TY  - JOUR
A1  - Caprioglio, Pietro
A1  - Stolterfoht, Martin
A1  - Wolff, Christian Michael
A1  - Unold, Thomas
A1  - Rech, Bernd
A1  - Albrecht, Steve
A1  - Neher, Dieter
T1  - On the relation between the open-circuit voltage and quasi-fermi level splitting in efficient perovskite solar cells
JF  - advanced energy materials
N2  - 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.
KW  - electro-optical materials
KW  - perovskite solar cells
KW  - photovoltaic devices
KW  - thin films
Y1  - 2019
U6  - https://doi.org/10.1002/aenm.201901631
SN  - 1614-6832
SN  - 1614-6840
VL  - 9
IS  - 33
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Caprioglio, Pietro
A1  - Zu, Fengshuo
A1  - Wolff, Christian Michael
A1  - Prieto, Jose A. Marquez
A1  - Stolterfoht, Martin
A1  - Becker, Pascal
A1  - Koch, Norbert
A1  - Unold, Thomas
A1  - Rech, Bernd
A1  - Albrecht, Steve
A1  - Neher, Dieter
T1  - High open circuit voltages in pin-type perovskite solar cells through strontium addition
JF  - Sustainable Energy & Fuels
N2  - 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.
Y1  - 2019
U6  - https://doi.org/10.1039/c8se00509e
SN  - 2398-4902
VL  - 3
IS  - 2
SP  - 550
EP  - 563
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  - 
TY  - JOUR
A1  - Collado-Fregoso, Elisa
A1  - Pugliese, Silvina N.
A1  - Wojcik, Mariusz
A1  - Benduhn, Johannes
A1  - Bar-Or, Eyal
A1  - Perdigon-Toro, Lorena
A1  - Hörmann, Ulrich
A1  - Spoltore, Donato
A1  - Vandewal, Koen
A1  - Hodgkiss, Justin M.
A1  - Neher, Dieter
T1  - Energy-gap law for photocurrent generation in fullerene-based organic solar cells
BT  - the case of low-donor-content blends
JF  - Journal of the American Chemical Society
N2  - The involvement of charge-transfer (CT) states in the photogeneration and recombination of charge carriers has been an important focus of study within the organic photovoltaic community. In this work, we investigate the molecular factors determining the mechanism of photocurrent generation in low-donor-content organic solar cells, where the active layer is composed of vacuum-deposited C-60 and small amounts of organic donor molecules. We find a pronounced decline of all photovoltaic parameters with decreasing CT state energy. Using a combination of steady-state photocurrent measurements and time-delayed collection field experiments, we demonstrate that the power conversion efficiency, and more specifically, the fill factor of these devices, is mainly determined by the bias dependence of photocurrent generation. By combining these findings with the results from ultrafast transient absorption spectroscopy, we show that blends with small CT energies perform poorly because of an increased nonradiative CT state decay rate and that this decay obeys an energy-gap law. Our work challenges the common view that a large energy offset at the heterojunction and/or the presence of fullerene clusters guarantee efficient CT dissociation and rather indicates that charge generation benefits from high CT state energies through a slower decay to the ground state.
Y1  - 2019
U6  - https://doi.org/10.1021/jacs.8b09820
SN  - 0002-7863
VL  - 141
IS  - 6
SP  - 2329
EP  - 2341
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Deschler, Felix
A1  - Neher, Dieter
A1  - Schmidt-Mende, Lukas
T1  - Perovskite semiconductors for next generation optoelectronic applications
JF  - APL Materials
Y1  - 2019
U6  - https://doi.org/10.1063/1.5119744
SN  - 2166-532X
VL  - 7
IS  - 8
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Hofmann, Alexander J. L.
A1  - Züfle, Simon
A1  - Shimizu, Kohei
A1  - Schmid, Markus
A1  - Wessels, Vivien
A1  - Jäger, Lars
A1  - Altazin, Stephane
A1  - Ikegami, Keitaro
A1  - Khan, Motiur Rahman
A1  - Neher, Dieter
A1  - Ishii, Hisao
A1  - Ruhstaller, Beat
A1  - Brütting, Wolfgang
T1  - Dipolar Doping of Organic Semiconductors to Enhance Carrier Injection
JF  - Physical review applied
N2  - If not oriented perfectly isotropically, the strong dipole moment of polar organic semiconductor materials such as tris-(8-hydroxyquinolate)aluminum (Alq3) will lead to the buildup of a giant surface potential (GSP) and thus to a macroscopic dielectric polarization of the organic film. Despite this having been a known fact for years, the implications of such high potentials within an organic layer stack have only been studied recently. In this work, the influence of the GSP on hole injection into organic layers is investigated. Therefore, we apply a concept called dipolar doping to devices consisting of the prototypical organic materials N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) as nonpolar host and Alq3 as dipolar dopant with different mixing ratios to tune the GSP. The mixtures are investigated in single-layer monopolar devices as well as bilayer metal/insulator/semiconductor structures. Characterization is done electrically using current-voltage (I-V) characteristics, impedance spectroscopy, and charge extraction by linearly increasing voltage and time of flight, as well as with ultraviolet photoelectron spectroscopy. We find a maximum in device performance for moderate to low doping concentrations of the polar species in the host. The observed behavior can be described on the basis of the Schottky effect for image-force barrier lowering, if the changes in the interface dipole, the carrier mobility, and the GSP induced by dipolar doping are taken into account.
