@article{PerdigonToroLeQuangPhuongElleretal.2022, author = {Perdigon-Toro, Lorena and Le Quang Phuong, and Eller, Fabian and Freychet, Guillaume and Saglamkaya, Elifnaz and Khan, Jafar and Wei, Qingya and Zeiske, Stefan and Kroh, Daniel and Wedler, Stefan and Koehler, Anna and Armin, Ardalan and Laquai, Frederic and Herzig, Eva M. and Zou, Yingping and Shoaee, Safa and Neher, Dieter}, title = {Understanding the role of order in Y-series non-fullerene solar cells to realize high open-circuit voltages}, series = {Advanced energy materials}, volume = {12}, journal = {Advanced energy materials}, number = {12}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1614-6832}, doi = {10.1002/aenm.202103422}, pages = {13}, year = {2022}, abstract = {Non-fullerene acceptors (NFAs) as used in state-of-the-art organic solar cells feature highly crystalline layers that go along with low energetic disorder. Here, the crucial role of energetic disorder in blends of the donor polymer PM6 with two Y-series NFAs, Y6, and N4 is studied. By performing temperature-dependent charge transport and recombination studies, a consistent picture of the shape of the density of state distributions for free charges in the two blends is developed, allowing an analytical description of the dependence of the open-circuit voltage V-OC on temperature and illumination intensity. Disorder is found to influence the value of the V-OC at room temperature, but also its progression with temperature. Here, the PM6:Y6 blend benefits substantially from its narrower state distributions. The analysis also shows that the energy of the equilibrated free charge population is well below the energy of the NFA singlet excitons for both blends and possibly below the energy of the populated charge transfer manifold, indicating a down-hill driving force for free charge formation. It is concluded that energetic disorder of charge-separated states has to be considered in the analysis of the photovoltaic properties, even for the more ordered PM6:Y6 blend.}, language = {en} } @article{PerdigonToroLeQuangPhuongZeiskeetal.2021, author = {Perdig{\´o}n-Toro, Lorena and Le Quang Phuong, and Zeiske, Stefan and Vandewal, Koen and Armin, Ardalan and Shoaee, Safa and Neher, Dieter}, title = {Excitons dominate the emission from PM6}, series = {ACS energy letters / American Chemical Society}, volume = {6}, journal = {ACS energy letters / American Chemical Society}, number = {2}, publisher = {American Chemical Society}, address = {Washington}, issn = {2380-8195}, doi = {10.1021/acsenergylett.0c02572}, pages = {557 -- 564}, year = {2021}, abstract = {Non-fullerene acceptors (NFAs) are far more emissive than their fullerene-based counterparts. Here, we study the spectral properties of photocurrent generation and recombination of the blend of the donor polymer PM6 with the NFA Y6. We find that the radiative recombination of free charges is almost entirely due to the re-occupation and decay of Y6 singlet excitons, but that this pathway contributes less than 1\% to the total recombination. As such, the open-circuit voltage of the PM6:Y6 blend is determined by the energetics and kinetics of the charge-transfer (CT) state. Moreover, we find that no information on the energetics of the CT state manifold can be gained from the low-energy tail of the photovoltaic external quantum efficiency spectrum, which is dominated by the excitation spectrum of the Y6 exciton. We, finally, estimate the charge-separated state to lie only 120 meV below the Y6 singlet exciton energy, meaning that this blend indeed represents a high-efficiency system with a low energetic offset.}, language = {en} } @article{ZeiskeSandbergZarrabietal.2022, author = {Zeiske, Stefan and Sandberg, Oskar J. and Zarrabi, Nasim and Wolff, Christian Michael and Raoufi, Meysam and Pe{\~n}a-Camargo, Francisco and Gutierrez-Partida, Emilio and Meredith, Paul and Stolterfoht, Martin and Armin, Ardalan}, title = {Static disorder in lead halide perovskites}, series = {The journal of physical chemistry letters}, volume = {13}, journal = {The journal of physical chemistry letters}, number = {31}, publisher = {American Chemical Society}, address = {Washington}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.2c01652}, pages = {7280 -- 7285}, year = {2022}, abstract = {In crystalline and amorphous semiconductors, the temperature-dependent Urbach energy can be determined from the inverse slope of the logarithm of the absorption spectrum and reflects the static and dynamic energetic disorder. Using recent advances in the sensitivity of photocurrent spectroscopy methods, we elucidate the temperature-dependent Urbach energy in lead halide perovskites containing different numbers of cation components. We find Urbach energies at room temperature to be 13.0 +/- 1.0, 13.2 +/- 1.0, and 13.5 +/- 1.0 meV for single, double, and triple cation perovskite. Static, temperature-independent contributions to the Urbach energy are found to be as low as 5.1 ?