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The Electronic Structure of MAPI-Based Perovskite

Solar Cells: Detailed Band Diagram Determination
by Photoemission Spectroscopy Comparing Classical
and Inverted Device Stacks
Tim Hellmann, Chittaranjan Das, Tobias Abzieher, Jonas A. Schwenzer, Michael Wussler,
Ralph Dachauer, Ulrich W. Paetzold, Wolfram Jaegermann, and Thomas Mayer*

1. Introduction
High power conversion efficiency (PCE) perovskite solar cells (PSCs) rely on
optimal alignment of the energy bands between the perovskite absorber and Organic–inorganic lead halide perov-
skite solar cells (PSCs) have been inten-
the adjacent charge extraction layers. However, since most of the materials
sively studied over the past decade,
and devices of high performance are prepared by solution-based techniques,
reaching record power conversion effi-
a deposition of films with thicknesses of a few nanometers and therefore ciencies (PCEs) of more than 25%.[1]
a detailed analysis of surface and interface properties remains difficult. To In addition, encouraging progress
identify the respective photoactive interfaces, photoelectron spectroscopy has also been demonstrated in terms
measurements are performed on device stacks of methylammonium-lead- of low-cost upscaling deposition and
iodide (MAPI)-based PSCs in classical and inverted architectures in the dark improved stability that may allow com-
and under illumination at open-circuit conditions. The analysis shows that mercialization of this ambitious tech-
nology in the near future.[2] To further
vacuum-deposited MAPI perovskite absorber layers are n-type, independent
advance the PCE, it is of fundamental
of the architecture and of the charge transport layer that it is deposited on interest to investigate the given band
(n-type SnO2 or p-type NiOx). It is found that the majority of the photo- energy diagram, by identifying the inter-
voltage is formed at the n-MAPI/p-HEL (hole extraction layer) junction for face at which the photovoltage inside the
both architectures, highlighting the importance of this interface for further PSC develops. The working principle of
improvement of the photovoltage and therefore also the PCE. Finally, an this kind of solar cell is still a topic of
experimentally derived band diagram of the completed devices for the dark extensive scientific debate requiring more
experimental evidence to arrive at more
and the illuminated case is presented.
definitive conclusions.
PSCs are commonly distinguished into
two different architectures: i) the classical
T. Hellmann, Dr. C. Das, M. Wussler, Dr. R. Dachauer,
Prof. W. Jaegermann, Dr. T. Mayer
architecture (also called n-i-p structure), where the front con-
Surface Science Group tact is an n-type electron extraction layer (EEL) and the back
Materials Science Department contact is a p-type hole extraction layer (HEL) and ii) the
Technical University of Darmstadt inverted architecture (also referred to as p-i-n structure), where
Alarich-Weiss-Straße 2, 64287 Darmstadt, Germany the n-EEL and the p-HEL are exchanged. For a PSC with an
E-mail: [email protected]
intrinsic perovskite absorber, the built-in potential in the dark
Dr. T. Abzieher, Dr. J. A. Schwenzer, Dr. U. W. Paetzold
Light Technology Institute and the photovoltage under illumination will be formed at both
Karlsruhe Technology Institute the n-EEL/i-perovskite interface and at the i-perovskite/p-HEL
Engesserstraße 13, 76131 Karlsruhe, Germany interface. Understanding the device physics and especially
Dr. U. W. Paetzold the band alignment across the interfaces will help to identify
Institute of Microstructure Technology strategies to improve PSCs. This knowledge can trigger the
Karlsruhe Institute of Technology
Hermann-von-Helmholtz-Platz 1
development of new charge extraction layers that can form
76344 Eggenstein-Leopoldshafen, Germany suitable interfaces to the perovskite absorber to maximize the
open-circuit voltage (VOC) and thus the PCE.[3–8] Up to date,
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.202002129. large efforts have been made to further boost the PCE by using
various EELs[9] and HELs[6,10–13] or by exchanging the metal
© 2020 The Authors. Published by Wiley-VCH GmbH. This is an open
access article under the terms of the Creative Commons Attribution- contacts,[14] however, due to a lack of knowledge about the
NonCommercial-NoDerivs License, which permits use and distribution energy band diagram, often on an empirical basis without gen-
in any medium, provided the original work is properly cited, the use is eralized guidelines.
non-commercial and no modifications or adaptations are made. Kelvin probe force microscopy (KFPM) and electron-beam-
DOI: 10.1002/aenm.202002129 induced current (EBIC) measurements have been performed

