Decoupling Optical and Electronic Optimization of Organic Solar Cells Using High-performance Temperature-stable Tio 2 / Ag/ Tio 2 Electrodes

An electrode structured with a TiO 2 /Ag/TiO 2 (TAT) multilayer as indium tin oxide (ITO) replacement with a superior thermal stability has been successfully fabricated. This electrode allows to directly tune the optical cavity mode towards maximized photocurrent generation by varying the thickness of the layers in the sandwich structure. This enables tailored optimization of the transparent electrode for different organic thin film photovoltaics without alteration of their electro-optical properties. Organic photovoltaic featuring our TAT multilayer shows an improvement of ∼12% over the ITO reference and allows power conversion efficiencies (PCEs) up to 8.7% in PTB7:PC 71 BM devices. C 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License. Organic photovoltaic (OPV) devices have attracted much interest during the last two decades, due to the possibility of low-cost fabrication, lightweight, flexibility, and simple fabrication processing. 1–4 Power conversion efficiencies (PCEs) up to 10% have been reported recently, 5,6 even though this is still inferior to the theoretically predicted 20%-24% efficiency for organic single junction devices. 7 OPVs are classified within the distinct class of excitonic solar cells, i.e., coulombically bound electron-hole pairs are generated upon light-absorption with binding energies exceeding the thermal energy (k B T). The electrochemical driving-force given at a type II staggered heterointer-face is necessary for free charge carrier generation. 8 Therefore, only excitons generated within the exciton diffusion length (typically around 10 nm) towards a donor-acceptor interface are successfully harvested. Internal quantum efficiencies (IQEs) up to 100% have been reported. 9 In case of the IQE being unity, every absorbed photon, i.e., generated exciton is separated and all photogenerated polarons are extracted from the active layer and collected at the external electrodes of the device. Electronically optimized organic thin films with suitable donor-acceptor macro-phase separation exhibiting such high IQE can only be realized using film thicknesses around 100 nm, which results in severe performance losses due to limited light absorption. 10,14 In contrast, thicker layers exhibiting virtually complete photon harvesting but suffer from reduced IQEs owing to pronounced charge carrier recombination losses. This trade-off motivates researchers to introduce light management structures into the photocurrent-generating layers that either localize the electromagnetic energy in the near-field of plasmonic nanostructures or increase the optical path length due to scattering into lateral modes. 15,16 One requirement for their successful implementation is that the structural changes due to the light …

2][3][4] Power conversion efficiencies (PCEs) up to 10% have been reported recently, 5,6 even though this is still inferior to the theoretically predicted 20%-24% efficiency for organic single junction devices. 7OPVs are classified within the distinct class of excitonic solar cells, i.e., coulombically bound electron-hole pairs are generated upon light-absorption with binding energies exceeding the thermal energy (k B T).The electrochemical driving-force given at a type II staggered heterointerface is necessary for free charge carrier generation. 8Therefore, only excitons generated within the exciton diffusion length (typically around 10 nm) towards a donor-acceptor interface are successfully harvested.Internal quantum efficiencies (IQEs) up to 100% have been reported. 9][11][12][13] Electronically optimized organic thin films with suitable donor-acceptor macro-phase separation exhibiting such high IQE can only be realized using film thicknesses around 100 nm, which results in severe performance losses due to limited light absorption. 10,14In contrast, thicker layers exhibiting virtually complete photon harvesting but suffer from reduced IQEs owing to pronounced charge carrier recombination losses.This trade-off motivates researchers to introduce light management structures into the photocurrent-generating layers that either localize the electro-magnetic energy in the near-field of plasmonic nanostructures or increase the optical path length due to scattering into lateral modes. 15,16One requirement for their successful implementation is that the structural changes due to the light management structures do not influence the electronic properties of the organic layer, which is crucial especially for randomly intermixed bulk heterojunction (BHJ) devices.Therefore, it is necessary to introduce a simple and suitable device design ideally featuring flat interfaces in order to allow for decoupling of optical and electronic optimization.Here, we focus on the tunability of the coherent electro-magnetic field distribution in flat interface OPVs that naturally define an optical cavity (Figure 1).The tunability of the cavity is accessible by replacing the commonly used indium tin oxide (ITO) with a TiO 2 /Ag/TiO 2 (TAT) sandwich structure and a variation of the respective layer thicknesses.In particular, variation of the thickness of the bottom TiO 2 layer does not influence the electronic properties of the electrode since the charge collecting second TiO 2 layer, which is in contact with the organic active layer, remains unchanged.8][19] ITO has been commonly used for various optoelectronic devices as transparent electrode due to its excellent transparency and electrical properties.However, the price of ITO is rising due to the limited availability of indium. 20,21Besides, ITO deposition requires high-temperature vacuum processing and ITO has a low thermal stability caused by ion diffusion at temperatures exceeding 300 • C. 22 The thickness of the ITO layer determines its properties (electronic and optical transmission).ITO thin films have a fixed thickness of around 200 nm for optimum performance for solar cell applications.These drawbacks of ITO are the driving force for researchers to investigate alternative materials-a number of promising candidates have been already identified.One class are doped metal oxides such as Al-and Ga-doped ZnO (AZO and GZO), which are cheaper than ITO. 19Additionally, the use of conducting carbon materials including carbon nanotubes, graphene, and conducting polymers such as poly(3,4-ethylenedioxythiophene):poly-(styrenesulfonate) (PE-DOT:PSS) has been proposed, which allows solution-processing of the transparent electrode. 23,24owever, most alternative materials are inadequate as replacement for ITO due to their lower optical transparency and/or conductivity in comparison to ITO.
