Janne Halme

Device Physics of Dye Solar Cells

Design of new materials for nanostructured dye solar cells (DSC) requires understanding the link between the material properties and cell efficiency. This paper gives an overview of the fundamental and practical aspects of the modeling and characterization of DSCs, and integrates the knowledge into a user-friendly DSC device model. Starting from basic physical and electrochemical concepts, mathematical expressions for the IV curve and differential resistance of all resistive cell components are derived and their relation to electrochemical impedance spectroscopy (EIS) is explained. The current understanding of the associated physics is discussed in detail and clarified. It is shown how the model parameters can be determined from complete DSCs by current dependent EIS and incident-photon-to-collected-electron (IPCE) measurements, supplemented by optical characterization, and used to quantify performance losses in DSCs. The paper aims to give a necessary theoretical background and practical guidelines for establishing an effective feedback-loop for DSC testing and development.

Dye Solar Cells on ITO-PET Substrate with TiO2 Recombination Blocking Layers

Atomic-layer-deposited TiO 2 recombination blocking layers were prepared on indium tin oxide-poly(ethylene terephthalate) (ITO-PET) photoelectrode substrates for dye solar cells and were examined using several electrochemical methods. The blocking layers increased the open-circuit voltage at low light intensities. At high light intensities, a decrease in the fill factor (FF) due to the additional resistance of the current transport through the layer was more significant than the positive effect by the reduced recombination. The decrease in the FF was reduced by a thermal treatment that made the blocking layer more conductive due to a structural change from an amorphous to a crystalline form. Therefore, thinner blocking layers of this type are required for plastic cells prepared at low temperature than for conventional glass dye solar cells made with temperature processing.

Stability of Dye Solar Cells with Photoelectrode on Metal Substrates

In this study, the stability of dye solar cells DSCs with different kinds of metals as the photoelectrode substrate is studied.Stainless steels StSs, Inconel, and titanium substrates were tested to find stable substrate options. Photovoltaic characterization,electrochemical impedance spectroscopy EIS, scanning electron microscopy, and substrate polarization measurements were usedin the characterization. DSCs based on different grades of StS suffered from rapid degradation of efficiency within few hours inlight soaking. Good stability was demonstrated with DSCs with Inconel and Ti photoelectrode substrates. The Inconel substrateshave a thick passive oxide layer, which is likely related to good stability. However, according to the EIS analysis, the oxide layerof Inconel substrates increased resistive losses, which caused a lower fill factor and photovoltaic efficiency compared to theTi-based cells.© 2010 The Electrochemical Society. DOI: 10.1149/1.3374645 All rights reserved.Manuscript submitted December 17, 2009; revised manuscript received February 19, 2010. Published April 21, 2010.

Effect of electrolyte bleaching on the stability and performance of dye solar cells

Degradation of dye solar cells (DSCs) under severe ageing conditions may lead to loss of the tri-iodide in the electrolyte - a phenomenon known as electrolyte bleaching. Monitoring changes in the tri-iodide concentration as a result of degradation mechanisms and understanding their causes and effects are fundamental for improving the long-term stability of DSCs. In this contribution a strongly accelerated ageing test (1 Sun visible light, 1.5 Suns UV light, T = 110 °C for 12 h) was performed on DSCs in a double-sealed masterplate configuration to purposely induce severe electrolyte bleaching, and its effects on the performance and stability of DSCs with different initial tri-iodide concentrations [I3(-)]0 were investigated. The cells with low [I3(-)]0 suffered a severe loss in short circuit current density JSC (up to 85%). Also a significant loss of open circuit voltage VOC was observed and this loss was proportional to [I3(-)]0 with the highest VOC drop observed with the highest [I3(-)]0. Non-destructive analysis techniques based on the limited current density, JSCvs. light intensity, and photographic image analysis, were used to quantify the [I3(-)] loss, which was found to be ca. 50 mM and independent of [I3(-)]0. Quantitative model based VOC analysis in terms of changing [I3(-)] revealed that the degradation responsible for the VOC drop was dominated by an unknown mechanism that is unrelated to [I3(-)]0. The methods and results reported here help separating and identifying different degradation mechanisms related to electrolyte bleaching in DSCs.

A durable SWCNT/PET polymer foil based metal free counter electrode for flexible dye-sensitized solar cells

An ITO free, highly conductive PET foil is fabricated by depositing aqueous single-walled carbon nanotube (SWCNT) ink that exhibits remarkable durability when exposed to severe mechanical stability tests. Excellent adhesion of the SWCNT film on PET was obtained by aging the ink overnight at 50 °C before deposition. A counter electrode for a dye-sensitized solar cell was fabricated by electro-polymerizing the PEDOT polymer over the SWCNT film which gave 7% solar cell efficiency and low (0.4 Ω cm2) charge transfer resistance.

