Synthesis of InP-based core-shell Quantum dots using a novel phosphine precursor - phosphinecarboxamide Yi Wang 1 , Jack Howley 2 , Erica Neves de Faria 2 , Chen Huang 3,4 , Sadie Carter-Searjeant 1 , Simon Fairclough 5 , Angus Kirkland 3,4 , Jason J. Davis 7 , Falak Naz 6 , Muhammad Tariq Sajjad 6 , Jose Goicoechea 2* , Mark Green 1* 1 Department of Physics, King’s College London, The Strand, London, WC2R 2LS, UK. 2 Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK. 3 Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, UK. 4 Electron Physical Sciences Imaging Centre, Diamond Light Source, Harwell Science Innovation Campus. Fermi Ave, Didcot, OX110DE, UK. 5 Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge, CB3 0FS, UK. 6 London Centre for Energy Engineering (LCEE), School of Engineering, London South Bank University, 103 Borough Road, London, SE1 0AA, UK. 7 Physical and Theoretical Chemistry Laboratory, South Parks Road, Oxford, OX1 3QZ Physical and Theoretical Chemistry Laboratory, South Parks Road, Oxford, OX1 3QZ Body of abstract Quantum dots (QDs) are now some of the most widely used nanomaterial for optical imaging, with a broad range of colours commercially available. Indium phosphide (InP) based QDs are a prospective replacement to the II-VI family of nanoparticles, particularly the cadmium (Cd) based ones currently in use. InP-based QDs maintain bright photoluminescence while being non-toxic, unlocking QD’s potential for clinical applications. In the past few decades, the choice for phosphorus precursors in the synthesis of InP-based QDs have been restricted to tris(trimethylsilyl) phosphine 1,2 and tris(dimethylamino)phosphine 3 , however both are air-sensitive and highly reactive.This research focused on synthesising InZnP/ZnS core/shell QDs in a one-pot reaction, using a novel air-stable precursor – phosphinecarboxamide 4 . The size and emission wavelengths were tuneable by adjusting the ratio of precursors, and/or the reaction time. Also, we focused on making the QDs water soluble via phase transfer 5 , applying the polymer encapsulation nanocrystal phase transfer technique with poly(styrene-co-maleic anhydride) (PSMA) and ethanolamine (EA), opening up the possibilities on bioimaging application. References 1. Healy, M.D., Laibinis, P.E., Stupik, P.D. & Barron, A.R. The reaction of indium(III) chloride with tris(trimethylsilyl)phosphine: a novel route to indium phosphide. Journal of the Chemical Society, Chemical Communications, 359-360 (1989). 2. Wells, R.L., Aubuchon, S.R., Kher, S.S., Lube, M.S. & White, P.S. Synthesis of Nanocrystalline Indium Arsenide and Indium Phosphide from Indium(III) Halides and Tris(trimethylsilyl)pnicogens. Synthesis, Characterization, and Decomposition Behavior of I3In.cntdot. P(SiMe3)3. Chemistry of Materials 7 , 793-800 (1995). 3. Liu, P. et al. Green InP/ZnSeS/ZnS Core Multi‐Shelled Quantum Dots Synthesized with Aminophosphine for Effective Display Applications. Advanced Functional Materials 31 (2021). 4. Jupp, A.R. & Goicoechea, J.M. Phosphinecarboxamide: a phosphorus-containing analogue of urea and stable primary phosphine. J Am Chem Soc 135 , 19131-19134 (2013). 5. Lees, E.E., Nguyen, T.-L., Clayton, A.H.A. & Mulvaney, P. The Preparation of Colloidally Stable, Water-Soluble, Biocompatible, Semiconductor Nanocrystals with a Small Hydrodynamic Diameter. ACS Nano 3 , 1121-1128 (2009).
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