Charge collection and pore filling in solid-state dye-sensitized solar cells.

Nanotechnology 19:42 (2008) 424003

Authors:

Henry J Snaith, Robin Humphry-Baker, Peter Chen, Ilkay Cesar, Shaik M Zakeeruddin, Michael Grätzel

Abstract:

The solar to electrical power conversion efficiency for dye-sensitized solar cells (DSCs) incorporating a solid-state organic hole-transporter can be over 5%. However, this is for devices significantly thinner than the optical depth of the active composites and by comparison to the liquid electrolyte based DSCs, which exhibit efficiencies in excess of 10%, more than doubling of this efficiency is clearly attainable if all the steps in the photovoltaic process can be optimized. Two issues are currently being addressed by the field. The first aims at enhancing the electron diffusion length by either reducing the charge recombination or enhancing the charge transport rates. This should enable a larger fraction of photogenerated charges to be collected. The second, though less actively investigated, aims to improve the physical composite formation, which in this instance is the infiltration of mesoporous TiO(2) with the organic hole-transporter 2,2',7,7'-tetrakis(N,N-di-p-methoxypheny-amine)-9,9'-spirobifluorene (spiro-MeOTAD). Here, we perform a broad experimental study to elucidate the limiting factors to the solar cell performance. We first investigate the charge transport and recombination in the solid-state dye-sensitized solar cell under realistic working conditions via small perturbation photovoltage and photocurrent decay measurements. From these measurements we deduce that the electron diffusion length near short-circuit is as long as 20 µm. However, at applied biases approaching open-circuit potential under realistic solar conditions, the diffusion length becomes comparable with the film thickness, ∼2 µm, illustrating that real losses to open-circuit voltage, fill factor and hence efficiency are occurring due to ineffective charge collection. The long diffusion length near short-circuit, on the other hand, illustrates that another process, separate from ineffective charge collection, is rendering the solar cell less than ideal. We investigate the process of TiO(2) mesopore infiltration with spiro-MeOTAD by examining the cross-sectional images of and performing photo-induced absorption spectroscopy on devices with a range of thickness, infiltrated with spiro-MeOTAD with a range of concentrations. We present our interpretation of the mechanism for material infiltration, and by improving the casting conditions demonstrate efficient charge collection through devices of over 7 µm in thickness. This investigation represents an improvement in our understanding of the limiting factors to the dye-sensitized solar cell. However, much work, focused on composite formation and improved kinetic competition, is required to realize the true potential of this concept.

Charge collection and pore filling in solid-state dye-sensitized solar cells

Nanotechnology 19:42 (2008)

Authors:

HJ Snaith, R Humphry-Baker, P Chen, I Cesar, SM Zakeeruddin, M Grätzel

Abstract:

The solar to electrical power conversion efficiency for dye-sensitized solar cells (DSCs) incorporating a solid-state organic hole-transporter can be over 5%. However, this is for devices significantly thinner than the optical depth of the active composites and by comparison to the liquid electrolyte based DSCs, which exhibit efficiencies in excess of 10%, more than doubling of this efficiency is clearly attainable if all the steps in the photovoltaic process can be optimized. Two issues are currently being addressed by the field. The first aims at enhancing the electron diffusion length by either reducing the charge recombination or enhancing the charge transport rates. This should enable a larger fraction of photogenerated charges to be collected. The second, though less actively investigated, aims to improve the physical composite formation, which in this instance is the infiltration of mesoporous TiO2 with the organic hole-transporter 2,2′,7,7′-tetrakis(N,N-di-p- methoxypheny-amine)-9,9′-spirobifluorene (spiro-MeOTAD). Here, we perform a broad experimental study to elucidate the limiting factors to the solar cell performance. We first investigate the charge transport and recombination in the solid-state dye-sensitized solar cell under realistic working conditions via small perturbation photovoltage and photocurrent decay measurements. From these measurements we deduce that the electron diffusion length near short-circuit is as long as 20 μm. However, at applied biases approaching open-circuit potential under realistic solar conditions, the diffusion length becomes comparable with the film thickness, ∼2 μm, illustrating that real losses to open-circuit voltage, fill factor and hence efficiency are occurring due to ineffective charge collection. The long diffusion length near short-circuit, on the other hand, illustrates that another process, separate from ineffective charge collection, is rendering the solar cell less than ideal. We investigate the process of TiO2 mesopore infiltration with spiro-MeOTAD by examining the cross-sectional images of and performing photo-induced absorption spectroscopy on devices with a range of thickness, infiltrated with spiro-MeOTAD with a range of concentrations. We present our interpretation of the mechanism for material infiltration, and by improving the casting conditions demonstrate efficient charge collection through devices of over 7 μm in thickness. This investigation represents an improvement in our understanding of the limiting factors to the dye-sensitized solar cell. However, much work, focused on composite formation and improved kinetic competition, is required to realize the true potential of this concept. © IOP Publishing Ltd.

