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Article history: Information about the unoccupied states is crucial to both fundamental and applied physics of organic
Received 7 March 2015 semiconductors. However, there were no available experimental methods that meet the requirement of
Received in revised form 30 June 2015 such research. In this review, we describe a new experimental method to examine the unoccupied states,
Accepted 3 July 2015
called low-energy inverse photoemission spectroscopy (LEIPS). An electron having the kinetic energy
Available online 13 July 2015
lower than the damage threshold of organic molecules is introduced to a sample film, and an emitted
photon in the near-ultraviolet range is detected with high resolution and sensitivity. Unlike the previ-
Keywords:
ous inverse photoemission spectroscopy, the sample damage is negligible and the overall resolution is a
Low-energy inverse photoemission
spectroscopy
factor of two improved to 0.25 eV. Using LEIPS, electron affinity of organic semiconductor can be deter-
Unoccupied state mined with the same precision as photoemission spectroscopy for ionization energy. The instruments
Electron affinity including an electron source and photon detectors as well as application to organic semiconductors are
Organic semiconductor presented.
© 2015 Published by Elsevier B.V.
http://dx.doi.org/10.1016/j.elspec.2015.07.003
0368-2048/© 2015 Published by Elsevier B.V.
H. Yoshida / Journal of Electron Spectroscopy and Related Phenomena 204 (2015) 116–124 117
IPES was first pursued in the X-ray range since 1940s (see Ref.
[26]). Studies of IPES in the vacuum ultraviolet (VUV) range started
with the introduction of the bandpass photon detector using the
Geiger–Müller tube and optical filter in 1970s [24,27]. The iodine
gas-filled Geiger–Müller serves as the high pass filter with the sen-
sitivity beyond 9.2 eV and the optical filter of CaF2 as low pass filter
with the cut-off energy of 10 eV making a bandpass sensitivity cen-
tered at 9.7 eV with the half-width at maximum (FWHM) of 0.7 eV.
This VUV photon detector has high quantum efficiency and large
solid angle of the photon collection as well as is easy to construct.
This work established IPES as a standard spectroscopic technique
Fig. 1. Principle of inverse photoemission spectroscopy. (a) Electron kinetic energy for surface science. Here, we call this experimental method as VUV-
Ek is scanned with detecting photons at a fixed energy h (isochormat mode). (b) IPES. The energy resolution has been improved by changing the
Electron kinetic energy Ek is fixed and photons with various energies are analyzed
filled gases and the optical filters [28–34]. The Geiger–Müller tube
using a spectrometer (TPE mode).
was replaced with a solid state detector to improve the stability
of operation [35–37]. Most of the IPES studies of organic materials
was as high as 0.5 eV that is substantially lower than PES [20]. In have been conducted using the bandpass detector so as to minimize
Fig. 2a compares the first and second scans of the IPES spectra the sample damage. The disadvantage is low-flexibility of bandpass
of hexatriacontane (n-C36 H74 ) at the incident electron density of property because the bandpass sensitivity is obtained by the com-
1.1 × 10−3 A m−2 [18]. The peak at 2.5 eV in the first scan shifts to bination of the photon-sensitive and filter materials. The center of
4 eV in the second scan demonstrating that the sample is seriously the passband is always around 10 eV, and the energy resolution is
damaged by the electron bombardment during the measurement. as high as 0.5 eV for a practical sensitivity.
Fig. 2b shows the combined UPS [21] and IPES (the energy res- For the analysis of photons in the VUV range, spectrometers have
olution is 0.8 eV) [22] spectra of copper phthalocyanine (CuPc). been also used [38–46]. However, these spectrometers were low
Apparently, the onset region is not clear in the IPES spectrum owing in the photon detection efficiency because of the low reflectivity
to the low energy resolution. of gratings in the VUV range and the small solid angel of photon
The difficulties of IPES originate from the inherently low sig- collection. The application to organic materials was thus limited to
nal intensity. The cross section of IPES is 3 or 5 orders magnitude the highly durable molecules such as fullerenes [47,48].
smaller than that of PES [23]. In order to gain a sufficient signal- Since the electron affinity of organic semiconductors mostly
to-noise ratio, an intense electron beam is introduced to a sample falls in the range between 2 and 5 eV [49,50], the energy of inci-
resulting in the sample damage. The photon is analyzed with a spe- dent electron ranges between 5 and 15 eV when the VUV photons
cially designed detector which is optimized to gain high sensitivity are detected by the bandpass photon detector. The electron beam
and lose the energy resolution [24]. in this energy range causes serious damage to organic samples.
