Direct measurement of electron affinity of carbazole-based self-

assembled monolayer used as hole-selective layer in high-

efficiency perovskite solar cells

Aruto Akatsuka1), Makoto Miura1), Gaurav Kapil2), Shuzi Hayase2,3) and Hiroyuki Yoshida4,5)*

1) Graduate School of Science and Engineering, Chiba University, 1-33 Yayoi-cho, Inage-ku,
Chiba, 263-8522, Japan.
2) i-Powered Energy System Research Center, The University of Electro-Communications, 1-5-
1 Chofugaoka, Chofu, Tokyo, 182-8585, Japan.
3) Graduate School of Informatics and Engineering, The University of Electro-Communications,
1-5-1 Chofugaoka, Chofu, Tokyo, 182-8585, Japan.
4) Graduate School of Engineering, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba, 263-
8522, Japan.
5) Molecular Chirality Research Center, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba,
263-8522, Japan.

Abstract

Carbazole-based self-assembled monolayers (SAMs) have received considerable attention as

hole-selective layers (HSLs) in inverted perovskite solar cells. As an HSL, the electron-blocking
capability is important and directly related to electron affinity (EA). Low-energy inverse
photoelectron spectroscopy (LEIPS) is the most reliable method for EA measurement. However,
the intense electron-impact-induced fluorescence from the carbazole interferes with the
measurement. By improving the photon detector, we were able to measure 2PACz and MeO-
2PACz LEIPS spectra and determine their respective EAs of 1.73 eV and 1.48 eV. These small
EA values ensure effective electron-blocking capability of HSLs regardless of the type of
perovskite layer.

*Corresponding Author: [email protected]

1
Perovskite solar cells (PSCs) have attracted tremendous attention because they can be fabricated
[1]
by a low-cost solution process and achieve a power conversion efficiency (PCE) of 26.1% .
2,2',7,7'-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-OMeTAD) is
exclusively used as a hole-selective layer (HSL) in a normal (n-i-p) structure PSC with high PCE.
However, spiro-OMeTAD requires doping and has stability issues [2]. On the other hand, such
stable polymers as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT:PSS)
and poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) are used as an HSL in an inverted
(p-i-n) structure PSC [3]. However, the polymer layer is usually around 10 to 40 nm thick, which
decreases light transmission and electrical conductivity [4].

A self-assembled monolayer (SAM) has been developed as a substitute for these polymer HSLs.
As SAM-based HSL is very thin (approximately 1 nm) [5] and firmly binds to a transparent
[4]
electrode, it hardly absorbs light and has high stability . Among the various SAM materials,
carbazole derivatives are the most widely studied. A carbazole-based SAM molecule comprises a
carbazole backbone, an anchor moiety binding to the transparent electrode surface, and an alkyl
chain connecting the carbazole backbone and the anchor moiety. The SAM molecules with alkyl
chains CnH2n of various lengths (n = 2, 4, 6) and substituents such as methyl and methoxy groups
have been developed [6].

To achieve good performance as HSL, high hole collection efficiency and electron-blocking
capability are required, and these can be assessed from the HOMO and LUMO energy levels,
respectively. If the vacuum level alignment is assumed for simplicity, the ionization energy (IE;
HOMO energy level with reference to the vacuum level) should lie between the IE of the
perovskite surface and the work function of the transparent electrode. Conversely, the electron
affinity (EA; the LUMO energy level with reference to the vacuum level) should be smaller than
that of the perovskite layer for electron blocking. Therefore, precise and reliable IE and EA values
of HSL are essential to evaluate and choose a suitable SAM material. In addition, interfacial
hole/electron recombination crucially impacts PSC performance. The recombination rate depends
on IE and EA as well as the trap density [6,7]. To discuss the recombination dynamics in detail,
accurate IE and EA values of HSL are indispensable.