+/- 0.5, 4.7 +/- 0.3, and 3.3 +/- 0.9 meV for the same systems. Our results suggest that, at a low temperature, the dominant static disorder in perovskites is derived from zero-point phonon energy rather than structural disorder. This is unusual for solution-processed semiconductors but broadens the potential application of perovskites further to quantum electronics and devices.}, language = {en} } @article{ZeiskeSandbergKurpiersetal.2022, author = {Zeiske, Stefan and Sandberg, Oskar J. and Kurpiers, Jona and Shoaee, Safa and Meredith, Paul and Armin, Ardalan}, title = {Probing charge generation efficiency in thin-film solar cells by integral-mode transient charge extraction}, series = {ACS photonics}, volume = {9}, journal = {ACS photonics}, number = {4}, publisher = {American Chemical Society}, address = {Washington}, issn = {2330-4022}, doi = {10.1021/acsphotonics.1c01532}, pages = {1188 -- 1195}, year = {2022}, abstract = {The photogeneration of free charges in light-harvesting devices is a multistep process, which can be challenging to probe due to the complexity of contributing energetic states and the competitive character of different driving mechanisms. In this contribution, we advance a technique, integral-mode transient charge extraction (ITCE), to probe these processes in thin-film solar cells. ITCE combines capacitance measurements with the integral-mode time-of-flight method in the low intensity regime of sandwich-type thin-film devices and allows for the sensitive determination of photogenerated charge-carrier densities. We verify the theoretical framework of our method by drift-diffusion simulations and demonstrate the applicability of ITCE to organic and perovskite semiconductor-based thin-film solar cells. Furthermore, we examine the field dependence of charge generation efficiency and find our ITCE results to be in excellent agreement with those obtained via time-delayed collection field measurements conducted on the same devices.}, language = {en} } @article{SunSandbergNeheretal.2022, author = {Sun, Bowen and Sandberg, Oskar and Neher, Dieter and Armin, Ardalan and Shoaee, Safa}, title = {Wave optics of differential absorption spectroscopy in thick-junction organic solar cells}, series = {Physical review applied / The American Physical Society}, volume = {17}, journal = {Physical review applied / The American Physical Society}, number = {5}, publisher = {American Physical Society}, address = {College Park}, issn = {2331-7019}, doi = {10.1103/PhysRevApplied.17.054016}, pages = {12}, year = {2022}, abstract = {Differential absorption spectroscopy techniques serve as powerful techniques to study the excited species in organic solar cells. However, it has always been challenging to employ these techniques for characterizing thick-junction organic solar cells, especially when a reflective top contact is involved. In this work, we present a detailed and systematic study on how a combination of the presence of the interference effect and a nonuniform charge-distribution profile, severely manipulates experimental spectra and the decay dynamics. Furthermore, we provide a practical methodology to correct these optical artifacts in differential absorption spectroscopies. The results and the proposed correction method generally apply to all kinds of differential absorption spectroscopy techniques and various thin-film systems, such as organics, perovskites, kesterites, and two-dimensional materials. Notably, it is found that the shape of differential absorption spectra can be strongly distorted, starting from 150-nm active-layer thickness; this matches the thickness range of thick-junction organic solar cells and most perovskite solar cells and needs to be carefully considered in experiments. In addition, the decay dynamics of differential absorption spectra is found to be disturbed by optical artifacts under certain conditions. With the help of the proposed correction formalism, differential spectra and the decay dynamics can be characterized on the full device of thin-film solar cells in transmission mode and yield accurate and reliable results to provide design rules for further progress.}, language = {en} } @article{SandbergKurpiersStolterfohtetal.2020, author = {Sandberg, Oskar J. and Kurpiers, Jona and Stolterfoht, Martin and Neher, Dieter and Meredith, Paul and Shoaee, Safa and Armin, Ardalan}, title = {On the question of the need for a built-in potential in Perovskite solar cells}, series = {Advanced materials interfaces}, volume = {7}, journal = {Advanced materials interfaces}, number = {10}, publisher = {Wiley}, address = {Hoboken}, issn = {2196-7350}, doi = {10.1002/admi.202000041}, pages = {8}, year = {2020}, abstract = {Perovskite semiconductors as the active materials in efficient solar cells exhibit free carrier diffusion lengths on the order of microns at low illumination fluxes and many hundreds of nanometers under 1 sun conditions. These lengthscales are significantly larger than typical junction thicknesses, and thus the carrier transport and charge collection should be expected to be diffusion controlled. A consensus along these lines is emerging in the field. However, the question as to whether the built-in potential plays any role is still of matter of some conjecture. This important question using phase-sensitive photocurrent measurements and theoretical device simulations based upon the drift-diffusion framework is addressed. In particular, the role of the built-in electric field and charge-selective transport layers in state-of-the-art p-i-n perovskite solar cells comparing experimental findings and simulation predictions is probed. It is found that while charge collection in the junction does not require a drift field per se, a built-in potential is still needed to avoid the formation of reverse electric fields inside the active layer, and to ensure efficient extraction through the charge transport layers.