Synergistic Effects of Interfacial Modifiers Enhance Current and Voltage in Hybrid Solar Cells

To unleash the full potential of hybrid solar cells, it is imperative to get significant photocurrent contribution from both the sensitizing dye and the polymeric hole transporter. Here we report on the interfacial modifier 4-mercaptopyridine (4-MP), which induces controlled orientation of poly(3-hexylthiophene) (P3HT), the most widely used hole transporting polymer for hybrid solar cells, at the interface. 4-MP optimizes the charge separating interface between P3HT and a squaraine dye-decorated TiO 2 , inducing enhanced contribution to photocurrent generation by the polymer. In combination with 4-tert-butylpyridine, which enhances the open circuit potential in dye-sensitized and hybrid solar cells but reduces the photocurrent, a synergis-tic effect is observed and it is possible to enhance both open circuit voltage and photocurrent simultaneously. Similar effects on device performance are also found for two other commonly used dye molecules, a fullerene derivative and a common indoline dye. © 2013 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License. Hybrid metal oxide-polymer solar cells represent an emerging technology that holds the advantage of pronounced difference in dielectric constants of electron donor and acceptor compounds, con-trollable phase separation, and chemical stability compared to conventional organic photovoltaic. 1 A widely used geometry for hybrid solar cells consists of a dye-sensitized nanostructured TiO 2 electrode processed from a nanoparticle paste, which is infiltrated with a strongly absorbing hole transporting polymer. 2–4 Typically, this polymer is a polyphenylene vinylene 5 or poly(3-hexylthiophene) (P3HT), 6 which is the current baseline donor polymer in organic solar cell research. 7, 8 P3HT forms highly ordered crystallites when in its regio-regular configuration. 9 Crystalline P3HT exhibits additional absorption features due to π-π stacking between polymer chains, extending the absorption spectrum up to 650 nm. 10 Furthermore, the hole mobility of P3HT is increased significantly during crystallization, especially in π-π stacking direction and along the polymer backbone. 11 In order to maximize the efficiency of P3HT-based photovoltaics, it is imperative to control the orientation of the P3HT crystallites. Recently, Canesi et al. reported on a massive efficiency improvement of hybrid solar cells based on bare TiO 2 and P3HT using the modifier 4-mercaptopyridine (4-MP). 12 This pyridine self-assembles into a monolayer on the TiO 2 surface and induces a face-on alignment of P3HT, giving rise to significantly improved charge separation efficiencies and resulting in improved short circuit current density (J SC). Thus, they were able to …

To unleash the full potential of hybrid solar cells, it is imperative to get significant photocurrent contribution from both the sensitizing dye and the polymeric hole transporter.Here we report on the interfacial modifier 4-mercaptopyridine (4-MP), which induces controlled orientation of poly(3-hexylthiophene) (P3HT), the most widely used hole transporting polymer for hybrid solar cells, at the interface.4-MP optimizes the charge separating interface between P3HT and a squaraine dye-decorated TiO 2 , inducing enhanced contribution to photocurrent generation by the polymer.In combination with 4-tert-butylpyridine, which enhances the open circuit potential in dye-sensitized and hybrid solar cells but reduces the photocurrent, a synergistic effect is observed and it is possible to enhance both open circuit voltage and photocurrent simultaneously.Similar effects on device performance are also found for two other commonly used dye molecules, a fullerene derivative and a common indoline dye.© 2013 Author(s).All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.
Hybrid metal oxide-polymer solar cells represent an emerging technology that holds the advantage of pronounced difference in dielectric constants of electron donor and acceptor compounds, controllable phase separation, and chemical stability compared to conventional organic photovoltaic. 13][4] Typically, this polymer is a polyphenylene vinylene 5 or poly(3-hexylthiophene) (P3HT), 6 which is the current baseline donor polymer in organic solar cell research. 7, 8P3HT forms highly ordered crystallites when in its regio-regular configuration. 9Crystalline P3HT exhibits additional absorption features due to π-π stacking between polymer chains, extending the absorption spectrum up to 650 nm. 10 Furthermore, the hole mobility of P3HT is increased significantly during crystallization, especially in π -π stacking direction and along the polymer backbone. 11In order to maximize the efficiency of P3HT-based photovoltaics, it is imperative to control the orientation of the P3HT crystallites.Recently, Canesi et al. reported on a massive efficiency improvement of hybrid solar cells based on bare TiO 2 and P3HT using the modifier 4-mercaptopyridine (4-MP). 12This pyridine self-assembles into a monolayer on the TiO 2 surface and induces a face-on alignment of P3HT, giving rise to significantly improved charge separation efficiencies and resulting in improved short circuit current density (J SC ).Thus, they were able to boost the efficiency from 0.37% to 0.95% and even further to 1.13% after thermal annealing of the polymer.
