Electric Fields Control TiO2(e–) + I3– → Charge Recombination in

Letter pubs.acs.org/JPCL

Electric Fields Control TiO2(e−) + I3− → Charge Recombination in DyeSensitized Solar Cells Renato N. Sampaio,†,‡ Ryan M. O’Donnell,†,§ Timothy J. Barr,†,§ and Gerald J. Meyer*,†,§ †

Department of Chemistry and Materials Science and Engineering, Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, United States ‡ Institute of Physics, Federal University of Uberlândia, João Naves de Á vila Avenue 2121, 593, Santa Mônica, Uberlândia, Minas Gerais, Brazil ABSTRACT: The electric fields generated by excited-state electron injection into anatase TiO2 nanocrystallites are screened by cations present in the external electrolyte. With some assumptions, a newly discovered electroabsorption signature enables quantification of the electric field strength experienced by surface-anchored dye molecules. Here, it was found that the fields increased in the order Na+ < Li+ < Mg2+ < Ca2+, with magnitudes of 1.1 MV/ cm for Na+ and 2.2 MV/cm for Ca2+, values that were insensitive to whether the anion was iodide or perchlorate. The magnitude of the field was directly related to average TiO2(e−) + I3− → charge recombination rate constants abstracted from time-resolved kinetic data. Extrapolation to zero field provided an estimate of recombination dynamics when diffusion alone controlled I3− mass transport, k = 300 s−1. The decreased rate constants measured after excited-state injection were attributed to migration of I3− away from the TiO2. Cation transference coefficients were tabulated that ranged from t = 0.97 for Ca2+ to 0.40 for Na+ and represented the ability of the unscreened electric field to block the TiO2(e−) + I3− → charge recombination reaction. This data provides the first compelling evidence that the anionic nature of I3− inhibits unwanted charge recombination in dye-sensitized solar cells. SECTION: Energy Conversion and Storage; Energy and Charge Transport

E

compelling evidence that the anionic nature of these redox mediators is at all relevant to operational DSSCs. The mesoporous TiO2 thin films utilized in this study were sensitized to visible light by [Ru(dtb)2(dcb)](PF6)2, where dtb is 4,4′-(tert-butyl)2-2,2′-bipyridine and dcb is 4,4′-(CO2H)22,2′-bipyridine, abbreviated Ru(dtb)2(dcb)/TiO2. This sensitizer was selected as it gives rise to a very large amplitude electroabsorption signature, although conventional sensitizers such as isothiocyante Ru polypyridyl compounds as well as D−π−A type organic compounds behave similarly.1,2 Figure 1 shows the visible absorption spectra of a Ru(dtb)2(dcb)/TiO2 thin film immersed in neat acetonitrile and in acetonitrile solutions that contain 100 mM iodide with Li+, Na+, Mg2+, or Ca2+ cations. The extinction coefficients were calculated relative to Ru(dtb)2(dcb)/TiO2 in CH3CN, which was assumed to have the same value as the [Ru(dtb)2(dcb)](PF6)2 dissolved in CH3CN. A significant red shift in the metal-to-ligand chargetransfer (MLCT) absorption was observed in the electrolyte solutions relative to neat CH3CN as well as a small decrease in the maximum absorption intensity. The magnitude of the red shift increased in the order Na+ < Li+ < Mg2+ ≈ Ca2+. These data with the iodide salts are in excellent agreement with that previously reported for the perchlorate salts, which is consistent

