Thermopower measurements on pentacene transistors

We present the first thermoelectric measurements on pentacene field effect transistors. We report high values of the Seebeck coefficient at room temperature between 240 and 500 micro V/K depending on the dielectric surface treatment. These values are independent of the thickness of the channel and of the applied gate voltage. Two contributions to the Seebeck coefficient are clearly identified: the expected contribution that is dependent on the position of the transport level and reflects the activated character of carrier generation, and an unexpected intrinsic contribution of 265 plus minus 40 micro V/K that is independent of the temperature and the treatment of the oxide surface. This value corresponds to an unusually large lattice vibrational entropy of 3 kB per carrier. We demonstrate that this intrinsic vibrational entropy arises from lattice hardening induced by the presence of the charge-carrier. Our results provide direct evidence of the importance of electronic polarization effects on charge transport in organic molecular semiconductors.

Transistors organiques ultraminces à base de pentacène

Adrian von Mühlenen

The goal of this thesis is to contribute to the understanding of charge transport in organic field-effect transistors (OFETs) made of pentacene. Organic thin-film transistors (OTFTs) with active layers thicknesses of 5, 10, 20, and 100 nm were fabricated in order to examine their structure and electrical characteristics and identify the key parameters that affect the charge transport in these devices. The conductivity of the pentacene films determined via four probe measurements suggests the presence of extrinsic charge carriers, or residual carriers, which have a large influence on device performance and electrical characteristics. The origin of these carriers is discussed in terms of a charge-transfer process occurring between the organic semiconductor and the electron acceptor states of the gate oxide surface. The gate interface is studied by varying the density of residual carriers via modification of the oxide surface by different plasma treatments with or without using subsequent deposition of various molecular monolayers. The OFETs yielded residual carrier densities ranging from 5 × 109 et 1 × 1013 cm-2 depending on the gate interface modification. The electrical characteristics such as the film conductivity and field-effect mobility are shown to be dependent on the density of residual carriers. Based on the measured density of residual carriers the OFETs are classified into two groups : devices based on doped and on un-doped pentacene. Temperature-dependent measurements of the field-effect mobility and the film conductivity performed on these devices reveal a thermally-activated character. This suggests that charge transport in the examined devices occurs via hopping between localized states. Based on the activation energies of the film conductivity and the field-effect mobility, the difference in energy between the Fermi and the transport level Δε is estimated to be between 10 and 160 meV depending on the density of residual carriers. This range of values is in agreement with thermoelectric power measurements performed on the same devices. The thermoelectric power is discussed in terms of two contributions : one that is dependent on Δε and another constant term that is independent of temperature and gate interface modification. The latter contribution was measured to be 265 ± 40 μV/K and originates from the creation of the phonon cloud associated with local changes in intermolecular interaction. This suggests that the charge carrier in the channel is dressed with a cloud of polarization, an electronic polaron.

EPFL2007

Interface issues in organic semiconductor based devices

Mauro Castellani

The present doctoral thesis aims to contribute to the field of organic semiconductor physics and technology, both of which have become fast growing disciplines. Two technological applications are emerging from these research efforts: Organic light-emitting diodes (OLEDs) and organic field-effect transistors (OFETs). OLEDs are already being fabricated on an industrial level today, while some fundamental issues still remain to be resolved for OFETs. During the last ten years, research interest has been continuously shifting from the bulk properties of organic semiconductors to their interfaces. Such issues are in fact addressed in this thesis work and include different interactions of thin organic layers with their environments. In the field of OLEDs, a multitude of issues have been investigated here. Most importantly and in contrast to most publications in this field, OLED's with complex device architectures that fully compete with standard devices performancewise have been fabricated and characterized. An oxygen plasma treatment of indium-tin-oxide anode has been shown to reduce the injection performance while enhancing the quantum efficiency. Two different mechanisms are proposed to explain this. Going a step further, the life-time behavior of such devices has been examined. Different aging mechanisms were identified: in short term and intermediate term aging, an oxygen plasma treatment of anode clearly reduces the operational voltage. Bulk degradation of the organic electroluminescent layer then becomes predominant for long term aging. Another important finding concerns the formation of exciplexes at organic/organic heterojunctions: In devices comprising a high hole injection barrier between the hole-transport and the electron-transport layer, the dominant formation of exciplexes is identified by a red-shifted shoulder in the electroluminescent spectrum and a low quantum yield. In contrast to that, the quantum efficiency is increased markedly by minimizing this hole barrier. In such devices, the formation of exciplexes is beneficial for device performance, since it facilitates hole transfer across the heterojunction. For the first time, the operational currents could be divided into different radiative and non-radiative recombination channels of exciplexes and excitons respectively. This quantification was further developed to simulate current-versus-voltage behavior and quantum efficiency. The work on pentacene based devices was initiated by fabricating ultrathin pentacene films on polished sapphire and by characterizing them with a temperature variable four probe setup. Oxygen plasma treatment of the substrate introduces oxygen radicals onto the surface and subsequent pentacene deposition leads to electron extraction from the pentacene molecules to defects at the oxide surface. Such an increase of charge carrier density within the semiconducting layer enhances its conductivity. Using a thick, aliphatic self-assembled monolayer (SAM) as an intermediate layer, both the activation energy and the film resistance increase by at least an order of magnitude compared to devices without SAM. Hence, charge transfer to the substrate is inhibited. The OFETs fabricated for this thesis work are all based on pentacene as a semiconductor and the gate interface was the focus of interest. Two different device types were fabricated: One device category comprises ultra-thin film OFETs (10nm). In such devices contact resistance is negligible. This gives rise to a dependence of device behavior on the gate interface. For this reason, the dielectric constant of the gate insulator was varied by changing the gate materials: the hole mobility is enhanced four-fold by using an aliphatic SAM at the gate interface instead of an oxygen plasma treated alumina (Al2O3). This effect has been interpreted in terms of self-trapping at the interface and its reduction by a low-k dielectric gate. In addition the on-off ratio was enhanced by a factor of 20, thanks to the SAM-inhibited pentacene doping due to a reduced semiconductor/substrate interaction. The second OFETdevice category was based on thicker (80nm) pentacene films. Their behavior is injection controlled. This finding originates in the application of a top contact configuration which implies that the carriers cross the granular material to reach the channel. Impedance spectroscopic measurements on different metal-insulator-semiconductor diodes unveiled a morphology dependent transveral mobility, which is linked to the degree of structural disorder in the film. In conclusion: Understanding of the various physical processes occurring at the different interfaces (anode and organic/organic interfaces in OLEDs, gate interface in OFETs) has considerably improved the performance of organic semiconductor based devices.

