Direct measurement of the temperature coefficient of the electron quasi-fermi level in dye-sensitized nanocrystalline solar cells using a titanium sensor electrode

A novel type of dye-sensitized cell (DSC) with a passivated titanium sensor electrode located on top of the nanocrystalline titanium dioxide layer has been used to study the temperature dependence of the electron quasi-Fermi level relative to the I3-/I- redox-Fermi level under short circuit conditions. The results show that the Fermi level decreases with increasing temperature (-1.76 meV K(-1)) as predicted for diffusive electron transport at short circuit. A smaller temperature dependence (-0.25 meV K(-1)) of the position of the TiO2 conduction band relative to the I3-/I- redox-Fermi level was deduced from the shifts in the trap distribution. An expression for the temperature dependence of the open circuit voltage, U(photo), has been derived. The experimentally observed temperature dependence of U(photo) gave values of the activation energy (0.25 eV) and preexponential factor (10(8) s(-1)) for the transfer of electrons from the conduction band of the nanocrystalline TiO2 to triiodide ions.     

Grain morphology and trapping effects on electron transport in dye-sensitized nanocrystalline solar cells

We have examined the combined effects of grain morphology and electron trapping on the transient response of photoelectrons moving through the TiO2 grains in a dye-sensitized nanocrystalline solar cell using a multi-time-scale random walk Monte Carlo model. Our use of a multi-time-scale approach enables us to simulate transport for electrons moving through spherical connected grains in a three-dimensional (3D) voided network and look at the effect of the size of interparticle boundaries on carrier dynamics. We can also address similar times to those over which measurements are taken, namely, 0.1 ms. These times are long because of deep traps in the TiO2 grains. The grains have 2-fold connectivity in one dimension (linear chains) or 4-fold or 6-fold connectivity in three dimensions and traps with an exponential distribution of energies. Photoelectrons are generated by a light pulse of short duration. The spatial distribution of the photogenerated electron density from this pulse either has a uniform profile or is peaked on the electrolyte side. We show that the constrictions at the grain necks slow the electrons, making trapping more likely and hence further delaying their passage to the extracting electrode. By comparing our results for 4-fold and 6-fold coordinated particles on a cubic lattice with 2-fold coordinated particles on linear chains, we show that transport is slowed in the former case due to the additional paths available to the electrons in the 3D network. We also find that the charge and current transients cannot be fit to an analytical solution of the continuum equations with an effective diffusion coefficient even at long times. Therefore, caution must be exercised when attempting to fit experimental transient data with an effective diffusion coefficient.     

强度调制光电流谱研究纳晶薄膜电极过程

用强度调制光电流谱研究半导体纳晶薄膜电极光生电荷的界面转移和输运动力学过程.从测量不同外加电压和不同硫化钠溶液浓度下CdSe纳晶薄膜电极的光电流响应得到了参数:归一化稳态光电流和表面态寿命,分析界面空穴的直接转移和通过表面态的间接转移过程.通过测量不同背景光强下TiO2纳晶薄膜电极的电子扩散系数研究电子输运过程.应用HCl化学处理方法明显增大了电子扩散系数,改善了电子在TiO2纳晶薄膜电极中的输运性能.     

Comparison of Trap‐state Distribution and Carrier Transport in Nanotubular and Nanoparticulate TiO2 Electrodes for Dye‐Sensitized Solar Cells

Dye‐sensitized solar cells (DSCs) with nanotubular TiO₂ electrodes of varying thicknesses are compared to DSCs based on conventional nanoparticulate electrodes. Despite the higher degree of order in one‐dimensional nanotubular electrodes, electron transport times and diffusion coefficients, determined under short‐circuit conditions, are comparable to those of nanoparticulate electrodes. The quasi‐Fermi level, however, is much lower in the nanotubes, suggesting a lower concentration of conduction band electrons. This provides evidence for a much higher diffusion coefficient for conduction band electrons in nanotubes than in nanoparticulate films. The electron lifetime and the diffusion length are significantly longer in nanotubular TiO₂ electrodes than in nanoparticulate films. Nanotubular electrodes have a trap distribution that differs significantly from nanoparticulate electrodes; they possess relatively deeper traps and have a characteristic energy of the exponential distribution that is more than two times that of nanoparticulate electrodes.     

