AlPbOAg as a solid electrolyte cell

Thin film AlPbOAg sandwich solid electrolyte cells are obtained by vacuum evaporation on glass substrates; PbO is grown thermally by oxidizing vapour-deposited lead at 150 °C on the bottom aluminium electrode. A.c. and d.c. conductivity studies on symmetrical AlPbOAl sandwich cells indicate that PbO is an ionic conductor. The AlPbOAg sandwich cell is seen to generate a short-circuit current of few nanoampères and a dark voltage in the range 400–800 mV in air ambient, silver being the positive electrode. The discharge characteristics of the cells are studied and a cell reaction is proposed. The variation in cell voltage with temperature and white light illumination is also studied. The photovoltage of the cell is found to add to its dark voltage. The short-circuit current of the cell is also observed to increase with illumination.     

Water soluble polymer/carbon nanotube bulk heterojunction solar cells

We report the characteristics of polymer/quantum dot solar cells fabricated using a water-soluble polymer and carbon nanotubes in a bulk heterojunction configuration. The water-soluble polythiophene polymer showed significant photoresponse and the potential for use in photovoltaics. The addition of carbon nanotubes to the polymer resulted in an order of magnitude increase in the photoconductivity. Improved charge separation and collection was evidenced by the large difference between light and dark conductivities as well as the increase in both open circuit voltage and short circuit current. Finally, photovoltaic cells using aligned nanotubes showed further improvement in the photoconductivity and IV characteristics.     

Effect of solid polymer electrolyte on the sensitization of photocurrents in solid-state electrochemical cells using conducting polypyrrole

The effect of small concentration of methylene blue dye on photocurrents was studied in the solid-state photoelectrochemical cells fabricated using conducting polypyrrole-coated electrodes sandwiched with solid-polymer electrolyte, namely, polyvinylpyrrolidone with phosphoric acid. A maximum photosensitivity factor (S=I _l/I _d, where I _l is the photocurrent and I _d is the dark current) of the order of 5 is observed. The current–voltage (I–V) characteristics in such cells reveal that charge transport is mainly governed by the space charge effect. Comparison of the results presented in this paper with the ones we reported earlier [23] indicates that the matrix in which dye has been incorporated plays an important role in such sensitization processes. A matrix that can efficiently transport the photogenerated charge carriers is observed to be more suitable for such dye-sensitized devices.     

D.C. I–V characteristics and steady-state photoconductivity of Au/Pb2CrO5/SnO2 sandwich-structure films under illumination in the visible region

The room temperature d.c. current–voltage (I–V) characteristics of an Au/Pb2CrO5/SnO2 sandwich-structure 1.39 μm thick film have been measured for d.c. voltages, Vd.c., in the range 0.25 V≤Vd.c.≤5.0 V. These measurements were carried out under both dark and visible-light illumination conditions. For Vd.c.<2.5 V, the I–V curves of the sample in both dark and light environments were found to be non-linear and conform to space-charge-limited (SCL) current governed by traps uniformly distributed in energy. At higher d.c. voltages, a nearly Mott–Gurney V2 behaviour of the dark current has been observed, whereas the I–V behaviour of the illuminated specimen was a combination of an ohmic conduction and a V2 dependence at low illumination levels and became highly ohmic at large light intensities. This behaviour can be understood in terms of a reduction in the SCL dark current in favour of a larger ohmic d.c. photocurrent as a result of neutralization of the majority-carrier space charge by the photogenerated minority carriers of the electron–hole pairs produced under the illumination with visible light of energy ℏω≅EG(∼2.1–2.3 eV for the Pb₂CrO₅ material). The d.c. photocurrent, I_phot, at a fixed d.c. voltage, was found to follow a power-law dependence on light intensity, F, of the form I_phot∝F^γ, with the exponent γ being dependent on the applied d.c. voltage. At the low-voltage side (V_d.c.<1.5 V), γ∼0.5, a value usually obtained when the photoconductivity behaviour is governed by bimolecular recombination mechanisms. As the d.c. voltage is increased further, γ increases monotonically until it saturates at a value of about 0.9 for d.c. voltages beyond 3.5 V, where monomolecular recombination processes seem to be more operative with increasing d.c. voltage. This revised version was published online in November 2006 with corrections to the Cover Date.     