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to help identifying at which interfaces a built-in potential exists To contribute toward clarifying these controversially dis-
in the dark and a photovoltage is generated under cussed results, specifically designed experiments are presented
illumination.[15–19] However, in KFPM measurements the posi- in this work. XPS and ultraviolet photoelectron spectroscopy
tion of the Fermi level in the energy gap of the different layers (UPS) measurements in the dark and under illumination are
and the electronic structure including the band line up and used on different device stacks in classical architecture (front
band bending at the interfaces can only be concluded from the contact: n-SnO2) and inverted device architecture (front con-
variation of the work function throughout the device. tact: p-NiOx), keeping the device at open-circuit condition, and
In 2014, Edri et  al.[15] performed EBIC measurements on making a direct comparison for the distribution of the photo-
cross-sections of classical architecture devices using TiO2 as voltage of both architectures. In addition, full devices are pre-
EEL and spiro-MeOTAD as HEL. The authors there found two pared with the vacuum-deposited MAPI films with stabilized
humps of EBIC in the methylammonium-lead-iodide (MAPI) efficiencies of 13.7% and 11.6% for the inverted and classical
near the contacts and stated that this is typically found for a solar cells (see Figure S1, Supporting Information). The inter-
p-i-n structure, with MAPI being the intrinsic absorber. While faces where the photovoltages appear, are analyzed in more
we agree that a p-i-n structure leads to two humps in EBIC, we detail, either by classical step-by-step interface experiments[32]
believe that other structures can do so as well. For example, or by preparing and measuring a tapered cross-section.[33] For
an n-doped instead of an intrinsic perovskite, will results in a both architectures, it is proven that at the interfaces where the
similar EBIC shape, if the contact layers act as efficient electron SPV forms under illumination, a built-in potential exists in the
bocking HEL and hole blocking EEL. Similarly, Bergmann et al. dark. As a result, for both architectures the used MAPI films
performed KFPM measurements on cross-sections of com- are observed to be n-type in the dark, independent of the sub-
pleted devices and interpreted the contact potential distribu- strate (EEL or HEL) that they are deposited on. Under illumi-
tion corresponding to a p-i-n-structure.[16] Cai et al. could move nation, an SPV for MAPI on the p-type substrate (p-NiOx) is
the potential drop from the TiO2/MAPI interface to the MAPI/ observed, which shifts the Fermi level to appear in the middle
spiro-MeOTAD interface by changing the PbI2 to MAI ratio of of the band gap. For MAPI on the n-type substrate (n-SnO2)
the MAPI precursor solution and thereby the thereby the n- no light-induced SPV is observed and only after depositing the
or p-doping level of the MAPI film.[20] This is to be expected, p-type layer on top of MAPI the SPV appears. For both
since it has been reported that the doping of the perovskite can architectures, the photovoltage is therefore identified at the
be influenced by controlling its PbI2 to MAI ratio either pre- p-HEL/n-MAPI heterojunction. It is further concluded that
depositional in the precursor solution or post-depositonal by the investigated devices are working as n+-n-p-devices for the
annealing.[21–24] classical and as p-n-n-devices for the inverted architecture as
In contrast to KFPM, photoelectron spectroscopy (PES) compared to the n-i-p-structure or p-i-n-structure, that is often
allows to directly measure the electronic structure as well as assumed in literature. To further improve the VOC and there-
the chemical state of the material. Under illumination, the fore the PCE of PSCs, it is therefore recommended to focus
surface photovoltage (SPV) can be measured as well, if the on optimizing the interface properties of the n-MAPI/p-HEL
sample is grounded adequately. The SPV is a potential differ- interface. The importance of the n-MAPI/p-HEL interface
ence between the surface Fermi level of the sample stack and might also explain, why many of the recently reported passiva-
its back contact connected to the ground of the X-ray photo- tion layers that are used to improve the PCE are employed in
electron spectroscopy (XPS) system. It usually results from between the perovskite absorber and the HEL.[34–38]
the separation of photogenerated charge carriers via a built-
in field at one of the interfaces inside the sample.[25,26] Since
the SPV corresponds to the VOC of the device, identifying the 2. Results
interfaces at which the SPV and therefore the VOC develope
will help to further improve the device performance. The SPV 2.1. Laying Out the Strategy: How to Determine the Band
is visible in PES by the shift of all emission lines from their Structure using PES
electronic equilibrium conditions in the dark to higher or
lower binding energies, depending if it is a positive or nega- In this work, the energy band diagram of devices in classical
tive SPV, respectively. PES studies of MAPI do often report a and inverted architecture is determined and directly compared.
substrate-dependent Fermi level position of MAPI. For n-type The layer stack sequences that are used for both architectures
substrates, the Fermi level of MAPI is often reported close to are displayed in Figure  1a. For the classical architecture, the
the conduction band minimum (CBM), while it is observed in layer stack sequence indium tin oxide (ITO)/n+-SnO2/MAPI/p-
the middle of the band gap for p-type substrates.[27–30] Zu et al. spiro-MeOTAD/Au is employed, whereas for the inverted archi-
observed that the perovskite is n-type on p-type poly(triaryl) tecture the sequence ITO/p-NiOx/MAPI/C60/bathocuproine
amine (PTAA) substrates in the dark and the perovskite (BCP)/Au is used. The letters “n-” and “p-” are used in this
appears intrinsic under illumination, due to the formation of work to describe whether the respective material is an EEL (e.g.,
an SPV. They argued that the perovskite is p-type in the bulk n-SnO2) or an HEL (e.g., p-NiOx). An illuminated sample during
with a downward band bending at the MAPI/vacuum surface the PES measurement is illustrated in Figure 1b. The ITO layer
that makes the surface to appear n-type.[31] However, with is connected to the electrical ground of the XPS machine, which
their experiments they could not verify if the involved SPV means that the potentials of all other layers on top are electri-
appears at the MAPI/vacuum surface or at a different inter- cally floating and an SPV between the ITO front contact and the
face below. top layer can build up. The effect of an SPV under illumination

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Figure 1.  a) Classical (left) and inverted (right) layer stack sequences employed in this work, b) an illuminated layer stack during the PES measurement
with an SPV formed in the classical layer stack, and c) the resulting shift (ESPV) of a core level emission line due to the light-induced SPV. EB,D and EB,L
represent the binding energies in the dark and under illumination, respectively. A theoretical p-n-junction in the dark with d) the built-in potential Vbi
and e) under illumination with the formed photovoltage ESPV.

