Ultraviolet photoelectron spectroscopy measurements of Spiro/Perovskite/m-

TiO2/c-TiO2/FTO stack
Spiro-OMeTAD/Perovskite/m-TiO2/c-TiO2/FTO stack

SECO Valence band region

 = 4.0 eV Spiro-OMeTAD
17.2 eV 0.8 eV
Intensity (arb. units)

 = 4.6 eV
Perovskite
16.6 eV 1.1 eV

 = 3.6 eV
17.6 eV 3.5 eV m-TiO2
 = 4.5 eV
16.7 eV 3.7 eV c-TiO2

 = 4.6 eV
16.6 eV 3.7 eV FTO

18 17 16 15 8 7 6 5 4 3 2 1 0 -1 -2

Spiro- Binding energy (eV)

OMeTAD/Perovskite with IL/m-TiO2/c-TiO2/FTO stack

SECO Valence band region

Spiro-OMeTAD
17.1 eV  = 4.1 eV
0.8 eV
Intensity (arb. units)

 = 4.5 eV Perovskite
1.1 eV with IL
16.7 eV

 = 3.6 eV
17.6 eV 3.5 eV m-TiO2

 = 4.5 eV
16.7 eV 3.7 eV c-TiO2

 = 4.6 eV
16.6 eV 3.7 eV FTO

18 17 16 15 8 7 6 5 4 3 2 1 0 -1 -2
Binding energy (eV)
 Spiro-OMeTAD/Perovskite with PIL/m-TiO2/c-TiO2/FTO stack

SECO Valence band region

 = 4.1 eV Spiro-OMeTAD
17.1 eV 0.8 eV
Intensity (arb. units)

 = 4.7 eV Perovskite
1.1 eV
16.5 eV with PIL

 = 3.6 eV
17.6 eV 3.5 eV m-TiO2
 = 4.5 eV
16.7 eV 3.7 eV c-TiO2

 = 4.6 eV
16.6 eV 3.7 eV FTO

18 17 16 15 8 7 6 5 4 3 2 1 0 -1 -2
Binding energy (eV)

Table 1: Summary of electronic structure parameters of the different layers of the perovskite solar cell

Sample Ф VB onset (eV) IP (eV) Egopt (eV)

(eV)
FTO 4.6 3.7 8.3
c-TiO2 4.5 3.7 8.2 ≈3.7*
m-TiO2 3.6 3.5 7.1
Perovskite 4.6 1.1 5.7 ≈1.5*
Perovskite with IL 4.5 1.1 5.6 ≈1.5*
Perovskite with PIL 4.7 1.1 5.8 ≈1.5*
Spiro on Perovskite 4.0 0.8 4.8 3.5^
Spiro on Perovskite with IL 4.1 0.8 4.9 3.5^
Spiro on Perovskite with 4.1 0.8 4.9 3.5^
PIL
** Ф-Work function; VB onset- Valence Band onset; IP-Ionization potential; Egopt-Optical band gap
* Values obtained by Silvia (please check it, am I right) ^ Value of the electronic band gap taken from
the literature1
As can be seen from Table 1, three measured films of perovskite material show quite
comparable values of the electronic structure parameters, which are in the range of the error of
UPS measurements (± 0.1 eV).
It might be inferred that the parameters of electronic structure of the perovskite film surface do
not change much with the addition of ionic or polyionic liquid additives. Also, measured optical
band gaps for three perovskite films show the same value (very similar), which shows good
agreement with the values of electronic band gap reported for FAPbI 3 in the literature.2-4 It is
expected, that the electronic band gap of the measured perovskite films is wider for a couple
of meV than here reported optical band gap. Also, it is expected that the presence of Cs has
certain effect on the increase of the band gap in this case. In addition, subsequently deposited
films of spiro-OMeTAD, onto three different perovskite films, show the same/reproducible
values of the electronic structure parameters. Measured ionization potential of three spiro-
OMeTAD three films shows good agreement with reported values of around 5 eV.1, 5-6
Here, we should keep in mind that in UPS measurements were performed on the films which
thickness is anticipated to be of a magnitude of hundreds of nanometers (except c-TiO 2). Thus,
with the sensitivity of UPS measurements (< 2nm) we could probe only the surface of films, and
cannot discuss phenomena exactly at the interface of materials such as e.g. band banding.
However, this rather static picture of the alignment of the bands of different materials can
provide us a clue about matching of relevant energy levels of used materials, thus the potential
performance of a device.

