This paper analyzes the small signal ac impedance of electron diffusion and recombination in a spatially restricted situation with application in systems such as porous TiO2 nanostructured photoelectrodes and intrinsically conducting polymers. It is shown that the diffusion−recombination model with the main types of boundary conditions assumes a finite set of possible behaviors in the frequency domain, which are classified according to relevant physical parameters. There are four possible cases:  (i) the impedance of finite diffusion with reflecting boundary, (ii) the impedance of finite diffusion with absorbing boundary, (iii) the impedance of diffusion-reaction in semiinfinite space or Gerischer impedance, and (iv) the impedance that combines Warburg response at high frequency and a reaction arc at low frequency. The generality of the approach is discussed in terms of the spatial distribution of the electrochemical potential or quasi-Fermi level and also in terms of the transmission line representation....

Theory of the Impedance of Electron Diffusion and Recombination in a Thin Layer

We review the application of impedance spectroscopy in dye-sensitized solar cells, quantum dot-sensitized solar cells and organic bulk heterojunction solar cells. We emphasize the interpretation of the impedance parameters for determining the internal features of the device, concerning the carrier distribution, materials properties such as the density of states and/or doping of the semiconductors, and the match of energy levels for photoinduced charge generation and separation. Another central task is the determination of recombination mechanisms from the measured resistances, and the factors governing the device performance by combined analysis of resistances as a function of voltage and current–voltage curves.

Characterization of nanostructured hybrid and organic solar cells by impedance spectroscopy

Arylamine organic dyes with donor (D), π-bridge (π) and acceptor (A) moieties for dye-sensitized solar cells (DSCs) have received great attention in the last decade because of their high molar absorption coefficient, low cost and structural variety. In the early stages, the efficiency of DSCs with arylamine organic dyes with D–π–A character was far behind that of DSCs with ruthenium(II) complexes partly due to the lack of information about the relationship between the chemical structures and the photovoltaic performance. However, exciting progress has been recently made, and power conversion efficiencies over 10% were obtained for DSCs with arylamine organic dyes. It is thus that the recent research and development in the field of arylamine organic dyes employing an iodide/triiodide redox couple or polypyridyl cobalt redox shuttles as the electrolytes for either DSCs or solid-state DSCs has been summarized. The cell performance of the arylamine organic dyes are compared, providing a comprehensive overview of arylamine organic dyes, demonstrating the advantages/disadvantages of each class, and pointing out the field that needs to reinforce the research direction in the further application of DSCs.

Arylamine organic dyes for dye-sensitized solar cells

This paper presents a review of the redox and electrocatalytic properties of transition metal oxide electrodes, paying particular attention to the oxygen evolution reaction. Metal oxide materials may be prepared using a variety of methods, resulting in a diverse range of redox and electrocatalytic properties. Here we describe the most common synthetic routes and the important factors relevant to their preparation. The redox and electrocatalytic properties of the resulting oxide layers are ascribed to the presence of extended networks of hydrated surface bound oxymetal complexes termed surfaquo groups. This interpretation presents a possible unifying concept in water oxidation catalysis – bridging the fields of heterogeneous electrocatalysis and homogeneous molecular catalysis.

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Redox and electrochemical water splitting catalytic properties of hydrated metal oxide modified electrodes

Processes in the dark of electron transport and recombination in several nanoporous titanium dioxide films have been studied as a function of the applied potential, using the electrochemical impedance technique. Contact and bulk characteristics have been identified, decoupled, and interpreted, applying a transmission line model that identifies the following elements:  (i) the capacitance of the interface between the exposed surface of the substrate and the electrolyte, (ii) the electron transport resistance, (iii) the charge-transfer resistance distributed in the TiO2/electrolyte interface, and (iv) a distributed capacitive element related to charging the porous matrix. The model provides a satisfactory description of the spectra in widely different conditions of conductivity of the TiO2 phase. The electron conductivity has been determined as a function of applied potential and coincides for the different samples under study. Classical electrochemical frameworks of transport and interfacial charge transfe...

Decoupling of Transport, Charge Storage, and Interfacial Charge Transfer in the Nanocrystalline TiO2/Electrolyte System by Impedance Methods

Two new sensitizers for dye sensitized solar cells have been designed consisting of thiophene units asymmetrically functionalized by N-aryl carbazole. The di(tert-butyl) carbazole moieties acts as an electron donor group, the thiophene chain as a bridge group, and the cyanoacrylic acid as an anchoring and electron acceptor group. An increase of the conjugation length produces two main effects: first, it leads to a red-shift of the optical absorption of the dyes, resulting in an improved overlap of the absorption with the solar spectrum. Second, the oxidation potential decreases. The photovoltaic performance of this set of dyes as sensitizers in mesoporous TiO2 solar cells was investigated using electrolytes containing the iodide/triiodide redox couple. The dye with the best absorption characteristics showed the highest photocurrent but lower open circuit voltage due to more losses by recombination. A trend between structure (molecule dyes size) and recombination is demostrated using an analysis procedure ...

Francisco Fabregat Santiago

Papers

Quantification of the Effects of Recombination and Injection in the Performance of Dye-Sensitized Solar Cells Based on N-Substituted Carbazole Dyes

Application of a distributed impedance model in the analysis of conducting polymer films

Impedance spectroscopic analysis of high-performance dye sensitized solar cells based on nano-clay electrolytes