Recently, we have developed low-energy inverse photoemi- The damage threshold of organic materials is reported to about
ssion spectroscopy (LEIPS) [25]. This new technique have solved 5 eV [51] which corresponds to the energy of covalent bonds of
the issues of the previous IPES simultaneously by using electron organic molecules. If the energy of electron is lowered below 5 eV,
beam having the kinetic energy lower than the damage threshold the sample damage is expected to be reduced. In this case, the
of organic materials. In this review, we present the principle, instru- photon energy is estimated to be less than 5 eV, i.e., the near ultra-
ments, performance of LEIPS followed by several applications to the violet range (NUV). Basically, the NUV photons can be analyzed
organic semiconductors. easier than the VUV photons leading to the higher resolution and
(a) (b)
n-C36H74 CuPc
intensity (arb. units)
2nd scan
-5 0 5 10 -3 -2 -1 0 1 2 3
E – Evac / eV E – EF / eV
Fig. 2. Spectra of the previous IPES (VUV-IPES) demonstrating that (a) organic samples are damaged during the first scan [18], and (b) the energy resolution is substantially
lower than that of ultraviolet photoemission spectroscopy (UPS) [22].
118 H. Yoshida / Journal of Electron Spectroscopy and Related Phenomena 204 (2015) 116–124
(a)
A B C D E
(b)
3
(d)
(d)
beam diameter / mm
derivative
FWHM
0.23 eV
1
Fig. 3. (a) Schematic diagram of Erdman-Zipf electron gun. (b) The beam diameter at 20 mm downstream from the exit aperture E as a function of ratio between the potential
VD of electrode D and the beam energy Vo . The solid line is a guide to the eyes. Note that VD = 4Vo is recommended in the original literature [52]. (c) The sample current on
the polycrystalline Ag thin film as a function of electron kinetic energy. (d) The first derivative of the sample current showing the energy spread of the electron beam.
Fig. 4. Schematic diagrams of the LEIPS apparatus where photons are analyzed using (a) a bandpass filter [54] and (b) a spectrometer with the Czerny–Turner configuration
[55]. (c) The earlier IPES apparatus using the spectrometer shown for comparison [38–46].
sensitivity. The two issues of previous VUV-IPES can, therefore, be 3.1. Electron source
solved simultaneously by lowering the electron energy.
For the low-energy electron source, we used an electron gun
originally designed by Erdman and Zipf [52] after modifications
3. Instruments (Fig. 3a). In order to decrease the thermal spread of electron energy,
the tungsten filament was replaced with the barium oxide (BaO)
Based on the idea described above, we have developed instru- cathode. This cathode operates at about 1100 K and the thermal
ments consisting of an electron source and a photon detector. In this spread of electron is estimated to about 0.25 eV.
section, the performance of LEIPS is also demonstrated focusing on According to the original literature, this electron gun generates
the sample damage and energy resolution. a parallel electron beam while we need to optimize the spot size
H. Yoshida / Journal of Electron Spectroscopy and Related Phenomena 204 (2015) 116–124 119
of electron beam on the sample. The photons from the sample are
focused into the photon detector using a lens as mentioned later. a
The spot size of the electron on the sample determines the object
size of the optical system while the image size is determined by
diameter of a bandpass filter or width of the entrance slit of a spec-
trometer. Considering the efficient focusing of the photons into
the photon detector, the small spot size is preferable. On the other
Fig. 7. The LEIPS spectra of the image potential state regions of HOPG (solid line) together with the transmittance curve of the bandpass filter used for the measurement
(shaded area) [57]. The transmittance of the bandfilters are (a) at the center energy of 4.38 eV with the FWHM of 0.21 eV and (b) the center energy of 4.67 eV with the FWHM
0.05 eV.
H. Yoshida / Journal of Electron Spectroscopy and Related Phenomena 204 (2015) 116–124 121
Fig. 8. a) LEIPS spectra of a 15 nm-thick PTCDA film at photon energies indicated in the panel. The film was prepared on an ITO glass by vacuum deposition. b) The onset
kinetic energy of the LUMO-derived peak is plotted against the photon energy to determine the electron affinity.
