Design of high mobility DPP-based polymer semiconductors for organic thin film transistors

π-Conjugated polymers are the most promising semiconductor materials to enable printed organic thin film transistors (OTFTs) due to their excellent solution processability and mechanical robustness. However, solution-processed polymer semiconductors have shown poor charge transport properties mainly originated from the disordered polymer chain packing in the solid state as compared to the thermally evaporated small molecular organic semiconductors. The low charge carrier mobility, typically < 0.1 cm2 /V.s, of polymer semiconductors poses a challenge for most intended applications such as displays and radio-frequency identification (RFID) tags. Here we present our recent results on the dike topyrrolopyrrole (DPP)-based polymers and demonstrate that when DPP is combined with appropriate electron donating moieties such as thiophene and thienothiophene, very high charge carrier mobility values of ~1 cm2/V.s could be achieved.

Fast growth of polycrystalline graphene by chemical vapor deposition of ethanol on copper

High conductive graphene films can be grown on metal foils by chemical vapor deposition (CVD). We here analyzed the use of ethanol, an economic precursor, which results also safer than commonly-used methane. A comprehensive range of process parameters were explored in order to obtain graphene films with optimal characteristics in view of their use in optoelectronics and photovoltaics. Commercially-available and electro-polished copper foils were used as substrates. By finely tuning the CVD conditions, we obtained few-layer (2-4) graphene films with good conductivity (-500 Ohm/sq) and optical transmittance around 92-94% at 550 nm on unpolished copper foils. The growth on electro-polished copper provides instead predominantly mono-layer films with lower conductivity (>1000 Ohm/sq) and with a transmittance of 97.4% at 550 nm. As for the device properties, graphene with optimal properties as transparent conductive film were produced by CVD on standard copper with specific process conditions.

Giant Magnetoresistance and Related Properties of Rare Earth Manganates and Other Oxide Systems

Giant magnetoresistance (GMR), which was until recently confined to magnetic layered and granular materials, as well as doped magnetic semiconductors, occurs in manganate perovskites of the general formula Ln(1-x)A(x)MnO(3) (Ln = rare earth; A = divalent ion). These manganates are ferromagnetic at or above a certain value of x (or Mn4+ content) and become metallic at temperatures below the curie temperature, T-c. GMR is generally a maximum close to T-c or the insulator-metal (I-M) transition temperature, T-im. The T-c and %MR are markedly affected by the size of the A site cation, [r(A)], thereby affording a useful electronic phase diagram when T-c or T-im is plotted against [r(A)]. We discuss GMR and related properties of manganates in polycrystalline, thin-film, and single-crystal forms and point out certain commonalities and correlations. We also examine some unusual features in the electron-transport properties of manganates, in particular charge-ordering effects. Charge ordering is crucially dependent on [r(A)] or the e(g) band width, and the charge-ordered insulating state transforms to a metallic ferromagnetic state on the application of a magnetic field.

Halogen bonds in 2D supramolecular self-assembly of organic semiconductors

Weak interactions between bromine, sulphur, and hydrogen are shown to stabilize 2D supramolecular monolayers at the liquid–solid interface. Three different thiophene-based semiconducting organic molecules assemble into close-packed ultrathin ordered layers. A combination of scanning tunneling microscopy (STM) and density functional theory (DFT) elucidates the interactions within the monolayer. Electrostatic interactions are identified as the driving force for intermolecular Br⋯Br and Br⋯H bonding. We find that the S⋯S interactions of the 2D supramolecular layers correlate with the hole mobilities of thin film transistors of the same materials.

Stability of Fe3+ -VO defect pairs in polycrystalline Pb(Ti,Zr)O3

The intensity of the EPR signal with g = 5.985 arising from a ferric ion â oxygen vacancy defect pair (Fe3+ â VO) in PbTiO3, varies with the extent of PbO nonstoichiometry at constant Fe3+ content due to an increased oxygen vacancy concentration. In PZT solid solutions, the signal intensity decreases with an increase in Zr. A lower intensity is also noticed for Fe3+ â VO signals in PbZrO3. This behaviour is explained on the basis of PbO nonstoichiometry arising from independent Pb- and O-vacancies as well as the randomly distributed crystallographic shear (CS) plane defects. The contribution to PbO nonstoichiometry from CS planes is larger in high zirconium compositions of PZT.

Morphological structure of bismuth-doped n-type amorphous germanium sulphide semiconductors

Recent observation of n-type conduction in amorphous Ge20Ss_xBix at large bismuth concentrations (x = 11), which otherwise shows p-type conduction, has aroused considerable interest in the international scientific community [1]. The mechanism of such impurity incorporation in a germanium chalcogenide glass is not understood and is a topic of current interest. In our recent publications [2-10] we have brought to light some hitherto unknown and interesting features of bismuth dopants in chalcogen-rich Ge-X (X -- S, Se) glassy compositions. In this communication we present our new results of investigations on vitreous semiconductors Ge20S80 Bi using electron microscopy, electron diffraction of as-prepared and annealed/pressure quenched compositions. Our results provide conclusive support to the formation of composite clusters containing all the three elements, germanium, sulphur and bismuth, which crystallize in simpler stoichiometric compounds Bi2S3 and GeS2.

Hydrothermal synthesis of polycrystalline carbonates

Polycrystals of orthorhobic carbonates RCO3 (R = Sr, Ba and Pb) were synthesised for the first time using formic acid as mineraliser. The unit cell parameters of this synthetic pure carbonates are: BaCO3:a=5.309, B=8.889, C=6.401; srCO3:a=5.108, B=8.420, C=6.040; PbCO3: A=5.176, B=8.511, C=6.137.

