@article{StolterfohtCaprioglioWolffetal.2019, author = {Stolterfoht, Martin and Caprioglio, Pietro and Wolff, Christian Michael and Marquez, Jose A. and Nordmann, Joleik and Zhang, Shanshan and Rothhardt, Daniel and H{\"o}rmann, Ulrich and Amir, Yohai and Redinger, Alex and Kegelmann, Lukas and Zu, Fengshuo and Albrecht, Steve and Koch, Norbert and Kirchartz, Thomas and Saliba, Michael and Unold, Thomas and Neher, Dieter}, title = {The impact of energy alignment and interfacial recombination on the internal and external open-circuit voltage of perovskite solar cells}, series = {Energy \& environmental science}, volume = {12}, journal = {Energy \& environmental science}, number = {9}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1754-5692}, doi = {10.1039/c9ee02020a}, pages = {2778 -- 2788}, year = {2019}, abstract = {Charge transport layers (CTLs) are key components of diffusion controlled perovskite solar cells, however, they can induce additional non-radiative recombination pathways which limit the open circuit voltage (V-OC) of the cell. In order to realize the full thermodynamic potential of the perovskite absorber, both the electron and hole transport layer (ETL/HTL) need to be as selective as possible. By measuring the photoluminescence yield of perovskite/CTL heterojunctions, we quantify the non-radiative interfacial recombination currents in pin- and nip-type cells including high efficiency devices (21.4\%). Our study comprises a wide range of commonly used CTLs, including various hole-transporting polymers, spiro-OMeTAD, metal oxides and fullerenes. We find that all studied CTLs limit the V-OC by inducing an additional non-radiative recombination current that is in most cases substantially larger than the loss in the neat perovskite and that the least-selective interface sets the upper limit for the V-OC of the device. Importantly, the V-OC equals the internal quasi-Fermi level splitting (QFLS) in the absorber layer only in high efficiency cells, while in poor performing devices, the V-OC is substantially lower than the QFLS. Using ultraviolet photoelectron spectroscopy and differential charging capacitance experiments we show that this is due to an energy level mis-alignment at the p-interface. The findings are corroborated by rigorous device simulations which outline important considerations to maximize the V-OC. This work highlights that the challenge to suppress non-radiative recombination losses in perovskite cells on their way to the radiative limit lies in proper energy level alignment and in suppression of defect recombination at the interfaces.}, language = {en} } @article{ZhangHosseiniGunderetal.2019, author = {Zhang, Shanshan and Hosseini, Seyed Mehrdad and Gunder, Rene and Petsiuk, Andrei and Caprioglio, Pietro and Wolff, Christian Michael and Shoaee, Safa and Meredith, Paul and Schorr, Susan and Unold, Thomas and Burn, Paul L. and Neher, Dieter and Stolterfoht, Martin}, title = {The Role of Bulk and Interface Recombination in High-Efficiency Low-Dimensional Perovskite Solar Cells}, series = {Advanced materials}, volume = {31}, journal = {Advanced materials}, number = {30}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0935-9648}, doi = {10.1002/adma.201901090}, pages = {11}, year = {2019}, abstract = {2D Ruddlesden-Popper perovskite (RPP) solar cells have excellent environmental stability. However, the power conversion efficiency (PCE) of RPP cells remains inferior to 3D perovskite-based cells. Herein, 2D (CH3(CH2)(3)NH3)(2)(CH3NH3)(n-1)PbnI3n+1 perovskite cells with different numbers of [PbI6](4-) sheets (n = 2-4) are analyzed. Photoluminescence quantum yield (PLQY) measurements show that nonradiative open-circuit voltage (V-OC) losses outweigh radiative losses in materials with n > 2. The n = 3 and n = 4 films exhibit a higher PLQY than the standard 3D methylammonium lead iodide perovskite although this is accompanied by increased interfacial recombination at the top perovskite/C-60 interface. This tradeoff results in a similar PLQY in all devices, including the n = 2 system where the perovskite bulk dominates the recombination properties of the cell. In most cases the quasi-Fermi level splitting matches the device V-OC within 20 meV, which indicates minimal recombination losses at the metal contacts. The results show that poor charge transport rather than exciton dissociation is the primary reason for the reduction in fill factor of the RPP devices. Optimized n = 4 RPP solar cells had PCEs of 13\% with significant potential for further improvements.}, language = {en} } @article{CaprioglioZuWolffetal.2019, author = {Caprioglio, Pietro and Zu, Fengshuo and Wolff, Christian Michael and Prieto, Jose A. Marquez and Stolterfoht, Martin and Becker, Pascal and Koch, Norbert and Unold, Thomas and Rech, Bernd and Albrecht, Steve and Neher, Dieter}, title = {High open circuit voltages in pin-type perovskite solar cells through strontium addition}, series = {Sustainable Energy \& Fuels}, volume = {3}, journal = {Sustainable Energy \& Fuels}, number = {2}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2398-4902}, doi = {10.1039/c8se00509e}, pages = {550 -- 563}, year = {2019}, abstract = {The incorporation of even small amounts of strontium (Sr) into lead-base hybrid quadruple cation perovskite solar cells results in a systematic increase of the open circuit voltage (V-oc) in pin-type perovskite solar cells. We demonstrate via absolute and transient photoluminescence (PL) experiments how the incorporation