on the PES spectra is presented in Figure  1c, where the measurements. The induced change in the valence band posi-
positive SPV shifts the core level emission line of the measured tion with respect to the Fermi level reference would result in a
top layer to higher binding energies.[25,26] Respectively, a nega- wrong doping level assignment. In the third part, the results
tive SPV would result in a shift of the emission lines to lower from the PES measurements are used to construct full energy
binding energies. Similar dark and light measurements for band diagrams in the dark and under illumination for the clas-
MAPI films on n+-SnO2 and p-NiOx substrates are presented in sical and inverted architecture.
the first section of this work together with a discussion of the
influence of both substrates on the electronic structure of the
MAPI films and a potential SPV. Then, similar measurements 2.2. Electronic Structure of MAPI Thin Films on Different
on the respective back contact layer (spiro-MeOTAD and BCP) Substrates
and on finished device stacks with a gold electrode on top are
discussed. The experimental sample sequence is chosen in a First, the influence of the substrate on the Fermi level position
way that by comparing the dark and light measurements, the of the perovskite absorber is investigated and potential SPVs
interface at which the photovoltage is formed can be identified at the interface between the front contact and the perovskite
unambiguously and compared for both architectures. Sche- absorber are identified. The following XPS measurements will
matic band diagrams in the dark and under illumination are provide evidence that the Fermi level position of the deposited
shown in Figure  1d,e, for a simple n-p-junction. In the dark perovskite absorber is n-type, independent of the substrate
case, a built-in potential (Vbi, band bending) that limits the when measured in the dark. Additional X-ray diffraction (XRD)
magnitude of the SPV must be present. During the light meas- and UV/vis measurements of the perovskite films on SnO2 and
urements, the excited charge carriers result in a splitting of the NiOx are supplied in Figure S2 in the Supporting Information.
electron and hole quasi-Fermi levels and the formed SPV will The XRD shows in addition to the MAPI diffraction peaks only
reduce the built-in potentials, approaching a flat-band situation. small PbI2 peaks on SnO2, which are even smaller on NiOx.
Since in PES the reference Fermi level is fixed by grounding PES measurements on n+-SnO2/MAPI and p-NiOx/MAPI
the substrate, the quasi-Fermi level shift appears as a shift of stacks are performed in the dark and under illumination.
all core level emission lines and the valence band region to Figure 2 shows the XPS data of vacuum-deposited MAPI films
higher binding energies. It should be noted that an unnoticed for the classical architecture (grown on SnO2 substrates) (a to
SPV due to unintentional illumination can result in misinter- c) and for the inverted architecture grown on NiOx substrates
pretation of the data in PES, since in the nonequilibrium situ- (d to f). The valence band regions are displayed with a loga-
ation spectra will be shifted.[26,39,40] Therefore, extreme care has rithmic intensity scale. Often, the valence band maximum
been taken to avoid unintentional illumination during the dark (VBM) of a semiconductor is determined from a plot with a

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Figure 2.  a–c) (red curves) Detailed Pb4f scans, I3d5/2 scans, and valence band scans of MAPI films grown on SnO2 in the classical architecture and
d–f) (blue curves) on NiOx in the inverted architecture. The indices “D” and “L” and the light bulbs indicate whether the measurement was performed
in the dark or under illumination. The scale of the binding energy axis of all three figures is set to 10 eV to allow a better comparison of the light-
induced shifts.

linear intensity scale, by applying a linear fit to the leading edge core level to valence band distances of the I3d5/2 emission line
of the valence band spectrum and determining the intersection (618.22 eV) and the Pb4f7/2 emission line (137.28 eV) are close to
with zero counts. However, for organic–inorganic lead halide the values that were determined for the in-vacuo prepared ref-
perovskite like MAPI, Endres et  al. reported an unusually low erence sample (ΔEB,I3d5/2 = 618.10 eV and ΔEB,Pb4f7/2 = 137.19 eV,
density of states (DOS) at the valence band edge,[41] which see Table S1, Supporting Information). Under illumina-
can result in an erroneous estimation of the VBM binding tion, the Pb4f7/2 emission line appears at a binding energy of
energy, when it is determined from a plot with linear intensity 138.61 eV (see Figure 2a), the I3d5/2 emission at 619.54 eV (see
scale. This error may be avoided by using a logarithmic inten- Figure 2b), and the VBM at 1.36 eV (see Figure 2c). The shift of
sity scale, which enhances the low DOS at the valence band around 0.03 eV to higher binding energies is negligible and it
edge. Reported values for the VBM of MAPI vary from 1.15 to is assumed that the light has almost no effect on the binding
1.40 eV[41–43] when the value is determined from a logarithmic energy positions. Since there is no light-induced shift, it can
intensity plot and are as high as 1.55 eV[29] or even 1.78 eV[28] directly be concluded that no SPV is forming at the n+-SnO2/n-
when a linear intensity plot is used. In this work, the VBM MAPI interface. This is expected, given that the work functions
values of the perovskite absorbers were determined from a of SnO2 (4.15  eV) and MAPI (4.02  eV) are close to each other
logarithmic intensity plot since this method seems to give the (see Figure S4, Supporting Information), meaning that no
more reliable values. To exclude that the VBM is misinterpreted built-in potential should form at this contact.
by surface contaminations due to the samples being handled For the inverted architecture in Figure  2d–f in the dark, the
in ambient atmosphere, a reference perovskite sample was pre- Pb4f7/2 and I3d5/2 emission lines and the VBM appear at about
pared inside the vacuum and measured without exposing it to 0.1 eV higher binding energies as compared to the classical archi-
the ambient atmosphere. The distances between the core levels tecture, indicating an n-type MAPI as well. MAPI is therefore
and the VBM (ΔEB,I3d5/2 = 618.10 eV and ΔEB,Pb4f7/2 = 137.19 eV) observed to be n-type, independent of the substrate material (n+-
are then compared to the other perovskite samples, since these SnO2 or p-NiOx) it is deposited on. After turning on the light,
values are material constants. A more detailed discussion on the Pb4f7/2 and I3d5/2 emission line and the VBM are shifting
the determination of the VBM of the perovskite absorber is by 0.70  eV toward lower binding energies. A similar shift to
given in the Supporting Information (see Figure S3). For the lower binding energies appears for four other perovskites (FAPI,
classical architecture in the dark, the VBM of MAPI is located CsFAPI, MAFAPI, and CsMAFAPI) when spin-coated on NiOx
1.35  eV below the Fermi level (see Figure  2c) indicating an as well (see Figure S5b, Supporting Information). With these
n-type character as the band gap is 1.58 eV. The Pb4f7/2 emission perovskite absorbers used in solar cells, efficiencies of 16.4%,
line (see Figure  2a) appears at 138.56  eV and the I3d5/2 emis- 17.0%, 19.2%, and 17.4% were obtained. When the four perov-
sion at 619.50 eV (see Figure 2b), which is in accordance with skites are spin-coated on SnO2 instead, no light-induced shift is
literature values for MAPI grown on n-type substrates.[44–46] The observed (see Figure S5a, Supporting Information) indicating

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Figure 3.  a) He I scans of a spiro-MeOTAD film deposited on top of the SnO2/MAPI stack, b) C1s scans of a BCP film that was evaporated on top of
a NiOx/MAPI/C60 stack, and He I scans of completed devices in the c) classical and d) inverted structure. The letters “D” and “L” indicate whether
the measurement was performed in the dark or under illumination. The scale of the binding energy axis of all figures is set to 10 eV to allow a better
comparison of the light-induced shifts.

