Akatsuka et al.

Direct measurement of electron affinity of carbazole-based

self-assembled monolayer used as hole-selective layer in high-

efficiency perovskite solar cells

Aruto Akatsuka1,Akatsuka,1 Makoto Miura1,Miura,1 Gaurav Kapil2,Kapil,2 Shuzi Hayase2Hayase,2,3

and Hiroyuki Yoshida4,5,a)*

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.

1
5
Molecular Chirality Research Center, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba, 263-8522,

Japan.

*a)
Corresponding Author to whom correspondence should be addressed: [email protected]

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.

Perovskite solar cells (PSCs) have attracted tremendous attention because they can be fabricated by a

low-cost solution process and achieve a power conversion efficiency (PCE) of 26.1% [%.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

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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

electrode, it hardly absorbs light and has high stability [.4]. 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, and 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

1
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]gap4 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

materials [.8-–10]. 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

1
a combination of a bandpass filter and a photomultiplier. LEIPS has enabled thickness-dependent

measurements to study the interface energy level alignment of unoccupied states [,23], the precise

determination of exciton binding energy [8]energy8 and polarization energy [,24-–26], the electron

injection barrier in organic light emitting diode [,27], analysis of the charge separation mechanism in

organic solar cells [28,29] and measuring the on-site coulomb repulsion energy (Hubberd U) in

polymers [,30], etc. Recently, the angle-resolved measurement to observe conduction band structure

[31,32]
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.

1
 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-

Communications. After annealing the samples at 100 °C 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 °C for 1 min to remove the solvent.

The samples were kept in a nitrogen atmosphere and transported to Chiba University for

LEIPS measurement. The details of the LEIPS setup are described elsewhere [.33]. 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),

1
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, the signal

intensity of the photon detector tail region should be sufficiently high. Furthermore, the inverse

photoelectron process has a very small cross section [,37], 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

1
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 (FigureFig. 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 speciallyin particular, 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]counter39 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.

1
FigureFIG. 1.: LEIPS spectra of 2PACz measured with a bandpass filter (232 and 260 nm) and a

photomultiplier tube (Hamamatsu Photonics R585s).

FigureFIG. 2.: Sensitivity curves of photon detector. (a) Quantum efficiencies of photomultiplier

tubes R585s [43]R585s43 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.

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 (FigureFig. 4).

1
FigureFIG. 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]- eV45-–5.9 eV [46] eV45,46 for 2PACz and 5.1 eV [45] eV45 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 FigureFig. 4. The transport gaps calculated

as the difference between 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 ten 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.

1
 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 ¼

of the transport gap and 1/3 of the optical gap [.8]. 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 bandwideband 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]
)respectively51) owing to band dispersion [.[52,53].] We show the corrected energy levels of MAPbI3

in Figure Fig. 4 [51].451.51 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

1
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 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]),cell56) the LUMO

energy level of the present SAMs is expected to always be well above the CB of any perovskite layer

for the PSC.

FigureFIG. 4: . Energy level diagram of carbazole-based SAMs 2PACz and MeO-2PACz, and

perovskites MAPbI3 [51-MAPbI351–53] 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 90°°) and the ionization energies (numbers in

red/blue rotated upward by 90°°).

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 and

1
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

ACKNOWLEDGMENTS

We thank Mr. Daisuke Hamamura for his help in measuring UV-vis spectra and Prof.Professor

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

AUTHOR DECLARATIONS

Conflict of Interest

The authors have no conflicts to disclose.

Author Contributions

1
Aruto Akatsuka: Conceptualization (supporting); Data curation (equal); Formal analysis (equal);

Writing – original draft (equal); Writing – review & editing (supporting). Makoto Miura: Data

curation (equal); Formal analysis (equal); Methodology (equal). Gaurav Kapil: Data curation

(supporting). Shuzi Hayase: Conceptualization (equal); Supervision (supporting). Hiroyuki

Yoshida: Conceptualization (lead); Funding acquisition (lead); Methodology (lead); Supervision

(lead); Writing – original draft (equal); Writing – review & editing (lead).

DATA AVAILABILITY

The data that support the findings of this study are available from the corresponding author upon
reasonable request

supporting data for this study are available from the corresponding author upon reasonable

request.

AUTHOR CONTRIBUTIONS

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.

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