Dispersion of Few-Layer Black Phosphorus in Binary Polymer Blend and Block Copolymer Matrices

Year: 2021

Authors: Coiai S., Passaglia E., Pinna S., Legnaioli S., Borsacchi S., Dinelli F., Ferretti A.M., Caporali M., Serrano-Ruiz M., Peruzzini M., Cicogna F.

Autors Affiliation: CNR-ICCOM, Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organo Metallici, SS Pisa, Via Moruzzi 1, Pisa, 56124, Italy; CISUP, Centro per l´Integrazione della Strumentazione Scientifica dell´Università di Pisa, Pisa, 56126, Italy; CNR-INO, Consiglio Nazionale delle Ricerche, Istituto Nazionale di Ottica, Via Moruzzi 1, Pisa, Italy; CNR-SCITEC, Consiglio Nazionale delle Ricerche, Istituto di Scienze e Tecnologie Chimiche, Via G. Fantoli 16/15, Milano, Italy; CNR-ICCOM, Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti OrganoMetallici, Via Madonna del Piano 10, Sesto Fiorentino (FI), 50019, Italy

Abstract: Exfoliated black phosphorus (bP) embedded into a polymer is preserved from oxidation, is stable to air, light, and humidity, and can be further processed into devices without degrading its properties. Most of the examples of exfoliated bP/polymer composites involve a single polymer matrix. Herein, we report the preparation of biphasic polystyrene/poly(methyl methacrylate) (50/50 wt.%) composites containing few-layer black phosphorus (fl-bP) (0.6-1 wt.%) produced by sonicated-assisted liquid-phase exfoliation. Micro-Raman spectroscopy confirmed the integrity of fl-bP, while scanning electron microscopy evidenced the influence of fl-bP into the coalescence of polymeric phases. Furthermore, the topography of thin films analyzed by atomic force microscopy confirmed the effect of fl-bP into the PS dewetting, and the selective PS etching of thin films revealed the presence of fl-bP flakes. Finally, a block copolymer/fl-bP composite (1.2 wt.%) was prepared via in situ reversible addition-fragmentation chain transfer (RAFT) polymerization by sonication-assisted exfoliation of bP into styrene. For this sample,31P solid-state NMR and Raman spectroscopy confirmed an excellent preservation of bP structure.

Journal/Review: NANOMATERIALS

Volume: 11 (8)      Pages from: 1996-1  to: 1996-22

More Information: This research was partially founded by the European Research Council (ERC) under the European Union´s Horizon 2020 research and innovation program, project PHOSFUN “Phosphorene functionalization: a new platform for advanced multifunctional materials”, Grant Agreement No. 670173 and by Italian Ministry of Education, University and Research (MIUR), project PRIN 2017 FERMAT “Fast ElectRon dynamics in novel hybrid organic-2D MATerials”, 2017KFY7XF.
KeyWords: black phosphorus (bP), composites, block co-polymers, RAFT, NMR
DOI: 10.3390/nano11081996