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Title: Integer Charge Transfer and Hybridization at an Organic Semiconductor/Conductive Oxide Interface

Abstract

In this work we investigate the prototypical hybrid interface formed between PTCDA and conductive $$n$$-doped ZnO films by means of complementary optical and electronic spectroscopic techniques. We demonstrate that shallow donors in the vicinity of the ZnO surface cause an integer charge transfer to PTCDA, which is clearly restricted to the first monolayer. By means of DFT calculations, we show that the experimental signatures of the anionic PTCDA species can be understood in terms of strong hybridization with localized states (the shallow donors) in the substrate and charge back-donation, resulting in an effectively integer charge transfer across the interface. Charge transfer is thus not merely a question of locating the Fermi level above the PTCDA electron-transport level but requires rather an atomistic understanding of the interfacial interactions. The study reveals that defect sites and dopants can have a significant influence on the specifics of interfacial coupling and thus on carrier injection or extraction.

Authors:
 [1];  [2];  [3];  [1];  [4];  [4];  [4];  [1];  [5];  [1];  [2]
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  1. Friedrich Schiller Univ. Jena (Germany). Inst. für Festkörperphysik
  2. Univ. of Arizona, Tucson, AZ (United States)
  3. Georgia Inst. of Technology, Atlanta, GA (United States)
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  5. Georgia Inst. of Technology, Atlanta, GA (United States); King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Kingdom of Saudi Arabia)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Interface Science: Solar Electric Materials (CISSEM)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); German Research Foundation (DFG); National Science Foundation (NSF)
OSTI Identifier:
1210375
Grant/Contract Number:  
SC0001084; FR875/9-3; CHE0946869
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 119; Journal Issue: 9; Related Information: CISSEM partners with the University of Arizona (lead); Georgia Institute of Technology; National Renewable Energy Laboratory; Princeton University; University of Washington; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; solar (photovoltaic); electrodes - solar; charge transport; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing); charge transfer; oxides; interfaces; molecules; hybridization

Citation Formats

Gruenewald, Marco, Schirra, Laura K., Winget, Paul, Kozlik, Michael, Ndione, Paul F., Sigdel, Ajaya K., Berry, Joseph J., Forker, Roman, Brédas, Jean-Luc, Fritz, Torsten, and Monti, Oliver L. A. Integer Charge Transfer and Hybridization at an Organic Semiconductor/Conductive Oxide Interface. United States: N. p., 2015. Web. doi:10.1021/jp512153b.
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Gruenewald, Marco, Schirra, Laura K., Winget, Paul, Kozlik, Michael, Ndione, Paul F., Sigdel, Ajaya K., Berry, Joseph J., Forker, Roman, Brédas, Jean-Luc, Fritz, Torsten, & Monti, Oliver L. A. Integer Charge Transfer and Hybridization at an Organic Semiconductor/Conductive Oxide Interface. United States. https://doi.org/10.1021/jp512153b
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Gruenewald, Marco, Schirra, Laura K., Winget, Paul, Kozlik, Michael, Ndione, Paul F., Sigdel, Ajaya K., Berry, Joseph J., Forker, Roman, Brédas, Jean-Luc, Fritz, Torsten, and Monti, Oliver L. A. Wed . "Integer Charge Transfer and Hybridization at an Organic Semiconductor/Conductive Oxide Interface". United States. https://doi.org/10.1021/jp512153b. https://www.osti.gov/servlets/purl/1210375.
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@article{osti_1210375,
title = {Integer Charge Transfer and Hybridization at an Organic Semiconductor/Conductive Oxide Interface},
author = {Gruenewald, Marco and Schirra, Laura K. and Winget, Paul and Kozlik, Michael and Ndione, Paul F. and Sigdel, Ajaya K. and Berry, Joseph J. and Forker, Roman and Brédas, Jean-Luc and Fritz, Torsten and Monti, Oliver L. A.},
abstractNote = {In this work we investigate the prototypical hybrid interface formed between PTCDA and conductive $n$-doped ZnO films by means of complementary optical and electronic spectroscopic techniques. We demonstrate that shallow donors in the vicinity of the ZnO surface cause an integer charge transfer to PTCDA, which is clearly restricted to the first monolayer. By means of DFT calculations, we show that the experimental signatures of the anionic PTCDA species can be understood in terms of strong hybridization with localized states (the shallow donors) in the substrate and charge back-donation, resulting in an effectively integer charge transfer across the interface. Charge transfer is thus not merely a question of locating the Fermi level above the PTCDA electron-transport level but requires rather an atomistic understanding of the interfacial interactions. The study reveals that defect sites and dopants can have a significant influence on the specifics of interfacial coupling and thus on carrier injection or extraction.},
doi = {10.1021/jp512153b},
journal = {Journal of Physical Chemistry. C},
number = 9,
volume = 119,
place = {United States},
year = {2015},
month = {2}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/jp512153b
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Cited by: 51 works
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Figures / Tables:

Figure 1 Figure 1: a) Imaginary part ϵ" of the dielectric function of PTCDA on 30 nm ZnO on quartz glass for nominal thicknesses ranging from submonolayers up to 7 MLE extracted from the DRS shown in Supplementary Figure 1. For comparison ϵ" spectra of 1 MLE PTCDA on inert mica, 1more » MLE of PTCDA partially potassium-doped providing pronounced new features of PTCDA radical anions at low photon energies (investigated in detail previously), polycrystalline (pc) PTCDA and the dramatically broadened spectra of 1 MLE of PTCDA on Au(111) and Ag(111) are shown in the bottom panel. b) ΔDRS of PTCDA on quartz glass for nominal thicknesses ranging from submonolayers up to 1 MLE. The graphs are labeled according to the scheme (m +1) - m referring to eq. (2).« less
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