that the observed shift is not a measurement artifact of this spe- analysis provided in this work, the band bending appears at the
cific sample but rather a general behavior of organic–inorganic p-HEL/n-MAPI interface instead. Having the photovoltage at
lead halide perovskites. Since this shift on p-NiOx substrates the interface between the perovskite absorborber and the HEL
appears for both the vacuum-deposited and spin-coated perov- will be proven using the classical architecture, where the SPV is
skite films, it can be excluded that the deposition process has shown to appear at the n-MAPI/p-spiro-MeOTAD interface (see
an influence on the interface at which the photovoltage appears. Figure  3a), and therefore the n-MAPI/p-HEL interface as well.
This is important to note, since it is known, that the direct co- It is emphasized at this point that with the PES setup used in
evaporation of MAPI on metal oxides can result in nonstoichio- this work, even exceedingly small amounts of background light
metric growth in the initial nanometers. For example, PbI2 or resulted in an SPV and consequently a shift of all PES spectra
PbO may form initially.[28] The light-induced shift of the different toward lower binding energies. For this reason, it was neces-
perovskites on p-NiOx is attributed to the formation of a SPV at sary to turn off the pressure gauge inside the measurement
the p-NiOx/n-MAPI interface. Under illumination, the binding chamber and to use an Al window in between the X-ray source
energy positions of the perovskite absorber appear at positions and the sample to avoid that scattered light can reach the sample
that indicate an intrinsic MAPI, but this is only caused by the and thereby distort the results. In literature, even X-ray-source-
SPV-induced shift and therefore a non-equilibrium situation of induced photovoltages have been observed.[26,39,40] Experimental
the perovskite film as it was schematically described in Figure 1e. PES data of perovskite absorbers can therefore be very easily
Considering the high work function difference between MAPI misinterpreted if the background-light-induced SPV is not con-
(4.16  eV) and NiOx (5.41  eV) (see Figure S4, Supporting Infor- sidered, which might be the case for other studies reported in lit-
mation), the formation of a built-in potential in the dark at this erature. However, it can be excluded that the X-ray source or UPS
interface is expected. In a detailed analysis performed on the lamp gives rise to an SPV, since the Fermi level of the Au back
NiOx/MAPI interface using a tapered cross-section approach,[33] contact of the full device appears at the expected value of 0  eV
the presence of a band bending inside the MAPI and thus a (see Figure  3c,d) and only shifts when the external light source
built-in potential at this interface is demonstrated (see Figure is turned on. There are XPS studies on MAPI films on top of
S6, Supporting Information). Under illumination, this built-in p-HEL substrates in literature that report a Fermi level of the
potential acts as driving force for the extraction of the excited perovskite positioned in the middle of the band gap and therefore
holes out of the perovskite absorber into the underlying NiOx a more intrinsic MAPI layer. This intrinsic appearance of MAPI
layer which results in a negative SPV and therefore a shift of is usually explained by a substrate effect. A group performed PES
the core levels and the valence band to lower binding energies. measurements to investigate the electronic properties of MAPI
It should be noted that Zu et  al. also observed a light-induced depending on the substrate and found a VBM of 1.55  eV for
shift to lower binding energies, when performing PES measure- n-TiO2, 1.58 eV for n-ZnO, 0.84 eV for p-MoO3, and 0.95 eV for
ments on different perovskite absorbers deposited on p-PTAA p-PEDOT:PSS (poly(3,4-ethylenedioxythiophene):polystyrene sul-
substrates but explained it with a p-type bulk of the perovskite fonate).[29] Similarly, a VBM of 1.4  eV for MAPI on n-TiO2 and
and a downward band bending at the MAPI/vacuum surface that a slightly p-type MAPI with a VBM of 0.7  eV on p-NiOx were
makes the surface appear n-type.[31] Based on the more detailed reported using UPS.[47] Other publications reported VBM values

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Figure 4.  Schematic band diagrams derived from the PES measurements for devices in classical architecture. a) In the dark with band bending at the
MAPI/spiro-MeOTAD interface and b) under illumination with the band bending changing to a flat-band situation, giving rise to the VOC. The white
horizontal extension of the Fermi level in b) shows the Fermi level of the ground and therefore the reference energy for the PES measurements.

between 0.9 and 1.38  eV for p-type substrates and 1.69–1.77  eV devices are further completed by depositing the back contacts
for n-type substrates[27] or a VBM of 1.78 eV for MAPI grown on and finally a 25  nm thin gold film. PES measurements in the
n-PEIE (polyethyleneimine) and 1.24 or 1.14 eV for p-MoO3 and dark and under illumination are performed for the two clas-
p-PEDOT:PSS when using UPS, respectively.[28] According to the sical architecture device stacks (ITO/n+-SnO2/MAPI/p-spiro-
findings presented in this work, it should be considered that lit- MeOTAD and ITO/n+-SnO2/MAPI/p-spiro-MeOTAD/Au) and
erature reports of intrinsic MAPI films on p-HEL substrates are for two inverted architecture device stacks (ITO/p-NiOx/MAPI/
n-type MAPI films as well, but with an unnoticed SPV, which C60/BCP and ITO/p-NiOx/MAPI/C60/BCP/Au). By comparing
results in a misinterpretation of the PES spectra. the measurements of these four different device stacks, the
Based on the presented experiments, it was clearly shown interfaces at which the photovoltage is formed are identified
that the doping of the substrate has no or only negligible influ- for both architectures. For both architectures, the photovoltage
ence on the Fermi level position of MAPI and that MAPI thin appears at the n-MAPI/p-HEL interface. Furthermore, the
films are n-type on n+-SnO2 as well as on p-NiOx substrates. On results allow to construct full band diagrams for both architec-
p-NiOx substrates, measurements under illumination result in tures in the dark and under illumination (see Figures 4 and 5).
the formation of an SPV at the interface between the perovskite For the classical architecture, a doped spiro-MeOTAD film
absorber and NiOx and the perovskite absorber appears to be is spin-coated on top of the n+-SnO2/n-MAPI stack and the
intrinsic if one is not aware of the SPV. This light-induced shift valence band region is measured in the dark and under illumi-
on NiOx substrates was observed for FAPI, CsFAPI, MAFAPI, nation (see Figure 3a). In the dark, the VBM of spiro-MeOTAD
and CsMAFAPI perovskite films as well indicating that this is a appears at 0.64 eV and shifts by 0.66 eV to higher binding ener-
general behavior for organic–inorganic lead halide perovskites. gies upon illumination, indicating a light-induced SPV which
For the n+-SnO2/n-MAPI interface, no SPV was observed. must be located at the n-MAPI/p-spiro-MeOTAD interface. Any
other interface in the device stack below can be excluded as the
origin of the SPV, since no light-induced shift was visible for
2.3. Determination of the Photovoltage Distribution throughout the n+-SnO2/n-MAPI stack (see Figure  2a–c). Under illumina-
the Device tion, the quasi-Fermi levels of electrons and holes split and a
near flat band situation is induced, shifting the PES spectra
Having investigated the influence of the substrate mate- to higher binding energies. Identifying the SPV of the clas-
rial on the electronic structure of the perovskite absorber, the sical architecture at the n-MAPI/p-spiro-MeOTAD interface is

