Adsorption behavior of Zn porphyrins on a (1 0 1) face of anatase TiO2

Zając, Łukasz; Bodek, Lukasz; Such, Bartosz

doi:10.1016/j.apsusc.2018.02.278

Cited by 2 publications

(2 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…While the presence of other molecules in the stack appears to reduce the strength of pentacene binding to TiO 2 from −1.91 to −1.83 eV per molecule, the monolayers are overwhelmingly stabilized by molecule−surface interactions in line with recent experimental observations for conjugated adsorbates on (101) anatase. 23 Consequently, each molecule in a stack adopts a local geometry that is almost identical to the isolated molecule, with minimal changes in the tilt angle (see Figure 2d).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Pentacene/TiO₂Anatase Hybrid Interface Study by Scanning Probe Microscopy and First Principles Calculations

Todorović

Stetsovych

Moreno

et al. 2018

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

The understanding and control of the buried interface between functional materials in optoelectronic devices is key to improving device performance. We combined atomic resolution scanning probe microscopy with first-principles calculations to characterize the technologically relevant organic/inorganic interface structure between pentacene molecules and the TiO anatase (101) surface. A multipass atomic force microscopy imaging technique overcomes the technical challenge of imaging simultaneously the corrugated anatase substrate, molecular adsorbates, monolayers, and bilayers at the same level of detail. Submolecular resolution images revealed the orientation of the adsorbates with respect to the substrate and allowed direct insights into interface formation. Pentacene molecules were found to physisorb parallel to the anatase substrate in the first contact layer, passivating the surface and promoting bulk-like growth in further organic layers. While molecular electronic states were not significantly hybridized by the substrate, simulations predicted localized pathways for molecule-surface charge injection. The localized states were associated with the molecular lowest unoccupied molecular orbital inside the oxide conduction band, pointing to efficient transfer of photo-induced electron charge carriers across this interface in prospective photovoltaic devices. In uncovering the atomic arrangement and favorable electronic properties of the pentacene/anatase interface, our findings testify to the maturity and analytic power of our methodology in further studies of organic/inorganic interfaces.

show abstract

Section: ■ Results and Discussionmentioning

confidence: 99%

Pentacene/TiO₂Anatase Hybrid Interface Study by Scanning Probe Microscopy and First Principles Calculations

Todorović

Stetsovych

Moreno

et al. 2018

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

show abstract

“…This reference substrate may be obtained by reducing the molecule-surface interaction. The first step in this direction was to exploit the anisotropic surface corrugation of rutile-TiO2(110) to drive the oriented growth of both polyconjugated aromatics [15,[17][18][19][20][21] and porphyrins [22][23][24][25]. However, significant charge transfer may take place between large aromatic molecules and defects of the rutile surface [26].…”

Section: Introductionmentioning

confidence: 99%

Evaluation of molecular orbital symmetry via oxygen-induced charge transfer quenching at a metal-organic interface

Cojocariu

Sturmeit

Zamborlini

et al. 2020

Applied Surface Science

View full text Add to dashboard Cite

Thin molecular films under model conditions are often exploited as benchmarks and case studies to investigate the electronic and structural changes occurring on the surface of metallic electrodes. Here we show that the modification of a metallic surface induced by oxygen adsorption allows the preservation of the geometry of a molecular adlayer, giving access to the determination of molecular orbital symmetries by means of near-edge x-ray absorption fine structure spectroscopy, NEXAFS. As a prototypical example, we exploited Nickel Tetraphenyl Porphyrin molecules deposited on a bare and on an oxygen pre-covered Cu(100) surface. We find that adsorbed atomic oxygen quenches the charge transfer at the metal-organic interface but, in contrast to a thin film sample, maintains the ordered adsorption geometry of the organic molecules. In this way, it is possible to disentangle π* and σ* symmetry orbitals, hence estimating the relative oscillator strength of core level transitions directly from the experimental data, as well as to evaluate and localize the degree of charge transfer in a coupled system. In particular, we neatly single out the σ* contribution associated with the N 1s transition to the mixed N 2px,y-Ni 3dx 2 -y 2 orbital, which falls close to the leading π*-symmetry LUMO resonance.

show abstract

Adsorption behavior of Zn porphyrins on a (1 0 1) face of anatase TiO2

Cited by 2 publications

References 41 publications

Pentacene/TiO₂Anatase Hybrid Interface Study by Scanning Probe Microscopy and First Principles Calculations

Pentacene/TiO₂Anatase Hybrid Interface Study by Scanning Probe Microscopy and First Principles Calculations

Evaluation of molecular orbital symmetry via oxygen-induced charge transfer quenching at a metal-organic interface

Contact Info

Product

Resources

About

Adsorption behavior of Zn porphyrins on a (1 0 1) face of anatase TiO2

Cited by 2 publications

References 41 publications

Pentacene/TiO2Anatase Hybrid Interface Study by Scanning Probe Microscopy and First Principles Calculations

Pentacene/TiO2Anatase Hybrid Interface Study by Scanning Probe Microscopy and First Principles Calculations

Evaluation of molecular orbital symmetry via oxygen-induced charge transfer quenching at a metal-organic interface

Contact Info

Product

Resources

About

Adsorption behavior of Zn porphyrins on a (1 0 1) face of anatase TiO2

Pentacene/TiO₂Anatase Hybrid Interface Study by Scanning Probe Microscopy and First Principles Calculations

Pentacene/TiO₂Anatase Hybrid Interface Study by Scanning Probe Microscopy and First Principles Calculations