Simultaneous determination of carrier lifetime and electron density-of-states in P3HT:PCBM organic solar cells under illumination by impedance spectroscopy

We report new insights into recombination kinetics in poly(3-hexylthiophene):methanofullerene (P3HT:PCBM) bulk heterojunction (BHJ) solar cells, based on simultaneous determination of the density of states (DOS), internal recombination resistance, and carrier lifetime, at different steady states, by impedance spectroscopy. A set of measurements at open circuit under illumination was performed aiming to better understand the limitations to the photovoltage, which in this class of solar cells remains far below the theoretical limit which is the difference between the LUMO level of PCBM and the HOMO of P3HT (∼1.1 eV). Recombination kinetics follows a bimolecular law, being the recombination ti…

Inverted Solution Processable OLEDs Using a Metal Oxide as an Electron Injection Contact.

A new type of bottom-emission electroluminescent device is described in which a metal oxide is used as the electron-injecting contact. The preparation of such a device is simple. It consists of the deposition of a thin layer of a metal oxide on top of an indium tin oxide covered glass substrate, followed by the solution processing of the light-emitting layer and subsequently the deposition of a high-workfunction (air-stable) metal anode. This architecture allows for a low-cost electroluminescent device because no rigorous encapsulation is required. Electroluminescence with a high brightness reaching 5700 cd m–2 is observed at voltages as low as 8 V, demonstrating the potential of this new a…

Thickness scaling of space-charge-limited currents in organic layers with field- or density-dependent mobility

An exact solution is provided for the current density-voltage (J –V) characteristics of space-charge limited transport of a single carrier in organic layers with field-dependent mobility of the type μ (E) = μ0 exp (γ √E. The general scaling relationship for field-dependent mobility occurs in terms of the variables JL and V /L. For the density-dependence of the mobility found in organic field-effect transistor measurements, the thickness scaling occurs in terms of different variables, J1/βL and V /L. The proposed scaling is a useful test for distinguishing field- and carrier density-dependent mobility in disordered organic semiconductors. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Perimeter leakage current in polymer light emitting diodes

Observation of leakage current paths through the device perimeter in standard poly(phenylene vinylene)-based light-emitting devices is reported. Perimeter leakage currents govern the diode performance in reverse and low positive bias and exhibit an ohmic character. Current density correlates with the perimeter-to-area ratio thus indicating that leakage currents are mainly confined on polymer regions in the vicinity of metallic contact limits (device perimeter). © 2008 Elsevier B.V. All rights reserved.

Operating Modes of Sandwiched Light-Emitting Electrochemical Cells

Light-emitting electrochemical cells (LECs) are promising lighting devices in which the redistribution of ionic charges allows for double electronic carrier injection from air-stable electrodes. Uncertainties about the mode of operation are limiting the progress of these devices. Using fast (with respect to the current growth time) but resolutive electrical measurement techniques, the electronic transport mechanism in state-of-the-art sandwiched devices can be monitored as a function of the operation time. The results indicate the formation of doped transport layers adjacent to the electrodes that reduces the extent of the central neutral light-emitting layer where electronic transport is l…

Impedance of space-charge-limited currents in organic light-emitting diodes with double injection and strong recombination

The impedance model for a one-carrier space-charge-limited (SCL) current has been applied to explain some experimental features of double carrier organic light-emitting diodes. We report the analytical model of impedance of bipolar drift transport in SCL regime in the limit of infinite recombination. In this limit the ac impedance function is identical to that of a single carrier device, with a transit time modified by the sum of mobilities for electrons and holes, μn+μp. The static capacitance C(ω→0) is a factor of ¾ lower than the geometric capacitance, as observed for single carrier devices, but it is shifted to higher frequencies. It follows that impedance measurements in the dual-carri…

Band unpinning and photovoltaic model for P3HT:PCBM organic bulk heterojunctions under illumination

