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@ARTICLE{Leffler:891844,
author = {Leffler, Vanessa and Ehlert, Sascha and Förster, Beate and
Dulle, Martin and Förster, Stephan},
title = {{N}anoparticle {H}eat-{U}p {S}ynthesis: {I}n {S}itu {X}-ray
{D}iffraction and {E}xtension from {C}lassical to
{N}onclassical {N}ucleation and {G}rowth {T}heory},
journal = {ACS nano},
volume = {15},
number = {1},
issn = {1936-086X},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2021-01767},
pages = {840 - 856},
year = {2021},
abstract = {Heat-up synthesis routes are very commonly used for the
controlled large-scale production of semiconductor and
magnetic nanoparticles with narrow size distribution and
high crystallinity. To obtain fundamental insights into the
nucleation and growth kinetics is particularly demanding,
because these procedures involve heating to temperatures
above 300 °C. We designed a sample environment to perform
in situ SAXS/WAXS experiments to investigate the nucleation
and growth kinetics of iron oxide nanoparticles during
heat-up synthesis up to 320 °C. The analysis of the growth
curves for varying heating rates, Fe/ligand ratios, and
plateau temperatures shows that the kinetics proceeds via a
characteristic sequence of three phases: an induction Phase
I, a final growth Phase III, and an intermediate Phase II,
which can be divided into an early phase with the evolution
and subsequent dissolution of an amorphous transient state,
and a late phase, where crystalline particle nucleation and
aggregation occurs. We extended classical nucleation and
growth theory to account for an amorphous transient state
and particle aggregation during the nucleation and growth
phases. We find that this nonclassical theory is able to
quantitatively describe all measured growth curves. The
model provides fundamental insights into the underlying
kinetic processes especially in the complex Phase II with
the occurrence of a transient amorphous state, the
nucleation of crystalline primary particles, particle
growth, and particle aggregation proceeding on overlapping
time scales. The described in situ experiments together with
the extension of the classical nucleation and growth model
highlight the two most important features of nonclassical
nucleation and growth routes, i.e., the formation of
intermediate or transient species and particle aggregation
processes. They thus allow us to quantitatively understand,
predict, and control nanoparticle nucleation and growth
kinetics for a wide range of nanoparticle systems and
synthetic procedures.},
cin = {ER-C-1},
ddc = {540},
cid = {I:(DE-Juel1)ER-C-1-20170209},
pnm = {535 - Materials Information Discovery (POF4-535)},
pid = {G:(DE-HGF)POF4-535},
typ = {PUB:(DE-HGF)16},
pubmed = {33393769},
UT = {WOS:000613942700061},
doi = {10.1021/acsnano.0c07359},
url = {https://juser.fz-juelich.de/record/891844},
}