}, language = {en} } @article{ZhangChenArminetal.2017, author = {Zhang, Kai and Chen, Zhiming and Armin, Ardalan and Dong, Sheng and Xia, Ruoxi and Yip, Hin-Lap and Shoaee, Safa and Huang, Fei and Cao, Yong}, title = {Efficient large area organic solar cells processed by blade-coating with single-component green solvent}, series = {Solar Rrl}, volume = {2}, journal = {Solar Rrl}, number = {1}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {2367-198X}, doi = {10.1002/solr.201700169}, pages = {9}, year = {2017}, abstract = {While the performance of laboratory-scale organic solar cells (OSCs) continues to grow, development of high efficiency large area OSCs remains a big challenge. Although a few attempts to produce large area organic solar cells (OSCs) have been reported, there are still challenges on the way to realizing efficient module devices, such as the low compatibility of the thickness-sensitive active layer with large area coating techniques, the frequent need for toxic solvents and tedious optimization processes used during device fabrication. In this work, highly efficient thickness-insensitive OSCs based on PTB7-Th:PC71BM that processed with single-component green solvent 2-methylanisole are presented, in which both junction thickness limitation and solvent toxicity issues are simultaneously addressed. Careful investigation reveals that this green solvent prevents the evolution of PC71BM into large area clusters resulting in reduced charge carrier recombination, and largely eliminates trapping centers, and thus improves the thickness tolerance of the films. These findings enable us to address the scalability and solvent toxicity issues and to fabricate a 16 cm(2) OSC with doctor-blade coating with a state-of-the-art power conversion efficiency of 7.5\% using green solvent.}, language = {en} } @article{ArminChenJinetal.2018, author = {Armin, Ardalan and Chen, Zhiming and Jin, Yaocheng and Zhang, Kai and Huang, Fei and Shoaee, Safa}, title = {A Shockley-Type polymer}, series = {Advanced energy materials}, volume = {8}, journal = {Advanced energy materials}, number = {7}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1614-6832}, doi = {10.1002/aenm.201701450}, pages = {9}, year = {2018}, abstract = {Charge extraction rate in solar cells made of blends of electron donating/accepting organic semiconductors is typically slow due to their low charge carrier mobility. This sets a limit on the active layer thickness and has hindered the industrialization of organic solar cells (OSCs). Herein, charge transport and recombination properties of an efficient polymer (NT812):fullerene blend are investigated. This system delivers power conversion efficiency of >9\% even when the junction thickness is as large as 800 nm. Experimental results indicate that this material system exhibits exceptionally low bimolecular recombination constant, 800 times smaller than the diffusion-controlled electron and hole encounter rate. Comparing theoretical results based on a recently introduced modified Shockley model for fill factor, and experiments, clarifies that charge collection is nearly ideal in these solar cells even when the thickness is several hundreds of nanometer. This is the first realization of high-efficiency Shockley-type organic solar cells with junction thicknesses suitable for scaling up.}, language = {en} } @article{YazmaciyanStolterfohtBurnetal.2018, author = {Yazmaciyan, Aren and Stolterfoht, Martin and Burn, Paul L. and Lin, Qianqian and Meredith, Paul and Armin, Ardalan}, title = {Recombination losses above and below the transport percolation threshold in bulk heterojunction organic solar cells}, series = {Advanced energy materials}, volume = {8}, journal = {Advanced energy materials}, number = {18}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1614-6832}, doi = {10.1002/aenm.201703339}, pages = {8}, year = {2018}, abstract = {Achieving the highest power conversion efficiencies in bulk heterojunction organic solar cells requires a morphology that delivers electron and hole percolation pathways for optimized transport, plus sufficient donor:acceptor contact area for near unity charge transfer state formation. This is a significant structural challenge, particularly in semiconducting polymer:fullerene systems. This balancing act in the model high efficiency PTB7:PC70BM blend is studied by tuning the donor:acceptor ratio, with a view to understanding the