Figure 5.  Schematic band diagrams derived from the PES measurements for devices in inverted architecture. a) In the dark with a band bending at the
NiOx/MAPI interface and b) under illumination with the band bending changing to a flat-band situation, giving rise to the VOC. The white horizontal
extension of the Fermi level in b) shows the Fermi level of the ground and therefore the reference energy for the PES measurements.

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consistent with the results for the inverted architecture, where the same working principle, i.e. with the photovoltage induced
an SPV of 0.70  eV appeared at the p-NiOx/n-MAPI interface at the interface between n-MAPI and the p-HEL. Finally, a
(see Figure  1d–f). The work functions of MAPI (4.02  eV) and 25  nm gold film is deposited on top of the BCP to complete
spiro-MeOTAD (4.72 eV) differ by 0.70 eV (see Figure S4a, Sup- the device. The valence band spectra of the gold surface in the
porting Information), which enables the formation of a built-in dark and under illumination are presented in Figure  3d. The
potential at this heterojunction and is in good agreement with Fermi level appears at −0.02  eV for the dark measurement,
the light-induced shift of 0.66 eV observed for the VBM. By per- indicating that almost no X-ray-source-induced SPV is present.
forming a detailed analysis on the MAPI/spiro-MeOTAD inter- Under illumination, the Fermi level shifts by 0.83  eV to lower
face a band bending inside the spiro-MeOTAD and a flat band binding energies. This light-induced shift is 0.11  eV higher
inside the MAPI is identified (see Figure S7, Supporting Infor- compared to the light-induced shift of the NiOx/MAPI/C60/BCP
mation). Furthermore, the interface experiment provides evi- stack. As for the classical architecture, it is assumed (Figure 5)
dence that under illumination the band bending becomes flat, that the additional photovoltage of 0.11  V forms at the NiOx/
due to the formation of the SPV. The solar cell is finished by MAPI and not at the BCP/Au interface. The photovoltage of the
depositing a 25  nm gold contact on top of the spiro-MeOTAD completed device of 0.83 eV is comparable to the value that was
layer and measuring the gold valence band (see Figure 3c). In observed for the classical architecture (0.80  eV) and somewhat
the dark, the Fermi level appears at -0.04  eV, indicating that lower than the typical VOC extracted from J-V-measurements
almost no X-ray-source-induced SPV is present. The illumina- (1.03 eV, see Figure S1, Supporting Information). By comparing
tion shifts the Fermi level by 0.80 eV to higher binding energies, the light measurement for the classical and inverted structure,
which is a 0.14  eV higher shift compared to the n+-SnO2/n- it is obvious that the binding energy shifts in opposite direction
MAPI/p-spiro-MeOTAD stack. This additional photovoltage of result from the formation of SPVs of opposite polarities. The fact
0.14 V can be associated with the MAPI/spiro-MeOTAD as well that the large photovoltage for the inverted architecture is iden-
as the spiro-MeOTAD/Au interface. Since a quasi-Fermi level tified at the p-NiOx/n-MAPI interface is in accordance with the
splitting inside the spiro-MeOTAD without absorption seems observation for the classical architecture before. It is therefore
rather unlikely, we attribute it in Figure  4 to the latter case. concluded that the devices behave as n-n-p and p-n-n devices,
With 0.80  V, the photovoltage of the full device stack in PES instead of the commonly accepted idea of n-i-p and p-i-n
appears somewhat lower compared to the VOC of 1.05 V deter- devices.
mined from the J-V-measurements using a solar simulator (see
Figure S1, Supporting Information). The lower photovoltage in
the PES measurements is explained by the lower light inten- 2.4. Band Diagrams for the Classical and Inverted Architecture
sity (around 200 W m−2) compared to the AM 1.5G spectrum
(1000 W m−2) since for the given experimental setup the sample Based on the presented measurements, band diagrams for the
is illuminated from the top through the gold. More information classical and inverted architecture in the dark and under illu-
about the employed light source used to illuminate the samples mination at open-circuit conditions are constructed for MAPI
during the PES measurements and the estimate of the light solar cells for the first time in literature (see Figure  4 for the
intensity reaching the perovskite absorber is given in chapter 10 classical architecture and Figure 5 for the inverted architecture).
of the Supporting Information. Therefore, the full photovoltage Since no SPV is present at the SnO2/MAPI interface (see
of the classical architecture device has been identified at the Figure  2c), no band bending is present at this interface in the
back contact (n-MAPI/p-spiro-MeOTAD/Au), which was already dark. With the VBM of SnO2 (VBMSnO2  = 3.85 eV, see Figure S8a,
predicted in an earlier study, where the energy band diagram Supporting Information) and MAPI (VBMMAPI  = 1.35  eV, see
between MAPI and spiro-MeOTAD was investigated.[48] It is Figure  2c), an offset of 2.32  eV between the VBM of MAPI
concluded that the classical architecture is an n+-SnO2/n-MAPI/ and SnO2 results (ΔEVB), demonstrating an efficient blocking
p-spiro-MeOTAD structure and not an n-SnO2/i-MAPI/p-spiro- of holes. With the bandgaps of SnO2 (E g,SnO2 = 3.60  eV)[49]
MeOTAD structure as it is often referred to in literature.[15–17,19] and MAPI (Eg,MAPI  = 1.58  eV),[48] the CBM of SnO2 is posi-
In case of an n-i-p structure, the photovoltage would be split up tioned below the CBM of MAPI, which will allow electrons to
between the SnO2/MAPI and the MAPI/spiro-MeOTAD inter- be extracted from MAPI into the SnO2 layer. Given the SPV of
face. This is obviously not the case, since only after the deposi- 0.80  eV at the MAPI/spiro-MeOTAD interface, it is concluded
tion of spiro-MeOTAD an SPV appears. that a built-in potential of at least 0.80 eV exists at this interface
The inverted architecture (p-NiOx/n-MAPI) is finished for the dark case. A detailed analysis of the interface between
accordingly by depositing a 30 nm thick C60 film followed by a MAPI and spiro-MeOTAD by co-depositing spiro-MeOTAD and
3 nm thick BCP buffer layer on top of the C60 (see Figure 3b). LiTFSI on a MAPI surface shows that the band bending is pre-
In the dark, the C1s emission line appears at 285.11  eV and sent inside the spiro-MeOTAD (see Figure S7, Supporting Infor-
shifts by 0.72  eV to higher binding energies when turning on mation). With the VBM of MAPI and spiro-MeOTAD measured
the light. The absolute value of this shift is almost identical to at 1.35 and 0.64 eV, a valence band offset of 1.35 – 0.64 – 0.80 eV
the shift that was observed for the p-NiOx/n-MAPI stack (see = −0.09 eV between both materials is expected. Given the VBM
Figure  2d–f), therefore indicating that by adding the n-EEL, of 0.64  eV for spiro-MeOTAD, a maximum offset of 0.64  eV
the photovoltage does not further increase and no SPV forms is predicted between the valence band of spiro-MeOTAD and
at the n-MAPI/C60/BCP contact. As no photovoltage at the the Au Fermi level. The corresponding schematic band dia-
n-MAPI/C60/BCP contact is apparent, it is confirmed that gram is presented in Figure  4a. From the band structure, it is
the classical and inverted architectures function according to apparent that the SnO2 layer provides efficient hole blocking