IE in a solid can be determined by ultraviolet photoelectron spectroscopy (UPS) measurement of

a film. Conversely, EA is often predicted from the IE and the optical gap [4] assuming that the
transport gap (IE−EA) is equal to the optical gap. However, the transport gap and the optical gap
differ owing to the exciton binding energy (usually ranging from 0.2 eV to 1 eV) for organic

2
 [8-10]
materials . Thus, EA is often overestimated from the IE and the optical gap. IE and EA are
also estimated from the oxidation and reduction potentials derived from cyclic voltammetry (CV)
measurement. However, CV data are affected by the solvent and the supporting electrolyte, and
the measured values differ from those in the film [11-14]. In principle, EA can be best measured by
inverse photoelectron spectroscopy (IPES), which is regarded as the inversion process of UPS.
However, damage to organic materials by electron irradiation has hindered the application of
conventional IPES. Although IPES has provided unprecedent information about the unoccupied
states of organic semiconductors over 30 years [15-20], its applicability is limited. The development
of low-energy IPES (LEIPS) has made precise EA measurement possible [21,22]. In LEIPS, an
electron with less than 5 eV kinetic energy (i.e., the damage threshold of most organic materials)
and a photon emitted by the radiative transition from a free electron to the unoccupied states
(including LUMO) are detected. As the photon energy is in the near-ultraviolet or visible range,
the photons are detected by a combination of a bandpass filter and a photomultiplier. LEIPS has
enabled thickness-dependent measurements to study the interface energy level alignment of
[23] [8]
unoccupied states , the precise determination of exciton binding energy and polarization
[24-26] [27]
energy , the electron injection barrier in organic light emitting diode , analysis of the
[28,29]
charge separation mechanism in organic solar cells and measuring the on-site coulomb
[30]
repulsion energy (Hubberd U) in polymers , etc. Recently, the angle-resolved measurement to
[31,32]
observe conduction band structure has been achieved, which has never been possible with
the conventional IPES. However, the application of LEIPS to fluorescent molecules such as
carbazole derivatives is not straightforward because the carbazole derivatives generate intense
electron-induced fluorescence that interferes with the detection of the weak photon signal by
LEIPS. To observe the LEIPS spectrum of the carbazole derivatives, we need to improve the
experimental setup.

In this paper, we report EA measurements of carbazole-based SAMs as HSL using LEIPS. We

choose the two most widely used materials (2-(9H-Carbazol-9-yl)ethyl)phosphonic acid (2PACz)
and (2-(3,6-Dimethoxy-9H-carbazol-9-yl)ethyl)phosphonic acid (MeO-2PACz) as examples.
First, we explain the problem arising from the EA measurement of the SAMs using LEIPS.
Second, we show an improved experimental setup to solve this problem. Third, we measure the
LEIPS spectra of 2PACz and MeO-2PACz. The determined EAs corroborate the good electron-
blocking capability of these SAMs as HSL.

2PACz and MeO-2PACz film samples were prepared by spin coating 1 mM solutions of 2PACz
and MeO-2PACz in isopropyl alcohol (IPA) onto ITO substrates at the University of Electro-
3
Communications. After annealing the samples at 100 ℃ for 10 minutes, the unbonded 2PACz and
MeO-2PACz molecules on the ITO substrates were washed off with IPA, and the washed samples
were annealed at 100 ℃ for 1 min to remove the solvent.

The samples were kept in a nitrogen atmosphere and transported to Chiba University for LEIPS
[33]
measurement. The details of the LEIPS setup are described elsewhere . The samples were
irradiated with 1.0 to 6.5 eV electron beams. The emitted photons were detected by a bandpass
detector consisting of a bandpass filter and a photomultiplier. We have used the photomultiplier
tube, Hamamatsu Photonics R585s, since the development of LEIPS because of its low dark
counts. We find that the photomultiplier tube should be replaced in this work. Because the photon
detector is key to this work, we will discuss the details later. The work function was measured
from the onset of the sample current as a function of electron kinetic energy.

