William R. Salaneck

Electroluminescence in conjugated polymers

Research in the use of organic polymers as the active semiconductors in light-emitting diodes has advanced rapidly, and prototype devices now meet realistic specifications for applications. These achievements have provided insight into many aspects of the background science, from design and synthesis of materials, through materials fabrication issues, to the semiconductor physics of these polymers.

Indium–tin oxide treatments for single- and double-layer polymeric light-emitting diodes: The relation between the anode physical, chemical, and morphological properties and the device performance

We report combined studies of the influence of chemical and physical treatments on the properties of indium–tin oxide (ITO) thin films. The ITO films were also used as transparent anodes of polymeric light-emitting diodes (LEDs) incorporating poly(p-phenylene vinylene) (PPV) as the emitter material, with, or without, doped poly(3,4-ethylene dioxythiophene) (PEDOT) as a hole-injection/transport layer. Structures based on a soluble green derivative of PPV, poly(4,4′-diphenylene diphenylvinylene) were also tested. We studied chemical (aquaregia, degreasing, RCA protocol) and physical (oxygen and argon plasmas, Teflon, and paper rubbing) treatments and, in contrast to recently published work, we find that for Balzer Baltracon ITO, oxygen plasma and not aquaregia yields the highest efficiencies and luminances and the lowest drive voltages. For oxygen-plasma-treated anodes, the device efficiency clearly correlates with the value of the ITO surface work function, which in turn depends on the time of treatment. I...

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

Thermochromic and solvatochromic effects in poly(3-hexylthiophene)

Abstract We report thermochromic and solvatochromic effects in the soluble conductive polymer poly(3-hexylthiophene). Thin solid films of the polymer change colour at higher temperatures. The colour of solutions of the polymer can be changed by varying the composition of the solvent. Optical absorption in good solvents is similar to that of thin solid films at higher temperatures, while in poor solvents, absorption features similar to those found in solid films at low temperatures are observed. We discuss these effects with reference to the existence of a hitherto disregarded type of conformational defect, conformons. These are rotational defects on the polymer chain, leading to loss of planarity. High vacuum studies of the thermochromic effect in thin films using X-ray photoemission spectroscopy support this interpretation. The standard series of defects in conductive polymers, solitons, polarons and bipolarons, may have to be extended to include conformons.

Interfacial chemistry of Alq3 and LiF with reactive metals

The electronic structure and chemistry of interfaces between tris-(8-hydroxyquinoline) aluminum (Alq3) and representative group IA and IIA metals, Al, and Al/LiF have been studied by x-ray and ultraviolet photoelectron spectroscopies. Quantum-chemical calculations at the density functional theory level predict that the Alq3 radical anion is formed upon reaction with the alkali metals. In this case, up to three metal atoms can react with a given Alq3 molecule to form the trivalent anion. The anion formation results in a splitting of the N 1 s core level and formation of a new feature in the previously forbidden energy gap. Virtually identical spectra are observed in the Al/LiF/Alq3 system, leading to the conclusion that the radical anion is also formed when all three of these constituents are present. This is support by a simple thermodynamic model based on bulk heats of formation. In the absence of LiF or similar material, the reaction of Al with Alq3 appears to be destructive, with the deposited Al reacting directly with the quinolate oxygen. We proposed that in those circumstances where the radical anion is formed, it and not the cathode metal are responsible for the electron injection properties. This is borne out by producing excellent injecting contacts when Ag and Au are used as the metallic component of the cathode structure.

Characterization of the PEDOT-PSS system by means of X-ray and ultraviolet photoelectron spectroscopy

Abstract Thin films of an electrically conducting polymer blend, poly(3,4-ethylenedioxythiophene) oxidized with poly(4-styrenesulfonate), PEDOT-PSS, have been studied using X-ray and ultraviolet photoelectron spectroscopy. Special attention has been paid to thermal effects and the influence of hydrochloric acid on the chemical and electronic structures of the films, since these issues are important in applications of PEDOT-PSS as a hole-injecting electrode in polymer-based light emitting devices. Three chemically different species were identified in pristine PEDOT-PSS, namely poly(4-styrenesulfonic acid), poly(sodium 4-styrenesulfonate) and poly(3,4-ethylenedioxythiophene). The HCl-treatment is shown to lead to the conversion of the sodium salt into the free poly(styrenesulfonic acid). Heating of PEDOT-PSS films resulted in a decomposition of the free sulfonic acid component (presumably through loss of SO 3 ), whereas the sodium salt is thermally stable. It is shown that phase segregation occurs in the PEDOT-PSS system resulting in a surface entirely covered by PSS part of the PEDOT-PSS, as indicated by both XPS and UPS measurements.

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.

Thermochromism in poly(3‐hexylthiophene) in the solid state: A spectroscopic study of temperature‐dependent conformational defects

Reversible thermochromism in thin solid films of poly(3‐hexylthiophene), or P3HT, has been studied using ultraviolet and x‐ray photoelectron spectroscopies (UPS and XPS, respectively). The UPS and XPS spectra, as well as previously published optical absorption spectra, are analyzed using the results of valence effective Hamiltonian (VEH) quantum chemical calculations of the electronic structure of isolated polymer chains. The analysis of the spectra indicates that at elevated temperatures thermally induced electronic localization occurs as a consequence of thermally induced conformational disorder.

A two-dimensional-surface ‘state diagram’ for polyaniline

Abstract The use of a two-dimensional surface is proposed to enable convenient and unambiguous description of the electrically conducting state of polyaniline-based polymers.