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but does not contribute to the built-in field. In contrast, at the of 1.3  eV below the Fermi level, an electron concentration of
MAPI/spiro-MeOTAD interface efficient electron blocking is 7.6  ×  1020 cm−3 was measured. As the VBM positions of the
achieved by the energetically high lowest unoccupied molecular here presented perovskite films are slightly higher (1.35 and
orbital (LUMO) level of spiro-MeOTAD and a built-in field can 1.43 eV for MAPI on SnO2 and NiOx, respectively), charge car-
develop. The built-in potential (Vbb) of 0.80  eV is indicated by rier concentrations of 2.0  ×  1020 and 7  ×  1020 cm−3 were extrap-
the curved line. The illuminated case at open-circuit conditions olated using their systematic data. The derived absolute values
is presented in Figure  4b. At the MAPI/spiro-MeOTAD inter- for the charge carrier concentrations are in conflict to high dark
face the band bending inside the spiro-MeOTAD is changing resistivity often measured for the perovskite films.[54,55] In addi-
to a flat-band situation giving rise to the photovoltage, and a tion, a charge carrier concentration of 2  ×  1020 cm−3 for the
quasi-Fermi level splitting of the same magnitude appears MAPI perovskite on top of NiOx would result in a rather small
inside the perovskite absorber. The white horizontal extension space charge region of around 3–5.6  nm only (see Chapter 11
of the Fermi level shows the Fermi level of the grounded elec- of the Supporting Information for a detailed calculation). The
tron quasi-Fermi level, which is the reference energy for the derived charge carrier concentration values can therefore only
PES measurements. By comparing the VBM of spiro-MeOTAD be taken as rough estimates, as Hall measurements on thin
and the Fermi level of Au to the reference Fermi level of the MAPI perovskite films are challenging and the determination
ground (white broken line), it becomes evident why the SPV of the VBM in UPS is impeded by a low density of states near
results in a shift of the core levels and the valence band spectra the onset of the valence band.[41] As the Fermi level position
to higher binding energies. in the energy gap (measured in UPS as VBM position) enters
The band diagram for the inverted architecture in the dark exponentially in the calculation of the charge carrier concentra-
(see Figure 5a) is constructed accordingly. Since a photovoltage tion (see Chapter 12 of the Supporting Information), an uncer-
of 0.83 eV was assigned to the p-NiOx/n-MAPI interface, a band tainty of the VBM position by 100 meV leads to almost an order
bending of at least 0.83  eV exists at this interface. This band of magnitude variation in the calculated carrier concentration
bending is drawn inside the MAPI and not the NiOx, proven by both for the VBM measurements presented here as well as for
a detailed study of this interface (see Figure S6, Supporting Wang et al.[23] A dedicated cross-comparison of carrier concen-
Information). The VBM of MAPI (1.43  eV, see Figure  2f) and trations derived from photoemission, Hall-measurements, and
NiOx (0.53  eV, see Figure S8b, Supporting Information) dif- dark conductivity is needed in future.
fers by 0.90 eV, which results in a small valence band offset of Although there is a difference of a factor of around 3 in the
0.07 eV at this interface. The high offset of 2.07 eV between the doping levels, it is not expected that this difference can explain
CBM of NiOx and MAPI (ΔECB) allows for an efficient electron that the band bending is measured inside MAPI for the NiOx/
blocking. As previously discussed, no additional photovoltage MAPI contact and inside spiro-MeOTAD for the MAPI/spiro-
is identified at the n-MAPI/C60 interface, which is further veri- MeOTAD interface. The findings could be explained when it
fied by a detailed analysis of this interface in which no band is assumed that for the NiOx/MAPI interface, the alignment is
bending has been observed (see Figure S9, Supporting Infor- determined by pinning of the NiOx Fermi level to defect states
mation). For the VBM of C60, a value of 1.51 eV (see Figure S8c, at the nickel oxide surface, while the Fermi level in MAPI is
Supporting Information) is determined. The band gap of C60 free to move at this contact. On the other hand, the Fermi level
is assumed to be 1.67 eV.[50] This results in an aligned CBM of is pinned at the MAPI surface, while it is free to move inside
MAPI and LUMO of C60. With the LUMO of BCP being 1.96 eV spiro-MeOTAD at the MAPI/spiro-MeOTAD contact. Other
(see Figure S8c, Supporting Information) and a band gap effects, like a compensation of the contact-induced electric field
of 3.5 eV,[51] a large offset between the LUMO of C60 and BCP by ion migration at the MAPI/spiro-MeOTAD, but not at the
is predicted. However, this will not block the electrons from NiOx/MAPI contact may play a role as well.[56] Such mechanism
entering the LUMO of BCP, since the BCP buffer layer has was proposed for an external applied bias and may play a role as
only a thickness of 3 nm, therefore allowing electrons to tunnel well for the contact-induced potentials as well. The fact that the
through it. The tunneling of electrons through gap states of the work function difference between the HEL and the perovskite
BCP has been described in literature elsewhere.[51–53] The band absorber defines the VOC might explain why it is sometimes
diagram for the inverted architecture under illumination is pre- reported that the HEL variation has no or a small effect on the
sented in Figure 5b. VOC, since usually the effect of the ionization potential and not
In summary, for both architectures, the majority of the of the work function is investigated.[57–59] Thus, different HELs
photo­voltage is formed at the p-HEL/n-MAPI interface, which may have different ionization potentials, but similar Fermi level
means that it is necessary to optimize the energetic alignments positions with respect to the perovskite Fermi level.
at these interfaces to further increase the VOC and therefore also For the classical architecture, where the built-in potential is
the PCE. Interestingly, the band bending is measured inside observed inside the spiro-MeOTAD, strategies to increase the
the perovskite absorber for the NiOx/MAPI interface and inside photovoltage can either focus on i) increasing the built-in poten-
the HEL in case of the MAPI/spiro-MeOTAD interface. In tial inside spiro-MeOTAD, or ii) moving the built-in potential
order to explain this different position of the band bending, the into the perovskite absorber, as it is the case for the inverted
charge carrier concentrations of MAPI on SnO2 and NiOx are architecture where NiOx is used as HEL. Increasing the built-in
estimated. Wang et  al.[23] reported a combined photoemission potential inside spiro-MeOTAD should be possible by achieving
and Hall measurement study, relating VBM positions below a high work function difference between the perovskite absorber
the Fermi Level in photoemission to carrier concentrations and spiro-MeOTAD. This can, e.g., be done by increasing
from Hall measurements. For a perovskite film with the VBM the p-doping of spiro-MeOTAD (and therefore increasing its