Table 1
The compiled electron affinities of typical organic semiconductors. The uncertainties are calculated statistically (see text). The thicknesses are given for the vacuum deposited
films while the concentrations and solvents are indicated in the parentheses for the spin-coated films. For substrates, ITO has device-grade flatness while ITO/SiO2 is 10 or
20 nm-thick indium tin-oxide layer formed on a quartz glass plate [25] and may have higher roughness than ITO. SiO2 is a silicon wafer covered with a native oxide layer
while HOPG stands for highly oriented pyrolytic graphite.
error of a particular sample, the electron affinities of organic films as 4.2. Relevance to organic semiconductor devices
well as the ionization energies generally vary from sample to sam-
ple by about ±0.1 eV. This is exemplified by the difference of 3.76 eV TCTA, CBP, Ir(ppy)3 , BCP, and Alq3 are standard materials for
[62] and 3.84 eV [61] in the PC61 BM data of as-prepared films. The organic light-emitting diodes (OLEDs) whose electron affinities
electron affinity depends on the structure of film. For example, the were observed in the range between 1.6 and 2.1 eV. The frequently
electron affinity of PC61 BM film decreases by 0.1–0.2 eV when the referred values for the electron affinities were determined from the
crystallinity of the film increases [62]. Further, the energy levels optical gaps and the ionization energies to be 2.4 eV [66] (TCTA),
of the crystalline organic films depend on the molecular orienta- 3.0 eV [67] (CBP), 3.0 eV [67] (Ir(ppy)3 ), 3.2 eV [67] (BCP) and 3.3 eV
tion [4]. This is clearly demonstrated by the difference in electron [67] (Alq3 ). These values are by about 1 eV larger than that deter-
affinities of pentacene, 2.35 eV for the standing orientation, 2.70 eV mined by LEIPS. A modern OLED consists of multilayers and the
for the disordered film and 3.14 eV for the lying orientation. The energy level alignment between the layers are crucial to increase
orientation dependent electron affinities of perfluoropentacene, the efficiency and decrease the operation voltage. Such large dis-
picene, ␣-sexithiophene (6T) will be reported elsewhere [60,65]. crepancies in the electron affinities urge reconsideration of the
122 H. Yoshida / Journal of Electron Spectroscopy and Related Phenomena 204 (2015) 116–124
Voc = Id − Aa − ,
the commercially available devices. The LEIPS will be widely used [27] G. Denninger, V. Dose, H. Scheidt, VUV isochromat spectrometer for surface-
as a standard analytical method for organic electronics. analysis, Appl. Phys. 18 (1979) 375–380.
[28] V. Dose, T. Fauster, R. Schneider, Improved resolution in VUV isochromat spec-
troscopy, Appl. Phys. A-Mater. Sci. Process. 40 (1986) 203–207.
[29] D. Funnemann, H. Merz, 10 eV photon detector for inverse photoemission, J.
Acknowledgements Phys. E-Sci. Instrum. 19 (1986) 554–557.
[30] J.A. Lipton-Duffin, A.G. Mark, A.B. McLean, Photon detection with n-propanol
and C2 H6 O isomers, Rev. Sci. Instrum. 73 (2002) 3149–3153.
The author thanks Mr. Yamada, Dr. Richard Murdey, and Profes-
[31] J.A. Lipton-Duffin, A.G. Mark, G.K. Mullins, G.E. Contant, A.B. McLean, An inverse
sor Naoki Sato of Kyoto University for helpful discussion. This work photoemission system with large solid angle of detection and adjustable optical
is supported by JST PRESTO, JST A-STEP, JST ALCA and JSPS KAKENHI bandpass, Rev. Sci. Instrum. 75 (2004) 445–454.
(Grant number 26288007). [32] R. Stiepel, R. Ostendorf, C. Benesch, H. Zacharias, Vacuum ultraviolet photon
detector with improved resolution for inverse photoemission spectroscopy,
Rev. Sci. Instrum. 76 (2005) 063109.
