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 - TY - JOUR A1 - Zu, Fengshuo A1 - Schultz, Thorsten A1 - Wolff, Christian Michael A1 - Shin, Dongguen A1 - Frohloff, Lennart A1 - Neher, Dieter A1 - Amsalem, Patrick A1 - Koch, Norbert T1 - Position-locking of volatile reaction products by atmosphere and capping layers slows down photodecomposition of methylammonium lead triiodide perovskite JF - RSC Advances N2 - The remarkable progress of metal halide perovskites in photovoltaics has led to the power conversion efficiency approaching 26%. However, practical applications of perovskite-based solar cells are challenged by the stability issues, of which the most critical one is photo-induced degradation. Bare CH3NH3PbI3 perovskite films are known to decompose rapidly, with methylammonium and iodine as volatile species and residual solid PbI2 and metallic Pb, under vacuum under white light illumination, on the timescale of minutes. We find, in agreement with previous work, that the degradation is non-uniform and proceeds predominantly from the surface, and that illumination under N-2 and ambient air (relative humidity 20%) does not induce substantial degradation even after several hours. Yet, in all cases the release of iodine from the perovskite surface is directly identified by X-ray photoelectron spectroscopy. This goes in hand with a loss of organic cations and the formation of metallic Pb. When CH3NH3PbI3 films are covered with a few nm thick organic capping layer, either charge selective or non-selective, the rapid photodecomposition process under ultrahigh vacuum is reduced by more than one order of magnitude, and becomes similar in timescale to that under N-2 or air. We conclude that the light-induced decomposition reaction of CH3NH3PbI3, leading to volatile methylammonium and iodine, is largely reversible as long as these products are restrained from leaving the surface. This is readily achieved by ambient atmospheric pressure, as well as a thin organic capping layer even under ultrahigh vacuum. In addition to explaining the impact of gas pressure on the stability of this perovskite, our results indicate that covalently "locking" the position of perovskite components at the surface or an interface should enhance the overall photostability. Y1 - 2020 U6 - https://doi.org/10.1039/d0ra03572f SN - 2046-2069 VL - 10 IS - 30 SP - 17534 EP - 17542 PB - Royal Society of Chemistry CY - Cambridge 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 - Zhang, Shanshan A1 - Stolterfoht, Martin A1 - Armin, Ardalan A1 - Lin, Qianqian A1 - Zu, Fengshuo A1 - Sobus, Jan A1 - Jin, Hui A1 - Koch, Norbert A1 - Meredith, Paul A1 - Burn, Paul L. A1 - Neher, Dieter T1 - Interface Engineering of Solution-Processed Hybrid Organohalide Perovskite Solar Cells JF - ACS applied materials & interfaces N2 - 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%. KW - organohalide lead perovskites KW - solar cells KW - surface wetting KW - work function KW - oxygen plasma KW - transport layer Y1 - 2018 U6 - https://doi.org/10.1021/acsami.8b02503 SN - 1944-8244 VL - 10 IS - 25 SP - 21681 EP - 21687 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Wolff, Christian Michael A1 - Zu, Fengshuo A1 - Paulke, Andreas A1 - Toro, Lorena Perdigon A1 - Koch, Norbert A1 - Neher, Dieter T1 - Reduced Interface-Mediated Recombination for High Open-Circuit Voltages in CH3NH3PbI3 Solar Cells JF - Advanced materials N2 - Perovskite solar cells with all-organic transport layers exhibit efficiencies rivaling their counterparts that employ inorganic transport layers, while avoiding high-temperature processing. Herein, it is investigated how the choice of the fullerene derivative employed in the electron-transporting layer of inverted perovskite cells affects the open-circuit voltage (V-OC). It is shown that nonradiative recombination mediated by the electron-transporting