Abstract
In this chapter, we describe technical essences and several example works of angle-resolved photoelectron spectroscopy (ARPES) that is a surface science methodology to map out the electronic band structures of the matters. Successful results of demonstrating the valence band dispersion relations of crystalline organic semiconductor materials are introduced, which were acquired through resolution of inherent “sample charging” problems in photoelectron spectroscopy techniques. The effective mass of the valence hole and intermolecular transfer integral values of van-der-Waals molecular solids were directly derived as fundamental physical properties regulating the charge carrier transport in these solids. In addition, recent ARPES works on novel interface electronic structures of organic semiconducting molecules in contact with “quantum wells” in nanometer-thick metal thin-films are also reviewed.
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsReferences
Pope M, Swenberg CE (eds) (1999) Electronic processes in organic crystals and polymers, 2nd edn. Oxford University Press, New York
Inokuchi H (2006) The discovery of organic semiconductors. Its light and shadow. Org Electron 7(2):62–76
Eley DD (1948) Phthalocyanines as semiconductors. Nature 162(4125):819–819
Vartanyan A (1948) Semiconductor properties of organic dyes. 1. Phthalocyanines. Zhurnal Fizicheskoi Khimii 22(7):769–782
Akamatu H, Inokuchi H (1950) On the electrical conductivity of violanthrone, iso-violanthrone, and pyranthrone. J Chem Phys 18(6):810–811
Akamatu H, Inokuchi H (1952) Photoconductivity of violanthrone. J Chem Phys 20(9):1481–1482
Inokuchi H (1954) Photoconductivity of the condensed polynuclear aromatic compounds. Bull Chem Soc Jpn 27(I):22–27
Kudo K, Yamashina M, Moriizumi T (1984) Field effect measurement of organic dye films. Jpn J Appl Phys 23(1):130–130
Tang C (1986) Two-layer organic photovoltaic cell. Appl Phys Lett 48(2):183–185
Tang C, VanSlyke S (1987) Organic electroluminescent diodes. Appl Phys Lett 51(12):913–915
Hiramoto M, Fujiwara H, Yokoyama M (1991) Three-layered organic solar cell with a photoactive interlayer of codeposited pigments. Appl Phys Lett 58(10):1062–1064
Halls JJM, Walsh CA, Greenham NC, Marseglia EA, Friend RH, Moratti SC, Holmes AB (1995) Efficient photodiodes from interpenetrating polymer networks. Nature 376:498–500
Hüfner S (2003) Photoelectron spectroscopy, 3rd edn. Springer, Berlin
Grobman WD (1978) Angle-resolved photoemission from molecules in the independent-atomic-center approximation. Phys Rev B 17(12):4573–4585
Ueno N, Kitamura A, Okudaira KK, Miyamae T, Harada Y, Hasegawa S, Ishii H, Inokuchi H, Fujikawa T, Miyazaki T, Seki K (1997) Angle-resolved ultraviolet photoelectron spectroscopy of thin films of bis (1,2,5-thiadiazolo)-p-quinobis(1,3-dithiole) on the MoS2 surface. J Chem Phys 107(6):2079–2089
Nagamatsu S, Kera S, Okudaira K, Fujikawa T, Ueno N (2005) Multiple-scattering approach to angle-resolved ultraviolet photoelectron spectroscopy of large molecules. e-J Surf Sci Nanotechnol 3:461–465
Seah MP, Dench WA (1979) Quantitative electron spectroscopy of surfaces: a standard data base for electron inelastic mean free paths in solids. Surf Interface Anal 1(1):2
Nakayama Y, Kondoh H, Ohta T (2004) Structure-dependent mixed valence of Sm on Cu(111) studied by XPS and STM. Surf Sci 552(1–3):53–62
