Dokument

Zusammenfassung:
Im Rahmen dieser Arbeit wurde die selektive Reaktivität dreier prototypischer organischer Adsorbate (Ethen, Cyclooctin und Tetrahydrofuran) mit der Si(001)-Oberfläche mittels Rastertunnelmikroskopie untersucht. Das Rastertunnelmikroskop ermöglicht hierbei die direkte Beobachtung der Oberfläche im Realraum mit atomarer Auflösung. Auf diese Weise ist es möglich, die auftretenden Adsorptionsgeometrien relativ zur Struktur der Oberfläche zu identifizieren. Ein einzelnes Adsorbat kann dabei durchaus mehrere Adsorptionsgeometrien mit teilweise stark verschiedenen Häufigkeiten aufweisen. Durch sorgfältige, bedeckungsabhängige Experimente können diese relativen Reaktivitätsunterschiede untersucht werden. Durch Variation der Probentemperatur während der Dosierung der Adsorbate sind zudem weitere Rückschlüsse auf die zugrunde liegenden Reaktionsmechanismen der Adsorption möglich, beispielsweise die Existenz von Zwischenzuständen. Darüber hinaus wurden in dieser Arbeit gezielt lokal gestörte Adsorptionsplätze durch verschiedene Wasserstoffvorbedeckungen hergestellt und deren platzspezifische Reaktivität für die Adsorption der verschiedenen Moleküle untersucht, was ebenfalls Rückschlüsse auf den jeweiligen Reaktionsmechanismus zulässt. Ethen ist das kleinste einfach-ungesättigte organische Molekül, dessen nicht-dissoziative Adsorption an einem Dimer der Si(001)-Oberfläche bereits seit vielen Jahren intensiv untersucht wurde. Überraschenderweise konnte in dieser Arbeit eine zweite, bisher nicht identifizierte Adsorptionsgeometrie nachgewiesen werden, die über zwei Dimere erfolgt. Obwohl die neue Adsorptionsgeometrie mit einer geringeren platzspezifischen Reaktivität verbunden ist, liegen bei höheren Bedeckungen annähernd 20% der Moleküle in dieser Adsorptionsgeometrie vor. Als wichtigstes Ergebnis der Untersuchungen zu Ethen auf Si(001) ist allerdings die – im Vergleich zur Adsorption auf der sauberen Oberfläche – deutlich erhöhte platzspezifische Reaktivität von Ethen an lokal gestörten Konfigurationen des voradsorbierten Wasserstoffs hervorzuheben. Durch diese Experimente konnte somit erfolgreich gezeigt werden, dass es auch im Fall einer nicht-dissoziativen Adsorption eines organischen Moleküls auf Si(001) prinzipiell möglich ist, das Adsorptionsverhalten durch lokale Störungen stark zu beeinflussen beziehungsweise zu steuern. Die beobachteten Effekte können durch die Adsorption des Ethens über einen mobilen Precursorzustand erklärt werden, was durch Monte-Carlo-Simulationen bestätigt wurde. Innerhalb eines Precursor-Modells konnten weitergehende Simulationen auch die experimentell beobachteten Adsorbatverteilungen des Ethens auf der sauberen Si(001)-Oberfläche von kleinen bis maximalen Bedeckungen von einer Monolage zufriedenstellend beschreiben. Insgesamt konnte somit in dieser Arbeit ein schlüssiges neues Gesamtbild der Adsorption von Ethen auf der sauberen Si(001)-Oberfläche entwickelt werden. Cycloalkine sind cyclische Kohlenwasserstoffe, die sich durch eine Dreifachbindung und eine damit zusammenhängende starke Verspannung des Molekülrings auszeichnen. Der Einfluss dieser Kombination aus Dreifachbindung und zusätzlicher Ringspannung auf den Adsorptionsmechanismus wurde in dieser Arbeit am Beispiel von Cyclooctin untersucht. Als wichtigstes Ergebnis kann zunächst festgehalten werden, dass sich bei der Adsorption von Cyclooctin auf der Si(001)-Oberfläche in Raumtemperatur- und Tieftemperaturexperimenten im Wesentlichen das gleiche Adsorptionsverhalten beobachten lässt, im Gegensatz zu vielen anderen untersuchten Molekülen. Diese Beobachtung deutet auf einen direkten (barrierelosen) Adsorptionspfad ohne Precursorzustand hin. Ferner konnte gezeigt werden, dass Cyclooctin von kleinen bis zu fast vollständigen und wohlgeordneten Bedeckungen mit hoher Reaktivität auf der Si(001)-Oberfläche adsorbiert. Cyclooctin zeigt dabei primär zwei unterschiedliche Adsorptionsgeometrien, die symmetrisch zu einem Dimer beziehungsweise zu zwei Dimeren sind. Dies führt entlang der Dimerreihe zu wechselnden Molekülabständen von 1.5- beziehungsweise 2-fachen Dimerabständen. In guter Übereinstimmung von Experiment und ebenfalls durchgeführten Monte-Carlo-Simulationen konnte die Maximalbedeckung des Cyclooctins zu 0.58 ML bestimmt werden. In Experimenten an wasserstoffvorbedeckten Si(001)-Oberflächen konnte keine erhöhte platzspezifische Reaktivität an lokal gestörten Adsorptionsplätzen festgestellt werden. Diese Beobachtung untermauert das Vorliegen eines direkten Adsorptionsmechanismus, wodurch sich Cyclooctin sehr wahrscheinlich durch eine, verglichen mit anderen Molekülen, erhöhte chemische Selektivität für die Adsorption auf der Si(001)-Oberfläche auszeichnet. Aufgrund der Ergebnisse dieser Arbeit gilt Cyclooctin im Zusammenhang der Funktionalisierung von Halbleitern daher als vielversprechender Kandidat für den Übergang von einer Halbleiteroberfläche zu einer organischen Multilage. Die Untersuchungen zur Adsorption von Tetrahydrofuran auf der Si(001)-Oberfläche sollten unter anderem der Frage nach möglichen Reaktionen eines Lösungsmittels mit der Halbleiteroberfläche nachgehen. Trotz der Reaktionsträgheit von Tetrahydrofuran in der flüssigen Phase konnte eine unerwartete und erstaunlich komplexe Oberflächenchemie des Tetrahydrofurans auf der Si(001)-Oberfläche festgestellt werden. So werden bei unterschiedlichen Probentemperaturen grundverschiedene Adsorptionsgeometrien und außerdem eine vielschichtige Umordnung nach dem Tempern auf höhere Temperaturen beobachtet. Bei tiefen Temperaturen deuten die Ergebnisse auf einen dativ-gebundenen, metastabilen Zwischenzustand hin, der sich durch thermische Anregung irreversibel in die bei Raumtemperaturexperimenten beobachtete Adsorptionsgeometrie umwandeln lässt. Tempern der mit Tetrahydrofuran bedeckten Si(001)-Oberfläche auf Temperaturen von 700 K führt zu einer Reihe von unterschiedlichen Konfigurationen, die auf eine Zerlegung des Moleküls und insbesondere den Einbau von Sauerstoff in das Siliziumsubstrat hindeuten. Die bei thermischer Anregung beobachtete Umwandlung der Tieftemperatur-Konfiguration in die Raumtemperatur-Konfiguration kann auch durch den Tunnelprozess selbst, das heißt spitzeninduziert, hervorgerufen werden. Diese Effekte wurden eingehend untersucht und konnten auf eine elektronische Anregung zurückgeführt werden.

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