Simulation of forward dark current voltage characteristics of tandem solar cells

The transport mechanisms tailoring the shape of dark current-voltage characteristics of amorphous and microcrystalline silicon based tandem solar cell structures are explored with numerical simulations. Our input parameters were calibrated by fitting experimental current voltage curves of single and double junction structures measured under dark and illuminated conditions. At low and intermediate forward voltages the dark current-voltage characteristics show one or two regions with a current-voltage exponential dependence. The diode factor is unique in tandem cells with the same material in both intrinsic layers and two dissimilar diode factors are observed in tandem cells with different materials on the top and bottom intrinsic layers. In the exponential regions the current is controlled by recombination through gap states and by free carrier diffusion. At high forward voltages the current grows more slowly with the applied voltage. The current is influenced by the onset of electron space charge limited current (SCLC) in tandem cells where both intrinsic layers are of amorphous silicon and by series resistance of the bottom cell in tandem cells where both intrinsic layers are of microcrystalline silicon. In the micromorph cell the onset of SCLC becomes visible on the amorphous top sub-cell. The dark current also depends on the thermal generation of electron-hole (e-h) pairs present at the tunneling recombination junction. The highest dependence is observed in the tandem structure where both intrinsic layers are of microcrystalline silicon. The prediction of meaningless dark currents at low forward and reverse voltages by our code is discussed and one solution is given.     

Inside Front Cover: Mobility and Dynamics of Charge Carriers in Rubrene Single Crystals Studied by Flash‐Photolysis Microwave Conductivity and Optical Spectroscopy (Adv. Mater. 5/2008)

Electrodeless photoconductivity measurements of a rubrene single crystal are performed by microwave conductivity and transient optical spectroscopy, demonstrating anisotropy and ambipolarity. From these comprehensive studies, Akinori Saeki, Seiichi Tagawa, and co‐workers discuss on p. 920 the optoelectronic properties of rubrene single crystal in terms of charge recombination of holes and electrons, exciton–exciton annihilation, quantum efficiency of charge carrier generation, triplet contribution, and the extinction coefficients of ionic species accessed by pulse radiolysis.     

Electric field effect on photoconductivity decay in <Emphasis Type="Italic">n</Emphasis>-InSe single crystals

We have studied the effect of external electric field on the transient response of the intrinsic photoconductivity of n-InSe single crystals with various initial 77-K dark resistivities (ρ_d). The results demonstrate that the behavior of the intrinsic photoconductivity of the crystals depends on both ρ_d and applied voltage. In low electric fields, the predominant process in both the low-resistivity and high-resistivity crystals is the capture of current carriers at stoichiometric point defects in low and higher electric fields, respectively. At the same time, in the high-resistivity crystals in high electric fields the influence of partial disorder related to the layered crystal structure of the material should be taken into account.     

Structural, electrical and anisotropic properties of Tl4Se3S chain crystals

The structure, the anisotropy effect on the current transport mechanism and the space charge limited current in Tl₄Se₃S chain crystals have been studied by means of X-ray diffraction, electrical conductivity measurements along and perpendicular to the crystal's c-axis and the current voltage characteristics. The temperature-dependent electrical conductivity analysis in the region of 150–400 K, revealed the domination of the thermionic emission of charge carriers over the chain boundaries above 210 and 270 K along and perpendicular to the c-axis, respectively. Below these temperatures, the variable range hopping is dominant. At a consistent temperature range, the thermionic emission analysis results in conductivity activation energies of 280 and 182 meV, along and perpendicular to the c-axis, respectively. Likewise, the hopping parameters are altered significantly by the conductivity anisotropy. The current–voltage characteristics revealed the existence of hole trapping state being located at 350 meV above the valence band of the crystal.     

The effect of adsorbates on the space-charge-limited current in single ZnO nanowires

We studied the influence of adsorbates on the space-charge-limited current (SCLC) in individual ZnO nanowires through varying the bias voltage, laser illumination, and ambient pressure. In dark and air conditions, the free carriers were depleted by the surface adsorbates, and electrons injected from the electrode to the nanowire dominated the electron transport properties. Under laser illumination, the current-voltage characteristic was linear at low voltage and superlinear at high voltage, and the SCLC regime occurred at high voltages due to the surface desorption. The time response of photoconductivity further revealed the dynamic process of elimination of SCLC by desorption of oxygen molecules at the ZnO nanowire surface.     

Charge conduction and photogeneration process in hybrid materials of conjugated polymer and dye-sensitized TiO2 thin-film device

A thin-film hybrid structure consisting of dye-sensitized TiO₂ in combination with polypyrrole (PPy) is developed over indium tin oxide (ITO)-coated glass substrate. The steady-state photoconductivity and current–voltage (J–V) characteristics were recorded in the dark as well as under illumination for the fabricated device having the structure ITO/PPy/TY+TiO₂/Al. The current–voltage (J–V) characteristics of the device in the dark are explained by the formation of percolation networks of nano-particles between the electrodes. The device becomes symmetric at high voltage suggesting the electron injection from the electrodes into the conduction band of TiO₂ under both bias (reverse and forward) directions and the respective current is controled by charge carrier transport. Photoaction spectra of the device prove that the photogeneration of charge carriers is significantly enhanced and spectrally broadened only if electron transfer from the polymers to the dye is possible. It is also found that the increase in concentration of nano-particles changes the spectral shape of the hybrid structure as well as the photoresponse. These results show that a significant photoresponse can be achieved in hybrid materials of dye-sensitized TiO₂ nano-particles dispersed in conducting polymer.     