Impurity states in Sb-doped amorphous semiconductors

A systematic investigation of the effects of antimony dopant on the electronic transport properties of amorphous (GeSe3.5)100−xSbx under high pressure (up to 120 kbar) has been carried out down to liquid-nitrogen temperature for the first time. Differential thermal analysis and x-ray diffraction methods were used for the characterization of freshly prepared and pressure-quenched materials which indicated the presence of structural phase transition in both GeSe3.5 and (GeSe3.5)100−xSbx around 105 kbar pressure. Electrical transport data revealed the strong compositional dependence of the electronic conduction process. A distinct kink in the conductivity temperature plot at pressures>15 kbar was observed in the Sb-doped compositions indicating the presence of different conduction processes. An attempt has been made to interpret the pressure-induced effect in the transport properties of these glasses considering the possible presence of both thermally activated conduction in the extended states and hopping process in the localized tail states. However, the interpretation of the transport data is not straightforward and the pressure dependence of the thermoelectric power will be needed to complete the picture. Journal of Applied Physics is copyrighted by The American Institute of Physics.

New temperature fluctuation method for direct determination of thermal activation energy of deep levels in semiconductors

A new method is suggested where the thermal activation energy is measured directly and not as a slope of an Arrhenius plot. The sample temperature T is allowed to fluctuate about a temperature T0. The reverse-biased sample diode is repeatedly pulsed towards zero bias and the transient capacitance C1 at time t1 is measured The activation energy is obtained by monitoring the fluctuations in C1 and T. The method has been used to measure the activation energy of the gold acceptor level in silicon.

On the structural features of doped amorphous chalcogenide semiconductors

A study of Bi-doped amorphous (Ge42S58)100−xBix and Ge20S80−xBix has been carried out by differential thermal analysis (DTA) and X-ray diffraction methods so as to elucidate the impurity-induced modifications in the semiconductors. Thermal analysis reveals the presence of complex structural units in the modified material. An interesting feature of this study is the existence of a double glass transition in Ge20S80−xBix, which is reported for the first time in this system.

Electrical transport in layered crystalline semiconductors GeS doped with Ag, P impurities at high pressure

A study of the transport properties of layered crystalline semiconductors GeS (undoped and doped with Ag, P impurity) under quasihydrostatic pressure using Bridgman anvil system is made for the first time. Pressure-induced effects in undoped crystals reveal initial rise in resistivity followed by two broad peaks at higher pressures. Silver doping induces only minor changes in the behaviour except removing the second peak. Phosphorous impurity is found to have drastic effect on the transport properties. Temperature dependence of the resistivity exhibits two activation energies having opposite pressure coefficients. Results are discussed in the light of intrinsic features of the layered semiconductors.

Pressure induced effects in bulk amorphous n-type semiconductors(GeSe3.5)100âxBix

The effect of pressure on the electrical resistivity of amorphous n-type (GeSe3.5)100�xBix been studied in a Bridgeman anvil system up to a pressure of 90 kbar down to liquid nitrogen temperature. A continuous amorphous semiconductor to metal-like solid transition in the undoped GeSe3.5 is observed at room temperature. Incorporation of Bi in the GeSe3.5 network is found to significantly disturb the behaviour of the resistivity with pressure. With increasing Bi concentration a much broader variation in resistivity with pressure is observed. The temperature dependence of the resistivity and activation energy at different pressures is also measured and they are found to be composition dependent. Results are discussed in the light of the Phillips Model of ordered clusters in chalcogenide semiconductors.

Study of effects of dopants on structure of vitreous semiconductors (GeSe3.5)100-xMx (M = Bi, Sb) using high pressure techniques

An investigation of the problem of controlled doping of amorphous chalcogenide semiconductors utilizing a Bridgman anvil high pressure technique, has been undertaken. Bulk amorphous semiconducting materials (GeSe3.5)100-x doped with M = Bi (x = 2, 4, 10) and M = Sb (x = 10) respectively are studied up to a pressure of 100 kbar down to liquid nitrogen temperature, with a view to observe the impurity induced modifications. Measurement of the electrical conductivity of the doped samples under quasi-hydrostatic pressure reveals that the pressure induced effects in lightly doped (2 at % Bi) and heavily doped (x = 4, 10) semiconductors are markedly different. The pressure effects in Sb-doped semiconductors are quite different from those in Bi-doped material.

Adsorption of carbon monoxide on the surfaces of polycrystalline transition metals and alloys: electron energy loss and ultraviolet photoelectron spectral studies1

Adsorption of CO has been investigated on the surfaces of polycrystalline transition metals as well as alloys by employing electron energy loss spectroscopy (eels) and ultraviolet photoelectron spectroscopy (ups). CO adsorbs on polycrystalline transition metal surfaces with a multiplicity of sites, each being associated with a characteristic CO stretching frequency; the relative intensities vary with temperature as well as coverage. Whilst at low temperatures (80- 120 K), low coordination sites are stabilized, the higher coordination sites are stabilized at higher temperatures (270-300 K). Adsorption on surfaces of polycrystalline alloys gives characteristic stretching frequencies due to the constituent metal sites. Alloying, however, causes a shift in the stretching frequencies, indicating the effect of the band structure on the nature of adsorption. The up spectra provide confirmatory evidence for the existence of separate metal sites in the alloys as well as for the high-temperature and low-temperature phases of adsorbed CO.