Robust Dipolar Layers between Organic Semiconductors and Silver for Energy-Level Alignment

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Main Authors: Krajňák, Tomáš, Stará, Veronika, Procházka, Pavel, Planer, Jakub, Skála, Tomáš, Blatnik, Matthias, Čechal, Jan
Format: Preprint
Published: 2023
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author Krajňák, Tomáš
Stará, Veronika
Procházka, Pavel
Planer, Jakub
Skála, Tomáš
Blatnik, Matthias
Čechal, Jan
author_facet Krajňák, Tomáš
Stará, Veronika
Procházka, Pavel
Planer, Jakub
Skála, Tomáš
Blatnik, Matthias
Čechal, Jan
contents The interface between a metal electrode and an organic semiconductor (OS) layer has a defining role in the properties of the resulting device. To obtain a desired performance, interlayers are introduced to modify the adhesion and growth of OS and enhance the efficiency of charge transport through the interface. However, the employed interlayers face common challenges, including a lack of electric dipoles to tune the mutual position of energy levels, being too thick for efficient electronic transport, or being prone to intermixing with subsequently deposited OS layers. Here, we show that monolayers of 1,3,5-tris(4 carboxyphenyl)benzene (BTB) with fully deprotonated carboxyl groups on silver substrates form a compact layer resistant to intermixing while mediating energy level alignment and showing a large insensitivity to substrate termination. Employing a combination of surface-sensitive techniques, i.e., low-energy electron microscopy and diffraction, X-ray photoelectron spectroscopy, and scanning tunneling microscopy, we have comprehensively characterized the compact layer and proven its robustness against mixing with the subsequently deposited organic semiconductor layer. DFT calculations show that the robustness arises from a strong interaction of carboxylate groups with the Ag surface, and thus, the BTB in the first layer is energetically favored. Synchrotron radiation photoelectron spectroscopy shows that this layer displays considerable electrical dipoles that can be utilized for work function engineering and electronic alignment of molecular frontier orbitals with respect to the substrate Fermi level. Our work thus provides a widely applicable molecular interlayer and general insights necessary for engineering of charge injection layers for efficient organic electronics.
format Preprint
id arxiv_https___arxiv_org_abs_2312_08233
institution arXiv
publishDate 2023
record_format arxiv
spellingShingle Robust Dipolar Layers between Organic Semiconductors and Silver for Energy-Level Alignment
Krajňák, Tomáš
Stará, Veronika
Procházka, Pavel
Planer, Jakub
Skála, Tomáš
Blatnik, Matthias
Čechal, Jan
Materials Science
The interface between a metal electrode and an organic semiconductor (OS) layer has a defining role in the properties of the resulting device. To obtain a desired performance, interlayers are introduced to modify the adhesion and growth of OS and enhance the efficiency of charge transport through the interface. However, the employed interlayers face common challenges, including a lack of electric dipoles to tune the mutual position of energy levels, being too thick for efficient electronic transport, or being prone to intermixing with subsequently deposited OS layers. Here, we show that monolayers of 1,3,5-tris(4 carboxyphenyl)benzene (BTB) with fully deprotonated carboxyl groups on silver substrates form a compact layer resistant to intermixing while mediating energy level alignment and showing a large insensitivity to substrate termination. Employing a combination of surface-sensitive techniques, i.e., low-energy electron microscopy and diffraction, X-ray photoelectron spectroscopy, and scanning tunneling microscopy, we have comprehensively characterized the compact layer and proven its robustness against mixing with the subsequently deposited organic semiconductor layer. DFT calculations show that the robustness arises from a strong interaction of carboxylate groups with the Ag surface, and thus, the BTB in the first layer is energetically favored. Synchrotron radiation photoelectron spectroscopy shows that this layer displays considerable electrical dipoles that can be utilized for work function engineering and electronic alignment of molecular frontier orbitals with respect to the substrate Fermi level. Our work thus provides a widely applicable molecular interlayer and general insights necessary for engineering of charge injection layers for efficient organic electronics.
title Robust Dipolar Layers between Organic Semiconductors and Silver for Energy-Level Alignment
topic Materials Science
url https://arxiv.org/abs/2312.08233