Publication detail

Near-infrared absorbing hydrogen-bonded dithioketopyrrolopyrrole (DTPP) n-type semiconductors

KRATOCHVIL M. CIGANEK M. YUMUSAK C. SEELAJAROEN H. CISAROVA I. FABRY J. VALA M. LUNAK S. WEITER M. SARICIFTCI N.S. KRAJCOVIC J.

Original Title

Near-infrared absorbing hydrogen-bonded dithioketopyrrolopyrrole (DTPP) n-type semiconductors

Type

journal article in Web of Science

Language

English

Original Abstract

Optical and semiconducting properties of vacuum-deposited thin films of four hydrogen-bonded pigments were studied. Well-known 1,4-diketo-3,6-diphenyl-pyrrolo-[3,4-c]-pyrrole (Ph-DPP) and 1,4-diketo-3,6-(thiophen-2yl)-pyrrolo-[3,4-c]-pyrrole (Th-DPP) were transformed to their 1,4-dithioketo heteroanalogues (Ph-DTPP and ThDTPP) using Lawesson's reagent. X-ray single crystal structure determination confirmed the presence of CS-HN hydrogen bonds and a similar stack formation in both DTPPs, leading to relatively high decomposition temperatures, about 350 degrees C. According to density functional theory (DFT) calculations, thionation left HOMO (pi-type) level almost unchanged, considerably destabilized non-bonding orbital (n-orbital) localized on thioketo group, and significantly decreased LUMO (pi*-type) energy. Evolution of HOMO and LUMO energies was confirmed by cyclic voltammetry, establishing LUMO energy at -4.5 eV for both DTPPs, while a signature of high-lying n-orbital was detected through n pi* transition in the far-red/near-infrared area of absorption spectra, interpreted with help of time dependent DFT calculations on monomer and stacked dimer geometry. The lowest optical band-gap among the pigments under study was found to be 1.4 eV for Ph-DTPP thin film. Field effect mobilities, determined on a bottom-gate top-contact transistor, show DPPs as p-type and DTPPs as n-type semiconductors. The highest electron mobility mu e = 0.018 cm2 V-1 s- 1 was obtained for Ph-DTPP film in the device with aluminium source and drain electrodes.

Keywords

Organic photovoltaics; Hydrogen-bonded pigments; Dithioketopyrrolopyrrole; Diketopyrrolopyrrole; n-type semiconductors

Authors

KRATOCHVIL M.; CIGANEK M.; YUMUSAK C.; SEELAJAROEN H.; CISAROVA I.; FABRY J.; VALA M.; LUNAK S.; WEITER M.; SARICIFTCI N.S.; KRAJCOVIC J.

Released

13. 10. 2021

Publisher

ELSEVIER SCI LTD

Location

OXFORD

ISBN

1873-3743

Periodical

DYES AND PIGMENTS

Year of study

197

Number

1

State

United Kingdom of Great Britain and Northern Ireland

Pages from

109884

Pages to

109895

Pages count

11

URL

https://www.sciencedirect.com/science/article/pii/S0143720821007506?via%3Dihub

BibTex

@article{BUT172990,
  author="KRATOCHVIL M. and CIGANEK M. and YUMUSAK C. and SEELAJAROEN H. and CISAROVA I. and FABRY J. and VALA M. and LUNAK S. and WEITER M. and SARICIFTCI N.S. and KRAJCOVIC J.",
  title="Near-infrared absorbing hydrogen-bonded dithioketopyrrolopyrrole (DTPP) n-type semiconductors",
  journal="DYES AND PIGMENTS",
  year="2021",
  volume="197",
  number="1",
  pages="109884--109895",
  doi="10.1016/j.dyepig.2021.109884",
  issn="1873-3743",
  url="https://www.sciencedirect.com/science/article/pii/S0143720821007506?via%3Dihub"
}