layer is the limiting factor for the V-OC in the cells. By inserting an ultrathin layer of an insulating polymer between the active CH3NH3PbI3 perovskite and the fullerene, an external radiative efficiency of up to 0.3%, a V-OC as high as 1.16 V, and a power conversion efficiency of 19.4% are realized. The results show that the reduction of nonradiative recombination due to charge-blocking at the perovskite/organic interface is more important than proper level alignment in the search for ideal selective contacts toward high V-OC and efficiency. KW - electron-transport layers KW - nonradiative recombination KW - open-circuit voltage KW - perovskite solar cells Y1 - 2017 U6 - https://doi.org/10.1002/adma.201700159 SN - 0935-9648 SN - 1521-4095 VL - 29 PB - Wiley-VCH CY - Weinheim ER - TY - GEN A1 - Wolff, Christian Michael A1 - Canil, Laura A1 - Rehermann, Carolin A1 - Nguyen, Ngoc Linh A1 - Zu, Fengshuo A1 - Ralaiarisoa, Maryline A1 - Caprioglio, Pietro A1 - Fiedler, Lukas A1 - Stolterfoht, Martin A1 - Kogikoski, Junior, Sergio A1 - Bald, Ilko A1 - Koch, Norbert A1 - Unger, Eva L. A1 - Dittrich, Thomas A1 - Abate, Antonio A1 - Neher, Dieter T1 - Correction to 'Perfluorinated self-assembled monolayers enhance the stability and efficiency of inverted perovskite solar cells' (2020, 14 (2), 1445−1456) T2 - ACS nano Y1 - 2020 U6 - https://doi.org/10.1021/acsnano.0c08081 SN - 1936-0851 SN - 1936-086X VL - 14 IS - 11 SP - 16156 EP - 16156 PB - American Chemical Society CY - Washington, DC 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 - Schubert, Marcel A1 - Frisch, Johannes A1 - Allard, Sybille A1 - Preis, Eduard A1 - Scherf, Ullrich A1 - Koch, Norbert A1 - Neher, Dieter T1 - Tuning side chain and main chain order in a prototypical donor-acceptor copolymer BT - implications for optical, electronic, and photovoltaic characteristics JF - Elementary Processes in Organic Photovoltaics N2 - The recent development of donor–acceptor copolymers has led to an enormous improvement in the performance of organic solar cells and organic field-effect transistors. Here we describe the synthesis, detailed characterisation, and application of a series of structurally modified copolymers to investigate fundamental structure–property relationships in this class of conjugated polymers. The interplay between chemical structure and optoelectronic properties is investigated. These are further correlated to the charge transport and solar cell performance, which allows us to link their chemical structure to the observed physical properties. KW - Aggregate states KW - All-polymer heterojunctions KW - Alternating copolymers KW - Ambipolar charge transport KW - Ambipolar materials KW - Backbone modifications KW - Bilayer solar cells KW - Charge separation KW - Conformational disorder KW - Crystalline phases KW - Donor-acceptor copolymers KW - Electron traps KW - Energetic disorder KW - Energy-level alignment KW - Fermi-level alignment KW - Fermi-level pinning KW - Interface dipole KW - Interlayer KW - Intrachain order KW - Intragap states KW - Microscopic morphology KW - Mobility imbalance KW - Mobility relaxation KW - Monte Carlo simulation KW - Multiple trapping model KW - Nonradiative recombination KW - OFET KW - Open-circuit voltage KW - Optoelectronic properties KW - Partially alternating copolymers KW - Photo-CELIV KW - Photocurrent KW - Photovoltaic gap KW - Polymer intermixing KW - Recombination losses KW - Spectral diffusion KW - Statistical copolymers KW - Stille-type cross-coupling KW - Structure-property relationships KW - Time-dependent mobility KW - Time-of-flight (TOF) KW - Transient photocurrent KW - Ultraviolet photoelectron spectroscopy KW - Vacuum-level alignment KW - X-ray photoelectron spectroscopy Y1 - 2016 SN - 978-3-319-28338-8 SN - 978-3-319-28336-4 U6 - https://doi.org/10.1007/978-3-319-28338-8_10 SN - 0065-3195 