KW  - Carrier dynamics
KW  - Electric polarization
KW  - Optoelectronics
KW  - Organic electronics
KW  - Doped semiconductors
KW  - Interfaces
KW  - Organic LEDs
KW  - Organic semiconductors
Y1  - 2019
U6  - https://doi.org/10.1103/PhysRevApplied.12.064052
SN  - 2331-7019
VL  - 12
IS  - 6
PB  - American Physical Society
CY  - College Park
ER  - 
TY  - JOUR
A1  - Hosseini, Seyed Mehrdad
A1  - Roland, Steffen
A1  - Kurpiers, Jona
A1  - Chen, Zhiming
A1  - Zhang, Kai
A1  - Huang, Fei
A1  - Armin, Ardalan
A1  - Neher, Dieter
A1  - Shoaee, Safa
T1  - Impact of Bimolecular Recombination on the Fill Factor of Fullerene and Nonfullerene-Based Solar Cells
BT  - A Comparative Study of Charge Generation and Extraction
JF  - The journal of physical chemistry : C, Nanomaterials and interfaces
N2  - 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.
Y1  - 2019
U6  - https://doi.org/10.1021/acs.jpcc.8b11669
SN  - 1932-7447
VL  - 123
IS  - 11
SP  - 6823
EP  - 6830
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Hörmann, Ulrich
A1  - Zeiske, Stefan
A1  - Park, Soohyung
A1  - Schultz, Thorsten
A1  - Kickhoefel, Sebastian
A1  - Scherf, Ullrich
A1  - Blumstengel, Sylke
A1  - Koch, Norbert
A1  - Neher, Dieter
T1  - Direct observation of state-filling at hybrid tin oxide/organic interfaces
JF  - Applied physics letters
N2  - Electroluminescence (EL) spectra of hybrid charge transfer states at metal oxide/organic type-II heterojunctions exhibit bias-induced spectral shifts. The reasons for this phenomenon have been discussed controversially and arguments for either electric field-induced effects or the filling of trap states at the oxide surface have been put forward. Here, we combine the results of EL and photovoltaic measurements to eliminate the unavoidable effect of the series resistance of inorganic and organic components on the total voltage drop across the hybrid device. For SnOx combined with the conjugated polymer [ladder type poly-(para-phenylene)], we find a one-to-one correspondence between the blue-shift of the EL peak and the increase of the quasi-Fermi level splitting at the hybrid heterojunction, which we unambiguously assign to state filling. Our data are resembled best by a model considering the combination of an exponential density of states with a doped semiconductor. Published under license by AIP Publishing.
Y1  - 2019
U6  - https://doi.org/10.1063/1.5082704
SN  - 0003-6951
SN  - 1077-3118
VL  - 114
IS  - 18
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Kegelmann, Lukas
A1  - Tockhorn, Philipp
A1  - Wolff, Christian Michael
A1  - Márquez, José A.
A1  - Caicedo Dávila, Sebastián
A1  - Korte, Lars
A1  - Unold, Thomas
A1  - Loevenich, Wilfried
A1  - Neher, Dieter
A1  - Rech, Bernd
A1  - Albrecht, Steve
T1  - Mixtures of Dopant-Free Spiro-OMeTAD and Water-Free PEDOT as a Passivating Hole Contact in Perovskite Solar Cells
JF  - ACS applied materials & interfaces
N2  - Doped spiro-OMeTAD at present is the most commonly used hole transport material (HTM) in n-i-p-type perovskite solar cells, enabling high efficiencies around 22%. However, the required dopants were shown to induce nonradiative recombination of charge carriers and foster degradation of the solar cell. Here, in a novel approach, highly conductive and inexpensive water-free poly(3,4-ethylenedioxythiophene) (PEDOT) is used to replace these dopants. The resulting spiro-OMeTAD/PEDOT (SpiDOT) mixed films achieve higher lateral conductivities than layers of doped spiro-OMeTAD. Furthermore, combined transient and steady-state photoluminescence studies reveal a passivating effect of PEDOT, suppressing nonradiative recombination losses at the perovskite/HTM interface. This enables excellent quasi-Fermi level splitting values of up to 1.24 eV in perovskite/SpiDOT layer stacks and high open-circuit voltages (V-OC) up to 1.19 V in complete solar cells. Increasing the amount of dopant-free spiro-OMeTAD in SpiDOT layers is shown to enhance hole extraction and thereby improves the fill factor in solar cells. As a consequence, stabilized efficiencies up to 18.7% are realized, exceeding cells with doped spiro-OMeTAD as a HTM in this study. Moreover, to the best of our knowledge, these results mark the lowest nonradiative recombination loss in the V-OC (140 mV with respect to the Shockley-Queisser limit) and highest efficiency reported so far for perovskite solar cells using PEDOT as a HTM.