Adv. Energy Mater. 2020, 10, 2002129 2002129  (8 of 11) © 2020 The Authors. Published by Wiley-VCH GmbH
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work function), or by employing a different HEL that already 4. Experimental Section

exhibits a larger work function. To move the built-in poten-
All sample preparation took place at the Light Technology Institute at the
tial into the perovskite absorber, it is necessary to understand
Karlsruhe Institute of Technology (KIT). The devices investigated in this
why it appears inside the spiro-MeOTAD and not inside the work were deposited on pre-patterned ITO substrates (Luminescence
perovskite absorber. A reason for this can be the presence of Technology Corp., CAS: 50926-11-9) that were cleaned consecutively
gap states at the perovskite/spiro-MeOTAD interface, which in acetone (technical grade, VWR International, CAS: 67-64-1) and
results in a pinning of the Fermi level. Fermi level pinning can, isopropanol (technical grade, VWR International, CAS: 67-63-0) in an
e.g., be avoided by introducing buffer layers that passivate the ultrasonic bath for 10 min each. Right before the deposition of the first
gap states. Recently, several publications have reported empiri- charge extracting layer, the substrates were cleaned in an oxygen plasma
for 3 min. For the devices in classical architecture, SnO2 was used as the
cally developed strategies to improve device performance, electron extracting layer. The nanoparticular SnO2 layer was fabricated
by employing such passivation layers at the perovskite/HEL by a solution-based approach discussed in a previous report.[60] For this,
interface.[34–38] However, the exact mechanism behind these a commercial SnO2 colloidal dispersion (15 wt% dispersion, Alfa Aesar,
passivation strategies is still not investigated in detail. The find- CAS: 18282-10-5) was diluted in deionized water to a concentration of
ings reported in this study may give a first understanding about 2 wt%. The deposition of the solution on top of the ITO front electrode
the role of passivation layers at the perovskite/HEL interface. was performed by spin coating at 4000  rpm for 30 s followed by an
annealing at 250 °C for 30  min. The fabrication of the SnO2 layer
was carried out in ambient conditions. For the inverted architecture,
magnetron-sputtered NiOx was used as HEL which was deposited on
3. Conclusion top of the ITO front electrode. Sputtering was performed in a PVD 75
PRO-Line system (Kurt J. Lesker Company) by employing a green NiO
In this work, novel insights into the working principle of target (99.995% purity, Kurt J. Lesker Company, CAS: 1313-99-1) that
PSCs have been developed by using a detailed PES study of its was sputtered in a pure argon atmosphere at a process pressure of
involved interfaces. Specific junctions, stacks, and completed 1 mTorr and a power of 8 W in.−2. The thickness of the NiOx layer was
set to 20 nm.
solar cells in classical and inverted architecture were studied
To guarantee a sufficient homogeneity for the XPS investigations,
to identify at which interface the built-in potential is present in vacuum-processed perovskite absorbers were used in this work. The
the dark and where the photovoltage is created under illumi- deposition of the absorber was performed in a home-made evaporation
nation. The SPVs of the full devices that were measured using system by simultaneously evaporating lead iodide (PbI2, 99% purity,
PES are 0.80 and 0.83 V for the classical and inverted architec- Sigma-Aldrich, CAS: 10101-63-0) and methylammonium iodide (MAI,
tures, respectively. For both architectures, MAPI is measured as GreatCell Solar, CAS: 14965-49-2). The stoichiometry of the resulting
CH3NH3PbI3 absorber films was controlled by the PbI2 evaporation
n-type and the vast majority of the VOC is identified to appear
rate which was set to 0.3 Å s−1 for SnO2 substrates or 0.5 Å s−1 for NiOx
at the p-type/n-MAPI interface. It is experimentally shown that substrates and the MAI partial pressure which was held at 1.7 × 10−5 mbar
the Fermi level inside MAPI is not influenced by the substrate for SnO2 substrates or 3.0 × 10−5 mbar for NiOx substrates. During
it is grown on. The same behavior was also observed for FAPI, the deposition, the substrates were not actively cooled or heated. The
CsFAPI, MAFAPI, and CsMAFAPI perovskite absorbers. It is thickness of the absorber was set to about 350 nm. Excess MAI on the
further observed that the lead halide perovskite interfaces are surface of the absorber films was removed by a short post-treatment
extremely sensitive to light and form an SPV even due to unin- in isopropanol (99.5% anhydrous, Sigma-Aldrich, CAS: 67-63-0) in
nitrogen atmosphere after the deposition. For further information about
tentional illumination, which can result in wrong data interpre-
the vacuum-processed absorber fabrication, the reader is referred to
tation, since the perovskite is not measured in thermodynamic previous reports.[13,61]
