Poly(3-hexylthiophene) Nanoparticles Containing Thiophene-S,S-dioxide: Tuning of Dimensions, Optical and Redox Properties, and Charge Separation under Illumination.
We describe the preparation of poly(3-hexylthiophene-S,S-dioxide) nanoparticles using Rozen's reagent, HOF·CH3CN, either on poly(3-hexylthiophene) (P3HT) or on preformed P3HT nanoparticles (P3HT-NPs). In the latter case, core-shell nanoparticles (P3HT@PTDO-NPs) are formed, as confirmed by X-ray photoelectron spectroscopy measurements, indicating the presence of oxygen on the outer shell. The different preparation modalities lead to a fine-tuning of the chemical-physical properties of the nanoparticles. We show that absorption and photoluminescence features, electrochemical properties, size, and stability of colloidal solutions can be finely modulated by controlling the amount of oxygen present. Atomic force microscopy measurements on the nanoparticles obtained by a nanoprecipitation method from preoxidized P3HT (PTDO-NPs) display spherical morphology and dimensions down to 5 nm. Finally, Kelvin probe measurements show that the coexistence of p- and n-type charge carriers in all types of oxygenated nanoparticles makes them capable of generating and separating charge under illumination. Furthermore, in core-shell nanoparticles, the nanosegregation of the two materials, in different regions of the nanoparticles, allows a more efficient charge separation.
CNR-ISOF , Via P. Gobetti 101, I-40129 Bologna, Italy.
Francesca
0000-0001-5557-3816
F
Di Maria
CNR-ISOF , Via P. Gobetti 101, I-40129 Bologna, Italy.
Alberto
A
Zanelli
CNR-ISOF , Via P. Gobetti 101, I-40129 Bologna, Italy.|CNR-ISC , Via Fosso del Cavaliere 100, I-00133 Roma, Italy.
Andrea
A
Liscio
CNR-ISOF , Via P. Gobetti 101, I-40129 Bologna, Italy.
Alessandro
A
Kovtun
Department of Industrial Chemistry Toso Montanari, University of Bologna , Viale del Risorgimento 4, I-40136 Bologna, Italy.
Elisabetta
E
Salatelli
Department of Chemistry Giacomo Ciamician, University of Bologna , Via Selmi 2, I-40126 Bologna, Italy.|CNR-IMM , Via P. Gobetti 101, I-40129 Bologna, Italy.
Raffaello
0000-0003-4598-9556
R
Mazzaro
CNR-IMM , Via P. Gobetti 101, I-40129 Bologna, Italy.
Vittorio
V
Morandi
Department of Chemistry Giacomo Ciamician, University of Bologna , Via Selmi 2, I-40126 Bologna, Italy.
Giacomo
G
Bergamini
School of Chemistry, Tel-Aviv University , 69978 Tel Aviv, Israel.
Avshalom
A
Shaffer
School of Chemistry, Tel-Aviv University , 69978 Tel Aviv, Israel.
Shlomo
S
Rozen
Kelvin probe; Rozen’s reagent; X-ray photoelectron spectroscopy; core−shell nanoparticles; heterojunction; organic nanoparticles; polythiophene-S,S-dioxide