[33] M. Budke, V. Renken, H. Liebl, G. Rangelov, M. Donath, Inverse photoemi-
References ssion with energy resolution better than 200 meV, Rev. Sci. Instrum. 78 (2007)
083903.
[1] H. Ishii, K. Sugiyama, E. Ito, K. Seki, Energy level alignment and interfacial elec- [34] M. Maniraj, S.W. D’Souza, J. Nayak, A. Rai, S. Singh, B.N.R. Sekhar, S.R. Barman,
tronic structures at organic metal and organic organic interfaces, Adv. Mater. High energy resolution bandpass photon detector for inverse photoemission
11 (1999) 605–625. spectroscopy, Rev. Sci. Instrum. 82 (2011) 093901.
[2] S. Braun, W.R. Salaneck, M. Fahlman, Energy-level alignment at organic/metal [35] N. Babbe, W. Drube, I. Schafer, M. Skibowski, A simple and compact system for
and organic/organic interfaces, Adv. Mater. 21 (2009) 1450–1472. combined angular resolved inverse photoemission and photoemission in the
[3] N. Ueno, S. Kera, Electron spectroscopy of functional organic thin films: deep vacuum ultraviolet, J. Physi. E Sci. Instrum. 18 (1985) 158–160.
insights into valence electronic structure in relation to charge transport prop- [36] H. Namatame, M. Tamura, M. Nakatake, H. Sato, Y. Ueda, M. Taniguchi, M. Fuji-
erty, Prog. Surf. Sci. 83 (2008) 490–557. sawa, High-resolution band-pass photon detector for inverse-photoemission
[4] S. Duhm, G. Heimel, I. Salzmann, H. Glowatzki, R.L. Johnson, A. Vollmer, J.P. spectroscopy, J. Electron Spectrosc. Relat. Phenom. 80 (1996) 393–396.
Rabe, N. Koch, Orientation-dependent ionization energies and interface dipoles [37] F. Schedin, G. Thornton, R.I.G. Uhrberg, Windows and photocathodes for a high
in ordered molecular assemblies, Nat. Mater. 7 (2008) 326–332. resolution solid state bandpass ultraviolet photon detector for inverse photo-
[5] K. Seki, K. Kanai, Development of experimental methods for determining the emission, Rev. Sci. Instrum. 68 (1997) 41–46.
electronic structure of organic materials, Mol. Cryst. Liquid Cryst. 455 (2006) [38] G. Chauvet, R. Baptist, Inverse photoemission spectrometer in the range
145–181. 20–100 eV, J. Electron Spectrosc. Relat. Phenom. 24 (1981) 255–265.
[6] H. Yoshida, Measuring the electron affinity of organic solids: an indispensable [39] T. Fauster, F.J. Himpsel, J.J. Donelon, A. Marx, Spectrometer for momentum-
new tool for organic electronics, Anal. Bioanal. Chem. 406 (2014) 2231–2237. resolved Bremsstrahlung spectroscopy, Rev. Sci. Instrum. 54 (1983) 68–75.
[7] A. Otto, K.H. Frank, B. Reihl, Inverse photoemission of pyridine on silver(111), [40] T. Fauster, D. Straub, J.J. Donelon, D. Grimm, A. Marx, F.J. Himpsel,
Surf. Sci. 163 (1985) 140–152. Normal-incidence grating spectrograph with large acceptance for inverse pho-
[8] K.H. Frank, R. Dudde, E.E. Koch, Electron-affinity levels of benzene and azaben- toemission, Rev. Sci. Instrum. 56 (1985) 1212–1214.
zenes on Cu(111) and Au(110) revealed by inverse photoemission, Chem. Phys. [41] P.D. Johnson, S.L. Hulbert, R.F. Garrett, M.R. Howells, Normal incidence grat-
Lett. 132 (1986) 83–87. ing spectrometer designed for inverse photoemission-studies in the range
[9] K.H. Frank, P. Yannoulis, R. Dudde, E.E. Koch, Unoccupied molecular-orbitals 10–30 eV, Rev. Sci. Instrum. 57 (1986) 1324–1328.
of aromatic-hydrocarbons adsorbed on Ag(111), J. Chem. Phys. 89 (1988) [42] P.T. Andrews, Inverse photoemission, Vacuum 38 (1988) 257–260.