Determination of the density and energetic distribution of electron traps in dye-sensitized nanocrystalline solar cells

Electron transport and recombination in dye-sensitized nanocrystalline solar cells (DSCs) are strongly influenced by the presence of trapping states in the titanium dioxide particles, and collection of photoinjected electrons at the contact can require times ranging from milliseconds to seconds, depending on the illumination intensity. A direct method of determining the density and energetic distribution of the trapping states responsible for slowing electron transport has been developed. It involves extraction of trapped electrons by switching the cell from an open circuit to a short circuit after a period of illumination. An advantage of this charge extraction method is that it is less sensitive than other methods to shunting of the DSC by electron transfer at the conducting glass substrate. Results derived from charge extraction measurements on DSCs (with and without compact TiO(2) blocking layers) are compared with those obtained by analysis of the open circuit photovoltage decay.     

Interpretation of diffusion coefficients in nanostructured materials from random walk numerical simulation

We make use of the numerical simulation random walk (RWNS) method to compute the "jump" diffusion coefficient of electrons in nanostructured materials via mean-square displacement. First, a summary of analytical results is given that relates the diffusion coefficient obtained from RWNS to those in the multiple-trapping (MT) and hopping models. Simulations are performed in a three-dimensional lattice of trap sites with energies distributed according to an exponential distribution and with a step-function distribution centered at the Fermi level. It is observed that once the stationary state is reached, the ensemble of particles follow Fermi-Dirac statistics with a well-defined Fermi level. In this stationary situation the diffusion coefficient obeys the theoretical predictions so that RWNS effectively reproduces the MT model. Mobilities can be also computed when an electrical bias is applied and they are observed to comply with the Einstein relation when compared with steady-state diffusion coefficients. The evolution of the system towards the stationary situation is also studied. When the diffusion coefficients are monitored along simulation time a transition from anomalous to trap-limited transport is observed. The nature of this transition is discussed in terms of the evolution of electron distribution and the Fermi level. All these results will facilitate the use of RW simulation and related methods to interpret steady-state as well as transient experimental techniques.     

Direct measurement of the internal electron quasi-Fermi level in dye sensitized solar cells using a titanium secondary electrode

The spatial dependence of the electron quasi-Fermi level (QFL) in the interior of dye sensitized nanocrystalline solar cells (DSC) under short circuit conditions can be inferred from calculations based on a diffusive electron transport model. The calculations predict that the difference in the QFL between the electrolyte and contact sides of the TiO(2) layer under short circuit conditions at 1 sun could be as much as 0.5-0.7 eV. The predicted QFL profiles depend on assumptions made about energy positions, electron mobility, and the conduction band density of states. In this work, the position of the QFL at the electrolyte side of the dye sensitized TiO(2) film in a DSC has been measured using a thin passivated titanium contact deposited on top of the nanocrystalline TiO(2) by evaporation. The method allows changes in the electron QFL at all points on the IV characteristic of the cell to be monitored under dark and photostationary conditions. In addition, cells incorporating the titanium electrode can give information about the behavior of the QFL under dynamic conditions.     

Influence of surface area on charge transport and recombination in dye-sensitized TiO2 solar cells

The dependence of the electron transport and recombination dynamics on the internal surface area of mesoporous nanocrystalline TiO2 films in dye-sensitized solar cells was investigated. The internal surface area was varied by altering the average particle size in the films. The scaling of the photoelectron density and the electron diffusion coefficient at short circuit with internal surface area confirms the results of a recent study (Kopidakis, N.; Neale, N. R.; Zhu, K.; van de Lagemaat, J.; Frank, A. J. Appl. Phys. Lett. 2005, 87, 202106) that transport-limiting traps are located predominately on the surfaces of the particles. The recombination current density was found to increase superlinearly (with an exponent of 1.40 +/- 0.12) with the internal surface area. This result is at odds with the expected linear dependence of the recombination current density on the surface area when only the film thickness is increased. The observed scaling of the recombination current density with surface area is consistent with recombination being transport-limited. Evidence is also presented confirming that photoinjected electrons recombine with redox species in the electrolyte via surface states rather than from the TiO2 conduction band.     

