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

Journal Article · · Journal of Physical Chemistry. C
DOI:https://doi.org/10.1021/jp512153b· OSTI ID:1210375
 [1];  [2];  [3];  [1];  [4];  [4];  [4];  [1];  [5];  [1];  [2]
  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)
+ Show Author Affiliations

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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Interface Science: Solar Electric Materials (CISSEM)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Deutsche Forschungsgemeinschaft (DFG); National Science Foundation (NSF)
Grant/Contract Number:
SC0001084
OSTI ID:
1210375
Alternate ID(s):
OSTI ID: 1220723
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 9 Vol. 119; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (50)

Tailoring Electron-Transfer Barriers for Zinc Oxide/C 60 Fullerene Interfaces journal October 2014
Electronic Decoupling of Aromatic Molecules from a Metal by an Atomically Thin Organic Spacer journal December 2008
Alkali Metal Doped Organic Molecules on Insulators: Charge Impact on the Optical Properties journal August 2010
Transition Metal Oxides for Organic Electronics: Energetics, Device Physics and Applications journal August 2012
Defect-Driven Interfacial Electronic Structures at an Organic/Metal-Oxide Semiconductor Heterojunction journal May 2014
Interfacial Engineering of P3HT/ZnO Hybrid Solar Cells Using Phthalocyanines: A Joint Theoretical and Experimental Investigation journal April 2014
Organic Electronic Devices and Their Functional Interfaces journal July 2007
Electron Spin Resonance of Lattice Defects in Zinc Oxide journal August 1974
Modeling the optical constants of organic thin films: application to 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) journal September 2000
The lowest energy Frenkel and charge-transfer excitons in quasi-one-dimensional structures: application to MePTCDI and PTCDA crystals journal August 2000
Barrier formation at metal–organic interfaces: dipole formation and the charge neutrality level journal July 2004
The transport gap of organic semiconductors studied using the combination of direct and inverse photoemission journal June 2006
Energetics of metal–organic interfaces: New experiments and assessment of the field journal March 2009
Optical absorption spectra of ultrathin PTCDA films on gold single crystals: Charge transfer beyond the first monolayer journal December 2009
Optical and electronic interaction at metal–organic and organic–organic interfaces of ultra-thin layers of PTCDA and SnPc on noble metal surfaces journal September 2013
Electronic structure and electron dynamics at molecule?metal interfaces: implications for molecule-based electronics journal November 2004
Electronic properties of a zinc oxide surface modified by ultra-thin layers of conjugated organic molecules journal July 2005
Chemical bonding of PTCDA on Ag surfaces and the formation of interface states journal March 2006
Experimental determination of the attenuation length of electrons in organic molecular solids: The example of PTCDA journal May 2011
Defect-Induced Loss Mechanisms in Polymer–Inorganic Planar Heterojunction Solar Cells journal July 2013
Zinc Oxide as a Model Transparent Conducting Oxide: A Theoretical and Experimental Study of the Impact of Hydroxylation, Vacancies, Interstitials, and Extrinsic Doping on the Electronic Properties of the Polar ZnO (0002) Surface journal July 2012
Transparent Conducting Oxides of Relevance to Organic Electronics: Electronic Structures of Their Interfaces with Organic Layers journal September 2013
Energy Alignment, Molecular Packing, and Electronic Pathways: Zinc(II) Tetraphenylporphyrin Derivatives Adsorbed on TiO 2 (110) and ZnO(11–20) Surfaces journal November 2012
Delayed Electron Transfer through Interface States in Hybrid ZnO/Organic-Dye Nanostructures journal August 2013
Understanding Interfacial Electronic Structure and Charge Transfer: An Electrostatic Perspective journal August 2012
Free-electron-like dispersion in an organic monolayer film on a metal substrate journal November 2006
Organic semiconductor density of states controls the energy level alignment at electrode interfaces journal June 2014
Nanowire dye-sensitized solar cells journal May 2005
Universal energy-level alignment of molecules on metal oxides journal November 2011
Vertically-aligned nanostructures of ZnO for excitonic solar cells: a review journal January 2009
Optical differential reflectance spectroscopy of ultrathin epitaxial organic films journal January 2009
Modelling energy level alignment at organic interfaces and density functional theory journal January 2009
Influence of electrostatic fields on molecular electronic structure: insights for interfacial charge transfer journal January 2010
Optical differential reflectance spectroscopy on thin molecular films journal January 2012
Inverted bulk-heterojunction organic photovoltaic device using a solution-derived ZnO underlayer journal October 2006
Theoretical study of PTCDA adsorbed on the coinage metal surfaces, Ag(111), Au(111) and Cu(111) journal May 2009
Interface dipoles of organic molecules on Ag(111) in hybrid density-functional theory journal December 2013
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Determination of model-free Kramers-Kronig consistent optical constants of thin absorbing films from just one spectral measurement: Application to organic semiconductors journal November 2004
In situ differential reflectance spectroscopy of thin crystalline films of PTCDA on different substrates journal April 2005
Native point defects in ZnO journal October 2007
F4TCNQ on Cu, Ag, and Au as prototypical example for a strong organic acceptor on coinage metals journal April 2009
Metallization of ZnO ( 10 1 ¯ 0 ) by adsorption of hydrogen, methanol, and water: Angle-resolved photoelectron spectroscopy journal May 2010
Controlling the work function of ZnO and the energy-level alignment at the interface to organic semiconductors with a molecular electron acceptor journal April 2013
Influence of the Electron-Cation Interaction on Electron Mobility in Dye-Sensitized ZnO and TiO 2 Nanocrystals: A Study Using Ultrafast Terahertz Spectroscopy journal May 2010
Direct Observation of Photoinduced Bound Charge-Pair States at an Organic-Inorganic Semiconductor Interface journal June 2012
Space-Charge Transfer in Hybrid Inorganic-Organic Systems journal November 2013
Formation of Solid-State Excitons in Ultrathin Crystalline Films of PTCDA: From Single Molecules to Molecular Stacks journal August 2004
Interface Energetics and Level Alignment at Covalent Metal-Molecule Junctions: π-Conjugated Thiols on Gold journal May 2006
Impact of Bidirectional Charge Transfer and Molecular Distortions on the Electronic Structure of a Metal-Organic Interface journal December 2007

Cited By (6)

Doping-Induced Electron Transfer at Organic/Oxide Interfaces: Direct Evidence from Infrared Spectroscopy text January 2020
Hybridization-Induced Carrier Localization at the C 60 /ZnO Interface journal November 2015
The Impact of Dipolar Layers on the Electronic Properties of Organic/Inorganic Hybrid Interfaces journal May 2019
The role of initial and final states in molecular spectroscopies journal January 2019
Spectroscopy and control of near-surface defects in conductive thin film ZnO journal February 2016
Tailoring the growth and electronic structures of organic molecular thin films journal September 2019

Figures / Tables (5)

Figure 1(p. 9)figure Figure 1
Figure 2(p. 13)figure Figure 2
Table 1(p. 15)table Table 1
Figure 3(p. 16)figure Figure 3
Figure 4(p. 19)figure Figure 4

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
charge transfer
charge transport
electrodes - solar
hybridization
interfaces
molecules
oxides
solar (photovoltaic)
synthesis (novel materials)
synthesis (scalable processing)
synthesis (self-assembly)