Yoshida H, Sato N (2012) A precise analysis of the core-level energy difference between the surface and bulk region of organic semiconductor thin films. J Phys Chem C 116(18):10033–10038
Yoshida H, Ito E, Hara M, Sato N (2012) Core level energy differences between the surface and bulk of organic semiconductor films: the effect of electrostatic polarization energy. Synth Met 161(23–24):2549–2553
Nakayama Y, Morii K, Suzuki Y, Machida H, Kera S, Ueno N, Kitagawa H, Noguchi Y, Ishii H (2009) Origins of improved hole-injection efficiency by the deposition of MoO3 on the polymeric semiconductor poly(dioctylfluorene-alt -benzothiadiazole). Adv Funct Mater 19(23):3746–3752
Cazaux J (1999) Mechanisms of charging in electron spectroscopy. J Electron Spectrosc Relat Phenomena 105(2–3):155–185
Ueno N, Kera S (2008) Electron spectroscopy of functional organic thin films: deep insights into valence electronic structure in relation to charge transport property. Prog Surf Sci 83(10–12):490–557
Kazda C (1925) The photo-electric threshold for mercury. Phys Rev 26(5):643–654
Morris L (1931) Certain photoelectric properties of gold. Phys Rev 37(10):1263–1268
Fowler R (1931) The analysis of photoelectric sensitivity curves for clean metals at various temperatures. Phys Rev 38(1):45–56
Sebenne C, Bolmont D, Guichar G, Balkanski M (1975) Surface states from photoemission threshold measurements on a clean, cleaved, Si (111) surface. Phys Rev B 12(8):3280–3285
Miyazaki S, Maruyama T, Kohno A, Hirose M (1999) Photoelectron yield spectroscopy of electronic states at ultrathin SiO2/Si interfaces. Microelectron Eng 48:63–66
Szuber J (2000) New procedure for determination of the interface Fermi level position for atomic hydrogen cleaned GaAs(100) surface using photoemission. Vacuum 57(2):209–217
Watanabe I (1994) Optical oxidation potential: a new measure for reducing power. Anal Sci 10:229–239
Inumaru K, Okubo Y, Fujii T, Yamanaka S (2000) Effects of organic vapour adsorption on the photoelectron emission from Au thin films in atmospheric air. Phys Chem Chem Phys 2:3681–3685
Honda M, Kanai K, Komatsu K, Ouchi Y, Ishii H, Seki K (2007) Atmospheric effect of air, N2, O2, and water vapor on the ionization energy of titanyl phthalocyanine thin film studied by photoemission yield spectroscopy. J Appl Phys 102(10):103704
Kane EO (1962) Theory of photoelectric emission from semiconductors. Phys Rev 127(1):131–141
Kochi M, Harada Y, Hirooka T, Inokuchi H (1970) Photoemission from organic crystal in vacuum ultraviolet region. IV. Bull Chem Soc Jpn 43(9):2690–2702
Nakayama Y, Machida S, Tsunami D, Kimura Y, Niwano M, Noguchi Y, Ishii H (2008) Photoemission measurement of extremely insulating materials: capacitive photocurrent detection in photoelectron yield spectroscopy. Appl Phys Lett 92(15):153306
Himpsel F, Knapp J, VanVechten J, Eastman D (1979) Quantum photoyield of diamond(111) – a stable negative-affinity emitter. Phys Rev B 20(2):624–627
Ley L, Ristein J, Meier F, Riedel M, Strobel P (2006) Surface conductivity of the diamond: a novel transfer doping mechanism. Phys B Condens Matter 376–377:262–267
Sato N, Inokuchi H, Schmid B, Karl N (1985) Ultraviolet photoemission spectra of organic single crystals. J Chem Phys 83(11):5413–5419