A novel charge extraction method for the study of electron transport and interfacial transfer in dye sensitised nanocrystalline solar cells

A novel charge extraction method has been developed to study the transport, trapping and back reaction of photogenerated electrons in dye sensitised nanocrystalline cells (Grätzel cells). The cell is illuminated at open circuit until a steady state is reached in which the rates of photogeneration and of back reaction of electrons with tri-iodide are equal. The illumination is then interrupted, and the electron density is allowed to decay for a given time in the dark before short circuiting the cell using a solid state switch. For high efficiency cells, the integrated current measured at short circuit corresponds closely to the remaining electronic charge in the film. Small corrections are required to account for back reaction and substrate charging. The delay time between interruption of the illumination and short circuit charge extraction is varied systematically to follow the decay of electron concentration. Analysis of the time dependence of the electron charge indicates that the back reaction of electrons with I₃⁻ is second order in electron density, which is consistent with the formation of I₂^−. as an intermediate. Simultaneous measurement of the charge and photovoltage decay curves shows that the density of trap states decreases exponentially with trap depth.     

Electron transport in coumarin-dye-sensitized nanocrystalline TiO2 electrodes

We investigated electron transport kinetics in terms of electron diffusion coefficient (D) and electron lifetime (tau) in coumarin-dye-sensitized nanocrystalline TiO2 electrodes by intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS). We found that the values of tau for coumarin-dye-sensitized TiO2 electrodes were much shorter than that for an electrode coated with a Ru complex (N719 dye), suggesting that the back-electron-transfer process corresponding to recombination between conduction-band electrons in the TiO2 and I3- ions in the electrolyte occurs more easily in coumarin-dye-sensitized solar cells. In addition, the values of tau depended on the kind of coumarin dye, each of which has a different number of thiophene moieties, suggesting that the molecular structure of the adsorbed dyes also affects the kinetics of electron transport in the TiO2 electrodes.     

Reduction of electroactive polymers via polyelectron transfer processes at solid electrodes

The reduction of an electroactive polymer at an electrode involves the transfer of a large number of electrons to a single molecule. A quantitative study of this process indicates whether the system behaves ideally. The electron transfer process in polyvinylbenzophenone and in polyvinylbenzophenone-co-styrene in N,N-dimethylformamide solution was investigated by voltammetry at a rotating disk electrode. It is concluded that benzophenone (BP) groups attached to the polymer backbone are noninteracting electroactive centers and that every BP group is reducible at the electrode. The relationship between limiting current and molecular weight was examined quantitatively for a series of polymers of low dispersity with molecular weights ranging up to 300,000, and with a controlled, varied content of electroactive groups. The diffusion coefficient was determined as a function of molecular weight from the electrochemical data, and was found to be in good agreement with the theoretical model based on transport properties. The dependence of the diffusion coefficient on concentration of polymer and on temperature were investigated and activation energies determined.     

Calculation of activation energies for transport and recombination in mesoporous TiO2/dye/electrolyte films--taking into account surface charge shifts with temperature

Transient photovoltage and photocurrent measurements have been employed to determine the recombination and transport kinetics in operating dye-sensitized photovoltaic cells as a function of potential and temperature. Photocurrent transients have been taken at the open circuit potential, as opposed to the standard measurement at short circuit. Kinetic results have been used to calculate the activation energy as function of the Fermi level position in the TiO(2). In the calculation of activation energies, we have explicitly taken into account the temperature dependence of the offset between the electrolyte redox potential and the conduction band edge. This new method gives activation energies that decrease linearly as the Fermi level position moves toward the conduction band edge, as expected, but not found in previous studies. The results are consistent with the presence of a distribution of traps below the TiO(2) conduction band, the detrapping from which limits both the transport and the recombination of electrons.     