Figure 1 shows the LEIPS spectra of 2PACz measured with a bandpass filter (center wavelengths
of 232 nm and 260 nm) and a photomultiplier tube (Hamamatsu Photonics R585s). The spectral
onset shifted from -0.22 eV to 0.42 eV when the bandpass filter was changed from 232 nm to 260
nm. If the photon signal originated from the IPES process, the electron binding energy Eb = h –
Ek should be independent of the photon energy h. Because the onset difference of 0.6 eV
corresponds approximately to the photon energy difference, 5.3 eV (232 nm) and 4.8 eV (260 nm),
the process depends only on the electron energy Ek. Furthermore, the signal was observed even
below the Fermi level when the photon with the wavelength of 232 nm was detected. Likely, the
photon signal did not originate from the IPES process.

It is known that molecules display fluorescence by electron-impact excitation and photon

excitation [34]. Carbazole is a highly emissive molecule that shows fluorescence by electron impact
[35]
. Its spectrum is similar to photon-excited fluorescence due to the S1->S0 transition from 330
nm to 400 nm. It was reported that a small amount of impurities in carbazole samples may cause
fluorescence [36]. We used a bandpass filter with a center wavelength of 232 nm (5.28 eV) or 260
nm (4.79 eV), the energy of which seemed too high for fluorescence detection below 330 nm, and
inspected the sensitivity curves of our photon detector. Figure 2 shows the quantum efficiencies
of the R585s photomultiplier tube and of the photon detector combined with the bandpass filters.
The photon detector shows high sensitivity at the center wavelength of the bandpass filter (260 or
232 nm) and the long tail extending toward the long-wavelength region. Even around 330–400
nm where carbazole shows strong fluorescence, the photon detector has low but non-negligible
sensitivity. Because the photon signal intensity is the sensitivity integrated over the wavelength,

4
the signal intensity of the photon detector tail region should be sufficiently high. Furthermore, the
[37]
inverse photoelectron process has a very small cross section , and typical photon intensity in
the present measurement ranges from 10 to 100 cps, whereas the fluorescence induced by the
electron impact is so intense that it is sometimes visible to the naked eye. Therefore, we conclude
that the fluorescence from carbazole is so strong that a sufficient amount of photons are
transmitted through the bandpass filter to be detected by the photomultiplier tube.

The R585s photomultiplier tube uses a bi-alkali (Sb-Rb-Cs and Sb-K-Cs) photocathode and has
a sensitivity range of 700 nm to 160 nm (Figure 2). Conversely, a photomultiplier tube with a Cs-
Te “solar-blind” photocathode is not sensitive to wavelengths longer than 300 nm [38]. Aiming to
avoid the intense photon signal in the visible range, we combined a Cs-Te photomultiplier tube
with near-ultraviolet bandpass filters. Unfortunately, the Cs-Te photomultiplier tube for photon
counting use is not available, so we specially selected a low dark count tube from the
manufacture’s stock of Hamamatsu Photonics R821 and used it for photon counting.

Note that this problem is specific to LEIPS, because LEIPS analyzes visible/near-UV photons
whose energies are close to those of molecular fluorescence in the visible range. The high
energy selectivity is crucial to safely observe the LEIPS signal. Conversely, the conventional
IPES using the bandpass photon detector in the vacuum ultraviolet range has a sufficient energy
difference to block the molecular fluorescence. The photon detector developed by Dose, using a
gas-filled Geiger-Mueller counter [39] is totally insensitive to photons below the ionization
energy of the filled gas (> 9 eV of I2, isopropanol, acetone, etc. [40]). The solid-state bandpass
detector using the CuBe electron multiplier [41], which was later improved by coating the first
dynode with an alkali halide [42], also has negligible sensitivity in the visible range.

5
 Intensity (arb. unit)

-0.22
@232 nm

0.42

@260 nm

−1.5 −1.0 −0.5 0.0 0.5 1.0

Energy from EF (eV)

Figure 1: LEIPS spectra of 2PACz measured with a bandpass filter (232 and 260 nm) and a
photomultiplier tube (Hamamatsu Photonics R585s).