KW  - perovskite solar cell
KW  - selective contact
KW  - spiro-OMeTAD
KW  - PEDOT
KW  - recombination
KW  - passivation
KW  - quasi-Fermi level splitting
Y1  - 2019
U6  - https://doi.org/10.1021/acsami.9b01332
SN  - 1944-8244
SN  - 1944-8252
VL  - 11
IS  - 9
SP  - 9172
EP  - 9181
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Kniepert, Juliane
A1  - Paulke, Andreas
A1  - Perdigon-Toro, Lorena
A1  - Kurpiers, Jona
A1  - Zhang, Huotian
A1  - Gao, Feng
A1  - Yuan, Jun
A1  - Zou, Yingping
A1  - Le Corre, Vincent M.
A1  - Koster, Lambert Jan Anton
A1  - Neher, Dieter
T1  - Reliability of charge carrier recombination data determined with charge extraction methods
JF  - Journal of applied physics
N2  - Charge extraction methods are popular for measuring the charge carrier density in thin film organic solar cells and to draw conclusions about the order and coefficient of nongeminate charge recombination. However, results from such studies may be falsified by inhomogeneous steady state carrier profiles or surface recombination. Here, we present a detailed drift-diffusion study of two charge extraction methods, bias-assisted charge extraction (BACE) and time-delayed collection field (TDCF). Simulations are performed over a wide range of the relevant parameters. Our simulations reveal that both charge extraction methods provide reliable information about the recombination order and coefficient if the measurements are performed under appropriate conditions. However, results from BACE measurements may be easily affected by surface recombination, in particular for small active layer thicknesses and low illumination densities. TDCF, on the other hand, is more robust against surface recombination due to its transient nature but also because it allows for a homogeneous high carrier density to be inserted into the active layer. Therefore, TDCF is capable to provide meaningful information on the order and coefficient of recombination even if the model conditions are not exactly fulfilled. We demonstrate this for an only 100 nm thick layer of a highly efficient nonfullerene acceptor (NFA) blend, comprising the donor polymer PM6 and the NFA Y6. TDCF measurements were performed as a function of delay time for different laser fluences and bias conditions. The full set of data could be consistently fitted by a strict second order recombination process, with a bias- and fluence-independent bimolecular recombination coefficient k(2) = 1.7 x 10(-17)m(3) s(-1). BACE measurements performed on the very same layer yielded the identical result, despite the very different excitation conditions. This proves that recombination in this blend is mostly through processes in the bulk and that surface recombination is of minor importance despite the small active layer thickness. Published under license by AIP Publishing.
Y1  - 2019
U6  - https://doi.org/10.1063/1.5129037
SN  - 0021-8979
SN  - 1089-7550
VL  - 126
IS  - 20
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Le Corre, Vincent M.
A1  - Stolterfoht, Martin
A1  - Perdigón-Toro, Lorena
A1  - Feuerstein, Markus
A1  - Wolff, Christian Michael
A1  - Gil-Escrig, Lidon
A1  - Bolink, Henk J.
A1  - Neher, Dieter
A1  - Koster, L. Jan Anton
T1  - Charge Transport Layers Limiting the Efficiency of Perovskite Solar Cells: How To Optimize Conductivity, Doping, and Thickness
JF  - ACS Applied Energy Materials
N2  - 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.
KW  - perovskite solar cells
KW  - transport layers
KW  - conductivity
KW  - doping
KW  - charge transport
Y1  - 2019
U6  - https://doi.org/10.1021/acsaem.9b00856
SN  - 2574-0962
VL  - 2
IS  - 9
SP  - 6280
EP  - 6287
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Li, Tian-yi
A1  - Benduhn, Johannes
A1  - Qiao, Zhi
A1  - Liu, Yuan
A1  - Li, Yue
A1  - Shivhare, Rishi
A1  - Jaiser, Frank
A1  - Wang, Pei
A1  - Ma, Jie
A1  - Zeika, Olaf
A1  - Neher, Dieter
A1  - Mannsfeld, Stefan C. B.
