Fast and slow charge trapping and transport in organic semicondutors
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1 Research Collection Doctoral Thesis Fast and slow charge trapping and transport in organic semicondutors Author(s): Häusermann, Roger Publication Date: 2013 Permanent Link: Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library
2 Diss. ETH No Fast and Slow Charge Trapping and Transport in Organic Semiconductors A dissertation submitted to the ETH ZURICH for the degree of Doctor of Sciences presented by ROGER HÄUSERMANN Dipl. Phys. ETH born October 26th, 1979 citizen of Egliswil AG - Switzerland accepted on the recommendation of Prof. Dr. B. Batlogg, examiner Prof. Dr. Jun Takeya, co-examiner Prof. Dr. Beat Ruhstaller, co-examiner 2013
3 Abstract In this thesis charge transport and associated processes in organic semiconductors are investigated from various points of view to identify fundamental mechanisms limiting device performance. This will hopefully contribute to establish a more coherent picture for the charge transport and partially replace the patchwork of theories which are used nowadays. In the first study we developed a full organic photovoltaic cell (OPV) simulator. The fundamental processes have been implemented from light incoupling to charge extraction. We then studied the limiting processes for various steady state as well as transient simulations and compared the results with actual measurements. This shows that transient measurements are an important part to identify and distinguish concurrent processes. In the next study we investigated so called slow charge traps in organic fieldeffect transistor (OFET) which limit the device performance. Through careful comparison of several device stacks we have been able to identify a system where slow charge trapping occurs in the semiconductor and therefore eliminates charge trapping in the gate dielectric, which normally occurs in almost all OFET devices. The third study is then focused on a comparison of charge transport and trapping in a n-type material. Using various processing methods we have been able to produce OFETs with a wide range of crystallinity. This is an important step for understanding how order/disorder due to morphological differences influences the spectral density of trap states (trap DOS) and thus charge transport. The last study is a survey to summarize the trap DOS in state of the art OFETs. For this investigation we have compared publications from the last 25 years to have a coherent picture of charge traps for organic p- as well as n-type devices. A comparison to their inorganic counterparts is done as well. We also show a very simple method to extract the density of trap states from transfer 1
4 curve measurements. Furthermore we could show that organic n-type materials behave the same as the already well established p-type counterparts. Finally we have been able to produce rubrene single crystal OFETs which have the same trap DOS close to the surface as in the bulk of the single crystal. 2
5 Kurzfassung In dieser Dissertation untersuchen wir den Ladungstransport und damit verbundene Prozesse in organischen Halbleitern. Mittels verschiedener Modelle, Methoden und Messaufbauten werden organische Bauteile erforscht. Die unterschiedlichen Blickwinkel ermöglichen es, fundamentale Prozesse zu identifizieren, die die Leistungsfähigkeit von organischen Bauelementen limitieren. Diese Arbeit wird hoffentlich dazu beitragen, ein kompletteres und homogeneres Bild des Ladungstransportes zu etablieren und den Flickenteppich an verschiedenen Theorien und Modellen mindestens teilweise zu ersetzen. In der ersten Studie haben wir einen kompletten Simulator für organische Solarzellen entwickelt, bei dem alle Prozesse von der Einkopplung des Lichtes, bis zur Ladungsträgerextraktion physikalisch korrekt berücksichtigt wurden. Wir studierten den stationären Betrieb und das Ein- bzw. Ausschaltverhalten durch die Simulation. Diese Ergebnisse verglichen wir mit Messungen an Standard Solarzellen. Wir konnten zeigen, bei welchen Messungen, welche Parameter am meisten Einfluss haben und dass transiente Messungen ein wichtiger Schritt sind, um organische Solarzellen zu verstehen und fundamentale Prozesse zu unterscheiden. In der zweiten Studie untersuchten wir sogenannte langsame Einfangstellen in OFETs, welche der Anwendbarkeit von diesen Transistoren im Wege stehen. Durch eine sorgfältige Durchführung der Versuche und Vergleiche zwischen verschiedenen OFETs konnten wir erstmals einen Schichtaufbau identifizieren, bei dem die Ladungsträger im organischen Halbleiter eingefangen werden. Dadurch konnten wir das Einfangen von Ladungsträgern im Isolator unterdrücken, was sonst der Normalfall ist. Die dritte Studie beschäftigt sich mit dem Ladungstransport und Einfangstellen in einem n-typ Material. Wir benutzten verschiedene Herstellungsmetho- 3
6 den und erreichten es, Transistoren mit einem breiten Spektrum unterschiedlicher Morphologien herzustellen. Dadurch konnten wir zeigen, wie das Verhältnis zwischen Ordnung/Unordnung, die Menge und energetische Position von Einfangstellen zusammenhängen und den Ladungstransport limitieren. Das letzte Kapitel ist eine ausgedehnte Studie, die dichte und energetische Verteilungen von Einfangstellen in OFETs vergleicht. Dazu haben wir die Publikationen der letzten 25 Jahre gesammelt und verglichen, um ein umfassendes Bild von Einfangstellen in organischen wie anorganischen Halbleitern zu erhalten. Zusätzlich haben wir eine einfache Methode entwickelt, um die Einfangstellendichte in den verschiedenen FETs zu vergleichen. Als weiteres Resultat unserer Untersuchung konnten wir zeigen, dass sich organische n-typ Materialien wie die schon gut etablierten p-typ Materialien verhalten. Schliesslich zeigen wir, dass die Anzahl der Einfangstellen an der Oberfläche eines Rubren Einkristalls gleich gross ist, wie innerhalb des Kristalls. 4
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