional crossover and superconductivity.

Only one Bechgaard salt was found to be superconducting at ambient pressure which is (TMTTF)2ClO4 with a transition temperature of TC = 1.4 K. Several other salts become superconducting only under external pressure. The external pressure required to drive most Fabre-salts to superconductivity is so high, that under lab conditions superconductivity was observed only in one compound. A selection of the transition temperature and corresponding external pressure of several one-dimensional organic superconductors is shown in the table below.

MaterialTC (K)pext (kbar)
(TMTSF)2SbF60.3610.5
(TMTSF)2PF61.16.5
(TMTSF)2AsF61.19.5
(TMTSF)2ReO41.29.5
(TMTSF)2TaF61.3511
(TMTTF)2Br0.826

Two-dimensional (BEDT-TTF)2X

The layered structure of ET2X salts illustrated by k-(ET)2Cu2(CN)3. The yellow, grey, blue and red ellipsoids represent the sulfur, carbon, nitrogen and copper atoms, respectively. The hydrogen atoms are omitted for clarity. Layers of ET donor molecules are separated by polymeric Cu2(CN)3 anion sheets. k-(ET)2Cu2(CN)3 is a semiconductor, but a very similar k'-(ET)2Cu2(CN)3 polymorph is an ambient-pressure superconductor with TC ~ 5 K. K-(BEDT-TTF)2Cu2(CN)3 structure.png
The layered structure of ET2X salts illustrated by κ-(ET)2Cu2(CN)3. The yellow, grey, blue and red ellipsoids represent the sulfur, carbon, nitrogen and copper atoms, respectively. The hydrogen atoms are omitted for clarity. Layers of ET donor molecules are separated by polymeric Cu2(CN)3 anion sheets. κ-(ET)2Cu2(CN)3 is a semiconductor, but a very similar κ'-(ET)2Cu2(CN)3 polymorph is an ambient-pressure superconductor with TC ~ 5 K.

BEDT-TTF is the short form of bisethylenedithio-tetrathiafulvalene commonly abbreviated with ET. These molecules form planes which are separated by anions. The pattern of the molecules in the planes is not unique but there are several different phases growing, depending on the anion and the growth conditions. Important phases concerning superconductivity are the α- and θ- phase with the molecules ordering in a fishbone structure and the β- and especially κ-phase which order in a checkerboard structure with molecules being dimerized in the κ-phase. This dimerization makes the κ-phases special as they are not quarter- but half-filled systems, driving them into superconductivity at higher temperatures compared to the other phases.

The amount of possible anions separating two sheets of ET-molecules is nearly infinite. There are simple anions such as triiodide (I
3
), polymeric ones such as the very famous Cu[N(CN)2]Br and anions containing solvents for example Ag(CF3)4·112DCBE. The electronic properties of the ET-based crystals are determined by its growing phase, its anion and by the external pressure applied. The external pressure needed to drive an ET-salt with insulating ground state to a superconducting one is much less than those needed for Bechgaard salts. For example, κ-(ET)2Cu[N(CN)2]Cl needs only a pressure of about 300 bar to become superconducting, which can be achieved by placing a crystal in grease frozen below 0 °C (32 °F) and then providing sufficient stress to induce the superconducting transition. The crystals are very sensitive, which can be observed impressively in α-(ET)2I3 lying several hours in the sun (or more controlled in an oven at 40 °C, 104 °F). After this treatment one gets αTempered-(ET)2I3 which is superconducting.

In contrast to the Fabre or Bechgaard salts universal phase diagrams for all the ET-based salts have only been proposed yet. Such a phase diagram would depend not only on temperature and pressure (i.e. bandwidth), but also on electronic correlations. In addition to the superconducting ground state these materials show charge-order, antiferromagnetism or remain metallic down to lowest temperatures. One compound is even predicted to be a spin liquid.

The highest transition temperatures at ambient pressure and with external pressure are both found in κ-phases with very similar anions. κ-(ET)2Cu[N(CN)2]Br becomes superconducting at TC = 11.8 K at ambient pressure, and a pressure of 300 bar drives deuterated κ-(ET)2Cu[N(CN)2]Cl from an antiferromagnetic to a superconducting ground state with a transition temperature of TC = 13.1 K. The following table shows only a few exemplary superconductors of this class. For more superconductors, see Lebed (2008) in the references.

