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Uncovering The (un-)occupied Electronic Structure Of A Buried Hybrid Interface.

S. Vempati, J-C Deinert, L. Gierster, L. Bogner, C. Richter, N. Mutz, S. Blumstengel, A. Zykov, S. Kowarik, Y. Garmshausen, J. Hildebrandt, S. Hecht, J. Stähler
Published 2019 · Materials Science, Physics, Medicine

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The energy level alignment at organic/inorganic (o/i) semiconductor interfaces is crucial for any light-emitting or -harvesting functionality. Essential is the access to both occupied and unoccupied electronic states directly at the interface, which is often deeply buried underneath thick organic films and challenging to characterize. We use several complementary experimental techniques to determine the electronic structure of p -quinquephenyl pyridine (5P-Py) adsorbed on ZnO(1 0   -1 0). The parent anchoring group, pyridine, significantly lowers the work function by up to 2.9 eV and causes an occupied in-gap state (IGS) directly below the Fermi level E F. Adsorption of upright-standing 5P-Py also leads to a strong work function reduction of up to 2.1 eV and to a similar IGS. The latter is then used as an initial state for the transient population of three normally unoccupied molecular levels through optical excitation and, due to its localization right at the o/i interface, provides interfacial sensitivity, even for thick 5P-Py films. We observe two final states above the vacuum level and one bound state at around 2 eV above E F, which we attribute to the 5P-Py LUMO. By the separate study of anchoring group and organic dye combined with the exploitation of the occupied IGS for selective interfacial photoexcitation, this work provides a new pathway for characterizing the electronic structure at buried o/i interfaces.
This paper references
10.1016/J.PROGSURF.2007.03.002
Theory of two-photon photoemission spectroscopy of surfaces
H. Ueba (2007)
10.1016/J.SOLMAT.2012.07.006
Organic - Inorganic Hybrid Solar Cells: A Comparative Review
M. Wright (2012)
10.1021/jz501264x
Atomic-Scale Perspective of Ultrafast Charge Transfer at a Dye-Semiconductor Interface.
K. Siefermann (2014)
10.1126/science.1122190
Ultrafast Interfacial Proton-Coupled Electron Transfer
B. Li (2006)
10.1103/PHYSREVLETT.104.197401
Influence of the electron-cation interaction on electron mobility in dye-sensitized ZnO and TiO2 nanocrystals: a study using ultrafast terahertz spectroscopy.
H. Němec (2010)
10.1063/1.4967838
Ultrafast dynamics in solids probed by femtosecond time-resolved broadband electronic sum frequency generation
L. Foglia (2016)
10.1103/PhysRevB.91.235313
Local aspects of hydrogen-induced metallization of the ZnO(101¯0) surface
J. Deinert (2015)
10.1016/J.SURFREP.2014.09.003
Electron injection dynamics in dye-sensitized semiconductor nanocrystalline films
A. Furube (2014)
10.1021/JP306702T
Determination of the Electronic Energetics of CdTe Nanoparticle Assemblies on Au Electrodes by Photoemission, Electrochemical, and Photocurrent Studies
Y. Wang (2012)
10.1021/ACS.JPCC.6B01400
Observation of an Ultrafast Exciton Hopping Channel in Organic Semiconducting Crystals
T. Wang (2016)
10.1016/0032-3861(93)90313-Y
Crystal Structures, Phase Transitions and Energy Calculations of Poly(p-phenylene) Oligomers
K. N. Baker (1993)
10.1063/1.1839574
Breakdown of the mirror image symmetry in the optical absorption/emission spectra of oligo(para-phenylene)s.
G. Heimel (2005)
10.1103/PHYSREVB.94.125429
Free and trapped hybrid charge transfer excitons at a ZnO/small-molecule heterojunction
A. Panda (2016)
Dynamics at solid state surfaces and interfaces
U. Bovensiepen (2010)
10.1016/J.ELSPEC.2014.02.009
Formation of metal–organic interface states studied with 2PPE
Manuel Marks (2014)
10.1038/ncomms7754
Efficient light emission from inorganic and organic semiconductor hybrid structures by energy-level tuning
R. Schlesinger (2015)
10.1021/JP8101139
Effect of Anchoring Group on Electron Injection and Recombination Dynamics in Organic Dye-Sensitized Solar Cells
J. Wiberg (2009)
10.1016/0020-7381(78)80095-3
Rates of unimolecular pyridine ion decay and the heat of formation of C4H4
J. Eland (1978)
10.1002/PSSB.201090010
Inside Back Cover (Phys. Status Solidi B 6/2010)
C. Klingshirn (2010)
10.1103/PHYSREVLETT.92.127405
Five-wave-mixing spectroscopy of ultrafast electron dynamics at a si(001) surface.
C. Voelkmann (2004)
10.1063/1.430700