From UPS measurements the next energy level alignment diagrams can be derived:

Spiro-OMeTAD/Perovskite/m-TiO2/c-TiO2/FTO stack
 Spiro-OMeTAD/Perovskite with IL/m-TiO2/c-TiO2/FTO stack

Spiro- OMeTAD/Perovskite
with PIL/m-TiO2/c-TiO2/FTO stack
From ELA diagrams can be seen that the Fermi level is expected to be located close to the
conduction band minimum (CBM) of both TiO 2 layers. This expectation is based on the n-type
nature of TiO2 films, and previous UPS measurements of differently prepared TiO 2 films. Also,
according to the literature, it is expected that c-TiO 2 possess the wider electronic band gap in
comparison to mesoporous counterpart. 7-8 However, due to lack of knowledge of the electronic
band gap of TiO2 films, it is not easy to assess the alignment between the conduction band
minima of two TiO2 layers, as well as, offset between CBM of m-TiO 2 and CBM of perovskite thin
films, nevertheless, it is reasonable to expect that CBM of all three perovskite thin films is
above that of m-TiO2. Hence, it would be interesting in the future to better understand these
interfaces, and it might be that there over there lies the problem of the devices performance
(problems we face here in Bordeaux). Favourable ELA scenario was found at the spiro-
OMeTAD/Perovskite interface, where the HOMO level of molecule is found 0.3 eV above the
valence band maximum (VBM) of the perovskite film in all three samples.

SECO Valence band region

Intensity (arb. units)

Perovskite
 = 4.5 eV with IL
16.7 eV 1.1 eV

Perovskite
 = 4.7 eV with PIL
16.5 eV 1.1 eV

 = 4.6 eV Perovskite
16.6 eV 1.1 eV

17.5 17.0 16.5 16.0 14 12 10 8 6 4 2 0 -2

Binding energy (eV)

The spectra of valence band region of three perovskite films are then compared. Firstly, we look
at the spectrum of neat perovskite film. This signal of the valence band maximum (Eb = 2-6 eV)
is expected to stem from [PbI6]- octahedra of the perovskite structure, and dominated by I 5p
orbital. In particular, features between 2-4 eV can be mainly ascribed to I5p and mixing
between I 5p and Pb 6s, while signals between 4-6 eV are expected to be predominantly of the
Pb 6p character with less contribution of I 5p orbital. In the region of the valence band
maximum (Eb = 2-6 eV) appearance of spectral features are quite similar for the neat perovskite
and the film with the PIL additive, however it changes for the film with the IL additive. For the
neat perovskite film, down the binding energy axis, at around 8 eV we expect contribution of
the signal from C 2p orbital of the FA cation, than at around 9 eV from Pb 6s, and lastly
between 10 and 11 eV is expected signal from N 2p orbital of FA cation. Signal at 12-14 eV is
subscribed mostly to I 5s orbital. Further, when the additives are present in the film of
perovskite, it can be noticed that spectral features between about 6 - 8 eV and 9 -13 eV start
rising, which is especially visible in the case of added IL. Spectral features between 6 and 8 eV
are expected, beside carbon, also to have contributions from oxygen and sulfur, while between
9 and 13 eV beside nitrogen, we may also expect contribution of fluorine signal. Nonetheless,
particular contributions (e.g. TFSI part of IL and PIL) to spectral features are not easily to
subscribe.
Hence, from the appearance of the valence band region spectra of the three perovskite
samples can be inferred that higher amount of additive at the surface can be found for the
sample where IL acts as additive. This can be well seen in the figure where three spectra are
overlapped, where can be visually compared relative ratio between signals which are expected
to stem from perovskite and additive. For that purpose, spectra were normalized to the leading
features of the spectra (valence band maximum) composed mainly of I 5p orbital. This is not
bad choice regarding that the photoemission cross section of the orbital is higher than for
leading orbitals of other contributing elements, and that the purpose of the spectra comparison
is to roughly depict increase of signals which stem from additives. Resemblance in the shape of
signals stemming from additives comes from the resemblance of chemical structure of used
additives.9 For the determination of VB onsets of measured perovskite films was used a
logarithmic scale10-11, however for the clarity of data, here presented perovskite spectra are in a
linear scale.

Valence band region

Intensity (arb. units)

Perovskite
with IL
Perovskite
with PIL
Perovskite

14 12 10 8 6 4 2 0 -2
Binding energy (eV)
References:

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