Stephan Kirchmeyer

Scientific importance, properties and growing applications of poly(3,4-ethylenedioxythiophene)

This article summarises the industrial applications of poly-(3,4-ethylenedioxythiophene) (PEDT, PEDOT). The basic chemical and physical properties of PEDT are discussed to outline the fundamentals which lead to PEDT as a highly valuable electric and electronic material. PEDT applications are reviewed depending on the two different ways of preparation: in situ polymerisation of the monomer, usually carried out by the user, and applying the prefabricated polymer in the form of its water-based complex with poly(styrene sulfonic acid). Several applications like antistatic coatings, cathodes in capacitors, through-hole plating, OLEDs, OFETs, photovoltaics, and electrochromic applications are discussed in detail.

Electrochromic Window Based on Conducting Poly(3,4‐ethylenedioxythiophene)–Poly(styrene sulfonate)

A short survey of technological aspects of electrochromism with various electroactive species is given. Different approaches with inorganic and organic materials have been pursued in the past. So far widespread usage of this technology for large area applications has not been achieved. Nevertheless one major technical product, self-darkening rear-view mirrors for cars, is already well established. This article reviews some research results on electroactive polythiophenes, especially poly(3,4-alkylenedioxythiophenes). Some promising results with the commercially available electrically conducting polymer Baytron P (PEDT/PSS) are presented. It is demonstrated that an all solid-state electrochromic multilayer assembly based on a polymeric electrochromic material might be close to technical realization. The coating of large area substrates with aqueous poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) dispersion can be a way to an economically viable product.

Bottom-up organic integrated circuits

Self-assembly—the autonomous organization of components into patterns and structures—is a promising technology for the mass production of organic electronics. Making integrated circuits using a bottom-up approach involving self-assembling molecules was proposed in the 1970s. The basic building block of such an integrated circuit is the self-assembled-monolayer field-effect transistor (SAMFET), where the semiconductor is a monolayer spontaneously formed on the gate dielectric. In the SAMFETs fabricated so far, current modulation has only been observed in submicrometre channels, the lack of efficient charge transport in longer channels being due to defects and the limited intermolecular π–π coupling between the molecules in the self-assembled monolayers. Low field-effect carrier mobility, low yield and poor reproducibility have prohibited the realization of bottom-up integrated circuits. Here we demonstrate SAMFETs with long-range intermolecular π–π coupling in the monolayer. We achieve dense packing by using liquid-crystalline molecules consisting of a π-conjugated mesogenic core separated by a long aliphatic chain from a monofunctionalized anchor group. The resulting SAMFETs exhibit a bulk-like carrier mobility, large current modulation and high reproducibility. As a first step towards functional circuits, we combine the SAMFETs into logic gates as inverters; the small parameter spread then allows us to combine the inverters into ring oscillators. We demonstrate real logic functionality by constructing a 15-bit code generator in which hundreds of SAMFETs are addressed simultaneously. Bridging the gap between discrete monolayer transistors and functional self-assembled integrated circuits puts bottom-up electronics in a new perspective.

PEDT/PSS for efficient hole-injection in hybrid organic light-emitting diodes

Light-emitting diodes have been prepared by depositing three organic layers successively by spin-coat and evaporation techniques. The first layer of PEDT/PSS smoothens the ITO surface, reduces the probability of electrical shorts and is beneficial for a high overall yield of the operating devices. Above all, this layer promotes hole-injection as an important parameter for higher efficiencies and prolonged operation life. The second layer of spin-coated dendritic phenylamines (TDAPB) with high glass transition temperature modulates the injection of holes into the emitting layer, formed by evaporated Alq. By comparing characteristics and operation lifetime data of devices with and without PEDT/PSS it is shown that the combination of polymeric and monomeric organic layers leads to highly efficient devices, opening new ways to modify device architectures.

High-mobility organic thin-film transistors based on α,α′-didecyloligothiophenes

We have fabricated organic thin-film transistors and integrated circuits based on the small-molecule organic semiconductors α,α′-didecylquaterthiophene, α,α′-didecylquinquethiophene, and α,α′-didecylsexithiophene. The organic semiconductors were deposited by thermal evaporation, with solution-processed and cross linked poly-4-vinylphenol serving as the gate dielectric layer. We have found that bottom-contact devices based on these materials have better electrical performance than top-contact devices, presumably due to more efficient carrier injection from bottom contacts due to the presence of the relatively long alkyl chains substituted at the α- and ω-positions of the oligothiophene molecules. Bottom-contact transistors have carrier mobility as large as 0.5 cm2/V s and on/off current ratio as large as 105, and ring oscillators fabricated using bottom-contact transistors and α,α′-didecylsexithiophene as the organic active layer have signal propagation delay as low as 30 μs per stage.