Vollmer A, Jurchescu OD, Arfaoui I, Salzmann I, Palstra TTM, Rudolf P, Niemax J, Pflaum J, Rabe JP, Koch N (2005) The effect of oxygen exposure on pentacene electronic structure. Eur Phys J E 17(3):339–343
Nakayama Y, Machida S, Duhm S, Xin Q, Kera S, Ishii H, Ueno N (2011) Shed laser light on the valence band structures of organic semiconductor single crystals. J Jap Laser Process Soc 18(3):202–206 [in Japanese]
Sai N, Tiago M, Chelikowsky J, Reboredo F (2008) Optical spectra and exchange-correlation effects in molecular crystals. Phys Rev B 77(16):161306
Machida S, Nakayama Y, Duhm S, Xin Q, Funakoshi A, Ogawa N, Kera S, Ueno N, Ishii H (2010) Highest-occupied-molecular-orbital band dispersion of rubrene single crystals as observed by angle-resolved ultraviolet photoelectron spectroscopy. Phys Rev Lett 104(15):156401
Nakayama Y, Uragami Y, Machida S, Koswattage KR, Yoshimura D, Setoyama H, Okajima T, Mase K, Ishii H (2012) Full picture of the valence band structure of rubrene single crystals probed by angle-resolved and excitation energy dependent photoelectron spectroscopy. Appl Phys Expr 5(11):111601
Vollmer A, Ovsyannikov R, Gorgoi M, Krause S, Oehzelt M, Lindblad A, Mårtensson N, Svensson S, Karlsson P, Lundvuist M, Schmeiler T, Pflaum J, Koch N (2012) Two dimensional band structure mapping of organic single crystals using the new generation electron energy analyzer ARTOF. J Electron Spectrosc Relat Phenomena 185(3–4):55–60
Xie W, Prabhumirashi PL, Nakayama Y, Mcgarry KA, Geier ML, Uragami Y, Mase K, Douglas CJ, Ishii H, Hersam MC, Frisbie CD (2013) Utilizing carbon nanotube electrodes to improve charge injection and transport in bis(trifluoromethyl)-dimethyl-rubrene ambipolar single crystal transistors. ACS Nano 7(11):10245–10256
Nakayama Y, Uragami Y, Yamamoto M, Machida S, Kinjo H, Mase K, Koswattage KR, Ishii H (2014) Determination of the highest occupied molecular orbital energy of pentacene single crystals by ultraviolet photoelectron and photoelectron yield spectroscopies. Jpn J Appl Phys 53(1S):01AD03
Xin Q, Duhm S, Bussolotti F, Akaike K, Kubozono Y, Aoki H, Kosugi T, Kera S, Ueno N (2012) Accessing surface brillouin zone and band structure of picene single crystals. Phys Rev Lett 108(22):226401
Hasegawa S, Mori T, Imaeda K, Tanaka S, Yamashita Y, Inokuchi H, Fujimoto H, Seki K, Ueno N (1994) Intermolecular energy-band dispersion in oriented thin films of bis(1,2,5-thiadiazolo)-p-quinobis(1,3-dithiole) by angle-resolved photoemission. J Chem Phys 100(9):6969–6974
Koch N, Vollmer A, Salzmann I, Nickel B, Weiss H, Rabe J (2006) Evidence for temperature-dependent electron band dispersion in pentacene. Phys Rev Lett 96(15):156803
Lin Y-Y, Gundlach DJ, Nelson SF, Jackson TN (1997) Stacked pentacene layer organic thin-film transistors with improved characteristics. IEEE Electron Device Lett 18(12):606–608
Kakuta H, Hirahara T, Matsuda I, Nagao T, Hasegawa S, Ueno N, Sakamoto K (2007) Electronic structures of the highest occupied molecular orbital bands of a pentacene ultrathin film. Phys Rev Lett 98(24):247601
Hatch R, Huber D, Höchst H (2009) HOMO band structure and anisotropic effective hole mass in thin crystalline pentacene films. Phys Rev B 80(8):081411(R)
Hatch RC, Huber DL, Höchst H (2010) Electron–phonon coupling in crystalline pentacene films. Phys Rev Lett 104(4):047601
Bouchoms IPM, Schoonveld WA, Vrijmoeth J, Klapwijk TM (1999) Morphology identification of the thin film phases of vacuum evaporated pentacene on SiO2 substrates. Synth Met 104(3):175–178