A1  - Ma, Zaifei
A1  - Vandewal, Koen
A1  - Leo, Karl
T1  - Effect of H- and J-Aggregation on the Photophysical and Voltage Loss of Boron Dipyrromethene Small Molecules in Vacuum-Deposited Organic Solar Cells
JF  - The journal of physical chemistry letters
N2  - An understanding of the factors limiting the open-circuit voltage (V-oc) and related photon energy loss mechanisms is critical to increase the power conversion efficiency (PCE) of small-molecule organic solar cells (OSCs), especially those with near-infrared (NIR) absorbers. In this work, two NIR boron dipyrromethene (BODIPY) molecules are characterized for application in planar (PHJ) and bulk (BHJ) heterojunction OSCs. When two H atoms are substituted by F atoms on the peripheral phenyl rings of the molecules, the molecular aggregation type in the thin film changes from the H-type to J-type. For PHJ devices, the nonradiative voltage loss of 0.35 V in the J-aggregated BODIPY is lower than that of 0.49 V in the H-aggregated device. In BHJ devices with a nonradiative voltage loss of 0.35 V, a PCE of 5.5% is achieved with an external quantum efficiency (EQE) maximum of 68% at 700 nm.
Y1  - 2019
U6  - https://doi.org/10.1021/acs.jpclett.9b01222
SN  - 1948-7185
VL  - 10
IS  - 11
SP  - 2684
EP  - 2691
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Nikolis, Vasileios C.
A1  - Mischok, Andreas
A1  - Siegmund, Bernhard
A1  - Kublitski, Jonas
A1  - Jia, Xiangkun
A1  - Benduhn, Johannes
A1  - Hörmann, Ulrich
A1  - Neher, Dieter
A1  - Gather, Malte C.
A1  - Spoltore, Donato
A1  - Vandewal, Koen
T1  - Strong light-matter coupling for reduced photon energy losses in organic photovoltaics
JF  - Nature Communications
N2  - Strong light-matter coupling can re-arrange the exciton energies in organic semiconductors. Here, we exploit strong coupling by embedding a fullerene-free organic solar cell (OSC) photo-active layer into an optical microcavity, leading to the formation of polariton peaks and a red-shift of the optical gap. At the same time, the open-circuit voltage of the device remains unaffected. This leads to reduced photon energy losses for the low-energy polaritons and a steepening of the absorption edge. While strong coupling reduces the optical gap, the energy of the charge-transfer state is not affected for large driving force donor-acceptor systems. Interestingly, this implies that strong coupling can be exploited in OSCs to reduce the driving force for electron transfer, without chemical or microstructural modifications of the photoactive layer. Our work demonstrates that the processes determining voltage losses in OSCs can now be tuned, and reduced to unprecedented values, simply by manipulating the device architecture.
Y1  - 2019
U6  - https://doi.org/10.1038/s41467-019-11717-5
SN  - 2041-1723
VL  - 10
PB  - Nature Publ. Group
CY  - London
ER  - 
TY  - JOUR
A1  - Pisoni, Stefano
A1  - Stolterfoht, Martin
A1  - Lockinger, Johannes
A1  - Moser, Thierry
A1  - Jiang, Yan
A1  - Caprioglio, Pietro
A1  - Neher, Dieter
A1  - Buecheler, Stephan
A1  - Tiwari, Ayodhya N.
T1  - On the origin of open-circuit voltage losses in flexible n-i-p perovskite solar cells
JF  - Science and technology of advanced materials : STAM
N2  - The possibility to manufacture perovskite solar cells (PSCs) at low temperatures paves the way to flexible and lightweight photovoltaic (PV) devices manufactured via high-throughput roll-to-roll processes. In order to achieve higher power conversion efficiencies, it is necessary to approach the radiative limit via suppression of non-radiative recombination losses. Herein, we performed a systematic voltage loss analysis for a typical low-temperature processed, flexible PSC in n-i-p configuration using vacuum deposited C-60 as electron transport layer (ETL) and two-step hybrid vacuum-solution deposition for CH3NH3PbI3 perovskite absorber. We identified the ETL/absorber interface as a bottleneck in relation to non-radiative recombination losses, the quasi-Fermi level splitting (QFLS) decreases from similar to 1.23 eV for the bare absorber, just similar to 90 meV below the radiative limit, to similar to 1.10 eV when C-60 is used as ETL. To effectively mitigate these voltage losses, we investigated different interfacial modifications via vacuum deposited interlayers (BCP, B4PyMPM, 3TPYMB, and LiF). An improvement in QFLS of similar to 30-40 meV is observed after interlayer deposition and confirmed by comparable improvements in the open-circuit voltage after implementation of these interfacial modifications in flexible PSCs. Further investigations on absorber/hole transport layer (HTL) interface point out the detrimental role of dopants in Spiro-OMeTAD film (widely employed HTL in the community) as recombination centers upon oxidation and light exposure. [GRAPHICS] .