recombination loss mechanisms above and below the fullerene transport percolation threshold. The internal quantum efficiency is found to be strongly correlated to the slower carrier mobility in agreement with other recent studies. Furthermore, second-order recombination losses dominate the shape of the current density-voltage curve in efficient blend combinations, where the fullerene phase is percolated. However, below the charge transport percolation threshold, there is an electric-field dependence of first-order losses, which includes electric-field-dependent photogeneration. In the intermediate regime, the fill factor appears to be limited by both first- and second-order losses. These findings provide additional basic understanding of the interplay between the bulk heterojunction morphology and the order of recombination in organic solar cells. They also shed light on the limitations of widely used transport models below the percolation threshold.}, language = {en} } @article{ZhangStolterfohtArminetal.2018, author = {Zhang, Shanshan and Stolterfoht, Martin and Armin, Ardalan and Lin, Qianqian and Zu, Fengshuo and Sobus, Jan and Jin, Hui and Koch, Norbert and Meredith, Paul and Burn, Paul L. and Neher, Dieter}, title = {Interface Engineering of Solution-Processed Hybrid Organohalide Perovskite Solar Cells}, series = {ACS applied materials \& interfaces}, volume = {10}, journal = {ACS applied materials \& interfaces}, number = {25}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/acsami.8b02503}, pages = {21681 -- 21687}, year = {2018}, abstract = {Engineering the interface between the perovskite absorber and the charge-transporting layers has become an important method for improving the charge extraction and open-circuit voltage (V-OC) of hybrid perovskite solar cells. Conjugated polymers are particularly suited to form the hole-transporting layer, but their hydrophobicity renders it difficult to solution-process the perovskite absorber on top. Herein, oxygen plasma treatment is introduced as a simple means to change the surface energy and work function of hydrophobic polymer interlayers for use as p-contacts in perovskite solar cells. We find that upon oxygen plasma treatment, the hydrophobic surfaces of different prototypical p-type polymers became sufficiently hydrophilic to enable subsequent perovskite junction processing. In addition, the oxygen plasma treatment also increased the ionization potential of the polymer such that it became closer to the valance band energy of the perovskite. It was also found that the oxygen plasma treatment could increase the electrical conductivity of the p-type polymers, facilitating more efficient charge extraction. On the basis of this concept, inverted MAPbI(3) perovskite devices with different oxygen plasma-treated polymers such as P3HT, P3OT, polyTPD, or PTAA were fabricated with power conversion efficiencies of up to 19\%.}, language = {en} } @article{HosseiniRolandKurpiersetal.2019, author = {Hosseini, Seyed Mehrdad and Roland, Steffen and Kurpiers, Jona and Chen, Zhiming and Zhang, Kai and Huang, Fei and Armin, Ardalan and Neher, Dieter and Shoaee, Safa}, title = {Impact of Bimolecular Recombination on the Fill Factor of Fullerene and Nonfullerene-Based Solar Cells}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {123}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {11}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.8b11669}, pages = {6823 -- 6830}, year = {2019}, abstract = {Power conversion efficiencies of donor/acceptor organic solar cells utilizing nonfullerene acceptors have now increased beyond the record of their fullerene-based counterparts. There remain many fundamental questions regarding nanomorphology, interfacial states, charge generation and extraction, and losses in these systems. Herein, we present a comparative study of bulk heterojunction solar cells composed of a recently introduced naphthothiadiazole-based polymer (NT812) as the electron donor and two different acceptor molecules, namely, [6,6]-phenyl-C71-butyric acid methyl ester (PCBM)[70] and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene (ITIC). A comparison between the photovoltaic performance of these two types of solar cells reveals that the open-circuit voltage (Voc) of the NT812:ITIC-based solar cell is larger, but the fill factor (FF) is lower than that of the NT812:PCBM[70] device. We find the key reason behind this reduced FF in the ITIC-based device to be faster nongeminate recombination relative to the NT812:PCBM[70] system.