Here we report on the application of 4-MP in hybrid solar cells based on dye-sensitized TiO 2 electrodes with P3HT as hole transporter.A monolayer of 4-MP is deposited via a simple spincoating and subsequent washing after dye-sensitization of the TiO 2 nanoparticle electrode and before deposition of the hole transporting polymer.In our devices, incorporation of 4-MP enhances photocurrent a Author to whom correspondence should be addressed.Electronic mail: lukas.schmidt-mende@uni-konstanz.de

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Four different configurations were tested for each dye molecule to evaluate the impact of 4-MP on the device performance.Specifically, the four configurations are: no interfacial modifier as a reference, modification with tBP, modification with 4-MP, and finally a co-modification with both tBP and 4-MP.The 4-MP layer is applied after dye-sensitization via spincoating and subsequent washing in order to form a self-assembled monolayer.For the co-modified configuration, tBP is deposited first and 4-MP is applied on top.The actual mixing ratio is therefore unknown, but we assume that our processing results in a mixture of 4-MP and tBP on the surface since both molecules attach with the pyridine moiety to the TiO 2 and we expect similar binding energies for the two molecules.We also find similar results when spincoating a 1:1 mixture of tBP and 4-MP but choose a step-wise processing, which we find to give more reproducible solar cell devices.Chemical structures of tBP and 4-MP are shown in Figure 1(c).Atomistic simulations performed by Canesi et al. showed that 4-MP forms a highly ordered monolayer with the sulfhydryl groups pointing away from the TiO 2 , enabling the alignment of the P3HT alkyl side chains along the thiol rows with the polymer backbone lying planar on the TiO 2 surface. 12Therefore, the P3HT assembles in a face-on configuration, implying intimate contact between the polymer chromophores and the charge separating interface, as well as high hole mobility through the P3HT crystal perpendicular to the interface.
Current density-voltage curves under illumination with a 100 mW cm −2 Air Mass (AM) 1.5G solar simulator are shown in Figure 1(d) for the different configurations.Solar cells are kept in a light-tight metal holder covering the side and backsides of the devices to ensure that light is coupled in only through a shadow mask defining the active area of the device.Thus, overestimation of the J SC is avoided as described by Snaith. 23Power conversion efficiency (PCE), V OC , J SC , and fill factor (FF) for typical devices are summarized in Table ST1 in the supplementary material. 18The measurements show enhanced V OC after a tBP post-treatment of the TiO 2 for all dyes (V OC increases by 21%, 29%, and 28% for SQ2, D131, and PCBA, respectively), which is consistent with literature.A significant reduction of the J SC by 28% and 7% is measured for SQ2 and PCBA, respectively, whereas the J SC is not affected in case of D131.We attribute these differences to the position of the different lowest unoccupied molecular orbital (LUMO) levels of the dyes with respect to the P3HT.For D131, charge injection from the P3HT is impossible due to the lower LUMO of P3HT, which has already been discussed by Zhang et al. 2 However, for SQ2 and PCBA, the polymer can contribute to the photocurrent generation, as apparent from incident photon to current conversion efficiency (IPCE) plots shown by Mor et al. and Vaynzof et al., respectively. 16,19 or the fullerene, the polymer comes into play via charge injection into the PCBA, whereas a Förster resonance energy transfer is supposedly occurring between the SQ2 and P3HT.Application of tBP induces a dipole moment at the interface, which reduces the driving force for electron injection and supposedly for charge separation between P3HT and PCBA.Furthermore, tBP might physically space the polymer away from the dye molecule.This could explain the relatively strong effect in case of SQ2, since the efficiency of an energy transfer depends strongly on the distance between donor and acceptor.
When using 4-MP as interfacial modifier, we find a systematic increase in both V OC and J SC , consistent with the results for bare TiO 2 . 12The slight change in V OC is attributed to a shift in TiO 2 conduction band edge similar to the case of tBP, since 4-MP has a dipole moment, which points in the same direction but is smaller than that of tBP. 24For SQ2 and PCBA, which allow contribution from the polymer, the J SC is enhanced by 10% and 9%, respectively, whereas for D131 the increase is only 4%.Additionally, a significantly improvement in FF was measured for PCBA with 4-MP modification.