KW  - Perovskite solar cell
KW  - flexible
KW  - interface engineering
KW  - non-radiative recombination
KW  - quasi-Fermi level splitting
Y1  - 2019
U6  - https://doi.org/10.1080/14686996.2019.1633952
SN  - 1468-6996
SN  - 1878-5514
VL  - 20
SP  - 786
EP  - 795
PB  - Taylor & Francis
CY  - Abingdon
ER  - 
TY  - JOUR
A1  - Roland, Steffen
A1  - Kniepert, Juliane
A1  - Love, John A.
A1  - Negi, Vikas
A1  - Liu, Feilong
A1  - Bobbert, Peter
A1  - Melianas, Armantas
A1  - Kemerink, Martijn
A1  - Hofacker, Andreas
A1  - Neher, Dieter
T1  - Equilibrated Charge Carrier Populations Govern Steady-State Nongeminate Recombination in Disordered Organic Solar Cells
JF  - The journal of physical chemistry letters
N2  - We employed bias-assisted charge extraction techniques to investigate the transient and steady-state recombination of photogenerated charge carriers in complete devices of a disordered polymer-fullerene blend. Charge recombination is shown to be dispersive, with a significant slowdown of the recombination rate over time, consistent with the results from kinetic Monte Carlo simulations. Surprisingly, our experiments reveal little to no contributions from early time recombination of nonequilibrated charge carriers to the steady-state recombination properties. We conclude that energetic relaxation of photogenerated carriers outpaces any significant nongeminate recombination under application-relevant illumination conditions. With equilibrated charges dominating the steady-state recombination, quasi-equilibrium concepts appear suited for describing the open-circuit voltage of organic solar cells despite pronounced energetic disorder.
Y1  - 2019
U6  - https://doi.org/10.1021/acs.jpclett.9b00516
SN  - 1948-7185
VL  - 10
IS  - 6
SP  - 1374
EP  - 1381
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Schwarze, Martin
A1  - Schellhammer, Karl Sebastian
A1  - Ortstein, Katrin
A1  - Benduhn, Johannes
A1  - Gaul, Christopher
A1  - Hinderhofer, Alexander
A1  - Perdigon-Toro, Lorena
A1  - Scholz, Reinhard
A1  - Kublitski, Jonas
A1  - Roland, Steffen
A1  - Lau, Matthias
A1  - Poelking, Carl
A1  - Andrienko, Denis
A1  - Cuniberti, Gianaurelio
A1  - Schreiber, Frank
A1  - Neher, Dieter
A1  - Vandewal, Koen
A1  - Ortmann, Frank
A1  - Leo, Karl
T1  - Impact of molecular quadrupole moments on the energy levels at organic heterojunctions
JF  - Nature Communications
N2  - The functionality of organic semiconductor devices crucially depends on molecular energies, namely the ionisation energy and the electron affinity. Ionisation energy and electron affinity values of thin films are, however, sensitive to film morphology and composition, making their prediction challenging. In a combined experimental and simulation study on zinc-phthalocyanine and its fluorinated derivatives, we show that changes in ionisation energy as a function of molecular orientation in neat films or mixing ratio in blends are proportional to the molecular quadrupole component along the p-p-stacking direction. We apply these findings to organic solar cells and demonstrate how the electrostatic interactions can be tuned to optimise the energy of the charge-transfer state at the donor-acceptor interface and the dissociation barrier for free charge carrier generation. The confirmation of the correlation between interfacial energies and quadrupole moments for other materials indicates its relevance for small molecules and polymers.
Y1  - 2019
U6  - https://doi.org/10.1038/s41467-019-10435-2
SN  - 2041-1723
VL  - 10
PB  - Nature Publ. Group
CY  - London
ER  - 
TY  - JOUR
A1  - Shoaee, Safa
A1  - Armin, Ardalan
A1  - Stolterfoht, Martin
A1  - Hosseini, Seyed Mehrdad
A1  - Kurpiers, Jona
A1  - Neher, Dieter
T1  - Decoding Charge Recombination through Charge Generation in Organic Solar Cells
JF  - Solar RRL
N2  - 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.