Photoconductivity of iodine-doped single crystals of phthalocyanine

Single crystals of metal-free phthalocyanine (H₂Pc) and of copper phthalocyanine (CuPc) were grown in the presence of iodine vapour. The presence of iodine enhances the spectral dependence of photoconductivity of H₂Pc in the visible region but of CuPc in the near-IR region. The dark current is decreased but the photocurrent is increased by one order of magnitude in iodine-doped H₂Pc but in the case of iodine-doped CuPc both currents are increased by nearly three orders of magnitude. Introduction of iodine results in about one order of magnitude decrease in response time for both modifications. Thus the introduction of iodine into Pc crystals decreases the energy barrier for conduction and increases the drift mobility of charge carriers thereby enhancing the conductivity of the material.     

Stochastic models of partial discharge activity in solid and liquid dielectrics

A new model that can reproduce main stochastic features of partial discharge (PD) activity at AC and DC voltages was proposed. The type of PD activity because of microdischarges in small cavities present in dielectric materials was considered. Three different criteria were used to simulate an initiation of partial discharge inside voids. The simplest criterion of threshold type was used also to describe a decay of plasma in voids and subsequent decrease in conductivity to zero. After AC voltage was applied to solid dielectric, the narrow peaks of current in external circuit were observed in our simulations. Every peak corresponds to a moment of PD in a void. The behaviour of cavities in dielectric liquid under DC voltage was also simulated. In this case, PD activity is possible even under DC voltage because of both elongation of microbubbles present in a liquid and diffusion of charge carriers from the surface of a bubble into a liquid.     

Space charge limited currents in graded films

The equilibrium current density is calculated for films in which the conductivity is a function of depth. Three specific cases are considered: (a) conductivity falling monotically with distance away from the injecting electrode; (b) conductivity rising monotonically; and (c) conductivity sharply peaked in the middle of the specimen. In all cases the current density is ohmic at low voltage and obeys the Mott-Gurney law at high applied voltage. There is a smooth transition between the limits, with no negative resistance region, and switching is unlikely to occur for this combination of ohmic and space charge limited transport mechanisms.     

Water-soluble polythiophene-single walled carbon Nanotube bulk heterojunction

Two symmetrical terminal electrodes made of indium tin oxide (ITO) were employed to study the current-voltage characteristics of a bulk-heterojunction consisting of water soluble polythiophene and single walled carbon nanotubes (SWCNT). However, the current-voltage curves were asymmetrical, attributed to the polarization induced by the initial bias voltage. The polymer-SWCNT heterojunction were superior to the pristine polymer in both dark conductivity and photoconductivity by two orders of magnitude. Additionally, the open-cell voltage of 0.075 V was observed from the heterojunction even though the electrodes were symmetrical. The high conductivity and photoresponse originated from the high conductivity, high interconnectivity and hole doping capability of CNT.     

Effects of band gap illumination on surface layers of lead iodide

Thin films of lead iodide (PbI₂) decompose under band gap illumination, giving rise to iodine desorption and the formation of lead aggregates. We report on mass spectrometry, conductivity and photoconductivity measurements made in order to define the desorbing species and to elucidate the dissociation mechanism. The desorption rates of atomic and molecular iodine, together with the dark conductivity and the photoconductivity, were measured as functions of the PbI₂ film temperature in the range 300–500 K. The molecular desorption in particular seems to undergo a transition from a diffusion-controlled process (which governs the dark conductivity and the atomic iodine desorption) to a process dominated by the concentration of photoholes at temperatures above 400 K. At these temperatures a striking resemblance appears between the variations in the molecular iodine desorption and the photoconductivity with temperature. This leads us to suggest a model in which the iodine molecules are primarily evolved at special surface sites, e.g. grain boundaries, which also dominate the photoconductivity.     

Current transport mechanisms for heterojunctions of a-Se on various crystalline wafers (n-Si, p-Si and n-GaAs)

Heterojunction diodes fabricated by thermal evaporation of p-type amorphous selenium (a-Se) on various crystalline wafers (n-Si, p-Si and n-GaAs) are analyzed by measuring their current-voltage (J-V) characteristics. The measured J-V characteristics for the investigated devices of configuration Au/a-Se/c-wafer/Al, exhibit a rectifying behavior and the bulk effect of the a-Se layer. For low forward voltage, the conduction mechanism is dominated by recombination of the carriers in the amorphous side of the space charge region. At higher voltage, the J-V characteristics could be divided into two regions: an ohmic region and a space charge limited current region. The values of the activation energy obtained from the ohmic region are in agreement with those obtained from dc conductivity measurements in the same range of temperature. The reverse bias activation energy values at different temperatures are in agreement with those obtained from the temperature dependence of the forward saturation current, supporting the proposed recombination mechanism of conduction.     