Yoshida H, Sato N (2008) Crystallographic and electronic structures of three different polymorphs of pentacene. Phys Rev B 77(23):235205
Ohtomo M, Suzuki T, Shimada T, Hasegawa T (2009) Band dispersion of quasi-single crystal thin film phase pentacene monolayer studied by angle-resolved photoelectron spectroscopy. Appl Phys Lett 95(12):123308
Shimada T, Suzuki T, Ohtomo M, Hasegawa T (2009) Epitaxial growth and photoelectron spectroscopy of pentacene. Hyomen Kagaku (J Surf Sci Soc Jpn) 30(1):7–10 [in Japanese]
Puschnig P, Berkebile S, Fleming AJ, Koller G, Emtsev K, Seyller T, Riley JD, Ambrosch-Draxl C, Netzer FP, Ramsey MG (2009) Reconstruction of molecular orbital densities from photoemission data. Science 326(5953):702–706
Ziroff J, Forster F, Schöll A, Puschnig P, Reinert F (2010) Hybridization of organic molecular orbitals with substrate states at interfaces: PTCDA on silver. Phys Rev Lett 104(23):233004
Sundar VC, Zaumseil J, Podzorov V, Menard E, Willett RL, Someya T, Gershenson ME, Rogers JA (2004) Elastomeric transistor stamps: reversible probing of charge transport in organic crystals. Science 303(5664):1644–1646
Takeya J, Yamagishi M, Tominari Y, Hirahara R, Nakazawa Y, Nishikawa T, Kawase T, Shimoda T, Ogawa S (2007) Very high-mobility organic single-crystal transistors with in-crystal conduction channels. Appl Phys Lett 90(10):102120
Käfer D, Ruppel L, Witte G, Wöll C (2005) Role of molecular conformations in rubrene thin film growth. Phys Rev Lett 95(16):166602
Nakayama Y, Machida S, Minari T, Tsukagoshi K, Noguchi Y, Ishii H (2008) Direct observation of the electronic states of single crystalline rubrene under ambient condition by photoelectron yield spectroscopy. Appl Phys Lett 93(17):173305
Sato N, Seki K, Inokuchi H (1981) Polarization energies of organic solids determined by ultraviolet photoelectron spectroscopy. J Chem Soc Faraday Trans 2(77):1621–1633
Wang L, Chen S, Liu L, Qi D, Gao X, Wee ATS (2007) Thickness-dependent energy level alignment of rubrene adsorbed on Au(111). Appl Phys Lett 90(13):132121
Fukagawa H, Yamane H, Kataoka T, Kera S, Nakamura M, Kudo K, Ueno N (2006) Origin of the highest occupied band position in pentacene films from ultraviolet photoelectron spectroscopy: hole stabilization versus band dispersion. Phys Rev B 73(24):245310
Duhm S, Heimel G, Salzmann I, Glowatzki H, Johnson RL, Vollmer A, Rabe JP, Koch N (2008) Orientation-dependent ionization energies and interface dipoles in ordered molecular assemblies. Nat Mater 7(4):326–332
Duhm S, Xin Q, Hosoumi S, Fukagawa H, Sato K, Ueno N, Kera S (2012) Charge reorganization energy and small polaron binding energy of rubrene thin films by ultraviolet photoelectron spectroscopy. Adv Mater 24(7):901–905
Da Silva Filho DA, Kim E-G, Brédas J-L (2005) Transport properties in the rubrene crystal: electronic coupling and vibrational reorganization energy. Adv Mater 17(8):1072–1076
Li ZQ, Podzorov V, Sai N, Martin MC, Gershenson ME, Di Ventra M, Basov DN (2007) Light quasiparticles dominate electronic transport in molecular crystal field-effect transistors. Phys Rev Lett 99(1):016403
Coropceanu V, Cornil J, da Silva Filho DA, Olivier Y, Silbey R, Brédas J-L (2007) Charge transport in organic semiconductors. Chem Rev 107(4):926–952