6
 (a)
100
R585s
R821

quantum efficiency (%)

10

0.1

0.01
200 300 400 500 600 700
wavelengh (nm)
(b)
100
R585s + 260 nm
10 R821 + 260 nm
quantum efficiency (%)

0.1

0.01

0.001

1E-4

1E-5
200 250 300 350
wavelengh (nm)

(c)
10
R585s + 232 nm
1 R821 + 232 nm
quantum efficiency (%)

0.1

0.01

0.001

1E-4

1E-5
200 250 300 350
wavelengh (nm)

Figure 2: Sensitivity curves of photon detector. (a) Quantum efficiencies of photomultiplier tubes
R585s [43] and R821[44]. (b) Comparison of quantum efficiencies of photon detector comprised of
the bandpass filter (260 nm) and photomultiplier tubes R585s and R821. (c) The same as panel
(b) except for the bandpass filter with a center wavelength of 232 nm.

7
Figure 3 shows the LEIPS spectra of 2PACz and MeO-2PACz measured with the photon detector
consisting of a bandpass filter with a center wavelength of 285 nm and the photomultiplier tube
R821. We observed clear onsets at 3.49 eV (2PACz) and 3.32 eV (MeO-2PACz) above the Fermi
level. The LEIPS spectrum of pristine ITO substrate exhibits a gradual rise around 1 eV (not
shown). We assigned the small increases in the background to the signal from the ITO substrate.
When the 285 nm bandpass filter was replaced with a 260 nm one, the onset energies in the Ek
scale shifted by 0.51 eV, but the electron binding energies Eb were unchanged (3.42 eV for 2PACz
and 3.19 eV for MeO-2PACz), confirming that the spectral onsets originated from the IPES
process, namely, the transition from a free electron to the LUMO energy levels. The LEET spectra
in Figure 3 show that the work functions (or the vacuum level) are 5.21 eV (2PACz) and 4.80 eV
(MeO-2PACz). Using these work functions, we determined EAs to be 1.73 eV (2PACz) and 1.48
eV (MeO-2PACz) as the difference between the LEIPS onset and the vacuum level (Figure 4).
Sample Current (arb. unit)

5.21
Intensity (arb. unit)

3.49
2PACz

4.80
3.32
MeO-2PACz

0 1 2 3 4 4 5 6 7
Energy from EF (eV) Energy from EF (eV)

Figure 3: LEIPS (left) and LEET (right) spectra of 2PACz and MeO-2PACz measured by the
improved photon detector using the photomultiplier tube R821 and the bandpass filter with a
center wavelength of 285 nm.

The reported IEs are 5.6 eV [45]-5.9 eV [46] for 2PACz and 5.1 eV [45] for MeO-2PACz. The optical

gaps are 3.5 eV (2PACz) and 3.2 eV (MeO-2PACz) [45,46]. These values and the EAs determined

in this work are summarized in Figure 4. The transport gaps calculated as the difference between

8
IE and EA are 4.0–4.3 eV for 2PACz and 3.6 eV for MeO-2PACz. In previous studies, the EA (or
LUMO energy level) was estimated from the IE and the optical gap [45-49]. The estimated EA are
systematically about 0.5 eV larger (or the LUMO level is lower) than the LEIPS measurements.
The transmission coefficient for electron tunneling or the carrier population at the barrier is
exponentially related to the energy difference [50]. If we take the energy levels shown in Fig. 4, the
SAM thickness of 1 nm, the difference of 0.5 eV in barrier height leads to a four orders of
magnitude difference in the transmission coefficient for electron tunneling. The electron density
in the LUMO of the SAM layer can be up to 10 orders of magnitude different, assuming the
Boltzmann distribution (the values vary slightly depending on the energy parameters, but do not
affect the main conclusion). These estimates show that a difference of only 0.5 eV in barrier height
can make a significant difference in electron blocking capability, highlighting the importance of
accurate measurement of EA values.