VL - 272 SP - 243 EP - 265 PB - Springer CY - Berlin ER - TY - JOUR A1 - Schubert, Marcel A1 - Dolfen, Daniel A1 - Frisch, Johannes A1 - Roland, Steffen A1 - Steyrleuthner, Robert A1 - Stiller, Burkhard A1 - Chen, Zhihua A1 - Scherf, Ullrich A1 - Koch, Norbert A1 - Facchetti, Antonio A1 - Neher, Dieter T1 - Influence of aggregation on the performance of All-Polymer Solar Cells containing Low-Bandgap Naphthalenediimide Copolymers JF - dvanced energy materials N2 - The authors present efficient all-polymer solar cells comprising two different low-bandgap naphthalenediimide (NDI)-based copolymers as acceptors and regioregular P3HT as the donor. It is shown that these naphthalene copolymers have a strong tendency to preaggregate in specific organic solvents, and that preaggregation can be completely suppressed when using suitable solvents with large and highly polarizable aromatic cores. Organic solar cells prepared from such nonaggregated polymer solutions show dramatically increased power conversion efficiencies of up to 1.4%, which is mainly due to a large increase of the short circuit current. In addition, optimized solar cells show remarkable high fill factors of up to 70%. The analysis of the blend absorbance spectra reveals a surprising anticorrelation between the degree of polymer aggregation in the solid P3HT:NDI copolymer blends and their photovoltaic performance. Scanning near-field optical microscopy (SNOM) and atomic force microscopy (AFM) measurements reveal important information on the blend morphology. It is shown that films with high degree of aggregation and low photocurrents exhibit large-scale phase-separation into rather pure donor and acceptor domains. It is proposed that, by suppressing the aggregation of NDI copolymers at the early stage of film formation, the intermixing of the donor and acceptor component is improved, thereby allowing efficient harvesting of photogenerated excitons at the donoracceptor heterojunction. KW - aggregation KW - morphology KW - naphthalenediimide KW - organic semiconductors KW - organic photovoltaics Y1 - 2012 U6 - https://doi.org/10.1002/aenm.201100601 SN - 1614-6832 VL - 2 IS - 3 SP - 369 EP - 380 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Raoufi, Meysam A1 - Hörmann, Ulrich A1 - Ligorio, Giovanni A1 - Hildebrandt, Jana A1 - Pätzel, Michael A1 - Schultz, Thorsten A1 - Perdigon, Lorena A1 - Koch, Norbert A1 - List-Kratochvil, Emil A1 - Hecht, Stefan A1 - Neher, Dieter T1 - Simultaneous effect of ultraviolet radiation and surface modification on the work function and hole injection properties of ZnO thin films JF - Physica Status Solidi. A , Applications and materials science N2 - The combined effect of ultraviolet (UV) light soaking and self-assembled monolayer deposition on the work function (WF) of thin ZnO layers and on the efficiency of hole injection into the prototypical conjugated polymer poly(3-hexylthiophen-2,5-diyl) (P3HT) is systematically investigated. It is shown that the WF and injection efficiency depend strongly on the history of UV light exposure. Proper treatment of the ZnO layer enables ohmic hole injection into P3HT, demonstrating ZnO as a potential anode material for organic optoelectronic devices. The results also suggest that valid conclusions on the energy-level alignment at the ZnO/organic interfaces may only be drawn if the illumination history is precisely known and controlled. This is inherently problematic when comparing electronic data from ultraviolet photoelectron spectroscopy (UPS) measurements carried out under different or ill-defined illumination conditions. KW - charge injection across hybrid interfaces KW - energy-level alignments KW - hybrid metal oxides KW - organic interfaces Y1 - 2020 U6 - https://doi.org/10.1002/pssa.201900876 SN - 1862-6300 SN - 1862-6319 VL - 217 IS - 5 SP - 1 EP - 6 PB - Wiley-VCH CY - Weinheim ER -