J. H. Schön

Efficient organic photovoltaic diodes based on doped pentacene.

Recent work on solar cells based on interpenetrating polymer networks and solid-state dye-sensitized devices shows that efficient solar-energy conversion is possible using organic materials. Further, it has been demonstrated that the performance of photovoltaic devices based on small molecules can be effectively enhanced by doping the organic material with electron-accepting molecules. But as inorganic solar cells show much higher efficiencies, well above 15 per cent, the practical utility of organic-based cells will require their fabrication by lower-cost techniques, ideally on flexible substrates. Here we demonstrate efficiency enhancement by molecular doping in Schottky-type photovoltaic diodes based on pentacene—an organic semiconductor that has received much attention as a promising material for organic thin-film transistors, but relatively little attention for use in photovoltaic devices. The incorporation of the dopant improves the internal quantum efficiency by more than five orders of magnitude and yields an external energy conversion efficiency as high as 2.4 per cent for a standard solar spectrum. Thin-film devices based on doped pentacene therefore appear promising for the production of efficient ‘plastic’ solar cells.

Self-assembled monolayer organic field-effect transistors

The use of individual molecules as functional electronic devices was proposed in 1974 (ref. 1). Since then, advances in the field of nanotechnology have led to the fabrication of various molecule devices and devices based on monolayer arrays of molecules. Single molecule devices are expected to have interesting electronic properties, but devices based on an array of molecules are easier to fabricate and could potentially be more reliable. However, most of the previous work on array-based devices focused on two-terminal structures: demonstrating, for example, negative differential resistance, rectifiers, and re-configurable switching. It has also been proposed that diode switches containing only a few two-terminal molecules could be used to implement simple molecular electronic computer logic circuits. However, three-terminal devices, that is, transistors, could offer several advantages for logic operations compared to two-terminal switches, the most important of which is ‘gain’—the ability to modulate the conductance. Here, we demonstrate gain for electronic transport perpendicular to a single molecular layer (∼10–20 Å) by using a third gate electrode. Our experiments with field-effect transistors based on self-assembled monolayers demonstrate conductance modulation of more than five orders of magnitude. In addition, inverter circuits have been prepared that show a gain as high as six. The fabrication of monolayer transistors and inverters might represent an important step towards molecular-scale electronics.

Superconductivity in molecular crystals induced by charge injection

Progress in the field of superconductivity is often linked to the discovery of new classes of materials, with the layered copper oxides being a particularly impressive example. The superconductors known today include a wide spectrum of materials, ranging in complexity from simple elemental metals, to alloys and binary compounds of metals, to multi-component compounds of metals and chalcogens or metalloids, doped fullerenes and organic charge-transfer salts. Here we present a new class of superconductors: insulating organic molecular crystals that are made metallic through charge injection. The first examples are pentacene, tetracene and anthracene, the last having the highest transition temperature, at 4 K. We anticipate that many other organic molecular crystals can also be made superconducting by this method, which will lead to surprising findings in the vast composition space of molecular crystals.

Gate-induced superconductivity in a solution-processed organic polymer film

The electrical and optical properties of conjugated polymers have received considerable attention in the context of potentially low-cost replacements for conventional metals and inorganic semiconductors. Charge transport in these organic materials has been characterized in both the doped-metallic and the semiconducting state, but superconductivity has not hitherto been observed in these polymers. Here we report a distinct metal–insulator transition and metallic levels of conductivity in a polymer field-effect transistor. The active material is solution-cast regioregular poly(3-hexylthiophene), which forms relatively well ordered films owing to self-organization, and which yields a high charge carrier mobility (0.05–0.1 cm2 V-1 s-1) at room temperature. At temperatures below ∼2.35 K with sheet carrier densities exceeding 2.5 × 1014 cm-2, the polythiophene film becomes superconducting. The appearance of superconductivity seems to be closely related to the self-assembly properties of the polymer, as the introduction of additional disorder is found to suppress superconductivity. Our findings therefore demonstrate the feasibility of tuning the electrical properties of conjugated polymers over the largest range possible—from insulating to superconducting.

Superconductivity at 52 K in hole-doped C 60

Superconductivity in electron-doped C60 was first observed almost ten years ago. The metallic state and superconductivity result from the transfer of electrons from alkaline or alkaline-earth ions to the C60 molecule, which is known to be a strong electron acceptor. For this reason, it is very difficult to remove electrons from C60—yet one might expect to see superconductivity at higher temperatures in hole-doped than in electron-doped C60, because of the higher density of electronic states in the valence band than in the conduction band. We have used the technique of gate-induced doping in a field-effect transistor configuration to introduce significant densities of holes into C60. We observe superconductivity over an extended range of hole density, with a smoothly varying transition temperature Tc that peaks at 52 K. By comparison with the well established dependence of Tc on the lattice parameter in electron-doped C60, we anticipate that Tc values significantly in excess of 100 K should be achievable in a suitably expanded, hole-doped C60 lattice.