6][27] Sandwich structures based on TiO 2 are promising candidates due to their transparency in the visible, and the strong mechanical and chemical stability of TiO 2 . 28Dhar et al. demonstrated TAT multilayer electrodes with good optoelectronic properties exhibiting a sheet resistance (R sh ) of 5.7 Ω/sq and an average optical transmittance of 90% at 590 nm. 25 However, these structures have not been successfully applied to thin-film devices like OPVs, dye-sensitized solar cells (DSSC), or the recently emerging perovskite solar cells.
In this letter, we demonstrate that high-performance state-of-the-art OPVs using TAT multilayers as an ITO-free electrode allow for single junction efficiencies up to 8.7%.The possibility to individually control the film thicknesses in the multilayer allows for an optimization of the light intensity profile in the active layer as a function of the photoactive material, which directly translates into higher photocurrents and more efficient devices.
ITO-free transparent electrodes with a TAT multilayer structure on glass were prepared by sputtering at room temperature without any vacuum break (see Figure 1).To fabricate these OPVs, the ITO-free electrode consisting of the top TiO 2 layer as an electron collector was annealed at 400 • C for 30 min.This thermal processing is crucial for charge collection, directly evident from current density-voltage curves, mostly reflected in improved fill factors.In order to demonstrate thermal stability for the electrical property, the electrodes of TiO 2 (20 nm)-coated ITO (T/ITO) and TAT (20/12/28 nm) on glass were annealed at different temperature conditions (350-550 • C).Average values were calculated from measured R sh at four sides of a square and two cross of a center on the each sample.When the T/ITO electrode was annealed at 550 • C, the R sh value was significantly increased from 11.32 (without annealing) to 21.65 Ω/sq.In contrast, a slight increase of only 1.69 Ω/sq was observed in the TAT electrode after annealing at 550 • C (from 6.75 to 8.44 Ω/sq).Besides, R sh value of TAT electrode without annealing treatment is lower than that of T/ITO (11.23 Ω/sq).This indicates that the TAT electrodes have a high thermal stability and maintain their good electrical properties compared to T/ITO.Interestingly, the R sh of TAT electrodes is stable after annealing even at elevated temperatures up to 550 • C with slight increase in R sh value of only 1.69 Ω/sq (from 6.75 to 8.44 Ω/sq), whereas the R sh of TiO 2 -coated ITO (T/ITO) annealed at the same condition was significantly increased from 11.23 to 21.65 Ω/sq (Figure 2 and Table I).This indicates that the TAT electrodes have a high thermal stability and maintain their good electrical properties.In contrast, upon the same thermal treatments ITO electrodes show significantly deteriorating performance.Owing to this low thermal stability, ITO has been narrowly used only for the application of electric devices fabricated at temperatures below 300 • C. 22 The advantage of better thermal stability of our TAT electrodes provides a wide opportunity in this field and makes them viable for a number of devices based on TiO 2 electrodes like DSSCs, perovskite photovoltaics, and other hybrid inorganic-organic solar cells.