Capacitance analysis of P3HT:PCBM bulk heterojunction solar cells, in dark and under illumination, shows a linear Mott-Schottky characteristic at moderate reverse bias, indicating p-doping of the organic blend. The flatband potential under illumination is displaced negatively about 0.6 V with respect to dark conditions. A basic photovoltaic model is developed to explain this, in terms of electron transfer via surface states at the metal/organic interface. Surface states with a slow exchange kinetics, become charged under illumination, unpinning the band and decreasing the depletion layer at the electron extraction contact. This becomes a major factor limiting the performance of bulk heteroj…

The quantum relativistic harmonic oscillator: generalized Hermite polynomials

A relativistic generalisation of the algebra of quantum operators for the harmonic oscillator is proposed. The wave functions are worked out explicitly in configuration space. Both the operator algebra and the wave functions have the appropriate c→∞ limit. This quantum dynamics involves an extra quantization condition mc2/ωℏ = 1, 32, 2, … of a topological character.

Three physical quantum manifolds from the conformal group

Effects of Frequency Dependence of the External Quantum Efficiency of Perovskite Solar Cells

Perovskite solar cells are known to show very long response time scales, on the order of milliseconds to seconds. This generates considerable doubt over the validity of the measured external quantum efficiency (EQE) and consequently the estimation of the short-circuit current density. We observe a variation as high as 10% in the values of the EQE of perovskite solar cells for different optical chopper frequencies between 10 and 500 Hz, indicating a need to establish well-defined protocols of EQE measurement. We also corroborate these values and obtain new insights regarding the working mechanisms of perovskite solar cells from intensity-modulated photocurrent spectroscopy measurements, iden…

Plasmon-enhanced photocurrent in quasi-solid-state dye-sensitized solar cells by the inclusion of gold/silica core–shell nanoparticles in a TiO2 photoanode

Direct evidence of the effects of the localized surface plasmon resonance (LSPR) of gold nanoparticles (Au NPs) in TiO2 photoanodes on the performance enhancement in quasi-solid-state dye-sensitized solar cells (DSCs) is reported by comparing gold/silica core–shell nanoparticles (Au@SiO2 NPs) and hollow silica nanoparticles with the same shell size of the core–shell nanoparticles. The Au nanoparticles were shelled by a thin SiO2 layer to produce the core–shell structure, and the SiO2 hollow spheres were made by dissolving the Au cores of the gold/silica core–shell nanoparticles. Therefore, the size and morphology of the SiO2 hollow spheres were the same as the Au@SiO2 NPs. The energy conver…

Capacitance-voltage characteristics of organic light-emitting diodes varying the cathode metal: Implications for interfacial states

Capacitance-voltage $(C\text{\ensuremath{-}}V)$ characteristics of organic light-emitting diodes based on a polyphenylenevinylene have been measured by means of impedance spectroscopy. The effect of the metallic cathode (Au, Ag, Al, Mg, and Ba) was analyzed in the low-frequency region $(2\phantom{\rule{0.3em}{0ex}}\mathrm{Hz})$ of the capacitive response. The $C\text{\ensuremath{-}}V$ curves collapse into a single pattern in the low bias region, and exhibit a dependence on the cathode work function showing a crossover from positive to negative (inductive) values. The voltage corresponding to the onset of the inductive behavior shifts toward higher bias as the cathode work function increases…

Halide perovskite amplifiers integrated in polymer waveguides

Semiconductor organometallic halide perovskites (CH 3 NH 3 PbX 3 , X=Cl, Br, I) (HPVK) have emerged as a new promising material able to improve the optoelectronic technology performance. Although this material has mostly been applied to improve the efficiency of photovoltaic devices, it also shows amazing properties for photonic applications. In particular, HPVK exhibits high photoluminescence (PL) quantum yield (up to 70%) at room temperature together with a tunable band-gap controlled by its chemical composition. In addition, since HPVKs is deposited in solution at room conditions, it can be easily incorporated in different photonic structures to efficiently exploit its emission propertie…

Influence of the intermediate density-of-states occupancy on open-circuit voltage of bulk heterojunction solar cells with different fullerene acceptors