Trapping in organic field-effect transistors

Current–voltage characteristics of single- and polycrystalline organic field-effect transistors are analyzed. The effect of bulk, interface, and grain boundary traps is investigated. The frequently observed dependence of the field-effect mobility on the gate voltage is ascribed to trapping processes rather than to an intrinsic charge transport mechanism in these organic semiconductors. Furthermore, the thermally activated mobility in polycrystalline devices, frequently observed, is ascribed to the formation of a potential barrier at the grain boundaries of the polycrystalline semiconductor. The barrier height depends significantly on the trap density and the position of the Fermi energy and therefore on the gate voltage.

Modeling of the temperature dependence of the field-effect mobility in thin film devices of conjugated oligomers

A simple model is proposed for charge carrier transport across grain boundaries with an acceptor-like trap level. Potential wells between the grains are formed due to negatively charged grain boundaries. Based on this model, a variety of temperature dependencies of the charge carrier mobility can be described. Using realistic parameters, this model reproduces very well the measured temperature dependencies of the field-effect mobility in polycrystalline pentacene and oligothiophene thin film devices. Therefore, it seems to be difficult to investigate the intrinsic material properties of organic semiconductors using only polycrystalline field-effect devices, since they may be masked by the effects of traps and grain boundaries.

Perylene: A promising organic field-effect transistor material

Field-effect transistors based on single crystalline perylene have been prepared and analyzed in the temperature range from 50 to 300 K. Room temperature electron mobilities as high as 5.5 cm2/V s have been achieved. In addition, ambipolar device operation, i.e., n- and p-channel activity, is observed. The temperature dependence of the electron and hole mobilities is discussed in the limits of hopping and band-like transport mechanisms.

Superconductivity in CaCuO2 as a result of field-effect doping.

Understanding the doping mechanisms in the simplest superconducting copper oxide—the infinite-layer compound ACuO2 (where A is an alkaline earth metal)—is an excellent way of investigating the pairing mechanism in high-transition-temperature (high-Tc) superconductors more generally. Gate-induced modulation of the carrier concentration to obtain superconductivity is a powerful means of achieving such understanding: it minimizes the effects of potential scattering by impurities, and of structural modifications arising from chemical dopants. Here we report the transport properties of thin films of the infinite-layer compound CaCuO2 using field-effect doping. At high hole- and electron-doping levels, superconductivity is induced in the nominally insulating material. Maximum values of Tc of 89 K and 34 K are observed respectively for hole- and electron-type doping of around 0.15 charge carriers per CuO2. We can explore the whole doping diagram of the CuO2 plane while changing only a single electric parameter, the gate voltage.Understanding the doping mechanisms in the simplest superconducting copper oxide—the infinite-layer compound ACuO2 (where A is an alkaline earth metal)—is an excellent way of investigating the pairing mechanism in high-transition-temperature (high-Tc) superconductors more generally1,2,3,4. Gate-induced modulation of the carrier concentration5,6,7 to obtain superconductivity is a powerful means of achieving such understanding: it minimizes the effects of potential scattering by impurities, and of structural modifications arising from chemical dopants. Here we report the transport properties of thin films of the infinite-layer compound CaCuO2 using field-effect doping. At high hole- and electron-doping levels, superconductivity is induced in the nominally insulating material. Maximum values of Tc of 89 K and 34 K are observed respectively for hole- and electron-type doping of around 0.15 charge carriers per CuO2. We can explore the whole doping diagram of the CuO2 plane while changing only a single electric parameter, the gate voltage.

Origin of the deep center photoluminescence in CuGaSe2 and CuInS2 crystals

Photoluminescence (PL) of CuGaSe2 and CuInS2 single crystals, either as grown or Cu annealed, reveals a broad and clear deep emission band at hν≈Eg−0.6 eV. In both of these as-grown materials this band has a similar doublet structure with the two D1,D2 subbands separated by about 100 meV. After the Cu annealing all samples became highly compensated and an additional deep PL band (W band) appeared on the high energy side of these D bands. This suggests a closely similar origin of the emission for the both materials. By a straightforward model calculation we show that the changes in the shape and intensity of these emission bands—due to variation of temperature, excitation intensity or due to the Cu annealing—are well explained if we assume that the D1 and D2 PL subbands originate in the recombination between the closest and the second closest donor–acceptor pairs, with the essential ingredient of the emission center being an interstitial donor defect, i.e., either Cui or Gai in CuGaSe2 and Cui or Ini in Cu...