KW  - charge generation
KW  - charge transfers
KW  - non-Langevin recombination
KW  - spin-related factors
Y1  - 2019
U6  - https://doi.org/10.1002/solr.201900184
SN  - 2367-198X
VL  - 3
IS  - 11
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Stolterfoht, Martin
A1  - Caprioglio, Pietro
A1  - Wolff, Christian Michael
A1  - Marquez, Jose A.
A1  - Nordmann, Joleik
A1  - Zhang, Shanshan
A1  - Rothhardt, Daniel
A1  - Hörmann, Ulrich
A1  - Amir, Yohai
A1  - Redinger, Alex
A1  - Kegelmann, Lukas
A1  - Zu, Fengshuo
A1  - Albrecht, Steve
A1  - Koch, Norbert
A1  - Kirchartz, Thomas
A1  - Saliba, Michael
A1  - Unold, Thomas
A1  - Neher, Dieter
T1  - The impact of energy alignment and interfacial recombination on the internal and external open-circuit voltage of perovskite solar cells
JF  - Energy & environmental science
N2  - 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.
Y1  - 2019
U6  - https://doi.org/10.1039/c9ee02020a
SN  - 1754-5692
SN  - 1754-5706
VL  - 12
IS  - 9
SP  - 2778
EP  - 2788
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  - 
TY  - JOUR
A1  - Stolterfoht, Martin
A1  - Le Corre, Vincent M.
A1  - Feuerstein, Markus
A1  - Caprioglio, Pietro
A1  - Koster, Lambert Jan Anton
A1  - Neher, Dieter
T1  - Voltage-Dependent Photoluminescence and How It Correlates with the Fill Factor and Open-Circuit Voltage in Perovskite Solar Cells
JF  - Acs energy letters
N2  - Optimizing the photoluminescence (PL) yield of a solar cell has long been recognized as a key principle to maximize the power conversion efficiency. While PL measurements are routinely applied to perovskite films and solar cells under open circuit conditions (V-OC), it remains unclear how the emission depends on the applied voltage. Here, we performed PL(V) measurements on perovskite cells with different hole transport layer thicknesses and doping concentrations, resulting in remarkably different fill factors (FFs). The results reveal that PL(V) mirrors the current-voltage (JV) characteristics in the power-generating regime, which highlights an interesting correlation between radiative and nonradiative recombination losses. In particular, high FF devices show a rapid quenching of PL(V) from open-circuit to the maximum power point. We conclude that, while the PL has to be maximized at V-OC at lower biases < V-OC the PL must be rapidly quenched as charges need to be extracted prior to recombination.
Y1  - 2019
U6  - https://doi.org/10.1021/acsenergylett.9b02262
SN  - 2380-8195
VL  - 4
IS  - 12
SP  - 2887
EP  - 2892
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Ullbrich, Sascha
A1  - Benduhn, Johannes
A1  - Jia, Xiangkun
A1  - Nikolis, Vasileios C.
A1  - Tvingstedt, Kristofer
A1  - Piersimoni, Fortunato
A1  - Roland, Steffen
A1  - Liu, Yuan
A1  - Wu, Jinhan
A1  - Fischer, Axel
A1  - Neher, Dieter
A1  - Reineke, Sebastian
A1  - Spoltore, Donato
A1  - Vandewal, Koen
T1  - Emissive and charge-generating donor-acceptor interfaces for organic optoelectronics with low voltage losses
JF  - Nature materials
N2  - Intermolecular charge-transfer states at the interface between electron donating (D) and accepting (A) materials are crucial for the operation of organic solar cells but can also be exploited for organic light-emitting diodes(1,2). Non-radiative charge-transfer state decay is dominant in state-of-the-art D-A-based organic solar cells and is responsible for large voltage losses and relatively low power-conversion efficiencies as well as electroluminescence external quantum yields in the 0.01-0.0001% range(3,4). In contrast, the electroluminescence external quantum yield reaches up to 16% in D-A-based organic light-emitting diodes(5-7). Here, we show that proper control of charge-transfer state properties allows simultaneous occurrence of a high photovoltaic and emission quantum yield within a single, visible-light-emitting D-A system. This leads to ultralow-emission turn-on voltages as well as significantly reduced voltage losses upon solar illumination. These results unify the description of the electro-optical properties of charge-transfer states in organic optoelectronic devices and foster the use of organic D-A blends in energy conversion applications involving visible and ultraviolet photons(8-11).