lectrons injected into the mesoporous TiO2 nanocrystalline (anatase) thin films commonly used in dye-sensitized solar cells (DSSCs) generate an electric field that significantly perturbs the absorption spectra of the dye molecules anchored to its surface. The electroabsorption signature, similar to that observed in Stark spectroscopy, and the >1 MV/cm electric field magnitude were only recently discovered, and a full appreciation of how the presence of this field might be exploited for practical applications remains uncertain.1,2 The electroabsorption signature appears as a first derivative of the ground-state absorption that has proven to be a valuable experimental tool for the characterization of dye-sensitized TiO2 interfaces.3−7 Indeed, insight into the relative orientation of the molecular dipole as well as the dye−semiconductor distance has been revealed through systematic studies with different dye molecules.2,8 In addition, pulsed laser excitation has permitted the dynamics for charge screening by the electrolyte to be quantified on microsecond and longer time scales.9−11 Yet despite these advances in fundamental science, there is no clear indication that these electric fields have any practical relevance to the light-driven electron-transfer reactions that promote or inhibit electrical power generation in DSSCs. One would reasonably anticipate that the surface electric field would repel anions like tri-iodide and hence inhibit the unwanted charge recombination reaction with electrons injected into TiO2. However, until now, there has been no © 2014 American Chemical Society

Received: August 5, 2014 Accepted: September 8, 2014 Published: September 8, 2014 3265

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mesopores of TiO2 occurs with the same rate constant as that in fluid solution, k = 3 × 109 M−1 s−1.12 Hence, only the injected electrons and tri-iodide were expected to appreciably absorb light in the visible region on time scales greater than 1 μs. Shown in Figure 2b are representative spectra recorded 2.5 μs after laser excitation of the Ru(dtb)2(dcb)/TiO2 in acetonitrile electrolytes that represented the extremes that were observed, 100 mM NaI or 50 mM CaI2. The characteristic absorption of I3− at ∼360 nm and the weak absorption of the injected electrons at 600 nm were evident.13 The large first-derivative feature between ∼450 and 550 nm arises from a unidirectional shift of the ground-state absorption spectra induced by the injected electrons. In other words, the electrons injected into TiO2 generate an electric field that significantly blue shifts the MLCT absorption of the ruthenium compounds anchored to the surface.1 The magnitude of the intensity change and the spectral shift were significantly more pronounced when Ca2+-containing electrolytes were employed, behavior attributed to less effective screening of the electric field from the sensitizer. The field strengths were found to follow the order Na+ < Li+ < Mg2+ < Ca2+.10 The electric field strength reported by the Ru sensitizers was 1.1 MV/cm for Na+ and 2.2 MV/cm for Ca2+, with the magnitude of the electric fields calculated using previously reported methods and assumptions.1,10,14,15 Because the number of TiO2 electrons was held constant, the different field strengths were attributed to the ability of the cations to screen the field from the surfaceanchored sensitizers. Shown in Figure 3 are absorption changes monitored at 375 nm. This observation wavelength was chosen as the I3− anion absorbs strongly there and it represents an isosbestic point between I2•− and I3−.12 As a result, the concentration of I3− can be uniquely probed at this wavelength. The nonexponential kinetics were well described by the Kohlrausch−Williams− Watts (KWW) model, eq 2.

Figure 1. Visible absorbance spectra of a Ru(dtb)2(dcb)/TiO2 thin film immersed in acetonitrile in the absence (gray) or presence of 100 mM LiI (black), 100 mM NaI (red), 50 mM MgI2 (blue), and 50 mM CaI2 (green).

with the proposal that adsorption of these Lewis acidic cations to TiO2 induces the spectral shifts with negligible contributions from the anions.10 Partial electrochemical reduction of the sensitized TiO2 thin films in a standard three-electrode cell results in a blue shift of the MLCT absorption, as has been previously described.1,10 Figure 2a shows such data as difference spectra where the absorption spectra of the reduced film are subtracted from the initial spectrum under conditions where about 20 electrons were present in each TiO2 nanocrystallite. Pulsed laser excitation of the Ru(dtb)2(dcb)/TiO2 thin films immersed in the iodide acetonitrile electrolytes gave rise to significant absorption changes that were monitored on nanosecond and longer time scales. Light absorption by the Ru sensitizer resulted in rapid excited-state injection and sensitizer regeneration through iodide oxidation that were complete within a microsecond. The oxidation of iodide to triiodide in DSSCs is known to occur through disproportionation of an I2•− intermediate. Disproportionation within the

