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

• Published in: Dyes and pigments 2022-01, Vol.197, p.109884, Article 109884
• Main Authors: Kratochvil, Matous, Ciganek, Martin, Yumusak, Cigdem, Seelajaroen, Hathaichanok, Cisarova, Ivana, Fabry, Jan, Vala, Martin, Lunak, Stanislav, Weiter, Martin, Sariciftci, Niyazi Serdar, Krajcovic, Jozef
• Format: Article
• Language: English
• Subjects: Diketopyrrolopyrrole; Dithioketopyrrolopyrrole; Hydrogen-bonded pigments; n-type semiconductors; Organic photovoltaics
• ISSN: 0143-7208; 1873-3743
• DOI: 10.1016/j.dyepig.2021.109884

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-2-yl)-pyrrolo-[3,4-c]-pyrrole (Th-DPP) were transformed to their 1,4-dithioketo heteroanalogues (Ph-DTPP and Th-DTPP) 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 °C. According to density functional theory (DFT) calculations, thionation left HOMO (π-type) level almost unchanged, considerably destabilized non-bonding orbital (n-orbital) localized on thioketo group, and significantly decreased LUMO (π*-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 nπ* 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 μe = 0.018 cm2 V−1 s−1 was obtained for Ph-DTPP film in the device with aluminium source and drain electrodes. [Display omitted] •Thionated analogues of well-known organic semiconductors were studied.•Theoretical modeling is used to understand the effect of thionation on properties.•Thionated molecules show highly stabilized LUMO levels (∼−4.5 eV).•Shift to strong n-type charge transport was observed in thionated molecules.