7569–7576. [43] Y. Gao, M. Grioni, B. Smandek, J.H. Weaver, T. Tyrie, Inverse photoemission
[10] P. Yannoulis, K.H. Frank, E.E. Koch, Electronic-structure and orientation of spectrometer for interface studies, J. Phys. E Sci. Instrum. 21 (1988) 489–494.
anthracene on Ag(111), Surf. Sci. 241 (1991) 325–334. [44] M. Sancrotti, L. Braicovich, C. Chemelli, F. Ciccacci, E. Puppin, G. Trezzi, E.
[11] R. Dudde, B. Reihl, Complete electronic-structure of oriented films of hexatria- Vescovo, Ultraviolet inverse photoemission spectrograph with parallel mul-
contane, Chem. Phys. Lett. 196 (1992) 91–96. tichannel isochromat acquisition, Rev. Sci. Instrum. 62 (1991) 639–642.
[12] Y. Hirose, C.I. Wu, V. Aristov, P. Soukiassian, A. Kahn, Chemistry and electronic [45] T.E. Ollonqvist, I.J. Vayrynen, Normal incidence grating spectrometer for
properties of metal contacts on an organic molecular semiconductor, Appl. Surf. inverse-photoemission, Vacuum 46 (1995) 1177–1180.
Sci. 113 (1997) 291–298. [46] L. Kipp, M. Boehme, H. Carstensen, R. Claessen, M. Skibowski, Compact grating
[13] C.I. Wu, Y. Hirose, H. Sirringhaus, A. Kahn, Electron–hole interaction energy spectrometer for inverse photoemission spectroscopy, Rev. Sci. Instrum. 68
in the organic molecular semiconductor PTCDA, Chem. Phys. Lett. 272 (1997) (1997) 2144–2148.
43–47. [47] M.B. Jost, N. Troullier, D.M. Poirier, J.L. Martins, J.H. Weaver, L.P.F. Chibante,
[14] N. Sato, H. Yoshida, K. Tsutsumi, Photoemission and inverse photoemission R.E. Smalley, Band dispersion and empty electronic states in solid C60 – inverse
studies on a thin film of N,N -dimethylperylene-3,4,9,10-bis(dicarboximide), J. photoemission and theory, Phys. Rev. B 44 (1991) 1966–1969.
Electron Spectrosc. Relat. Phenom. 88 (1998) 861–865. [48] M.B. Jost, P.J. Benning, D.M. Poirier, J.H. Weaver, L.P.F. Chibante, R.E. Smalley,
[15] M. Gorgoi, W. Michaelis, T.U. Kampen, D. Schlettwein, D.R.T. Zahn, Thickness Occupied and unoccupied electronic states of solid C70 with comparison to C60 ,
dependence of the LUMO position for phthalocyanines on hydrogen passivated Chem. Phys. Lett. 184 (1991) 423–427.
silicon (111), Appl. Surf. Sci. 234 (2004) 138–143. [49] A. Kahn, N. Koch, W.Y. Gao, Electronic structure and electrical properties of
[16] S. Krause, M.B. Casu, A. Scholl, E. Umbach, Determination of transport levels of interfaces between metals and pi-conjugated molecular films, J. Polym. Sci. B
organic semiconductors by UPS and IPS, New J. Phys. 10 (2008) 085001. Polym. Phys. 41 (2003) 2529–2548.
[17] T. Nishi, T. Iwahashi, H. Yamane, Y. Ouchi, K. Kanai, K. Seki, Electronic struc- [50] P.I. Djurovich, E.I. Mayo, S.R. Forrest, M.E. Thompson, Measurement of the
tures of ionic liquids [Cn mim]+ BF4 − and [Cn mim]+ PF6 − studied by ultraviolet lowest unoccupied molecular orbital energies of molecular organic semi-
photoemission, inverse photoemission, and near-edge X-ray absorption fine conductors, Org. Electron. 10 (2009) 515–520.
structure spectroscopies, Chem. Phys. Lett. 455 (2008) 213–217. [51] B. Boudaiffa, P. Cloutier, D. Hunting, M.A. Huels, L. Sanche, Resonant formation
[18] K. Tsutsumi, H. Yoshida, N. Sato, Unoccupied electronic states in a hexatria- of DNA strand breaks by low-energy (3 to 20 eV) electrons, Science 287 (2000)
contane thin film studied by inverse photoemission spectroscopy, Chem. Phys. 1658–1660.
