Wojciech Osikowicz

The effects of solvents on the morphology and sheet resistance in poly(3,4-ethylenedioxythiophene)–polystyrenesulfonic acid (PEDOT–PSS) films

The effects of solvents on the morphology and sheet resistance in poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT-PSS) films

Photoelectron spectroscopy of thin films of PEDOT–PSS conjugated polymer blend: a mini-review and some new results

We present an overview of the photoelectron spectroscopy studies of thin films of the commercially important, electrically conducting polymer blend poly(3,4-ethylenedioxythiophene) oxidized with poly(4-styrenesulfonate), PEDOT-PSS. The issues discussed include the study of thermal effects, the influence of hydrochloric acid on the chemical and electronic structures of the films, phase segregation, as well as the energy level alignment at interfaces employing a PEDOT-PSS layer. All of these issues are important in applications of PEDOT-PSS as a hole-injecting electrode in polymer-based, light-emitting devices. Among the most important results are the identification of the three chemically different species in pristine PEDOT-PSS, namely poly(4-styrenesulfonic acid), poly(sodium 4-styrenesulfonate) and poly(3,4-ethylenedioxythiophene), the conversion of the sodium salt into free poly(styrenesulfonic acid) upon HCl treatment, and the decomposition of the free sulfonic acid component (presumably through loss of SO3H) induced by annealing. It is also shown that phase segregation occurs in the PEDOT-PSS system, resulting in a predominance of PSS in the surface region. This issue has been studied using different approaches, including X-ray photoelectron spectroscopy studies of the sulfur S(2p) and oxygen O(1s) core levels, ultraviolet photoelectron spectroscopy of the valence band region combined with reference measurements and quantum chemical calculations, as well as variable photon energy investigations of sulfur S(2p) core levels. It is demonstrated that, in the context of the energy level alignment at the polymer-metal interfaces, PEDOT-PSS shows metallic-like behavior. Due to the latter, the insertion of a thin PEDOT-PSS layer between the hole-injecting electrode ITO and a polymer layer of poly(bis-(2-dimethyloctylsilyl)-1,4-phenylenevinylene) leads to the lowering of the barrier for hole injection, independent of the work function of the underlying ITO. PEDOT-PSS is also used to show the alignment of the electrochemical potential across metal-polymer-metal structures.

Fermi-level pinning at conjugated polymer interfaces

Photoelectron spectroscopy has been used to map out energy level alignment of conjugated polymers at various organic-organic and hybrid interfaces. Specifically, we have investigated the hole-injection interface between the substrate and light-emitting polymer. Two different alignment regimes have been observed: (i) Vacuum-level alignment, which corresponds to the lack of vacuum-level offsets (Schottky–Mott limit) and (ii) Fermi-level pinning, where the substrate Fermi level and the positive polaronic level of the polymer align. The observation is rationalized in terms of spontaneous charge transfer whenever the substrate Fermi level exceeds the positive polaron/bipolaron formation energy per particle. The charge transfer leads to the formation of an interfacial dipole, as large as 2.1 eV.

From Ambi‐ to Unipolar Behavior in Discotic Dye Field‐Effect Transistors

Ambipolar, solution-processed thin-film transistors based on a discotic dye turn into unipolar behavior after thermal annealing. No evidence for temperature-induced change in injection barrier or interface trapping can be found to explain this phenomenon. Instead, a variation in morphology is considered as the cause for the observed transition from ambipolar to unipolar charge transport.

Energetics at Au top and bottom contacts on conjugated polymers

Photoelectron spectroscopy was employed to examine the energetics, and therefore charge injection barriers, at top and bottom contact configurations of gold and conjugated polymers, i.e., polymer spin coated on gold and vapor-deposited gold on polymer interfaces. Very similar results are obtained for both ex situ (contaminated) and in situ (clean) prepared interfaces: a 0.7–0.8eV decrease in the vacuum energy levels is consistently observed as compared to bare polycrystalline gold. These observations are explained by changes of the metal work function upon contacting either polymers or contaminants, associated with the reduction of the electron density tail that extends outside the metal surface.

Influence of the electrode work function on the energy level alignment at organic-organic interfaces

The energy level alignment at interfaces, in stacks comprising of (4,4′-N,N′-dicarbazolyl-biphenyl) (CBP), (4,4,4″-tris[3-methyl-phenyl(phenyl)amino]-triphenylamine) (m-MTDATA), and a conductive substrate, has been studied. We show that the alignment of energy levels depends on the equilibration of the chemical potential throughout the layer stack, while any electronic coupling between the individual layers is of lesser importance. This behavior is expected to occur for a broad class of weakly interacting interfaces and can have profound consequences for the design of organic electronic devices.

Transparent low-work-function indium tin oxide electrode obtainedby molecular scale interface engineering

A redox reaction between a monolayer of electron–donor molecules, tetrakis(dimethylamino)ethylene, and the indium tin oxide (ITO) surface results in a decrease of the ITO work function down to 3.7eV. The modified ITO surface may be used as electron injecting electrode in polymer light-emitting devices. Photoelectron spectroscopy measurements show that the low-work-function of the modified electrode remains upon exposure to air or gentle annealing; thus, making it a good candidate for inexpensive fabrication of organic/polymeric (opto)electronic devices.

Integer charge transfer at the tetrakis(dimethylamino)ethylene/Au interface

In organic-based electronics, interfacial properties have a profound impact on device performance. The lineup of energy levels is usually dependent on interface dipoles, which may arise from charge transfer reactions. In many applications, metal-organic junctions are prepared under ambient conditions, where direct overlap of the organic π system from the metal bands is prevented due to presence of oxides and/or hydrocarbons. We present direct experimental and theoretical evidence showing that the interface energetic for such systems is governed by exchange of an integer amount of electrons.

The electronic structure of n- and p-doped phenyl-capped 3,4-ethylenedioxythiophene trimer

A study was conducted on the effects of chemical doping on the chemical and electronic structure of condensed molecular solid films of the ethylenedioxythiophene (EDOT) trimer using ultraviolet pho ...

Core excitations of naphthalene: Vibrational structure versus chemical shifts

High-resolution x-ray photoelectron emission (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectra of naphthalene are analyzed in terms of the initial state chemical shifts and the vibrational fine structure of the excitations. Carbon atoms located at peripheral sites experience only a small chemical shift and exhibit rather similar charge-vibrational coupling, while the atoms in the bridging positions differ substantially. In the XPS spectra, C-H stretching modes provide important contributions to the overall shape of the spectrum. In contrast, the NEXAFS spectrum contains only vibrational progressions from particular C-C stretching modes. The accuracy of ab initio calculations of absolute electronic transition energies is discussed in the context of minute chemical shifts, the vibrational fine structure, and the state multiplicity.