Tuning Energy Level Alignment At Organic/Semiconductor Interfaces Using a Built-In Dipole in Chromophore鈥揃ridge鈥揂nchor Compounds

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• 作者：Sylvie Rangan ; Alberto Batarseh ; Keyur P. Chitre ; Andrew Kopecky ; Elena Galoppini ; Robert Allen Bartynski
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：June 19, 2014
• 年：2014
• 卷：118
• 期：24
• 页码：12923-12928
• 全文大小：296K
• 年卷期：v.118,no.24(June 19, 2014)
• ISSN：1932-7455

文摘

A chromophore鈥揵ridge鈥揳nchor molecular architecture is used to manipulate the molecular level energy position, with respect to the band edges of the substrate, of a chromophore bound to a surface via an anchor group. An energy shift of the chromophore鈥檚 frontier orbitals is induced by the addition of an oriented molecular dipole into the bridge part of the compound. This principle has been tested using three Zinc Tetraphenylporphyrin derivatives of comparable structure: two of which possess a dipole, but pointing in opposite directions and, for comparison, a compound without a dipole. UV鈥搗is absorption and emission spectroscopies have been used to probe the electronic structure of the compounds in solution, while UV photoemission spectroscopy has been used to measure the relative position of the molecular levels of the chromophore with respect to the band edges of a ZnO(11鈥?0) single crystal substrate. It is shown that the introduction of a molecular dipole does not alter the chromophore鈥檚 HOMO鈥揕UMO gap, and that the molecular level alignment of the compounds bound to the ZnO surface follows the behavior predicted by a simple parallel-plate capacitor model.