3 years ago

Axially Bound Ruthenium Phthalocyanine Monolayers on Indium Tin Oxide: Structure, Energetics, and Charge Transfer Properties

Axially Bound Ruthenium Phthalocyanine Monolayers on Indium Tin Oxide: Structure, Energetics, and Charge Transfer Properties
Kai-Lin Ou, Ramanan Ehamparam, Dominic V. McGrath, Luis E. Oquendo, Michael W. Liao, S. Scott Saavedra, Ambjorn K. Brynnel, Neal R. Armstrong
The efficiency of charge collection at the organic/transparent conducting oxide (TCO) interface in organic photovoltaic (OPV) devices affects overall device efficiency. Modifying the TCO with an electrochemically active molecule may enhance OPV efficiency by providing a charge-transfer pathway between the electrode and the organic active layer, and may also mitigate surface recombination. The synthesis and characterization of phosphonic acid-ruthenium phthalocyanine (RuPcPA) monolayer films on indium tin oxide (ITO), designed to facilitate charge harvesting at ITO electrodes, is presented in this work. The PA group was installed axially relative to the Pc plane so that upon deposition, RuPcPA molecules were preferentially aligned with the ITO surface plane. The tilt angle of 22° between the normal axes to the Pc plane and the ITO surface plane, measured by attenuated total reflectance (ATR) spectroscopy, is consistent with a predominately in-plane orientation. The effect of surface roughness on RuPcPA orientation was modeled, and a correlation was obtained between experimental and theoretical mean tilt angles. Based on electrochemical and spectroelectrochemical studies, RuPcPA monolayers are composed predominately of monomers. Electrochemical impedance spectroscopy (EIS) and potential modulated-ATR (PM-ATR) spectroscopy were used to characterize the electron-transfer (ET) kinetics of these monolayers. A rate constant of 4.0 × 103 s–1 was measured using EIS, consistent with a short tunneling distance between the chromophore and the electrode surface. Using PM-ATR, ks,opt values of 2.2 × 103 and 2.4 × 103 s–1 were measured using TE and TM polarized light, respectively; the similarity of these values is consistent with a narrow molecular orientation distribution and narrow range of tunneling distances. The ionization potential of RuPcPA-modified ITO was measured using ultraviolet photoelectron spectroscopy and the results indicate favorable energetics for hole collection at the RuPcPA/ITO interface, indicating that this type of TCO modification may be useful for enhancing charge collection efficiency in OPV devices.

Publisher URL: http://dx.doi.org/10.1021/acsami.7b07394

DOI: 10.1021/acsami.7b07394

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.