Interpretation of electron diffusion coefficient in organic and inorganic semiconductors with broad distributions of states

The carrier transport properties in nanocrystalline semiconductors and organic materials play a key role for modern organic/inorganic devices such as dye-sensitized (DSC) and organic solar cells, organic and hybrid light-emitting diodes (OLEDs), organic field-effect transistors, and electrochemical sensors and displays. Carrier transport in these materials usually occurs by transitions in a broad distribution of localized states. As a result the transport is dominated by thermal activation to a band of extended states (multiple trapping), or if these do not exist, by hopping via localized states. We provide a general view of the physical interpretation of the variations of carrier transport coefficients (diffusion coefficient and mobility) with respect to the carrier concentration, or Fermi level, examining in detail models for carrier transport in nanocrystalline semiconductors and organic materials with the following distributions: single and two-level systems, exponential and Gaussian density of states. We treat both the multiple trapping models and the hopping model in the transport energy approximation. The analysis is simplified by thermodynamic properties: the chemical capacitance, C(mu), and the thermodynamic factor, chi(n), that allow us to derive many properties of the chemical diffusion coefficient, D(n), used in Fick's law. The formulation of the generalized Einstein relation for the mobility to diffusion ratio shows that the carrier mobility is proportional to the jump diffusion coefficient, D(J), that is derived from single particle random walk. Characteristic experimental data for nanocrystalline TiO(2) in DSC and electrochemically doped conducting polymers are discussed in the light of these models.     

Spatial electron distribution and its origin in the nanoporous TiO2 network of a dye solar cell

Dye solar cells have been investigated by charge carrier extraction under short and open circuit conditions and an illumination intensity equivalent to 1 sun (AM 1.5). Under short circuit conditions, a surprisingly high amount of charge carriers stored in the nanoporous TiO2 network has been observed. A theoretical model was developed to describe the charge transport in the nanoporous TiO2 network of a dye solar cell, and the spatial distribution of the electron concentration was calculated. These results were compared with the experimental data of charge carriers stored in the TiO2 network under short and open circuit conditions. We were able to conclude that under short circuit conditions, the electrochemical potential of the electrons in the region far from the electrode is up to 550-570 meV higher than that of the electrons at the front electrode. This internal voltage is the driving force across the nanoporous TiO2 film under short circuit conditions.     

The Influence of Charge Transport and Recombination on the Performance of Dye‐Sensitized Solar Cells

Electrochemical impedance spectroscopy (EIS) and transient voltage decay measurements are applied to compare the performance of dye sensitized solar cells (DSCs) using organic electrolytes, ionic liquids and organic‐hole conductors as hole transport materials (HTM). Nano‐crystalline titania films sensitized by the same heteroleptic ruthenium complex NaRu(4‐carboxylic acid‐4′‐carboxylate) (4,4′‐dinonyl‐2,2′‐bipyridyl)(NCS)₂ , coded Z‐907Na are employed as working electrodes. The influence of the nature of the HTM on the photovoltaic figures of merit, that is, the open circuit voltage, short circuit photocurrent and fill factor is evaluated. In order to derive the electron lifetime, as well as the electron diffusion coefficient and charge collection efficiency, EIS measurements are performed in the dark and under illumination corresponding to realistic photovoltaic operating conditions of these mesoscopic solar cells. A theoretical model is established to interpret the frequency response off the impedance under open circuit conditions, which is conceptually similar to photovoltage transient decay measurements. Important information on factors that govern the dynamics of electron transport within the nanocrystalline TiO₂ film and charge recombination across the dye sensitized heterojunction is obtained.     

Dry excess electrons in room-temperature ionic liquids

In this article, we describe general trends to be expected at short times when an excess electron is generated or injected in different room-temperature ionic liquids (RTILs). Perhaps surprisingly, the excess electron does not localize systematically on the positively charged cations. Rather, the excess charge localization pattern is determined by the cation and anion HOMO/LUMO gaps and, more importantly, by their relative LUMO alignments. As revealed by experiments, the short-time (ps/ns) transient UV spectrum of excess electrons in RTILs is often characterized by two bands, a broad band at low energies (above 1000 nm) and another weaker band at higher energies (around 400 nm). Our calculations show that the dry or presolvated electron spectrum (fs) also has two similar features. The broad band at low energies is due to transitions between electronic states with similar character on ions of the same class but in different locations of the liquid. The lower-intensity band at higher energies is due to transitions in which the electron is promoted to electronic states of different character, in some cases on counterions. Depending on the chemical nature of the RTIL, and especially on the anions, excess electrons can localize on cations or anions. Our findings hint at possible design strategies for controlling electron localization, where electron transfer or transport across species can be facilitated or blocked depending on the alignment of the electronic levels of the individual species.     