Synthesis and thermal behaviour of α,α′-didecyloligothiophenes

α,α′-Didecylquater-, -quinque- and -sexi-thiophenes were synthesized by Kumada cross-coupling and oxidative coupling reactions. For the former reaction Pd(dppf)Cl2 was found to be a more efficient catalyst than the usually applied Ni(dppp)Cl2. Thermal behaviour of all new oligothiophenes was investigated by differential scanning calorimetry and polarizing optical microscopy. It was shown that all these compounds possess not only crystal phases but also high temperature ordered smectic mesophases and that the clearing point increases linearly with the number of conjugated thiophene rings. A degree of order in the crystal phase was estimated on the basis of thermodynamic data. The highest degree of order was proposed for α,α′-didecylquaterthiophene, which explains why the mobility of end-α,α′-capped quaterthiophenes in FET (field effect transistor) devices is comparable or sometimes better than those of corresponding quinque- and sexi-thiophene derivatives.

Gallium Complexes in Three‐Layer Organic Electroluminescent Devices

Organic light-emitting diodes fabricated by subsequently spin-coating two layers-a hole-transporting followed by a metal chelate emissive layer - onto poly(3,4-ethylene-dioxythiophene)/poly(styrenesulfonate) are presentedfor the first time. The electron-hole recombination occurs in a layer consisting of Ga complexes (see Figure), which exhibit high fluorescence quantum yields, and their emission spectra are blue-shifted relative to that of tris(8-hydroxyquinoline) aluminum. By doping this spin-coated emission layer with fluorescent emitters the emission band can be shifted within the visible spectral range.

Conjugated Organosilicon Materials for Organic Electronics and Photonics

In this chapter different types of conjugated organosilicon materials possessing luminescent and/or semiconducting properties will be described. Such macromolecules have various topologies and molecular structures: linear, branched and hyperbranched oligomers, polymers, and dendrimers. Specific synthetic ap- proaches to access these structures will be discussed. Special attention is devoted to the role of silicon in these structures and its influence on their optical and electri- cal properties, leading to their potential application in the emerging areas of organic and hybrid electronics.

Interfacial structure in semiconducting polymer devices

We discuss some recent findings relating to the structure of interfaces in semiconducting polymer devices. The structure of three different types of interface is characterized via neutron reflectivity and scanning force microscopy. In the first example we find that enrichment of dopant occurs at the surface of a doped polymeric conductor, and that this enriched layer penetrates several nanometres into the material. Secondly, we find that the interface between a semiconducting polymer and an insulating polymer is not molecularly sharp, but is rather broad with a width typically of the order of 1 nm. Finally we present some initial neutron reflectivity measurements on the interface between two different semiconducting polymers (one of which is deuterated). Again we find that this interface is diffuse, with a typical width of the order of a few nanometres.

Colloidchemical interactions of silica particles in the cu-CMP-process

Polishing slurries for the copper chemical mechanical planarization (CMP) process consist of a complex composition of highly stable nanoparticle suspensions in the presence of chemical additives for etching and protecting the surface. The target of such dispersions is to achieve perfectly smooth surfaces of low topography. Key factors are the surface roughness, local geometry and total flatness of the whole wafer. Surface defects like scratches, dishing, etching and erosion e.g. due to strong particle adsorption, aggregates or chemical impact have to be avoided. Particle wafer interactions between silica particles of a silica CMP-dispersion and a copper wafer surface were analyzed by electron cpectroscopy for chemical analysis (ESCA), scanning electon microscopy (SEM) and zetapotential-measurements. The colloidal stability of the silica dispersion over a broad pH-range of 2.3 to 9.8 was analyzed in the presence of Na+-, Mg2+-, Cu2+-, and Al3+-ions in terms of the critical coagulation concentration (CCC), change in particle size and pH. Silica particles strongly and irreversibly adsorbed to the predominantly oxidic copper wafer surface at pH 2.3 but not at pH > 4. Over the whole pH-range a high colloidal stability was observed with a maximum at pH 2.3. CCC-values of 100–300 mmol/L versus Cu2+ were obtained. Even at high pH of 9.8, the behaviour could not be explained by the Derjaguin- Landauer-Verley-Overbeek (DLVO) theory. In the presence of Cu2+-ions a higher colloidal stability compared to divalent Mg2+-ions was observed at high initial slurry-pH of 9.8. Due to the acidic reaction of Cu2+ in the aqueous environment, the pH was reduced to 2–3, where colloidal silica showed the highest stability. Even at high removal rates in the polishing process of 1000 nm/min, the released Cu2+-concentration (40 mmol/L) was lower than the critical coagulation concentration (100 mmol/L).