}, language = {en} } @article{ShoaeeArminStolterfohtetal.2019, author = {Shoaee, Safa and Armin, Ardalan and Stolterfoht, Martin and Hosseini, Seyed Mehrdad and Kurpiers, Jona and Neher, Dieter}, title = {Decoding Charge Recombination through Charge Generation in Organic Solar Cells}, series = {Solar RRL}, volume = {3}, journal = {Solar RRL}, number = {11}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {2367-198X}, doi = {10.1002/solr.201900184}, pages = {8}, year = {2019}, abstract = {The in-depth understanding of charge carrier photogeneration and recombination mechanisms in organic solar cells is still an ongoing effort. In donor:acceptor (bulk) heterojunction organic solar cells, charge photogeneration and recombination are inter-related via the kinetics of charge transfer states-being singlet or triplet states. Although high-charge-photogeneration quantum yields are achieved in many donor:acceptor systems, only very few systems show significantly reduced bimolecular recombination relative to the rate of free carrier encounters, in low-mobility systems. This is a serious limitation for the industrialization of organic solar cells, in particular when aiming at thick active layers. Herein, a meta-analysis of the device performance of numerous bulk heterojunction organic solar cells is presented for which field-dependent photogeneration, charge carrier mobility, and fill factor are determined. Herein, a "spin-related factor" that is dependent on the ratio of back electron transfer of the triplet charge transfer (CT) states to the decay rate of the singlet CT states is introduced. It is shown that this factor links the recombination reduction factor to charge-generation efficiency. As a consequence, it is only in the systems with very efficient charge generation and very fast CT dissociation that free carrier recombination is strongly suppressed, regardless of the spin-related factor.}, language = {en} } @article{ArminDurrantShoaee2017, author = {Armin, Ardalan and Durrant, James R. and Shoaee, Safa}, title = {Interplay Between Triplet-, Singlet-Charge Transfer States and Free Charge Carriers Defining Bimolecular Recombination Rate Constant of Organic Solar Cells}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {121}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.7b04825}, pages = {13969 -- 13976}, year = {2017}, abstract = {Despite the myriad of organic donor:acceptor materials, only few systems have emerged in the life of organic solar cells to, exhibit considerable reduced bimolecular recombination, with respect to the random encounter rate given by the Langevin equation. Monte Carlo simulations have revealed that the rate constant of the formation of electron-hole bound states depends on the random encounter of opposite charges and is nearly given by the Langevin equation for the domain sizes relevant to efficient bulk heterojunction systems. Recently, three studies :suggested that charge transfer states dissociating much faster than their decay rate to the ground state, can result in reduced bimolecular recombination by lowering the recombination rate to the ground state as a loss pathway. A separate study identified another loss pathway and suggested that forbidden back electron transfer from triplet charge transfer states to triplet excitons is a key to achieving reduced recombination. Herein we further explain the reduced bimolecular recombination by investigating the limitations of these two proposals. By solving kinetic rate equations for a BHJ system with realistic rates, we show that both of these previously presented conditions must only be held at the same time fora system to exhibit non-Langevin behavior. We demonstrate that suppression of both of the parallel loss channels of singlet and triplet states can be achieved through increasing the dissociation rate of the charge transfer states; a crucial requirement to achieve a high charge carrier extraction efficiency.}, language = {en} } @article{StolterfohtArminPhilippaetal.2016, author = {Stolterfoht, Martin and Armin, Ardalan and Philippa, Bronson and Neher, Dieter}, title = {The Role of Space Charge Effects on the Competition between Recombination and Extraction in Solar Cells with Low-Mobility Photoactive Layers}, series = {The journal of physical chemistry letters}, volume = {7}, journal = {The journal of physical chemistry letters}, publisher = {American Chemical Society}, address = {Washington}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.6b02106}, pages = {4716 -- 4721}, year = {2016}, abstract = {The competition between charge extraction and nongeminate recombination critically determines the current-voltage characteristics of organic solar cells (OSCs) and their fill factor. As a measure of this competition, several figures of merit (FOMs) have been put forward; however, the impact of space charge effects has been either neglected, or not specifically addressed. Here we revisit recently reported FOMs and discuss the role of space charge effects on the interplay between recombination and extraction. We find that space charge effects are the primary cause for the onset of recombination in so-called non-Langevin systems, which also depends on the slower carrier mobility and recombination coefficient. The conclusions are supported with numerical calculations and experimental results of 25 different donor/acceptor OSCs with different charge transport parameters, active layer thicknesses or composition ratios. The findings represent a conclusive understanding of bimolecular recombination for drift dominated photocurrents and allow one to minimize these losses for given device parameters.}, language = {en} }