MaterialTC (K)pext (kbar)
βH-(ET)2I31.50
θ-(ET)2I33.60
k-(ET)2I33.60
α-(ET)2KHg(SCN)40.30
α-(ET)2KHg(SCN)41.21.2
β’’-(ET)2SF5CH2CF2SO35.30
κ-(ET)2Cu[N(CN)2]Cl12.80.3
κ-(ET)2Cu[N(CN)2]Cl deuterated13.10.3
κ-(ET)2Cu[N(CN)2]Br deuterated11.20
κ-(ET)2Cu(NCS)210.40
κ-(ET)4Hg2.89Cl81.812
κH-(ET)2Cu(CF3)4·TCE9.20
κH-(ET)2Ag(CF3)4·TCE11.10

Even more superconductors can be found by changing the ET-molecules slightly either by replacing the sulfur atoms by selenium (BEDT-TSF, BETS) or by oxygen (BEDO-TTF, BEDO).

Some two-dimensional organic superconductors of the κ-(ET)2X and λ(BETS)2X families are candidates for the Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) phase when superconductivity is suppressed by an external magnetic field. [5]

Doped fullerenes

Structure of Cs3C60 Fulleride Cs3C60.jpg
Structure of Cs3C60

Superconducting fullerenes based on C60 are fairly different from other organic superconductors. The building molecules are no longer manipulated hydrocarbons but pure carbon molecules. In addition these molecules are no longer flat but bulky which gives rise to a three-dimensional, isotropic superconductor. The pure C60 grows in an fcc-lattice and is an insulator. By placing alkali atoms in the interstitials the crystal becomes metallic and eventually superconducting at low temperatures.

Unfortunately C60 crystals are not stable at ambient atmosphere. They are grown and investigated in closed capsules, limiting the measurement techniques possible. The highest transition temperature measured so far was TC = 33 K for Cs2RbC60.The highest measured transition temperature of an organic superconductor was found in 1995 in Cs3C60 pressurized with 15 kbar to be TC = 40 K. Under pressure this compound shows a unique behavior. Usually the highest TC is achieved with the lowest pressure necessary to drive the transition. Further increase of the pressure usually reduces the transition temperature. However, in Cs3C60 superconductivity sets in at very low pressures of several 100 bar, and the transition temperature keeps increasing with increasing pressure. This indicates a completely different mechanism then just broadening of the bandwidth.

MaterialTC (K)pext (mbar)
K3C60180
Rb3C6030.70
K2CsC60240
K2RbC6021.50
K5C608.40
Sr6C606.80
(NH3)4Na2CsC6029.60
(NH3)K3C602814.8

More organic superconductors

Next to the three major classes of organic superconductors (SCs) there are more organic systems becoming superconducting at low temperatures or under pressure. A few examples follow.

TTP-based SCs

TMTTF as well as BEDT-TTF are based on the molecule TTF (tetrathiafulvalene). Using tetrathiapentalene (TTP) as basic molecules one receives a variety of new organic molecules serving as cations in organic crystals. Some of them are superconducting. This class of superconductors was only reported recently and investigations are still under process.

Phenanthrene-type SCs

Instead of using sulfated molecules or the fairly big Buckminster fullerenes recently it became possible to synthesize crystals from the hydrocarbon picene and phenanthrene. Doping the crystal picene and phenanthrene with alkali metals such as potassium or rubidium and annealing for several days leads to superconductivity with transition temperatures up to 18 K (−255 °C; −427 °F). For AxPhenanthrene, the superconductivity is possible unconventional. Both phenanthrene and picene are called phenanthrene-edge-type polycyclic aromatic hydrocarbon. The increasing number of benzene rings results in higher Tc.

Graphite intercalation SCs

Crystal structure of KC8 Potassium-graphite-xtal-3D-SF-B.png
Crystal structure of KC8

Putting foreign molecules or atoms between hexagon graphite sheets leads to ordered structures and to superconductivity even if neither the foreign molecule or atom nor the graphite layers are metallic. Several stoichiometries have been synthesized using mainly alkali atoms as anions.

Several TCs for unusual SCs

MaterialTC (K)
(BDA-TTP)2AsF65.8
(DTEDT)3Au(CN)24
K3.3Picene18
Rb3.1Picene6.9
K3Phenanthrene4.95
Rb3Phenanthrene4.75
CaC511.5
NaC25
KC80.14

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<span class="mw-page-title-main">Superconductivity</span> Electrical conductivity with exactly zero resistance

Superconductivity is a set of physical properties observed in certain materials where electrical resistance vanishes and magnetic fields are expelled from the material. Any material exhibiting these properties is a superconductor. Unlike an ordinary metallic conductor, whose resistance decreases gradually as its temperature is lowered, even down to near absolute zero, a superconductor has a characteristic critical temperature below which the resistance drops abruptly to zero. An electric current through a loop of superconducting wire can persist indefinitely with no power source.