Dielectric relaxation and thermal studies on dispersed phase polymer nanocomposite films

Dispersed phase polymer nanocomposite films (PNC) based on PMMA–LiClO₄+ n-YSZ, has been prepared. The effect of filler concentration on dielectric constant, tanδ and ac conductivity has been observed. For each PNC films the activation energy for relaxation (E_τ) is almost same as the activation energy for ion conduction (E_a). The dc conductivity, the hopping frequency of charge carriers have been obtained at different temperature from the analysis of the ac conductivity data. For all the PNC films, the concentration of charge carriers has been calculated at different temperature using Almond–West formalism. The estimated activation energies for the dc conductivity and the hopping frequency are different, which indicates that the both charge carrier mobility and concentration contribute significantly to the ionic conductivity of polymeric electrolyte. Contribution of charge carrier mobility to the total conductivity has also been confirmed from the differential scanning calorimetry analysis. Improvement in thermal stability has been noticed with filler addition.     

Ionic space-charge effects in solid state organic photovoltaics

The effect of mobile ions on the operation of donor-acceptor bilayer solar cells is studied. We demonstrate the large effect ions can have on the energetics of the solar cells, illustrated by (for instance) changing the output voltage of a cell in situ from 0.35 to 0.74 V. More importantly, it is shown ionic species do not obstruct the charge generating properties of the photovoltaic devices and ionic space charge can be used in situ to improve their efficiencies. The results obtained are explained by taking into account energetic changes at the donor-acceptor interface as well as built-in potentials, giving clear guidelines on how ionic species can offer many new and exciting functionalities to organic photovoltaics.     

A study on the DC electrical properties of PAN-based carbon fiber/polycarbonate composites

The DC conductivity and Hall effect studies were used to investigate the nature, type, and development of the charge carriers in conductive polymer composite containing PAN-based carbon fibers of different concentration. The dependence of the electrical conductivity on temperature is characterized by a two-stage electrical conduction process with a semiconducting type of behavior and two activation energies. It was found the measured Hall voltage varies linearly with Hall current with two different signs of slopes. This suggests that a composite of low fiber content is functioning as p-type material, and then changes to n-type with increasing the carbon fiber content more than 15 wt.%. The density of the charge carriers increases with carbon fiber content in a behavior similar to the electrical conductivity for all given composites, showing a percolation phenomenon. The calculated charge carriers density includes both the magnetostatic arising from the polycarbonate matrix and from the free charge carriers themselves. Considering the filled carbon fibers as a random semiconducting material, the results obtained for various composites were described in terms of the band structure model. Other approach of results analysis was based on the composite bulk morphology observed by the SEM microscopy.     

Investigation of exciton photodissociation, charge transport and photovoltaic response of poly(N-vinyl carbazole):TiO(2) nanocomposites for solar cell applications

The photogeneration of charge carriers in spin-coated thin films of nanocrystalline (nc-)TiO(2) particles dispersed in a semiconducting polymer, poly(N-vinylcarbazole) (PVK), has been studied by photoluminescence and charge transport measurements. The solvent and the TiO(2) particle concentration have been selected to optimize the composite morphology. A large number of small domains leading to a large interface and an improved exciton dissociation could be obtained with tetrahydrofuran (THF). The charge transport mechanism and trap distribution at low and high voltage in ITO/nc-TiO(2):PVK/Al diodes in the dark could be identified by current-voltage measurements and impedance spectroscopy. The transport mechanism is space charge limited with an exponential trap distribution in the high voltage regime (1-4?V), whereas a Schottky process with a barrier height of about 0.9?eV is observed at low bias voltages (<1?V). The current-voltage characteristics under white illumination have shown a dramatic increase of the short circuit current density J(sc) and open circuit voltage V(oc) for a 30% TiO(2) volume content corresponding to the morphology exhibiting the best dispersion of TiO(2) particles. A degradation of the photovoltaic properties is induced at higher compositions by the formation of larger TiO(2) aggregates. A procedure has been developed to extract the physical parameters from the J-V characteristics in the dark and under illumination on the basis of an equivalent circuit. The variation of the solar cell parameters with the TiO(2) composition confirms that the photovoltaic response is optimum for 30% TiO(2) volume content. It is concluded that the photovoltaic properties of nc-TiO(2):PVK nanocomposites are controlled by the interfacial area between the donor and the acceptor material and are limited by the dispersion of the TiO(2) nanoparticles in the polymer.