Electron density of states (DOS) and recombination kinetics of bulk heterojunction solar cells consisting of a poly(3-hexylthiophene) (P3HT) donor and two fullerene acceptors, either [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) or 4,4′-dihexyloxydiphenylmethano[60]fullerene (DPM6), have been determined by means of impedance spectroscopy. The observed difference of 125 mV in the output open-circuit voltage is attributed to significant differences of the occupancy of the DOS in both fullerenes. Whereas DPM6 exhibits a full occupation of the electronic band, occupancy is restricted to the tail of the DOS in the case of PCBM-based devices, implying a higher rise of the Fermi level in the D…

Recycled Photons Traveling Several Millimeters in Waveguides Based on CsPbBr 3 Perovskite Nanocrystals

Reabsorption and reemission of photons, or photon recycling (PR) effect, represents an outstanding mechanism to enhance the carrier and photon densities in semiconductor thin films. This work demonstrates the propagation of recycled photons over several mm by integrating a thin film of CsPbBr3 nanocrystals into a planar waveguide. An experimental set-up based on a frequency modulation spectroscopy allows to characterize the PR effect and the determination of the effective decay time of outcoupled photons. A correlation between the observed photoluminescence redshift and the increase of the effective decay time is demonstrated, which grows from 3.5 to near 9 ns in the best device. A stochast…

Relaxation of photogenerated carriers in P3HT:PCBM organic blends.

Relaxing in the sunlight. Long time-transient decays of photogenerated carriers in P3HT:PCBM blends for organic solar cells are interpreted in terms of the relaxation of hole carriers in a broad density of states. The after-pulse time-resolved microwave conductivity (TRMC) decays observed in P3HT:PCBM blends display a dependence on time close to t−β, independent of excitation intensity, in the 10 ns–1 μs range. This is explained in terms of the relaxation of carriers in a Gaussian density of states (DOS). The model is based on a demarcation level that moves with time by thermal release and retrapping of initially trapped carriers. The model shows that when the disorder is large the after-pu…

Interpretation of capacitance spectra and transit times of single carrier space-charge limited transport in organic layers with field-dependent mobility

The ac impedance characteristics of a single carrier with space-charge limited current (SCLC) transport in organic layers with field-dependent mobility is analyzed, indicating the similarities as well as the differences to the constant mobility case. The model provides capacitance spectra and transit times from different calculation methods, in relation to the electric field distribution in the SCLC regime. It is found that the low frequency capacitance lies in the range 3Cg/4 < Cif < Cg, with respect to the geometric capacitance Cg. An approximated expression for the variation of the transit time with applied bias is derived, in good agreement with exact calculations. Experimental results …

Crystalline-Size Dependence of Dual Emission Peak on Hybrid Organic Lead-Iodide Perovskite Films at Low Temperatures

In this work, we have investigated the crystalline-size dependence of optical absorption and photoluminescence emission of CH3NH3PbI3 films, which is necessary to identify the potential practical applications of the gadgets based on perovskite films. This study was carried out at low temperatures to minimize the extra complexity induced by thermal effects. The purpose was to clarify the origin of the dual emission peak previously reported in the literature. We found that the grain size is responsible for the appearance or disappearance of this dual emission on CH3NH3PbI3 at low temperatures, whereas we have inferred that the thickness of the perovskite layer is a much more important factor …

Millisecond radiative recombination in poly(phenylene vinylene)-based light-emitting diodes from transient electroluminescence

The current and electroluminescence transient responses of standard poly phenylene vinylene -based light-emitting devices have been investigated. The electroluminescence time response is longer milliseconds scale than the current switch-off time by more than one order of magnitude, in the case of small area devices 0.1 cm2 . For large area devices 6 cm2 the electroluminescence decay time decreases from 1.45 ms to 100 s with increasing bias voltage. The fast current decay limits the electroluminescence decay at higher voltages. Several approaches are discussed to interpret the observed slow decrease of electroluminescence after turning off the bias. One relies upon the Langevin-type bimolecu…

Negative capacitance caused by electron injection through interfacial states in organic light-emitting diodes

The negative capacitance frequently observed at low frequencies in organic light-emitting diodes (LEDs) is explained as a signature of sequential electron injection at the organic/metal interface first to states in the bandgap in the dipole layer and then to bulk states. The negative capacitance occurs when the interfacial states depart from equilibrium with the metal Fermi level due to an increasing rate of hopping to the bulk states. A simple kinetic model compares well with the experimental results and provides a new tool to investigate interfacial properties for improving the performance of organic LEDs.