EPFL2006

Mechanical properties and microstructure of a high carbon steel

Iva Tkalcec Vâju

This work is focussed on a high carbon tool steel used for the production of files. The mechanical properties of the files depend on a hardening thermal treatment that produces a martensitic structure. Thus, the motivation for this work is technological: we want to understand the effects of two types of thermal treatment on the file's mechanical properties. The first is a traditional thermal treatment in a cyanide bath (CN), while the other is performed in a conveyor belt furnace (BF). The files resulting from BF treatment have sometimes a poorer performance. In order to improve the quality of BF files, we study the relationship between the mechanical properties and the microstructure resulting from a particular thermal treatment. Transmission electron microscopy does not reveal a change in the microstructure produced by different thermal treatments, yet it does permit visualization of the complex material microstructure, consisting of a martensitic matrix with embedded carbides. On the other hand, thermoelectric power measurements allow a differentiation between CN and BF files in a fast and non-destructive manner: the measurements performed on the whole files show that the thermopower of BF files is lower. This result is attributed to a higher concentration of carbon soluted in the martensitic matrix. The yield stress and compression strength determined by compression testing, as well as the hardness measured by nanoindentation, are higher for the bulk of BF files, emphasizing the importance of soluted carbon in hardening the martensite. The mobility of point defects and dislocations, and their interaction, are studied by mechanical spectroscopy. The martensitic structure is characterized by a rich internal friction spectrum comprising several overlapping relaxation and material transformation peaks. The internal friction measured at room temperature is related to an athermal background due to the interaction between soluted carbon and dislocations. This background is higher for BF files. The internal friction spectrum indicates that, upon heating above 375 K, the material structure irreversibly changes due to tempering processes. Tempering effects on the material are studied combining several experimental techniques. A first stage of tempering, observed by differential scanning calorimetry, starts around 375 K and is related to carbon precipitation in the form of transition carbides. At this temperature, the thermopower and Young's modulus increase, and the internal friction and hardness decrease, implying that all these quantities are sensitive to soluted carbon. The hardness continuously decreases with tempering and no precipitation hardening is observed. A second stage of tempering is observed around 525 K, leading to cementite precipitation. X-ray diffraction allows quantitative determination of the concentration of carbon in solid solution by measuring the tetragonality of the martensite lattice. The evolution of carbon content during tempering is compared to the evolution of internal friction and thermoelectric power revealing a strong correlation between these quantities. Internal friction measured at room temperature is directly proportional to the carbon content. The measurement of the concentration of carbon by X-ray diffraction is used to determine the variation of carbon content in the file profile. Thermopower measurements indicate that BF files have a lower concentration of carbon in the teeth than in the bulk, while the opposite is found for CN files. This is confirmed by X-ray diffraction. Moreover, diffraction performed on the very surface of the teeth reveals a lower carbon concentration in BF than in CN files teeth, which is probably the origin of their lesser performance. It can be concluded that the concentration of carbon in solid solution in martensite is responsible for the steel's hardness and therefore for its resistance to wear.

EPFL2004