Development of a Versatile, Stable Droplet‐reactor for High Temperature Nanocrystal Synthesis
Author(s)
Nightingale, Adrian Matthew Le Cocq
Type
Thesis
Abstract
Colloidal nanocrystals exhibit interesting and useful size-dependent nanoscale phenomena (e.g.
tunable fluorescence in quantum dots and optical absorptions in gold and silver nanoparticles), large
surface areas and can be used for a variety of high-tech applications. Care must be taken to produce
nanocrystals with well defined size, shape and composition, however, as these parameters directly
affect the properties of the colloidal ensemble. Microreactors offer superior control over reaction
conditions relative to traditional bulk batch methods and as such offer an attractive route to
nanoparticle production. Hence there have been over a hundred papers reporting microfluidic
synthesis of nanocrystalline colloids since the first reports in 2002. The work described in this thesis
focussed on extending and improving the microfluidic method.
Continuous-flow reactors were used initially, however, deposition was found to be a pervading
problem with its severity varying with the material being synthesised. To address this problem a new
capillary-based droplet-flow reactor was developed in which droplets are generated by the direct
injection of confluent reagent streams within a stream of immiscible carrier fluid and, subsequently,
can be heated and optically characterised further downstream.
The reactor produced stable, controllable droplet flow over a wide range of flow rates, with droplet
volumes down to 30 nL, and proved to be highly effective: CdSe quantum dots were synthesised via a
high-temperature pyrolytic synthesis with strong control over particle size and size distribution.
Crucially, unlike previously reported high temperature droplet reactors, the reactor could be operated
indefinitely, without any degradation of the device and minimal variation in the product seen during
24 hours continuous production. To emphasise the versatility and applicability of the droplet reactor,
Ag, TiO2 and InP nanocrystals were synthesised (using both organic and aqueous syntheses) and an
automatic optimisation routine to reduce size distribution was applied to CdSe quantum dot
synthesis.
tunable fluorescence in quantum dots and optical absorptions in gold and silver nanoparticles), large
surface areas and can be used for a variety of high-tech applications. Care must be taken to produce
nanocrystals with well defined size, shape and composition, however, as these parameters directly
affect the properties of the colloidal ensemble. Microreactors offer superior control over reaction
conditions relative to traditional bulk batch methods and as such offer an attractive route to
nanoparticle production. Hence there have been over a hundred papers reporting microfluidic
synthesis of nanocrystalline colloids since the first reports in 2002. The work described in this thesis
focussed on extending and improving the microfluidic method.
Continuous-flow reactors were used initially, however, deposition was found to be a pervading
problem with its severity varying with the material being synthesised. To address this problem a new
capillary-based droplet-flow reactor was developed in which droplets are generated by the direct
injection of confluent reagent streams within a stream of immiscible carrier fluid and, subsequently,
can be heated and optically characterised further downstream.
The reactor produced stable, controllable droplet flow over a wide range of flow rates, with droplet
volumes down to 30 nL, and proved to be highly effective: CdSe quantum dots were synthesised via a
high-temperature pyrolytic synthesis with strong control over particle size and size distribution.
Crucially, unlike previously reported high temperature droplet reactors, the reactor could be operated
indefinitely, without any degradation of the device and minimal variation in the product seen during
24 hours continuous production. To emphasise the versatility and applicability of the droplet reactor,
Ag, TiO2 and InP nanocrystals were synthesised (using both organic and aqueous syntheses) and an
automatic optimisation routine to reduce size distribution was applied to CdSe quantum dot
synthesis.
Date Issued
2010-10
Date Awarded
2011-02
Copyright Statement
Attribution NoDerivatives 4.0 International Licence (CC BY-ND)
Advisor
de Mello, John
Creator
Nightingale, Adrian Matthew Le Cocq
Publisher Department
Chemistry
Publisher Institution
Imperial College London
Qualification Level
Doctoral
Qualification Name
Doctor of Philosophy (PhD)