equilibrium. This unintentional non-equilibrium situation Solar cells in classical architecture were equipped with
must be considered, not only when performing PES measure- a doped spiro-MeOTAD layer on top of the absorber as the
ments on lead halide perovskites but in any measurements HEL. For this, 80 mg mL−1 of spiro-MeOTAD (Luminescence
concerning Fermi level positioning in the dark and under Technology Corp., CAS: 207739-72-8) was dissolved in
illumination. Based on the PES results, an n+-SnO2/n-MAPI/ chlorobenzene (99.8% anhydrous, Sigma-Aldrich, CAS: 108-90-7).
After complete dissolution, 28.5  µL of 4-tert-butylpyridine (98% purity,
p-spiro-MeOTAD device architecture and a p-NiOx/n-MAPI/ Sigma-Aldrich, CAS: 3978-81-2) and 17.5  µL of a lithium stock solution
C60 device architecture is deduced for the devices with an n-p- were added to the solution. The lithium stock solution was prepared by
heterojunction between MAPI and the respective p-HEL that is dissolving 520  mg of bis(trifluoromethansulfonyl)imid (Sigma-Aldrich,
responsible for the solar cells VOC. For a further improvement CAS: 90076-65-6) in 1  mL of acetonitrile (99.8% anhydrous, Sigma-
of the device open-circuit potential and the PCE, it is therefore Aldrich, CAS: 75-05-8). The as-prepared solution was then deposited on
recommended to focus on optimizing the MAPI/HEL contact. top of the absorber by spin coating at 4000  rpm for 30 s in nitrogen
atmosphere without any post-annealing. Devices employing spiro-
Especially, strong p-doping of the HEL and a low offset between
MeOTAD as the HEL were kept in an oxygen atmosphere at 25% relative
the HEL ionization potential and the perovskite VBM with the humidity for about 12 h. For devices based on the inverted architecture,
HEL ionization potential just above the perovskite VBM should a double layer of the fullerene C60 (98% purity, Alfa Aesar, CAS: 99685-
lead to better device performance. Additional photovoltage 96-8) and BCP (Luminescence Technology Corp., CAS: 4733-39-5) was
experiments should be performed on p-doped MAPI perovskite used as the EEL. Both layers were deposited by thermal evaporation in a
films to investigate that the photovoltage will be formed at the Spectros evaporation system (Kurt J. Lesker Company). The 30 nm thick
EEL/MAPI contact. The findings of this work should also be fullerene layer was deposited at an evaporation rate of about 0.2 Å s−1
whereas the 3 nm thick BCP layer was deposited at 0.4 Å s−1. Finally, both
applicable for other perovskite absorbers (e.g., for wide band
device architectures were equipped with a 25  nm thick gold layer that
gap materials like CH3NH3PbBr3), since their larger band gap was thermally evaporated at an evaporation rate of 2 Å s−1.
compared to iodine-based perovskites is due to a lower lying Current–voltage characteristics of the solar cells were measured
VBM. in a Newport solar simulator both in forward and backward scan

Adv. Energy Mater. 2020, 10, 2002129 2002129  (9 of 11) © 2020 The Authors. Published by Wiley-VCH GmbH
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direction under simulated AM1.5G light emitted from a xenon lamp. Conflict of Interest
The intensity of the lamp was calibrated using a silicon reference solar
cell equipped with a KG5 filter. The scan rate during the measurement The authors declare no conflict of interest.
was kept constant at 600 mV s−1. The solar cells were actively cooled
to a temperature of 25 °C during the measurement by means of a
microcontroller-driven Peltier element.
For XRD investigations, a Bruker D8 DISCOVER system with Cu-Kα Keywords
radiation was used in a Bragg-Brentano configuration.
The optical characteristics were extracted out of the transmittance energy band diagrams, perovskite solar cells, photoelectron
and reflectance data, which were measured in a spectrophotometer spectroscopy, surface photovoltage
(PerkinElmer Lambda 1050). Absorptance was calculated based on
the measured reflectance and transmittance by using the formula Received: July 1, 2020
A = 1 − R − T. Revised: August 31, 2020
For the PES measurements, the samples were packed under nitrogen Published online: September 27, 2020
atmosphere and transported from the Karlsruhe Institute of Technology
to the Technical University of Darmstadt (TUD). To be able to measure
an SPV in the XPS analysis chamber, the samples were contacted
to the electrical ground at the ITO contact, so the potential of all the
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This work was supported by the German Research Foundation (DFG)
Y. Rosenwaks, G. Hodes, D. Cahen, Nano Lett. 2014, 14, 1000.
under the project title “Inverted non-fullerene organic solar cells” project
number 196886395 and within the priority program SPP 2196 under the [16] V. W.  Bergmann, S. A. L.  Weber, F. J.  Ramos, M. K.  Nazeeruddin,
project title “Interrogate” project number 423746744. Also funding by the M.  Gratzel, D.  Li, A. L.  Domanski, I.  Lieberwirth, S.  Ahmad,
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