Troisi A (2007) Prediction of the absolute charge mobility of molecular semiconductors: the case of rubrene. Adv Mater 19(15):2000–2004
Girlando A, Grisanti L, Masino M, Bilotti I, Brillante A, Della Valle R, Venuti E (2010) Peierls and holstein carrier-phonon coupling in crystalline rubrene. Phys Rev B 82(3):035208
Kera S, Yamane H, Ueno N (2009) First-principles measurements of charge mobility in organic semiconductors: valence hole–vibration coupling in organic ultrathin films. Prog Surf Sci 84(5–6):135–154
Hulea IN, Fratini S, Xie H, Mulder CL, Iossad NN, Rastelli G, Ciuchi S, Morpurgo AF (2006) Tunable Fröhlich polarons in organic single-crystal transistors. Nat Mater 5(12):982–986
Hsieh D, Qian D, Wray L, Xia Y, Hor YS, Cava RJ, Hasan MZ (2008) A topological Dirac insulator in a quantum spin hall phase. Nature 452(7190):970–974
Fleurence A, Friedlein R, Ozaki T, Kawai H, Wang Y, Yamada-Takamura Y (2012) Experimental evidence for epitaxial silicene on diboride thin films. Phys Rev Lett 108(24):245501
Chen P, Wu X, Sun X, Lin J, Ji W, Tan K (1999) Electronic structure and optical limiting behavior of carbon nanotubes. Phys Rev Lett 82(12):2548–2551
Ago H, Kugler T, Cacialli F, Salaneck WR, Shaffer MSP, Windle AH, Friend RH (1999) Work functions and surface functional groups of multiwall carbon nanotubes. J Phys Chem B 103(38):8116–8121
Himpsel FJ, Altmann KN, Crain JN, Kirakosian A, Lin J-L, Liebsch A, Zhukov VP (2002) Photoelectron spectroscopy of atomic wires. J Electron Spectrosc Relat Phenomena 126(1):89–99
Colvin V, Alivisatos A, Tobin J (1991) Valence-band photoemission from a quantum-dot system. Phys Rev Lett 66(21):2786–2789
Konchenko A, Nakayama Y, Matsuda I, Hasegawa S, Nakamura Y, Ichikawa M (2006) Quantum confinement observed in Ge nanodots on an oxidized Si surface. Phys Rev B 73(11):113311
Nakayama Y, Matsuda I, Hasegawa S, Ichikawa M (2006) Quantum regulation of Ge nanodot state by controlling barrier of the interface layer. Appl Phys Lett 88(25):253102
Nakayama Y, Matsuda I, Hasegawa S, Ichikawa M (2008) Growth, quantum confinement and transport mechanisms of Ge nanodot arrays formed on a SiO2 monolayer. e-J Surf Sci Nanotechnol 6(August):191–201
Chiang T-C (2000) Photoemission studies of quantum well states in thin films. Surf Sci Rep 39(7):181–235
Matsuda I, Tanikawa T, Hasegawa S, Yeom HW, Tono K, Ohta T (2004) Quantum-well states in ultra-thin metal films on semiconductor surfaces. e-J Surf Sci Nanotechnol 2(May):169–177
Kim J, Qin S, Yao W, Niu Q, Chou MY, Shih C-K (2010) Quantum size effects on the work function of metallic thin film nanostructures. Proc Natl Acad Sci U S A 107(29):12761–12765
Aballe L, Barinov A, Locatelli A, Heun S, Kiskinova M (2004) Tuning surface reactivity via electron quantum confinement. Phys Rev Lett 93(19):196103
Miyata N, Horikoshi K, Hirahara T, Hasegawa S, Wei C, Matsuda I (2008) Electronic transport properties of quantum-well states in ultrathin Pb(111) films. Phys Rev B 78(24):245405
Guo Y, Zhang Y-F, Bao X-Y, Han T-Z, Tang Z, Zhang L-X, Zhu W-G, Wang EG, Niu Q, Qiu ZQ, Jia J-F, Zhao Z-X, Xue Q-K (2004) Superconductivity modulated by quantum size effects. Science 306(5703):1915–1917
Tang S-J, Lee Y-R, Chang S-L, Miller T, Chiang T-C (2006) Umklapp-mediated quantization of electronic states in Ag films on Ge(111). Phys Rev Lett 96(21):216803