The striking result of this study is that the best solar cells are obtained for a combination of tBP and 4-MP.Using a 1:1 mixture of the two pyridines, the V OC can be increased by 18%, 28%, and 26% for SQ2, D131, and PCBA, respectively.Furthermore, when co-modifying with the two pyridines the J SC simultaneously increases, in contrast to modification only with tBP.Thus PCE enhancements of at least 40% were measured for the tBP and 4-MP combination, compared to solar cells without pyridine modifiers.We attribute this to a synergistic effect of the two pyridines, where tBP induces an increased V OC while 4-MP maintains a high J SC due to favorable alignment of the P3HT at the interface.
The impact of 4-MP on the photocurrent generation is also apparent from IPCE spectra, as shown in Figure 1(e).SQ2 and D131 both absorb complementary to P3HT, D131 in the blue and 042109-5  26 The resulting equivalent circuit is shown in Figure 2(b).The TiO 2 -organic interface is described by the parallel R-CPE units in the transmission line part of the equivalent circuit, where C μ describes the chemical capacitance of the interface and R R is associated with a recombination resistance. 27Fit results for these elements are summarized in Table I.Our results show that modification of the interface with 4-MP leads to significantly increased recombination resistances as compared to bare TiO 2 and tBP.High R R is also maintained when 4-MP is combined with tBP.Furthermore, the chemical capacitance is significantly reduced and higher values of n are found in presence of 4-MP.Although further research including a detailed impedance spectroscopy study at different illumination intensities and bias voltages is necessary to clarify the origin of this behavior, we believe that the 4-MP-induced P3HT alignment can lead to a lower number of interface trap states and the crystallinity of the polymer at the interface is supposed to improve the local charge mobility, which reduces charge carrier recombination. 28he reduced interfacial recombination suggested by impedance measurements is also supported by slightly improved charge carrier collection efficiencies η coll . 29Transient photocurrent and photovoltage decay experiments were performed on SQ2 samples in order to estimate η coll from exponential decay rates. 18Without pyridine modification η coll was found to be 85.7%, whereas higher values of 92.2%, 92.1%, and 90.4% can be achieved with tBP, 4-MP, and mixed pyridines, respectively.
Further insights into the properties of the modified interfaces are provided by light intensity dependent current density-voltage measurements.Figure 3 shows the J SC of SQ2 solar cells with different pyridine configurations as a function of illumination intensity.Data are subjected to a power law fit J SC = β • P 0 α , where P 0 is the illumination intensity and α and β are fit parameters.As described in literature, the exponent α typically ranges between 0.75 and 1, where smaller values indicate limitations due to charge carrier recombination and built-up of space charge. 30or 4-MP modified interfaces we find slightly higher values of α indicating reduced recombination and more rapid charge transport away from the interface.Note that while differences in α among the tested devices are small, 100 α increases by 5.2% and 3.3% for modification with 4-MP and mixed pyridines, respectively, compared to the device without pyridine.This implies that for light intensities in the order of one sun (100 mW cm −2 ) these small differences in α reflect noticeable differences in short circuit current generation, although the overall impact of space charge seems to be small for all pyridine configurations.
In conclusion we show that significant performance increases can be achieved in hybrid solar cells with different sensitizer dyes and P3HT as hole transporter using the interfacial modifier 4-MP.We attribute this to favorable orientation of the P3HT at the TiO 2 -polymer interface.When combining 4-MP with tBP, it is possible to simultaneously enhance J SC and V OC of the devices.Especially for dyes which allow a photocurrent contribution from the hole transporter the synergistic effect of the two pyridines plays an important role in pushing the efficiency.Contribution of the polymer to the charge generation is a prerequisite for taking advantage of the hybrid solar cell concept, making the combination of 4-MP and tBP interesting for this type of photovoltaic devices.Our detailed study on devices with a squaraine dye as a model system for such solar cells indicates that 4-MP improves the electronic properties of the inorganic-organic interface by promoting charge

TABLE I .
Impedance spectroscopy fit results (fits with ZView) for recombination resistance and constant phase element parameters (capacitance Q n and capacitor ideality factor n) representing the TiO 2 -P3HT interface for different pyridines.theoneused by Zhang et al. for TiO 2 -D131-P3HT hybrid solar cells.2Inorder to get good fitting results the model was extended by one additional R-constant phase element (CPE) component, which is associated with the polymer capping layer and the interface between polymer and top contact, in accordance with literature.