I(t ) = Io exp[−(kt )β ]

(2)

Here, β is inversely related to the width of an underlying Lévy distribution of rate constants, 0 < β < 1, and k is a characteristic rate constant. In kinetic analysis, the value of β was fixed to be 0.45, and k was allowed to float. An “average” rate constant was

Figure 2. Absorbance change of Ru(dtb)2(dcb)/TiO2 thin films measured (A) under conditions of approximately 20 TiO2(e−)s per TiO2 nanoparticle electrochemically generated in 100 mM solutions of NaClO4 (red), LiClO4 (black), Mg(ClO4)2 (blue), and Ca(ClO4)2 (green) and (B) 2.5 μs after pulsed 532 nm light excitation in 100 mM NaI (red, circles) and 50 mM CaI2 (green, triangles) acetonitrile solutions. 3266

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constant measured in the presence of the field to that in the absence has some analogy to transference coefficients, t = i/i0, that have been quantified in electrochemical cells.16 Here, t represents the fractional ability of the electric field to block the unwanted TiO2(e−) + I3− → charge recombination reaction. The t values are given in Table 1. It should be pointed out that other iodine species may also accept electrons in DSSCs. Indeed, there exists compelling evidence that molecular iodine I2 is reduced by TiO2(e−)s. As tri-iodide and molecular iodine are in equilibrium, eq 4, both are always present in solution.17 However, under the current experimental conditions, iodide was the only species present before laser excitation, and the concentrations of I3− generated with light were on the order of 10 μM, rendering the equilibrium concentration of I2 negligibly small. Hence, the present study has effectively stacked the deck to ensure that recombination occurs predominantly to tri-iodide. This differs from an operational DSSC where a mixture of 0.5 M LiI and 0.05 M I2 in an acetonitrile solution is typically utilized. The equilibrium constant for reaction 4 has been estimated to be Keq = 106, indicating that equilibrium concentrations are 0.45 M I−, 0.05 M I3−, and 2 μM I2.13

Figure 3. Absorption changes that correspond to TiO2(e−) + I3− → charge recombination measured in 100 mM LiClO4 (black), NaClO4 (red), Mg(ClO4)2 (blue), and mM Ca(ClO4)2 (green) acetonitrile solutions with 250 mM TBAI. Overlaid on the data are fits to the KWW function with β = 0.45. The inset shows a plot of the recombination rate constant versus the electric field.

I 2 + I− ⇌ I−3

It should also be emphasized that changing the cations in the electrolytes of DSSCs influences many parameters, including the transport of the injected electrons,18−20 dye regeneration,21 and the energy levels of the TiO2 acceptor states.10,22,23 Nevertheless, the implications of the results presented herein to DSSCs are clear and significant. Akin to enlarging the space− charge layer thickness in single semiconductor solar cells, increasing the Debye length for charge screening supports more spatially separated and longer-lived TiO2(e−), I3− donor− acceptor pairs. Hence, screening of the electric field by these alkali and alkaline earth cations in the electrolyte is detrimental to the solar conversion efficiency. This is particularly important at the power point and open-circuit conditions where the number of electrons is large and the TiO2(e−)s may be capable of accessing the two-electron reduction of I3−, E0(I3−/3I−) = 0.35 V, which is much more favorable than the one-electron reduction potential, E0(I3−/I2•−,I−) = −0.35 V versus NHE.13 Interestingly, complete screening of the electric field should instead be beneficial for the cationic Co(III/II) redox mediators, such as [Co(bpy)3]3+/2+, employed in champion DSSCs24 because migration will enhance the mass transfer of Co(III) to the interface where recombination with injected electrons occurs.

calculated as the first moment of this distribution using eq 3, and data are given in Table 1. kKWW =

kβ

()

Γ

1 β

(3)