Besides the superior thermal stability of TAT electrodes in comparison to ITO electrodes, they have the advantage that the absorption behaviour, i.e., the coherent electric field intensity (|E| 2 ) distribution inside the active layer of the device can be maximized by varying the thickness of the TiO 2 layers without the danger of structure-induced changes to the active layer morphology.Therefore, matching the optical cavity for an optimized active material, processing parameter like the active layer thickness results in a maximized device performance due to enhanced light harvesting while keeping the electronic properties of the organic layer completely unaffected.The computational results in Figure 1   that changes in thickness of the individual layers crucially influence the appearance of the optical cavity mode between ITO or TAT, and Ag back electrodes. 29igure 3 8% and open circuit voltage, V OC of 0.76 V) is reached with a significantly higher short-circuit current density (J SC ) of 17.54 mA/cm 2 .This is a relative enhancement of ∼12% in J SC ([J SC,TAT − J SC,T/ITO ]/J SC,T/ITO ) with slightly increased FF and V OC in comparison to a representative ITO-based device with a J SC of 15.64 mA/cm 2 (7.5% overall efficiency, FF of 64.3%, and V OC of 0.75 V).
In order to determine the origin of the superior performance, experimental external quantum efficiencies (EQEs) for two different OPVs featuring T/ITO and TAT multilayer electrodes are compared.As shown in Figure 3(b), the EQE in the wavelength range of 450-800 nm (i.e., the main absorption of the PTB7:PC 71 BM blend) with the TAT electrode is higher than with ITO, while there is a slight reduction in the EQE observed between 350 and 450 nm.These findings are in good agreement with simulated EQE spectra as evident from Figure 3(c).To verify the decoupling of the optical absorption and the IQE in the measured EQE data, relative EQE and relative total absorption calculated as (TAT-T/ITO)/TAT are compared (Figure 3(d)).Good agreement between relative EQE and relative total absorption was obtained, indicating that the IQE of the active film remains unchanged and the improvement in EQE can be directly attributed to the increase in light absorption.
Figure 4 shows the simulated optical electric field profiles in the TAT and T/ITO devices from Figure 3(a) as a function of the wavelength of incident light ranging from 450 nm to 750 nm.The full optical electric field profiles ranging 450-850 nm is presented in the supplementary material (see Figure S1 of the supplementary material). 30The simulations show that a higher intensity |E| 2 for wavelengths above 450 nm can be obtained in OPVs with TAT electrode compared to the T/ITO reference.Accordingly, light absorption is enhanced in this wavelength region, resulting in an improvement of device performance due to enhanced photocurrent generation.
While these are the representative results for one defined set of layer thicknesses of the TAT electrode, the optical electric field can be greatly influenced by the thickness of each layer in the sandwich electrode.This allows adjusting the TAT electrode to arbitrary active layers with different optimized film thicknesses and/or intrinsic optical properties.In other words, the presented TAT electrodes allow the tailored optimization of OPVs through the control of thickness of the TiO 2 layers in the TAT multilayer system.There, the optimum condition for the TAT electrode can be predicted using optical modelling of the respective photoactive film.
In order to outline this methodology, Figure 5 summarizes J SC simulations for OPVs structured as Ag (150 nm)/PEDOT:PSS (8 nm)/active layer on TiO 2 /ITO or TiO 2 /Ag/TiO 2 with dependencies of the layer thickness of ITO (x) vs TiO 2 (y) and bottom (x) vs top (y) of TiO 2 , respectively.The contour plots of J SC for OPVs with active layers of 95 nm of PTB7:PC 71 BM (Figures 5(a This result implies that the optimum condition for high-performance can be effectively discovered by controlling the thickness of each layer in the simulation for different types of photovoltaic devices with different absorption spectra of the photoactive materials and different active layer thicknesses.The highest J SC value in each condition is indicated by a red arrow.In the OPV with PTB7:PC 71 BM and ITO electrode (Figure 5(a)), the maximum J SC value of 18.5 mA/cm 2 is observed at the thickness condition of T ITO = 60 nm and T TiO 2 = 70 nm.In contrast, the OPV with exactly the same active layer and TAT electrode shows a highest J SC value of 17.5 mA/cm 2 (T bottom-TiO 2 = 20 nm, 12 nm Ag and T top-TiO 2 = 90 nm).While these results indicate slightly higher possible photocurrents in the ITO system, it should be noted that the fabrication of high-performance devices using such thicknesses is challenging because not only optical but also electrical properties of the multilayer devices should be considered.In the case of ITO, the resistance is exponentially increased as the film thickness is decreased.For instance, high sheet resistances (>R sh = 50 Ω/sq) have been reported for thicknesses below 100 nm, 31 which would directly result in reduced FFs.Hence, the optimum condition from optical simulations would not allow for achieving a high-performance device in case of the ITO electrode.In contrast, the conductivity of the TAT electrode is mostly provided by the thin Ag film, and the sheet resistance is only marginally influenced by the thickness of the top-and bottom-TiO 2 film (see Figure S2 of the supplementary material). 30urthermore, the simulations underline how important it is to optimize the active layer thickness to gain a maximum photocurrent generation in different active layer systems as shown for the two examples of PTB7-and P3HT-based OPVs.While commercial ITO substrates are typically fabricated at a fixed layer thickness at which balanced sheet resistance and transitivity are obtained, the TAT electrodes allow to individually adjust the layer thicknesses in order to maximize light absorption in the active layer.