KW  - Electronics, photonics and device physics
KW  - Optoelectronic devices and components
KW  - Photonic devices
KW  - Solar energy and photovoltaic technology
Y1  - 2019
U6  - https://doi.org/10.1038/s41563-019-0324-5
SN  - 1476-1122
SN  - 1476-4660
VL  - 18
IS  - 5
SP  - 459
EP  - 464
PB  - Nature Publ. Group
CY  - London
ER  - 
TY  - JOUR
A1  - Wang, Qiong
A1  - Mosconi, Edoardo
A1  - Wolff, Christian Michael
A1  - Li, Junming
A1  - Neher, Dieter
A1  - De Angelis, Filippo
A1  - Suranna, Gian Paolo
A1  - Grisorio, Roberto
A1  - Abate, Antonio
T1  - Rationalizing the molecular design of hole-selective contacts to improve charge extraction in Perovskite solar cells
JF  - dvanced energy materials
N2  - Two new hole selective materials (HSMs) based on dangling methylsulfanyl groups connected to the C-9 position of the fluorene core are synthesized and applied in perovskite solar cells. Being structurally similar to a half of Spiro-OMeTAD molecule, these HSMs (referred as FS and DFS) share similar redox potentials but are endowed with slightly higher hole mobility, due to the planarity and large extension of their structure. Competitive power conversion efficiency (up to 18.6%) is achieved by using the new HSMs in suitable perovskite solar cells. Time-resolved photoluminescence decay measurements and electrochemical impedance spectroscopy show more efficient charge extraction at the HSM/perovskite interface with respect to Spiro-OMeTAD, which is reflected in higher photocurrents exhibited by DFS/FS-integrated perovskite solar cells. Density functional theory simulations reveal that the interactions of methylammonium with methylsulfanyl groups in DFS/FS strengthen their electrostatic attraction with the perovskite surface, providing an additional path for hole extraction compared to the sole presence of methoxy groups in Spiro-OMeTAD. Importantly, the low-cost synthesis of FS makes it significantly attractive for the future commercialization of perovskite solar cells.
KW  - hole extraction
KW  - hole selective materials
KW  - perovskite solar cells
KW  - sulfur
KW  - triple-cation perovskite
Y1  - 2019
U6  - https://doi.org/10.1002/aenm.201900990
SN  - 1614-6832
SN  - 1614-6840
VL  - 9
IS  - 28
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Wolff, Christian Michael
A1  - Caprioglio, Pietro
A1  - Stolterfoht, Martin
A1  - Neher, Dieter
T1  - Nonradiative Recombination in Perovskite Solar Cells
BT  - the Role of Interfaces
JF  - Advanced materials
N2  - Perovskite solar cells combine high carrier mobilities with long carrier lifetimes and high radiative efficiencies. Despite this, full devices suffer from significant nonradiative recombination losses, limiting their V-OC to values well below the Shockley-Queisser limit. Here, recent advances in understanding nonradiative recombination in perovskite solar cells from picoseconds to steady state are presented, with an emphasis on the interfaces between the perovskite absorber and the charge transport layers. Quantification of the quasi-Fermi level splitting in perovskite films with and without attached transport layers allows to identify the origin of nonradiative recombination, and to explain the V-OC of operational devices. These measurements prove that in state-of-the-art solar cells, nonradiative recombination at the interfaces between the perovskite and the transport layers is more important than processes in the bulk or at grain boundaries. Optical pump-probe techniques give complementary access to the interfacial recombination pathways and provide quantitative information on transfer rates and recombination velocities. Promising optimization strategies are also highlighted, in particular in view of the role of energy level alignment and the importance of surface passivation. Recent record perovskite solar cells with low nonradiative losses are presented where interfacial recombination is effectively overcome-paving the way to the thermodynamic efficiency limit.
KW  - interfacial recombination
KW  - open-circuit voltage
KW  - perovskite solar cells
KW  - photoluminescence
Y1  - 2019
U6  - https://doi.org/10.1002/adma.201902762
SN  - 0935-9648
SN  - 1521-4095
VL  - 31
IS  - 52
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Würfel, Uli
A1  - Perdigon-Toro, Lorena
A1  - Kurpiers, Jona
A1  - Wolff, Christian Michael
A1  - Caprioglio, Pietro
A1  - Rech, Jeromy James
A1  - Zhu, Jingshuai
A1  - Zhan, Xiaowei
A1  - You, Wei
A1  - Shoaee, Safa
A1  - Neher, Dieter
A1  - Stolterfoht, Martin
T1  - Recombination between Photogenerated and Electrode-Induced Charges Dominates the Fill Factor Losses in Optimized Organic Solar Cells
JF  - The journal of physical chemistry letters
N2  - 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.
