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  - Yu, Jinde
A1  - Xing, Yifan
A1  - Shen, Zichao
A1  - Zhu, Yuanwei
A1  - Neher, Dieter
A1  - Koch, Norbert
A1  - Lu, Guanghao
T1  - Infrared spectroscopy depth profiling of organic thin films
JF  - Materials horizons
N2  - Organic thin films are widely used in organic electronics and coatings. Such films often feature film-depth dependent variations of composition and optoelectronic properties. State-of-the-art depth profiling methods such as mass spectroscopy and photoelectron spectroscopy rely on non-intrinsic species (vaporized ions, etching-induced surface defects), which are chemically and functionally different from the original materials. Here we introduce an easily-accessible and generally applicable depth profiling method: film-depth-dependent infrared (FDD-IR) spectroscopy profilometry based on directly measuring the intrinsic material after incremental surface-selective etching by a soft plasma, to study the material variations along the surface-normal direction. This depth profiling uses characteristic vibrational signatures of the involved compounds, and can be used for both conjugated and non-conjugated, neutral and ionic materials. A film-depth resolution of one nanometer is achieved. We demonstrate the application of this method for investigation of device-relevant thin films, including organic field-effect transistors and organic photovoltaic cells, as well as ionized dopant distributions in doped semiconductors.
Y1  - 2021
U6  - https://doi.org/10.1039/d0mh02047h
SN  - 2051-6347
SN  - 2051-6355
VL  - 8
IS  - 5
SP  - 1461
EP  - 1471
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  - 
TY  - JOUR
A1  - Wolff, Christian Michael
A1  - Zu, Fengshuo
A1  - Paulke, Andreas
A1  - Perdigón-Toro, Lorena
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  - Warby, Jonathan
A1  - Zu, Fengshuo
A1  - Zeiske, Stefan
A1  - Gutierrez-Partida, Emilio
A1  - Frohloff, Lennart
A1  - Kahmann, Simon
A1  - Frohna, Kyle
A1  - Mosconi, Edoardo
A1  - Radicchi, Eros
A1  - Lang, Felix
A1  - Shah, Sahil
A1  - Pena-Camargo, Francisco
A1  - Hempel, Hannes
A1  - Unold, Thomas
A1  - Koch, Norbert
A1  - Armin, Ardalan
A1  - De Angelis, Filippo
A1  - Stranks, Samuel D.
A1  - Neher, Dieter
A1  - Stolterfoht, Martin
T1  - Understanding performance limiting interfacial recombination in pin Perovskite solar cells
JF  - Advanced energy materials
N2  - Perovskite semiconductors are an attractive option to overcome the limitations of established silicon based photovoltaic (PV) technologies due to their exceptional opto-electronic properties and their successful integration into multijunction cells. However, the performance of single- and multijunction cells is largely limited by significant nonradiative recombination at the perovskite/organic electron transport layer junctions. In this work, the cause of interfacial recombination at the perovskite/C-60 interface is revealed via a combination of photoluminescence, photoelectron spectroscopy, and first-principle numerical simulations. It is found that the most significant contribution to the total C-60-induced recombination loss occurs within the first monolayer of C-60, rather than in the bulk of C-60 or at the perovskite surface. The experiments show that the C-60 molecules act as deep trap states when in direct contact with the perovskite. It is further demonstrated that by reducing the surface coverage of C-60, the radiative efficiency of the bare perovskite layer can be retained. The findings of this work pave the way toward overcoming one of the most critical remaining performance losses in perovskite solar cells.
KW  - C60
KW  - defects
KW  - interface recombination
KW  - loss mechanisms
KW  - perovskites
KW  - solar cells
Y1  - 2022
U6  - https://doi.org/10.1002/aenm.202103567
SN  - 1614-6832
SN  - 1614-6840
VL  - 12
IS  - 12
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  - 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  -