<span class="mw-page-title-main">State of matter</span> Distinct forms that matter take on

In physics, a state of matter is one of the distinct forms in which matter can exist. Four states of matter are observable in everyday life: solid, liquid, gas, and plasma. Many intermediate states are known to exist, such as liquid crystal, and some states only exist under extreme conditions, such as Bose–Einstein condensates, neutron-degenerate matter, and quark–gluon plasma. For a complete list of all exotic states of matter, see the list of states of matter.

Unconventional superconductors are materials that display superconductivity which does not conform to conventional BCS theory or its extensions.

<span class="mw-page-title-main">High-temperature superconductivity</span> Superconductive behavior at temperatures much higher than absolute zero

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A room-temperature superconductor is a material capable of displaying superconductivity at temperatures above 0 °C, which are commonly encountered in everyday settings. As of 2023, the material with the highest accepted superconducting temperature was highly pressurized lanthanum decahydride, whose transition temperature is approximately 250 K (−23 °C) at 200 GPa.

<span class="mw-page-title-main">Catenation</span> Bonding of atoms of the same element into chains or rings

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<span class="mw-page-title-main">Cryptand</span> Cyclic, multidentate ligands adept at encapsulating cations

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<span class="mw-page-title-main">Dicyanamide</span>

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<span class="mw-page-title-main">Fulleride</span> Chemical compound

Fullerides are chemical compounds containing fullerene anions. Common fullerides are derivatives of the most common fullerenes, i.e. C60 and C70. The scope of the area is large because multiple charges are possible, i.e., [C60]n (n = 1, 2...6), and all fullerenes can be converted to fullerides. The suffix "-ide" implies their negatively charged nature.

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<span class="mw-page-title-main">Denis Jérome</span> French experimental physicist

Denis Jerome is a French experimental physicist in the field of condensed matter, who contributed to the discovery of superconductivity in organic conductive matter.

Conduction zone refers to the network of electron paths between molecules in a conductor where electrons can flow along the paths at the same energy level, resulting in currents. An electron, with an energy level below the conduction zone, remains confined within its orbital inside the individual molecule and it cannot produce any current. To create currents in a conductor, electrons must be at a sufficient energy level to move in the conduction zone. So, the space in a conductor is divided into two different types of regions: the network of conduction zone and isolated cells around individual molecules, somewhat like cement and pebbles in a piece of concrete. A conduction zone does not always appear in all materials. It is necessary for conductors, but absent in insulators. A superconductor is a special conductor with valence orbitals intersecting the conduction zone. Therefore, the valence electrons move naturally in the conduction zone without the need for energy to elevate them to the conduction zone. It is important to note that the term conduction band refers to a different concept defined in band theory.

References

  1. Lebed, A. G. (Ed.) (2008). The Physics of Organic Superconductors and Conductors. Springer Series in Materials Science, Vol. 110. ISBN   978-3-540-76667-4
  2. Singleton, John; Mielke, Charles (2002). "Quasi-two-dimensional organic superconductors: A review". Contemporary Physics. 43 (2): 63. arXiv: cond-mat/0202442 . Bibcode:2002ConPh..43...63S. doi:10.1080/00107510110108681. S2CID   15343631.
  3. Jérome, D.; Mazaud, A.; Ribault, M.; Bechgaard, K. (1980). "Superconductivity in a synthetic organic conductor (TMTSF)2PF 6". Journal de Physique Lettres. 41 (4): 95–98. doi:10.1051/jphyslet:0198000410409500.
  4. Komatsu, Tokutaro; Matsukawa, Nozomu; Inoue, Takeharu; Saito, Gunzi (1996). "Realization of Superconductivity at Ambient Pressure by Band-Filling Control in κ-(BEDT-TTF)2 Cu2(CN)3". Journal of the Physical Society of Japan. 65 (5): 1340–1354. doi:10.1143/JPSJ.65.1340.
  5. Shimahara, H. (2008) "Theory of the Fulde-Ferrell-Larkin-Ovchinnikov State and Application to Quasi-Low-Dimensional Organic Superconductors", in The Physics of Organic Superconductors and Conductors. A. G. Lebed (ed.). Springer, Berlin.