Y1  - 2019
U6  - https://doi.org/10.1021/acs.jpclett.9b01175
SN  - 1948-7185
VL  - 10
IS  - 12
SP  - 3473
EP  - 3480
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Zhang, Shanshan
A1  - Hosseini, Seyed Mehrdad
A1  - Gunder, Rene
A1  - Petsiuk, Andrei
A1  - Caprioglio, Pietro
A1  - Wolff, Christian Michael
A1  - Shoaee, Safa
A1  - Meredith, Paul
A1  - Schorr, Susan
A1  - Unold, Thomas
A1  - Burn, Paul L.
A1  - Neher, Dieter
A1  - Stolterfoht, Martin
T1  - The Role of Bulk and Interface Recombination in High-Efficiency Low-Dimensional Perovskite Solar Cells
JF  - Advanced materials
N2  - 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.
KW  - 2D perovskites
KW  - interface recombination
KW  - perovskite solar cells
KW  - photoluminescence
KW  - V-OC loss
Y1  - 2019
U6  - https://doi.org/10.1002/adma.201901090
SN  - 0935-9648
SN  - 1521-4095
VL  - 31
IS  - 30
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Zu, Fengshuo
A1  - Amsalem, Patrick
A1  - Egger, David A.
A1  - Wang, Rongbin
A1  - Wolff, Christian Michael
A1  - Fang, Honghua
A1  - Loi, Maria Antonietta
A1  - Neher, Dieter
A1  - Kronik, Leeor
A1  - Duhm, Steffen
A1  - Koch, Norbert
T1  - Constructing the Electronic Structure of CH3NH3PbI3 and CH3NH3PbBr3 Perovskite Thin Films from Single-Crystal Band Structure Measurements
JF  - The journal of physical chemistry letters
N2  - Photovoltaic cells based on halide perovskites, possessing remarkably high power conversion efficiencies have been reported. To push the development of such devices further, a comprehensive and reliable understanding of their electronic properties is essential but presently not available. To provide a solid foundation for understanding the electronic properties of polycrystalline thin films, we employ single-crystal band structure data from angle-resolved photoemission measurements. For two prototypical perovskites (CH3NH3PbBr3 and CH3NH3PbI3), we reveal the band dispersion in two high-symmetry directions and identify the global valence band maxima. With these benchmark data, we construct "standard" photoemission spectra from polycrystalline thin film samples and resolve challenges discussed in the literature for determining the valence band onset with high reliability. Within the framework laid out here, the consistency of relating the energy level alignment in perovskite-based photovoltaic and optoelectronic devices with their functional parameters is substantially enhanced.
Y1  - 2019
U6  - https://doi.org/10.1021/acs.jpclett.8b03728
SN  - 1948-7185
VL  - 10
IS  - 3
SP  - 601
EP  - 609
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Zu, Fengshuo
A1  - Wolff, Christian Michael
A1  - Ralaiarisoa, Maryline
A1  - Amsalem, Patrick
A1  - Neher, Dieter
A1  - Koch, Norbert
T1  - Unraveling the Electronic Properties of Lead Halide Perovskites with Surface Photovoltage in Photoemission Studies
JF  - ACS applied materials & interfaces
N2  - The tremendous success of metal-halide perovskites, especially in the field of photovoltaics, has triggered a substantial number of studies in understanding their optoelectronic properties. However, consensus regarding the electronic properties of these perovskites is lacking due to a huge scatter in the reported key parameters, such as work function (Φ) and valence band maximum (VBM) values. Here, we demonstrate that the surface photovoltage (SPV) is a key phenomenon occurring at the perovskite surfaces that feature a non-negligible density of surface states, which is more the rule than an exception for most materials under study. With ultraviolet photoelectron spectroscopy (UPS) and Kelvin probe, we evidence that even minute UV photon fluxes (500 times lower than that used in typical UPS experiments) are sufficient to induce SPV and shift the perovskite Φ and VBM by several 100 meV compared to dark. By combining UV and visible light, we establish flat band conditions (i.e., compensate the surface-state-induced surface band bending) at the surface of four important perovskites, and find that all are p-type in the bulk, despite a pronounced n-type surface character in the dark. The present findings highlight that SPV effects must be considered in all surface studies to fully understand perovskites’ photophysical properties.
KW  - lead halide perovskite films
KW  - ultraviolet photoelectron spectroscopy
KW  - Kelvin probe
KW  - surface band bending
KW  - surface photovoltage
KW  - surface states
Y1  - 2019
U6  - https://doi.org/10.1021/acsami.9b05293
SN  - 1944-8244
SN  - 1944-8252
VL  - 11
IS  - 24
SP  - 21578
EP  - 21583
PB  - American Chemical Society
CY  - Washington
ER  -