Low temperature kinetics and energetics of the electron and hole traps in irradiated TiO2 nanoparticles as revealed by EPR spectroscopy

We have monitored exclusively the dynamics of photogenerated charge carriers trapping in deep traps and trapped electron-hole recombination in UV irradiated anatase TiO2 powders by electron paramagnetic resonance (EPR) spectroscopy at 10 K. The results reveal that the strategy of using low temperatures contributes to the stabilization of the charged pair states for hours by reducing the rate of electron-hole recombination processes. Since only the localized states such as holes trapped at oxygen anions and electrons trapped at coordinatively unsaturated cations are accessible to EPR spectroscopy, the time-dependent population and depopulation of these EPR signals reflect the kinetics and energetics of these trap states. The data support a model of sequential accumulation of deep trap site populations in which the initial fast direct trapping into a deep trap site is followed by slower carrier trap-to-trap hopping until a deep trap is encountered for both photogenerated electrons and holes. Effective modeling of the subsequent decay of trapped-holes is achieved by employing a first-order kinetics, whereas the decay of either surface- or inner-trapped electrons has both a fast and a slow component. The fast component is attributed to a trapped-electron and a free-hole recombination, and the slow component is attributed to trapped electron-hole recombination. The activation energies for the process of diffusion of trapped electrons from their Ti3+ trapping sites are estimated.     

Activation energy of electron transport in dye-sensitized TiO2 solar cells

Various characteristics of dye-sensitized nanostructured TiO2 solar cells, such as electron transport and electron lifetime, were studied in detail using monochromatic illumination conditions. The electron transport was found to be a thermally activated process with activation energies in the range of 0.10-0.15 eV for light intensities that varied 2 orders of magnitude. Electron lifetimes were determined using a new method and found to be significantly larger (>1 s) than previously determined. An average potential was determined for electrons in the nanostructured TiO2 under illumination in short-circuit conditions. This potential is about 0.2 V lower than the open-circuit potential at the same light intensity. The electron transport time varies exponentially with the internal potential at short-circuit conditions, indicating that the gradient in the electrochemical potential is the driving force for electron transport in the nanostructured TiO2 film. The applicability of the conventionally used trapping/detrapping model is critically analyzed. Although experimental results can be fitted using a trapping/detrapping model with an exponential distribution of traps, the distribution parameters differ significantly between different types of experiment. Furthermore, the experimental activation energies for electron transport are smaller than those expected in a trapping/detrapping model.     

Dye-sensitized solar cells based on oriented TiO2 nanotube arrays: transport, trapping, and transfer of electrons

Dye-sensitized solar cells fabricated using ordered arrays of titania nanotubes (tube lengths 5, 10, and 20 microm) grown on titanium have been characterized by a range of experimental methods. The collection efficiency for photoinjected electrons in the cells is close to 100% under short circuit conditions, even for a 20 microm thick nanotube array. Transport, trapping, and back transfer of electrons in the nanotube cells have been studied in detail by a range of complementary experimental techniques. Analysis of the experimental results has shown that the electron diffusion length (which depends on the diffusion coefficient and lifetime of the photoinjected electrons) is of the order of 100 microm in the titania nanotube cells. This is consistent with the observation that the collection efficiency for electrons is close to 100%, even for the thickest (20 microm) nanotube films used in the study. The study revealed a substantial discrepancy between the shapes of the electron trap distributions measured experimentally using charge extraction techniques and those inferred indirectly from transient current and voltage measurements. The discrepancy is resolved by introduction of a numerical factor to account for non-ideal thermodynamic behavior of free electrons in the nanostructured titania.