Trap-limited mobility in space-charge limited current in organic layers

Space-charge limited current transport in organic devices, relevant to the operation of a range of organic optoelectronic devices, is analyzed in the frequency domain. The classical multiple trapping picture with one transport state and one trap level is used as the basis for the descriptions. By varying the energetic and kinetic properties of the traps, we show that the admittance and the capacitance spectra are considerably modified depending on the interplay between the trap-limited mobility and the trap kinetics. We point out that capacitance steps at low-frequency, usually found in experiments, are observed only for slow traps. © 2008 Elsevier B.V. All rights reserved.

The origin of slow electron recombination processes in dye-sensitized solar cells with alumina barrier coatings

We investigate the effect of a thin alumina coating of nanocrystalline TiO2 films on recombination dynamics of dye-sensitized solar cells. Both coated and uncoated cells were measured by a combination of techniques: transient absorption spectroscopy, electrochemical impedance spectroscopy, and open-circuit voltage decay. It is found that the alumina barrier reduces the recombination of photoinjected electrons to both dye cations and the oxidized redox couple. It is proposed that this observed retardation can be attributed primarily to two effects: almost complete passivation of surface trap states in TiO2 that are able to inject electrons to acceptor species, and slowing down by a factor of…

Polymer/Perovskite Amplifying Waveguides for Active Hybrid Silicon Photonics

The emission properties of hybrid halide perovskites are exploited to implement a stable and very low power operation waveguide optical amplifier integrated in a silicon platform. By optimizing its design with a poly(methyl methacrylate) (PMMA) encapsulation, this novel photonic device presents a net gain of around 10 dB cm−1 and 3–4 nm linewidth with an energy threshold as low as 2 nJ pulse−1 and exhibiting no degradation after one year. This work was supported by Generalitat Valenciana (Project No. ISIC/2012/008), the Universitat Jaume I (Project No. 12I361.01/1), Spanish MINECO (Projects Nos. MAT2013-47192-C3-1-R and TEC2014-53727-C2-1-R) and EU-NAVOLCHI (Project No. 288869).

Determination of electron and hole energy levels in mesoporous nanocrystalline TiO2 solid-state dye solar cell

A study of a hybrid heterojunction solar cell based on nanocrystalline mesoporous TiO2 and the hole conductor spiro-OMeTAD (2,2′7,7′-tetrakis(N,N′-di-p-methoxyphenyl-amine)-9,9′-spiro-bifluorene) has been realized. Impedance and cyclic voltammetry techniques were used to measure the interfacial properties of the hybrid heterojunction and establish the energy levels of the solid-state electrolyte. It was observed that the energy levels of the organic hole transport material are changed when it forms a film deposited onto indium-doped tin oxide (ITO). Moreover, the HOMO level of the mono oxidized spiro-OMeTAD is well coupled with the HOMO level of the dye N719 (Ru(4,4′-dicarboxy-2,2′-bipyridy…

Online Meetings in Times of Global Crisis: Toward Sustainable Conferencing

International conferences are an essential component of the timely exchange of ideas and results in the scientific community, where scientists present their results, gain new insights, and meet colleagues and collaborators. In early 2020, a global pandemic caused by a coronavirus (SARS-CoV-2) and the corresponding disease (covid-19) resulted in a number of conferences being canceled or postponed. (1) To foster scientific exchange despite the restrictions, a range of initiatives were launched across the globe to move international conferences online. (2−8) [...]