As a proof of concept, the decoupled optical cavity optimization of devices equipped with the TAT multilayer electrodes is exemplarily performed, both by experiment and by simulation.For this purpose, only the bottom TiO 2 layer is varied in order to keep the thickness of the top layer comparable for the ITO and the TAT film.As found in optimization experiments, the thickness of the top TiO 2 layer influences the electronic properties of the device, mostly due to an increased series resistance and film roughness for thicker layers.While this issue requires further optimization of the TiO 2 processing in the future in order to enable even wider tunability, the fundamental principle presented in this publication is outlined also for variation of only the bottom TiO 16.89 ± 0.23 mA/cm 2 , respectively.The highest J SC value was 17.78 ± 0.31 mA/cm 2 for T bottom-TiO 2 of 28 nm, in good agreement with the simulated curves.By increasing T bottom-TiO 2 from 40 to 55 nm, the J SC values were gradually decreased from 16.30 ± 0.28 to 15.49 ± 0.80 mA/cm 2 .Detailed information for the device performance is presented in the supplementary material (see Table SI of the supplementary material). 30We note that the experimentally measured J SC value has a similar trend as the simulated J SC (≥T bottom-TiO 2 of 10 nm), although the J SC value in experimental results was slightly higher than the values obtained from simulations.To verify the decoupling of the optical absorption and the IQE in the measured EQE data (see Figure S3 of the supplementary material), 30 relative EQE and relative total absorption are compared (see Figure S4 of the supplementary material). 30Good agreement between relative EQE and relative total absorption in each condition was obtained, indicating that the improvement in EQE can be directly attributed to the increase in light absorption.In addition, the PCE follows the J SC tendency, as shown in Figure 6 (inset), underlining that the electronic properties of the active layer are not affected by tuning the TiO 2 bottom layer.This further implies that the change in thickness of the bottom-TiO 2 layer is exclusively responsible for the device performance as it directly determines the coherent electric field distribution in the active layer of the photovoltaic device.
We have achieved high performing OPVs exhibiting state-of-the-art efficiencies with the PTB7: PC 71 BM system using a TAT multilayer electrode as replacement for ITO.Our TAT multilayers show a superior thermal stability than T/ITO, making them viable for application in other photovoltaic systems like DSSCs and perovskite solar cells.As outlined by a combination of experiments and optical simulation, it is possible to tune the electric field intensity inside the device by controlling the thickness of the TAT layer, and with this the properties of the optical cavity.Our results show that in particular the front TiO 2 layer can be tuned in thickness without changing the electronic properties of the TAT electrode, which allows the tailored optimization of device performance for arbitrary active layer compositions and thicknesses.
) and 5(b)) and 300 nm of P3HT:PC 61 BM (Figures5(a) and 5(b)), representing two different examples of electronically optimized OPV active layers, show a pronounced current density-dependency on the layer thicknesses.
FIG. 6. Simulated and experimental J SC with PCE of device.Simulated J SC profile of TAT multilayer with fixed Ag/top-TiO 2 layer thickness of 12/20 nm (blue line) and experimental J SC (open square) with changing in the thickness of bottom-TiO 2 layer (5, 10, 28, 40, and 55 nm).Inset: PCE.The dotted line in Figure 5(b) represents this simulation result.

TABLE I .
Sheet resistivity (R sh ) of T/ITO and TAT electrodes with different annealing temperature.Summarized results of R sh of T/ITO and TAT electrodes shown in the Figure2.The unit of values in the table is Ω/sq.