Colloidal manganese-doped semiconductor
nanocrystals capable of pronounced intrinsic hightemperature
dual emission have been developed by
researchers at the University of Washington in the
US [Vlaskin et al., Nano Lett (2010) doi: 10.1021/
nl102135k].
There are some molecules that can show luminescence
at two different excited states, a process known
as dual emission which has led to the use of
these molecules in thermometric applications. In
most cases organic molecules have been used but
researchers are also keen to try out inorganic colloidal
semiconductor crystals as they show a good resistance
to photodegradation. However, the inorganic
nanocrystals investigated so far have suffered from
low thermometric sensitivity and poor ratiometric
detection.
Daniel Gamelin’s team has been studying dual
emission in Mn2+ doped nanocrystals for some time
and has finally overcome these problems. “Prior
results from our group had identified the possibility of
accessing this basic phenomenon in Mn-doped CdSe
nanocrystals, but encountered big difficulties because
of the need to work with very small nanocrystals
in order to have the correct energy alignment of
the two emissive states. Unfortunately, in those
very small nanocrystals, we could never get all of
the nanocrystals to be doped, so our signals were
always contaminated with undoped nanocrystals and
the results were very unreliable. To get around this
problem, we separated the tasks of doping and energy
gap tuning. We started with doping of wide-gap
ZnSe nanocrystals so that we could grow them large
enough that every nanocrystal contained Mn. We
could then tune the semiconductor energy gap down
to the correct range for this dual emission effect by
growing a narrower-gap shell of ZnCdSe around the
Mn-doped ZnSe cores. This turned out to provide
precisely the right control over both doping and
energy gap tuning to open up these materials for very
clean, high-temperature dual emission,” he explains
to Materials Today.
The nanocrystals that the team produced have two
distinct emissive excited states with a 10 000-fold
difference in luminescence rates. This means that
very small changes in temperature result in a very
large change in relative peak intensities with dual
emission being the dominant component of the overall
luminescence.
Temperature ranges from cryogenic to well above
room temperature can be achieved, where the dualemission
window is tuned by changing the energy gap
during nanocrystal fabrication.
Katerina Busuttil