Electron transport and recombination in dye-sensitized mesoporous TiO2 probed by photoinduced charge-conductivity modulation spectroscopy with Monte Carlo modeling.

J Am Chem Soc 130:39 (2008) 12912-12920

Authors:

Annamaria Petrozza, Chris Groves, Henry J Snaith

Abstract:

We present a combined experimental and theoretical investigation into the charge transport and recombination in dye-sensitized mesoporous TiO2. We electronically probe the photoinduced change in conductivity through in-plane devices while simultaneously optically probing signatures of the charge species. Our quasi-continuous wave technique allows us to build data sets of electron mobility and recombination versus charge density over a wide temperature range. We observe that the charge density dependence of mobility in TiO2 is strong at high temperatures and gradually reduces with reducing temperature, to an extent where at temperatures below 260 K the mobility is almost independent of charge density. The mobility first increases and then decreases with reducing temperature at any given charge density. These observed trends are surprising and consistent with the multiple-trapping model for charge transport only if the trap density-of-states (DoS) is allowed to become less deep and narrower as the temperature reduces. Our recombination measurements and simulations over a broad range of charge density and temperature are also consistent with the above-mentioned varying DoS function when the recombination rate constant is allowed to increase with temperature, itself consistent with a thermally activated charge-transfer process. Further to using the Monte Carlo simulations to model the experimental data, we use the simulations to aid our understanding of the limiting factors to charge transport and recombination. According to our model, we find that the charge recombination is mainly governed by the recombination reaction rate constant and the charge density dependence is mainly a result of the bimolecular nature of the recombination process. The implication to future material design is that if the mobility can be enhanced without increasing the charge density in the film, for instance by reducing the average trap depth, then this will not be at the sacrifice of comparably enhanced recombination and it will greatly increase the charge carrier diffusion lengths in dye-sensitized or mesoscopic solar cells.

High efficiency composite metal oxide-polymer electroluminescent devices: A morphological and material based investigation

Advanced Materials 20:18 (2008) 3447-3452

Authors:

D Kabra, MH Song, B Wenger, RH Friend, HJ Snaith

Abstract:

A comprehensive study of various metal oxides in mesoporous and compact forms for electron injection in highly luminescent composite oxide-polymer light emitting diodes (COPLED) was presented. An improved performance with higher luminance and lower turn on voltage without O2 plasma treatment of the ITO prior to metal-oxide deposition is observed. It is found that the compact TiO2 performs considerably better than the mesoporous TiO2 and that the compact ZnO electron injection layer performs better than mesoporous and compact anatase. The higher current densities are due to leakage current through metal-oxide compact layers, and improvement of this deposition is found to increase the performance. Introducing a photonic structure into the metal oxide layers is found to enhance the optical out-coupling and electroluminescance efficiency.

High extinction coefficient "antenna" dye in solid-state dye-sensitized solar cells: A photophysical and electronic study

Journal of Physical Chemistry C 112:20 (2008) 7562-7566

Authors:

HJ Snaith, CS Karthikeyan, A Petrozza, J Teuscher, JE Moser, MK Nazeeruddin, M Thelakkat, M Grätzel

Abstract:

We present a photophysical and device-based investigation of a new bipyridyl-NCS ruthenium complex sensitizer with an extended n system, in both sensitized TiO2 and incorporated into solid-state dye-sensitized solar cells. We compare this new sensitizer to an analog dye without the extended π system. We observe very similar excited-state absorption spectra and charge recombination kinetics for the two systems. However, the π-extended senstizer has a phenomenally enhanced molar extinction coefficient which translates into far greater light harvesting and current collection in solid-state dye-sensitized solar cells. We also infer from transient photovoltage measurements that positioning the pendent extended n system away from the TiO2 surface has induced a favorable dipole shift, generating enhanced open-circuit voltage. The resulting power conversion efficiency for the solar cell has been increased from 2.4% to 3.2% when comparing the new sensitizer to an analogy with no pendent group. © 2008 American Chemical Society.