Lin M-K, Nakayama Y, Wang C-Y, Hsu J-C, Pan C-H, Machida S, Pi T-W, Ishii H, Tang S-J (2012) Interfacial properties at the organic-metal interface probed using quantum well states. Phys Rev B 86(15):155453
Yoshimura D, Ishii H, Ouchi Y, Ito E, Miyamae T, Hasegawa S, Okudaira KK, Ueno N, Seki K (1999) Angle-resolved ultraviolet photoelectron spectroscopy and theoretical simulation of a well-ordered ultrathin film of tetratetracontane (n-C44H90) on Cu(100). Phys Rev B 60(12):9046–9060
Forster F, Hüfner S, Reinert F (2004) Rare gases on noble-metal surfaces: an angle-resolved photoemission study with high energy resolution. J Phys Chem B 108(38):14692–14698
Nakayama Y, Lin M-K, Wang C-Y, Pi T-W, Ishii H, Tang S-J (2012) Interface electronic structure of zinc-phthalocyanine on the silver thin-film quantum-well. e-J Surf Sci Nanotechnol 10:149–152
Häming M, Scheuermann C, Schöll A, Reinert F, Umbach E (2009) Coverage dependent organic–metal interaction studied by high-resolution core level spectroscopy: SnPc (sub)monolayers on Ag(111). J Electron Spectrosc Relat Phenomena 174(1–3):59–64
Gargiani P, Angelucci M, Mariani C, Betti MG (2010) Metal-phthalocyanine chains on the Au(110) surface: interaction states versus d-metal states occupancy. Phys Rev B 81(8):085412
Kröger I, Stadtmüller B, Stadler C, Ziroff J, Kochler M, Stahl A, Pollinger F, Lee T-L, Zegenhagen J, Reinert F, Kumpf C (2010) Submonolayer growth of copper-phthalocyanine on Ag(111). New J Phys 12(8):083038
Giovanelli L, Amsalem P, Angot T, Petaccia L, Gorovikov S, Porte L, Goldoni A, Themlin J-M (2010) Valence band photoemission from the Zn-phthalocyanine/Ag(110) interface: charge transfer and scattering of substrate photoelectrons. Phys Rev B 82(12):125431
Lin M-K, Nakayama Y, Chen C-H, Wang C-Y, Jeng H-T, Pi T-W, Ishii H, Tang S-J (2013) Tuning gap states at organic-metal interfaces via quantum size effects. Nat Commun 4:2925
Ishiyama N, Kubo M, Kaji T, Hiramoto M (2013) Tandem organic solar cells formed in co-deposited films by doping. Org Electron 14(7):1793–1796
Yamane H, Kosugi N (2013) Substituent-induced intermolecular interaction in organic crystals revealed by precise band-dispersion measurements. Phys Rev Lett 111(8):086602
Nakayama Y, Niederhausen J, Machida S, Uragami Y, Kinjo H, Vollmer A, Rabe JP, Koch N, Ishii H (2013) Valence band structure of rubrene single crystals in contact with an organic gate dielectric. Org Electron 14(7):1825–1832
Yoshida H (2012) Near-ultraviolet inverse photoemission spectroscopy using ultra-low energy electrons. Chem Phys Lett 539–540:180–185
Yamamoto M, Terui T, Ueda R, Imazu K, Tamada K, Sakano T, Matsuda K, Ishii H, Noguchi Y (2012) Photoinduced conductance switching in a dye-doped gold nanoparticle transistor. Appl Phys Lett 101(2):023103
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2015 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Nakayama, Y., Ishii, H. (2015). Exploration into the Valence Band Structures of Organic Semiconductors by Angle-Resolved Photoelectron Spectroscopy. In: Kumar, C.S.S.R. (eds) Surface Science Tools for Nanomaterials Characterization. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-44551-8_10
Download citation
DOI: https://doi.org/10.1007/978-3-662-44551-8_10
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-662-44550-1
Online ISBN: 978-3-662-44551-8
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)