Lett. 361 (2002) 367–373. [52] P.W. Erdman, E.C. Zipf, Low-voltage, high-current electron-gun, Rev. Sci.
[19] Z. Li, S.Q. Sun, X. Li, R. Schlaf, The impact of inverse photoemission spectroscopy Instrum. 53 (1982) 225–227.
measurements on regioregular poly(3-hexylthiophene) films, Appl. Phys. Lett. [53] N.G. Stoffel, P.D. Johnson, A low-energy high-brightness electron-gun for
104 (2014) 021606. inverse photoemission, Nucl. Instrum. Methods Phys. Res. Sect. A-Accel. Spec-
[20] D.R.T. Zahn, G.N. Gavrila, M. Gorgoi, The transport gap of organic semi- trom. Dect. Assoc. Equip. 234 (1985) 230–234.
conductors studied using the combination of direct and inverse photoemission, [54] H. Yoshida, Note: low energy inverse photoemission spectroscopy apparatus,
Chem. Phys. 325 (2006) 99–112. Rev. Sci. Instrum. 85 (2014) 016101.
[21] R. Murdey, N. Sato, M. Bouvet, Frontier electronic structures in fluorinated [55] H. Yoshida, Low-energy inverse photoemission spectroscopy using a high-
copper phthalocyanine thin films studied using ultraviolet and inverse pho- resolution grating spectrometer in the near ultraviolet range, Rev. Sci. Instrum.
toemission spectroscopies, Mol. Cryst. Liquid Cryst. 455 (2006) 211–218. 84 (2013) 103901.
[22] H. Yoshida, K. Tsutsumi, N. Sato, Unoccupied electronic states of 3d-transition [56] L. Reimer, in: P.W. Hawkes (Ed.), Transmission Electron Microscopy: Physics
metal phthalocyanines (MPc: M = Mn, Fe, Co, Ni, Cu and Zn) studied by inverse of Image Formation and Microanalysis, Springer Series in Optical Sciences,
photoemission spectroscopy, J. Electron Spectrosc. Relat. Phenom. 121 (2001) Springer, Berlin, 1997.
83–91. [57] K. Yamada, Study on orientation dependence of electronic states investigated
[23] J.B. Pendry, New probe for unoccupied bands at surfaces, Phys. Rev. Lett. 45 as a solid effect on electronic structure of organic semiconductor films: con-
(1980) 1356–1358. trolling the molecular orientation and precise determination of the electron
[24] V. Dose, VUV isochromat spectroscopy, Appl. Phys. 14 (1977) 117–118. affinities using low-energy inverse photoemission spectroscopy (Master the-
[25] H. Yoshida, Near-ultraviolet inverse photoemission spectroscopy using ultra- sis), Graduate School of Science, Kyoto University, Kyoto, 2015 (in Japanese).
low energy electrons, Chem. Phys. Lett. 539–540 (2012) 180–185. [58] H. Yoshida, K. Yoshizaki, Electron affinities of organic materials used for organic
[26] J.K. Lang, Y. Baer, Bremsstrahlung isochromat spectroscopy using a modified light-emitting diodes: a low-energy inverse photoemission study, Org. Elec-
XPS apparatus, Rev. Sci. Instrum. 50 (1979) 221–226. tron. 20 (2015) 24–30.
124 H. Yoshida / Journal of Electron Spectroscopy and Related Phenomena 204 (2015) 116–124
[59] W. Han, H. Yoshida, N. Ueno, S. Kera, Electron affinity of pentacene thin film [67] C. Adachi, R. Kwong, S.R. Forrest, Efficient electrophosphorescence using a
studied by radiation-damage free inverse photoemission spectroscopy, Appl. doped ambipolar conductive molecular organic thin film, Org. Electron. 2
Phys. Lett. 103 (2013) 123303. (2001) 37–43.
