Publication detail

Multiscale Analysis of Phase Transformations in Self-Assembled Layers of 4,4 '-Biphenyl Dicarboxylic Acid on the Ag(001) Surface

PROCHÁZKA, P. GOSALVEZ, M. KORMOŠ, L. DE LA TORRE, B. GALLARDO, A. ALBERDI-RODRIGUEZ, J. CHUTORA, T. MAKOVEEV, A. SHAHSAVAR, A. ARNAU, A. JELÍNEK, P. ČECHAL, J.

Original Title

Multiscale Analysis of Phase Transformations in Self-Assembled Layers of 4,4 '-Biphenyl Dicarboxylic Acid on the Ag(001) Surface

Type

journal article in Web of Science

Language

English

Original Abstract

Understanding the nucleation and growth kinetics of thin films is a prerequisite for their large-scale utilization in devices. For self-assembled molecular phases near thermodynamic equilibrium the nucleation-growth kinetic models are still not developed. Here, we employ real-time low-energy electron microscopy (LEEM) to visualize a phase transformation induced by the carboxylation of 4,4'-biphenyl dicarboxylic acid on Ag(001) under ultra-high-vacuum conditions. The initial (alpha) and transformed (beta) molecular phases are characterized in detail by X-ray photoemission spectroscopy, single-domain low-energy electron diffraction, roomtemperature scanning tunneling microscopy, noncontact atomic force microscopy, and density functional theory calculations. The phase transformation is shown to exhibit a rich variety of phenomena, including Ostwald ripening of the a domains, burst nucleation of the beta domains outside the alpha phase, remote dissolution of the alpha domains by nearby beta domains, and a structural change from disorder to order. We show that all phenomena are well described by a general growth-conversion-growth (GCG) model. Here, the two-dimensional gas of admolecules has a dual role: it mediates mass transport between the molecular islands and hosts a slow deprotonation reaction. Further, we conclude that burst nucleation is consistent with a combination of rather weak intermolecular bonding and the onset of an additional weak many-body attractive interaction when a molecule is surrounded by its nearest neighbors. In addition, we conclude that Ostwald ripening and remote dissolution are essentially the same phenomenon, where a more stable structure grows at the expense of a kinetically formed, less stable entity via transport through the 2D gas. The proposed GCG model is validated through kinetic Monte Carlo (kMC) simulations.

Keywords

self-assembly; low-energy electron microscopy; scanning probe microscopy; kinetic Monte Carlo; phase transformation; surfaces

Authors

PROCHÁZKA, P.; GOSALVEZ, M.; KORMOŠ, L.; DE LA TORRE, B.; GALLARDO, A.; ALBERDI-RODRIGUEZ, J.; CHUTORA, T.; MAKOVEEV, A.; SHAHSAVAR, A.; ARNAU, A.; JELÍNEK, P.; ČECHAL, J.

Released

23. 6. 2020

Publisher

AMER CHEMICAL SOC

Location

WASHINGTON

ISBN

1936-0851

Periodical

ACS Nano

Year of study

14

Number

6

State

United States of America

Pages from

7269

Pages to

7279

Pages count

11

URL

BibTex

@article{BUT164933,
  author="Pavel {Procházka} and Miguel A. {Gosalvez} and Lukáš {Kormoš} and Bruno {de la Torre} and Aurelio {Gallardo} and Joseba {Alberdi-Rodriguez} and Taras {Chutora} and Anton Olegovich {Makoveev} and Azin {Trllová Shahsavar} and Andres {Arnau} and Pavel {Jelínek} and Jan {Čechal}",
  title="Multiscale Analysis of Phase Transformations in Self-Assembled Layers of 4,4 '-Biphenyl Dicarboxylic Acid on the Ag(001) Surface",
  journal="ACS Nano",
  year="2020",
  volume="14",
  number="6",
  pages="7269--7279",
  doi="10.1021/acsnano.0c02491",
  issn="1936-0851",
  url="https://pubs.acs.org/doi/10.1021/acsnano.0c02491"
}