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Novel phosphorus precursors to group III-V semiconductor nanoparticles

Abstract:

The development of novel phosphorus precursors to group III-V semiconductor nanoparticles is described in this thesis. An overview of semiconductor nanoparticles, colloquially referred to as quantum dots (QDs), is presented in Chapter 1, including strategies for the preparation of InP QDs from typical phosphorus precursors.

Chapter 2 explores the reactivity of the parent phosphinecarboxamide (H2PC(O)NH2) in solution towards common InP QD precursors. The preparation of InP clusters and a novel N-functionalised phosphinecarboxamide using H2PC(O)NH2 is discussed. Both H2PC(O)NH2 and N-functionalised phosphinecarboxamides are found to be effective sources of PH3 in solution upon thermal decomposition in pyridine at 105oC.

Chapter 3 describes the use of an N-functionalised phosphinecarboxamide as a novel air-stable phosphorus precursor to core/shell In(Zn)P/ZnS QDs. A synthetic protocol is optimised to afford core/shell In(Zn)P/ZnS QDs with size-dependant photoluminescence emission maxima between 550 and 650 nm, with full width at half maxima (FWHM) between 68 and 128 nm.

Chapter 4 explores the reactivity of N-, N,N-, and P-functionalised phosphinecarboxamides in solution. The effect of phosphinecarboxamide side-chain functionalisation on reactivity is also discussed.

Finally, Chapter 5 discusses the use of functionalised phosphinecarboxamides for the preparation of In(Zn)P/ZnS QDs and the unique size control that they afford. Carboxylate functionalised phosphinecarboxamides are used to prepare core/shell In(Zn)P/ZnS QDs with size-dependant photoluminescence emission maxima between 550 and 620 nm and FWHM between 83 and 114 nm. Additionally, the unexpected use of a P-functionalised phosphinecarboxamide as an air-stable precursor to size-uniform InP QDs is described, which display a photoluminescence maximum at 546 nm and a FWHM of 75 nm.

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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Inorganic Chemistry
Oxford college:
Queen's College
Role:
Author

Contributors

Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Role:
Supervisor
ORCID:
0000-0001-7734-1709
Institution:
Indiana University Bloomington
Role:
Supervisor


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Funder identifier:
https://ror.org/0439y7842
Programme:
Oxford Inorganic Chemistry for Future Manufacturing (OxICFM) Centre for Doctoral Training


DOI:
Type of award:
DPhil
Level of award:
Doctoral
Awarding institution:
University of Oxford

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