Linking optical and electrical small amplitude perturbation techniques for dynamic performance characterization of dye solar cells

This paper unifies the analytical models used widely but thus far mostly separately for electrical and optical small amplitude perturbation measurements of nanostructured electrochemical dye solar cells (DSC): electrochemical impedance spectroscopy (EIS), intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS). The models are linked by expressing the kinetic boundary condition used for solving the time-dependent continuity equation of electrons in IMPS and IMVS analysis in terms of the series and parallel impedance components found in the complete equivalent circuit impedance model of DSC. As a result, analytical expressions are derived for potentiostatic IMPS and galvanostatic IMVS transfer functions of complete DSCs that are applicable at any operating point along the solar cell current-voltage (IV) curve. In agreement with the theory, impedance spectrum calculated as a ratio of IMVS and IMPS transfer functions measured near the maximum power point matches exactly with the impedance spectrum measured directly with EIS. Consequently, both IMPS-IMVS and EIS yield equal estimates for the electron diffusion length. The role of the chemical capacitance of the nanostructured semiconductor photoelectrode in the interpretation of the so-called RC attenuation of the IMPS response is clarified, as well as the capacitive frequency dispersion in IMPS and IMVS.

Investigation of Temperature and Aging Effects in Nanostructured Dye Solar Cells Studied by Electrochemical Impedance Spectroscopy

Effects of aging and cyclically varying temperature on the electrical parameters of dye solar cells were analyzed with electrochemical impedance spectroscopy. Photoelectrode total resistance increased as a function of time due to increasing electron transport resistance in the film. On the other hand, photoelectrode recombination resistance was generally larger, electron lifetimes in the were film longer, and charge transfer resistance on the counter electrode was smaller after the temperature treatments than before them. These effects correlated with the slower deterioration rate of the temperature-treated cells, in comparison to the reference cells.

Analysis of dye degradation products and assessment of the dye purity in dye-sensitized solar cells.

RATIONALE For commercialization of dye-sensitized solar cells (DSSCs), improvement of their long-term stability and efficiency is important. A key component in solar cells is the dye, its high purity and high stability. Here, methods for dye extraction and purification, and for determination of dye purity and dye degradation in DSSCs, were developed. METHODS A method was developed for extraction of the dye Z907 from intact solar cells using a water/ethanol mixture containing tetrabutylammonium hydroxide. The N719 dye synthesized in our laboratory was purified by gel filtration on Sephadex LH20. These dyes, along with the dyes N3 and RuL2 (NC)2, were analyzed using nuclear magnetic resonance (NMR) spectroscopy and liquid chromatography coupled to an electrospray ionization quadrupole-time-of-flight mass analyzer (LC/MS) operating in negative ionization mode. RESULTS Purification of the synthesized N719 removed several impurities, including its undesired isomer with the thiocyanate ligand attached to ruthenium through sulfur instead of nitrogen. The dyes N719 and Z907 were successfully extracted from solar cells and together with N3 and RuL2 (NC)2 analyzed by LC/MS, although N719 isomerized almost immediately in basic aqueous solution. The [M-H](-1) ions were observed and the measured mass was within a ±6 ppm range from the exact mass. CONCLUSIONS LC/MS in combination with NMR spectroscopy was shown to provide useful information on dye structure, purity, and on the efficiency of the purification methods. These methods allow for further studies of solar cell dyes, which may provide the detailed information needed for the improvement and eventual commercialization of the solar cell technology.

Comparative analysis of ceramic-carbonate nanocomposite fuel cells using composite GDC/NLC electrolyte with different perovskite structured cathode materials

A comparative analysis of perovskite structured cathode materials, La0.65Sr0.35MnO3 (LSM), La0.8Sr0.2CoO3 (LSC), La0.6Sr0.4FeO3 (LSF) and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF), was performed for a ceramic-carbonate nanocomposite fuel cell using composite electrolyte consisting of Gd0.1Ce0.9O1.95 (GDC) and a eutectic mixture of Na2CO3 and Li2CO3. The compatibility of these nanocomposite electrode powder materials was investigated under air, CO2 and air/CO2 atmospheres at 550 °C. Microscopy measurements together with energy dispersive X-ray spectroscopy (EDS) elementary analysis revealed few spots with higher counts of manganese relative to lanthanum and strontium under pure CO2 atmosphere. Furthermore, electrochemical impedance (EIS) analysis showed that LSC had the lowest resistance to oxygen reduction reaction (ORR) (14.12 Ω∙cm2) followed by LSF (15.23 Ω∙cm2), LSCF (19.38 Ω∙cm2) and LSM (>300 Ω∙cm2). In addition, low frequency EIS measurements (down to 50 μHz) revealed two additional semi-circles at frequencies around 1 Hz. These semicircles can yield additional information about electrochemical reactions in the device. Finally, a fuel cell was fabricated using GDC/NLC nanocomposite electrolyte and its composite with NiO and LSCF as anode and cathode, respectively. The cell produced an excellent power density of 1.06 W/cm2 at 550 °C under fuel cell conditions.

Symmetry analysis of the numerical instabilities in the transfer matrix method

This paper discusses the numerical exponential instability of the transfer matrix method (TMM) in the framework of the symmetry formalism. This numerical weakness is attributed to a series of increasingly extreme exponentials that appear in the TMM when it is applied to geometries involving total internal reflection (TIR) or very high absorption. We design a TMM formalism that identifies the internal symmetries of the multilayer geometry. These symmetries suggest particular transformations of a reference system in the TMM that improve its ill-conditioned exponentials. To illustrate the numerical improvements, we present examples with calculations of electric fields.