of Sr significantly reduces the non-radiative recombination losses in the neat perovskite layer. We show that Sr segregates at the perovskite surface, where it induces important changes of morphology and energetics. Notably, the Sr-enriched surface exhibits a wider band gap and a more n-type character, accompanied with significantly stronger surface band bending. As a result, we observe a significant increase of the quasi-Fermi level splitting in the neat perovskite by reduced surface recombination and more importantly, a strong reduction of losses attributed to non-radiative recombination at the interface to the C-60 electron-transporting layer. The resulting solar cells exhibited a V-oc of 1.18 V, which could be further improved to nearly 1.23 V through addition of a thin polymer interlayer, reducing the non-radiative voltage loss to only 110 meV. Our work shows that simply adding a small amount of Sr to the precursor solutions induces a beneficial surface modification in the perovskite, without requiring any post treatment, resulting in high efficiency solar cells with power conversion efficiency (PCE) up to 20.3\%. Our results demonstrate very high V-oc values and efficiencies in Sr-containing quadruple cation perovskite pin-type solar cells and highlight the imperative importance of addressing and minimizing the recombination losses at the interface between perovskite and charge transporting layer.}, language = {en} } @article{CaprioglioStolterfohtWolffetal.2019, author = {Caprioglio, Pietro and Stolterfoht, Martin and Wolff, Christian Michael and Unold, Thomas and Rech, Bernd and Albrecht, Steve and Neher, Dieter}, title = {On the relation between the open-circuit voltage and quasi-fermi level splitting in efficient perovskite solar cells}, series = {advanced energy materials}, volume = {9}, journal = {advanced energy materials}, number = {33}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1614-6832}, doi = {10.1002/aenm.201901631}, pages = {10}, year = {2019}, abstract = {Today's perovskite solar cells (PSCs) are limited mainly by their open-circuit voltage (VOC) due to nonradiative recombination. Therefore, a comprehensive understanding of the relevant recombination pathways is needed. Here, intensity-dependent measurements of the quasi-Fermi level splitting (QFLS) and of the VOC on the very same devices, including pin-type PSCs with efficiencies above 20\%, are performed. It is found that the QFLS in the perovskite lies significantly below its radiative limit for all intensities but also that the VOC is generally lower than the QFLS, violating one main assumption of the Shockley-Queisser theory. This has far-reaching implications for the applicability of some well-established techniques, which use the VOC as a measure of the carrier densities in the absorber. By performing drift-diffusion simulations, the intensity dependence of the QFLS, the QFLS-VOC offset and the ideality factor are consistently explained by trap-assisted recombination and energetic misalignment at the interfaces. Additionally, it is found that the saturation of the VOC at high intensities is caused by insufficient contact selectivity while heating effects are of minor importance. It is concluded that the analysis of the VOC does not provide reliable conclusions of the recombination pathways and that the knowledge of the QFLS-VOC relation is of great importance.}, language = {en} } @article{LeCorreStolterfohtPerdigonToroetal.2019, author = {Le Corre, Vincent M. and Stolterfoht, Martin and Perdig{\´o}n-Toro, Lorena and Feuerstein, Markus and Wolff, Christian Michael and Gil-Escrig, Lidon and Bolink, Henk J. and Neher, Dieter and Koster, L. Jan Anton}, title = {Charge Transport Layers Limiting the Efficiency of Perovskite Solar Cells: How To Optimize Conductivity, Doping, and Thickness}, series = {ACS Applied Energy Materials}, volume = {2}, journal = {ACS Applied Energy Materials}, number = {9}, publisher = {American Chemical Society}, address = {Washington}, issn = {2574-0962}, doi = {10.1021/acsaem.9b00856}, pages = {6280 -- 6287}, year = {2019}, abstract = {Perovskite solar cells (PSCs) are one of the main research topics of the photovoltaic community; with efficiencies now reaching up to 24\%, PSCs are on the way to catching up with classical inorganic solar cells. However, PSCs have not yet reached their full potential. In fact, their efficiency is still limited by nonradiative recombination, mainly via trap-states and by losses due to the poor transport properties of the commonly used transport layers (TLs). Indeed, state-of-the-art TLs (especially if organic) suffer from rather low mobilities, typically within 10(-5) and 10(-2) cm(-2) V-1 s(-1), when compared to the high mobilities, 1-10 cm(-2) V-1 s(-1), measured for perovskites. This work presents a comprehensive analysis of the effect of the mobility, thickness, and doping density of the transport layers based on combined experimental and modeling results of two sets of devices made of a solution-processed high-performing triple-cation (PCE approximate to 20\%). The results are also cross-checked on vacuum-processed MAPbI(3) devices. From this analysis, general guidelines on how to optimize a TL are introduced and especially a new and simple formula to easily calculate the amount of doping necessary to counterbalance the low mobility of the TLs.