Table 1. TiO2(e−) + I3− → Charge Recombination with the Indicated Cations +

Na Li+ Mg2+ Ca2+

electric field (MV/cm)a

k (s−1)b

kKWW (s−1)

t

1.1 1.3 1.8 2.2

450 210 160 20

180 80 60 10

0.40 0.73 0.80 0.97

(4)

Electric field change measured after the potentiostatic injection of approximately 20 TiO2(e−)s per nanoparticle. bβ fixed to 0.45. a

The inset of Figure 3 is a plot of the recombination rate constant versus the electric field. This and the raw experimental data clearly show a marked electric field dependence for the unwanted TiO2(e−) + I3− → charge recombination rate constant. This correlation provides compelling evidence that the larger the electric field, the slower the unwanted charge recombination reaction with I3−. Recall that I3− is generated within the mesopores after the disproportionation of two I2•− ions. Mass transfer of I3− by both diffusion and migration to the TiO2 surface must then occur before recombination is possible. Extrapolation of the best-fit line to zero electric field provides an estimate of the diffusional contributions to the recombination reaction that occurs in the absence of an electric field, k = 300 s−1. Because rate constants are proportional to current, the total current at zero field is the diffusional current, i0 = id. The rate constants decrease when electrons are injected into TiO2 because the anionic charge of the I3− is repelled by the field generated by the TiO2(e−)s. Hence, the total current decreases in the presence of the field due to migration of I3− away from the TiO2 interface, i = id − im. The ratio of the average rate

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Present Address §

R.M.O., T.J.B., and G.J.M.: Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy through Grant DE-FG02-96ER14662 is 3267

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(17) Richards, C. E.; Anderson, A. Y.; Martiniani, S.; Law, C.; O’Regan, B. C. The Mechanism of Iodine Reduction by TiO2 Electrons and the Kinetics of Recombination in Dye-Sensitized Solar Cells. J. Phys. Chem. Lett. 2012, 3, 1980−1984. (18) Kambe, S.; Nakade, S.; Kitamura, T.; Wada, Y.; Yanagida, S. Influence of the Electrolytes on Electron Transport in Mesoporous TiO2−Electrolyte Systems. J. Phys. Chem. B 2002, 106, 2967−2972. (19) Wang, H.; Bell, J.; Desilvestro, J.; Bertoz, M.; Evans, G. Effect of Inorganic Iodides on Performance of Dye-Sensitized Solar Cells. J. Phys. Chem. C 2007, 111, 15125−15131. (20) Wang, H.; Peter, L. M. Influence of Electrolyte Cations on Electron Transport and Electron Transfer in Dye-Sensitized Solar Cells. J. Phys. Chem. C 2012, 116, 10468−10475. (21) Pelet, S.; Moser, J.-E.; Grätzel, M. Cooperative Effect of Adsorbed Cations and Iodide on the Interception of Back Electron Transfer in the Dye Sensitization of Nanocrystalline TiO2. J. Phys. Chem. B 2000, 104, 1791−1795. (22) Kelly, C. A.; Farzad, F.; Thompson, D. W.; Stipkala, J. M.; Meyer, G. J. Cation-Controlled Interfacial Charge Injection in Sensitized Nanocrystalline TiO2. Langmuir 1999, 15, 7047−7054. (23) Redmond, G.; Fitzmaurice, D. Spectroscopic Determination of Flatband Potentials for Polycrystalline Titania Electrodes in Nonaqueous Solvents. J. Phys. Chem. 1993, 97, 1426−1430. (24) Mathew, S.; et al. Dye-Sensitized Solar Cells with 13% Efficiency Achieved Through the Molecular Engineering of Porphyrin Sensitizers. Nat. Chem. 2014, 6, 242−247.

gratefully acknowledged for support (G.J.M.). R.M.O. would also like to thank the National Science Foundation for a Graduate Research Fellowship under Grant No. DGE-1232825. R.N.S. would like to thank the National Council for Scientific and Technological Development (CNPq) for support under Grant No. 244501/2012-2.

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