Temporary negative ions and electron affinities of benzene and N‐heterocyclic molecules: pyridine, pyridazine, pyrimidine, pyrazine, and s‐triazine
I. Nenner (1975)
10.1103/PHYSREVB.65.212202
Transient photoluminescence ofpara-hexaphenyl layers
E. Faulques (2002)
10.1063/1.3243851
Electronic structure at the perylene-tetracarboxylic acid dianhydride/Ag(111) interface studied with two-photon photoelectron spectroscopy.
S. Sachs (2009)
10.1021/jacs.6b03524
Revealing the Origin of Fast Electron Transfer in TiO2-Based Dye-Sensitized Solar Cells.
H. Wei (2016)
10.1016/0040-6090(95)07081-8
Structural studies of parasexiphenyl thin films: Importance of the deposition parameters
L. Athouël (1996)
10.1039/c004944c
Band-offset engineering in organic/inorganic semiconductor hybrid structures.
S. Blumstengel (2010)
10.1039/C2JM15868J
Vacuum-processable ladder-type oligophenylenes for organic–inorganic hybrid structures: synthesis, optical and electrochemical properties upon increasing planarization as well as thin film growth
B. Kobin (2012)
10.1021/ja801682u
Ultrafast electron transfer dynamics at NH3/Cu(111) interfaces: determination of the transient tunneling barrier.
J. Stähler (2008)
10.1103/PHYSREVB.87.155311
Controlling the work function of ZnO and the energy-level alignment at the interface to organic semiconductors with a molecular electron acceptor
Raphael Schlesinger (2013)
10.1016/J.RSER.2016.11.273
Zinc oxide based dye-sensitized solar cells: A review
R. Vittal (2017)
10.1080/00268976.2013.794981
Electronic structure and dynamics of quasi-2D states of vanadyl naphthalocyanine on Au(111)†
N. Ilyas (2013)
10.1021/ACS.JPCC.5B10725
Probing Electronic Structures of Organic Semiconductors at Buried Interfaces by Electronic Sum Frequency Generation Spectroscopy
Y. Li (2015)
Weinheim: Wiley-VCH) 2 115 20 Marks M, Schöll A and Höfer
M Wolf (2013)
10.1002/9783527646463
Dynamics at Solid State Surfaces and Interfaces, Vol. 2: Fundamentals
U. Bovensiepen (2012)
10.1021/JZ1016203
Optically Induced Inter- and Intrafacial Electron Transfer Probed by Two-Photon Photoemission: Electronic States of Sexithiophene on Au(111)
E. Varene (2011)
10.1038/nmat3159
Universal energy-level alignment of molecules on metal oxides.
Mark T. Greiner (2011)
10.1002/adma.201305351
Defect-driven interfacial electronic structures at an organic/metal-oxide semiconductor heterojunction.
Paul Winget (2014)
10.1002/9783527646463.CH3
Surface States and Adsorbate‐Induced Electronic Structure
T. Fauster (2012)
10.1021/nn102002x
How isolated are the electronic states of the core in core/shell nanoparticles?
Z. Xie (2011)
10.1021/JA00360A004
Chain-length dependence of electronic and electrochemical properties of conjugated systems: polyacetylene, polyphenylene, polythiophene, and polypyrrole
J. Bredas (1983)
10.1021/cr100156x
Hybrid resonant organic-inorganic nanostructures for optoelectronic applications.
V. Agranovich (2011)
10.1016/J.SUSC.2005.06.044
The electronic structure of methanol covered TiO2(110) surfaces
K. Onda (2005)
10.1063/1.1740205
Microwave Spectrum and Dipole Moment of Pyridine
Billy B. DeMore (1954)
10.1016/J.SURFREP.2004.09.002
Electronic structure and electron dynamics at molecule?metal interfaces: implications for molecule-based electronics
X. Zhu (2004)
10.1002/PSSB.200983195
65 years of ZnO research – old and very recent results
C. Klingshirn (2010)
10.1002/ADTS.201800108
Electronic and Optical Excitations at the Pyridine/ZnO(101¯0) Hybrid Interface
O. Turkina (2019)
10.1021/JP402042A
Delayed Electron Transfer through Interface States in Hybrid ZnO/Organic-Dye Nanostructures
C. Strothkaemper (2013)
Thin Solid Films
M. Ferenets (2010)
10.1103/PHYSREVB.68.125417
Angle-resolved photoelectron spectroscopy study of the anion-derived dangling-bond band on ZnO(101̄0)
K. Ozawa (2003)
10.1103/PHYSREVB.81.205322
Metallization of ZnO(101̄0) by adsorption of hydrogen, methanol, and water: Angle-resolved photoelectron spectroscopy
K. Ozawa (2010)
10.1063/1.4936759
Charge transfer excitons at ZnMgO/P3HT heterojunctions: Relation to photovoltaic performance
M. Eyer (2015)
10.1016/J.PROGSURF.2007.03.001
Ultrafast interfacial electron transfer from the excited state of anchored molecules into a semiconductor
L. Gundlach (2007)
10.1063/1.4827017
Large work function reduction by adsorption of a molecule with a negative electron affinity: pyridine on ZnO(1010).
O. Hofmann (2013)



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