We calculated the exciton binding energies from the difference between the transport and optical
gaps, and they were 0.5–0.8 eV for 2PACz and 0.4 eV for MeO-2PACz. We recently reported that
the exciton binding energy of organic semiconductors and polymers is approximately 1/4 of the
[8]
transport gap and 1/3 of the optical gap . Although we predicted an exciton binding energy of
approximately 1 eV, the observed exciton binding energies are smaller than this prediction
probably because a positive or negative charge is stabilized near the metallic electrodes owing to
the efficient screening [23].

From the obtained EAs, we discuss the electron-blocking capability of SAMs. The energy level
alignment at the SAM–perovskite interface should lie between two limiting cases, namely, the
Fermi level alignment (the Schottky limit) and the vacuum level alignment (the Bardeen limit).
Figure 4 shows the conduction band (CB) minima and the valence band (VB) maxima with the
Fermi level alignment of representative perovskite CH3NH3PbI3 (MAPbI3) and wide band gap
perovskite for silicon/perovskite tandem solar cell Cs0.2NH2CH=NH2(FA)0.8PbI3Br1.2
(Cs0.2FA0.8PbI1.8Br1.2). The UPS and LEIPS of MAPbI3 measured at normal angles cannot access
the VB and CB edges (VB at -1.55 eV and CB at 0.97 eV from the Fermi level, respectively [51])
owing to band dispersion [52,53]. We show the corrected energy levels of MAPbI3 in Figure 4 [51].
The LUMO energy levels of the SAMs are located more than 3 eV above the CB of the both
perovskite layers in the case of the Schottky limit. On the other hand, assuming a vacuum level
alignment, the energy barrier (difference between the LUMO energy level of SAM and the CB of
perovskite) becomes approximately 2 eV, which is still sufficiently high to efficiently block the
electrons at the SAM/perovskite also in the Bardeen limit. Because the band gaps of perovskites
9
for efficient PSCs are between 1 and 2 eV (theoretically, the best optical gap is 0.8–1.4 eV for the
single cell and 1.7 eV and 1 eV for the double-layered tandem cell [56]), the LUMO energy level
of the present SAMs is expected to always be well above the CB of any perovskite layer for the
PSC.

Figure 4: Energy level diagram of carbazole-based SAMs 2PACz and MeO-2PACz, and
perovskites MAPbI3 [51-53] and Cs0.2FA0.8PbI1.8Br1.2[54,55]. The values (in eV) are with reference to

the Fermi level except for the electron affinities (numbers in white) and the optical transition
energies (numbers in black rotated upward by 90o) and the ionization energies (numbers in
red/blue rotated upward by 90o).

In conclusion, we established an experimental method to determine the EAs of carbazole

derivatives in a solid. The EA values of organic materials are best determined by LEIPS. However,
when the sample surface is irradiated with an electron beam for LEIPS measurement, the
carbazole derivatives emit strong fluorescence induced by electron impact in the visible range,
which interferes with the LEIPS measurement. We used a “solar-blind” photomultiplier tube with
a Cs-Te photocathode to separate the LEIPS signal from the fluorescence and observed the LEIPS
spectra. The present method applies to not only carbazole-based SAMs but also other emissive
organic semiconductors. We applied this technique to prototypical carbazole SAMs used as HSL

10
and determined their EAs to be 1.73 eV (2PACz) and 1.48 eV (MeO-2PACz). These EAs are
smaller than the previously reported values, implying that the carbazole-based SAMs have better
electron blocking capability than previously thought.

Acknowledgments

We thank Mr. Daisuke Hamamura for his help in measuring UV-vis spectra and Prof. Kazuki
Nakamura of Chiba University for allowing us to use the UV-vis spectrometer. This work was
supported by JST−MIRAI (JPMJMI22E2) and JSPS-KAKENHI (23H03939).

Conflict of interest declaration

The authors have no conflicts of interest to disclose.

Data Availability

Supporting data for this study are available from the corresponding author upon reasonable
request.

Author Contributions

HY, AA, and SH planned this work. MM and HY developed the photon detector. AA and MM
measured and analyzed the data. GK and SH prepared the samples. AA and HY wrote the
manuscript.

11
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