[60] H. Yoshida, K. Yamada, J. Tsutsumi, N. Sato, A complete description of ioniza- [68] C.J. Brabec, A. Cravino, D. Meissner, N.S. Sariciftci, T. Fromherz, M.T. Rispens, L.
tion energy and electron affinity in organic solids: determining contributions Sanchez, J.C. Hummelen, Origin of the open circuit voltage of plastic solar cells,
from electronic polarization, energy band dispersion and molecular orienta- Adv. Funct. Mater. 11 (2001) 374–380.
tion, Phys. Rev. B, in press. [69] Y. Ie, M. Karakawa, S. Jinnai, H. Yoshida, A. Saeki, S. Seki, S. Yamamoto, H. Ohkita,
[61] H. Yoshida, Low-energy inverse photoemission study on the electron affini- Y. Aso, Electron-donor function of methanofullerenes in donor-acceptor bulk
ties of fullerene derivatives for organic photovoltaic cells, J. Phys. Chem. C 118 heterojunction systems, Chem. Comm. 50 (2014) 4123–4125.
(2014) 24377–24382. [70] N. Sato, K. Seki, H. Inokuchi, Polarization energies of organic-solids determined
[62] Y.F. Zhong, S. Izawa, K. Hashimoto, K. Tajima, T. Koganezawa, H. Yoshida, by ultraviolet photoelectron-spectroscopy, J. Chem. Soc. Faraday Trans. 2 (77)
Crystallization-induced energy level change of 6,6-phenyl C-61-butyric acid (1981) 1621–1633.
methyl ester (PCBM) film: impact of electronic polarization energy, J. Phys. [71] Q. Wei, K. Tajima, Y. Tong, S. Ye, K. Hashimoto, Surface-segregated mono-
Chem. C 119 (2015) 23–28. layers: a new type of ordered monolayer for surface modification of organic
[63] N. Zhou, M.-G. Kim, S. Loser, J. Smith, H. Yoshida, X. Guo, C.K. Song, H. Jin, Z. semiconductors, J. Am. Chem. Soc. 131 (2009) 17597–17604.
Chen, S.M. Yoon, A.J. Freeman, R.P.H. Chang, A. Facchetti, T.J. Marks, Amorphous [72] Y. Geng, Q. Wei, K. Hashimoto, K. Tajima, Dipole layer formation by sur-
oxide alloys as interfacial layers with broadly tunable electronic structures for face segregation of regioregular poly(3-alkylthiophene) with alternating
organic photovoltaic cells, Proc. Natl. Acad. Sci. U. S. A. 112 (2015) 7897–7902. alkyl/semifluoroalkyl side chains, Chem. Mater. 23 (2011) 4257–4263.
[64] J. Hwang, A. Wan, A. Kahn, Energetics of metal-organic interfaces: new exper- [73] W. Gao, A. Kahn, Controlled p-doping of zinc phthalocyanine by coevaporation
iments and assessment of the field, Mater. Sci. Eng. R-Rep. 64 (2009) 1–31. with tetrafluorotetracyanoquinodimethane: a direct and inverse photoemi-
[65] K. Yamada, R. Shiraishi, K. Nakao, R. Murdey, N. Sato, R. Makino, Y. Suda, K. ssion study, Appl. Phys. Lett. 79 (2001) 4040.
Yonezawa, T. Yamaguchi, S. Kera, H. Yoshida, A method to evaluate accurate val- [74] Y. Zhong, S. Izawa, K. Hashimoto, K. Tajima, T. Koganezawa, H. Yoshida,
ues of the ionization energy and electron affinity of an organic semiconductor Crystallization-induced energy level change of [6,6]-phenyl-C61-butyric acid
from the electrochemical oxidation and reduction potentials of its compo- methyl ester (PCBM) film: impact of electronic polarization energy, J. Phys.
nent molecule: correction for the electrostatic energy (2015) (submitted for Chem. C 119 (2015) 23–28.
publication). [75] W.N. Han, K. Yonezawa, R. Makino, K. Kato, A. Hinderhofer, R. Murdey,
[66] S.H. Kim, J. Jang, J.Y. Lee, Relationship between host energy levels and device R. Shiraishi, H. Yoshida, N. Sato, N. Ueno, S. Kera, Quantitatively identical
performances of phosphorescent organic light-emitting diodes with triplet orientation-dependent ionization energy and electron affinity of diindenop-
mixed host emitting structure, Appl. Phys. Lett. 91 (2007) 083511. erylene, Appl. Phys. Lett. 103 (2013) 253301.