}, language = {en} } @article{WuerfelPerdigonToroKurpiersetal.2019, author = {W{\"u}rfel, Uli and Perdig{\´o}n-Toro, Lorena and Kurpiers, Jona and Wolff, Christian Michael and Caprioglio, Pietro and Rech, Jeromy James and Zhu, Jingshuai and Zhan, Xiaowei and You, Wei and Shoaee, Safa and Neher, Dieter and Stolterfoht, Martin}, title = {Recombination between Photogenerated and Electrode-Induced Charges Dominates the Fill Factor Losses in Optimized Organic Solar Cells}, series = {The journal of physical chemistry letters}, volume = {10}, journal = {The journal of physical chemistry letters}, number = {12}, publisher = {American Chemical Society}, address = {Washington}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.9b01175}, pages = {3473 -- 3480}, year = {2019}, abstract = {Charge extraction in organic solar cells (OSCs) is commonly believed to be limited by bimolecular recombination of photogenerated charges. However, the fill factor of OSCs is usually almost entirely governed by recombination processes that scale with the first order of the light intensity. This linear loss was often interpreted to be a consequence of geminate or trap-assisted recombination. Numerical simulations show that this linear dependence is a direct consequence of the large amount of excess dark charge near the contact. The first-order losses increase with decreasing mobility of minority carriers, and we discuss the impact of several material and device parameters on this loss mechanism. This work highlights that OSCs are especially vulnerable to injected charges as a result of their poor charge transport properties. This implies that dark charges need to be better accounted for when interpreting electro-optical measurements and charge collection based on simple figures of merit.}, 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{TockhornSutterCruzBournazouetal.2022, author = {Tockhorn, Philipp and Sutter, Johannes and Cruz Bournazou, Alexandros and Wagner, Philipp and J{\"a}ger, Klaus and Yoo, Danbi and Lang, Felix and Grischek, Max and Li, Bor and Li, Jinzhao and Shargaieva, Oleksandra and Unger, Eva and Al-Ashouri, Amran and K{\"o}hnen, Eike and Stolterfoht, Martin and Neher, Dieter and Schlatmann, Rutger and Rech, Bernd and Stannowski, Bernd and Albrecht, Steve and Becker, Christiane}, title = {Nano-optical designs for high-efficiency monolithic perovskite-silicon tandem solar cells}, series = {Nature nanotechnology}, volume = {17}, journal = {Nature nanotechnology}, number = {11}, publisher = {Nature Publishing Group}, address = {London [u.a.]}, issn = {1748-3387}, doi = {10.1038/s41565-022-01228-8}, pages = {1214 -- 1221}, year = {2022}, abstract = {Designing gentle sinusoidal nanotextures enables the realization of high-efficiency perovskite-silicon solar cells
Perovskite-silicon tandem solar cells offer the possibility of overcoming the power conversion efficiency limit of conventional silicon solar cells. Various textured tandem devices have been presented aiming at improved optical performance, but optimizing film growth on surface-textured wafers remains challenging. Here we present perovskite-silicon tandem solar cells with periodic nanotextures that offer various advantages without compromising the material quality of solution-processed perovskite layers. We show a reduction in reflection losses in comparison to planar tandems, with the new devices being less sensitive to deviations from optimum layer thicknesses. The nanotextures also enable a greatly increased fabrication yield from 50\% to 95\%. Moreover, the open-circuit voltage is improved by 15 mV due to the enhanced optoelectronic properties of the perovskite top cell. Our optically advanced rear reflector with a dielectric buffer layer results in reduced parasitic absorption at near-infrared wavelengths. As a result, we demonstrate a certified power conversion efficiency of 29.80\%.}, language = {en} } @article{PerdigonToroZhangMarkinaetal.2020, author = {Perdig{\´o}n-Toro, Lorena and Zhang, Huotian and Markina, Anastaa si and Yuan, Jun and Hosseini, Seyed Mehrdad and Wolff, Christian Michael and Zuo, Guangzheng and Stolterfoht, Martin and Zou, Yingping and Gao, Feng and Andrienko, Denis and Shoaee, Safa and Neher, Dieter}, title = {Barrierless free charge generation in the high-performance PM6:Y6 bulk heterojunction non-fullerene solar cell}, series = {Advanced materials}, volume = {32}, journal = {Advanced materials}, number = {9}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0935-9648}, doi = {10.1002/adma.201906763}, pages = {9}, year = {2020}, abstract = {Organic solar cells are currently experiencing a second golden age thanks to the development of novel non-fullerene acceptors (NFAs). Surprisingly, some of these blends exhibit high efficiencies despite a low energy offset at the heterojunction. Herein, free charge generation in the high-performance blend of the donor polymer PM6 with the NFA Y6 is thoroughly investigated as a function of internal field, temperature and excitation energy. Results show that photocurrent generation is essentially barrierless with near-unity efficiency, regardless of excitation energy. Efficient charge separation is maintained over a wide temperature range, down to 100 K, despite the small driving force for charge generation. Studies on a blend with a low concentration of the NFA, measurements of the energetic disorder, and theoretical modeling suggest that CT state dissociation is assisted by the electrostatic interfacial field which for Y6 is large enough to compensate the Coulomb dissociation barrier.}, 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} }