Controllable Growth of Semiconductor Heterostructures
A R T I C L E S
materials epitaxially grow on the suitable crystallographic facet
offered by seeds, leading to heterostructure nanomaterials.
Therefore, a proper lattice mismatch between the growing
crystallographic facets of two different types of nanomaterials
is required. Some cases of heterostructures fabricated through
seeded growth have been reported, such as metal-metal,6
metal-semiconductor,7 and semiconductor-semiconductor8
systems.
In catalyst-assisted growth, including solution-liquid-solid
(SLS)5d,10 and “supercritical fluid-liquid-solid” (SLFS)
methods,5d,10b a metal or alloy with a low melting point is used
as a catalyst for growing nanowires. This route works at a
relatively elevated temperature, at which the metal nanoparticle
catalyst shows liquid or quasi-liquid owing to its smaller size
and low melt points, dissociates the dissolved precursor, and
absorbs the species that can be dissolved in the catalyst. The
aim materials grow from the resulting supersaturation catalyst
at the liquid-solid interface in a manner that minimizes the
interface energy. In such a proposed model, the liquid catalyst
acts as a medium for transporting species from the solution phase
to the solid product. There are several prerequisites for the
catalyst:11a (1) the melting point must be below the reaction
temperature causing the catalyst particles to be liquid or quasi-
liquid; (2) the solubility of the aim materials in the catalyst
should be limited; (3) there is no possibility to form a solid
solution between catalyst and aim materials. To date, the catalyst
nanoparticles that meet the above prerequisites are exclusively
chosen from metals such as AlxGa1-x alloys,5b In,5c Bi,5f Au,5g,h
or Au@Bi core-shell nanoparticles,5e which is more suitable
for preparing semiconductor nanowires or heterostructures of
metal-semiconductor. Compared with the catalytic growth of
semiconductor nanowires, the catalytic growth of 1D semicon-
ductor-semiconductor nanoheterostructure is quite rare. Recently,
the catalytic fabrication of Cu2S-In2S3 heterostructure by using
Cu1.94S NCs as a catalyst has been reported, in which copper
sulfide underwent transformations in both crystalline structure
and chemical composition (from monoclinic djurleite to hex-
agonal chalcocite) during the formation of the heterostructure,11a
whereas the same heterostructures were also prepared by using
Cu2S NCs as seeds in solution.11b More interestingly, Cu2S-
CuInS2 heterostructure was fabricated in the same reaction
system as Hyeon’s including the same precursors through a Cu2S
seed mediated method.12 From these results, we learned that
copper sulfide can act as both seed or catalyst in a similar
reaction system, and In3+ does not dissolve in hexagonal phase
Cu2S but in monoclinic phase Cu1.94S. More interesting, even
though In3+ can dissolve in Cu1.94S, no CuInS2 species are
formed in the copper sulfide. The origin for these is not clear
at the present time and further studies are urgently needed. Also,
understanding these not only can allow precise control over the
fabrication of semiconductor-semiconductor heterostructures,
especially for I-III-VI2 ternary semiconductor compounds such
as AgInS2,13 CuInS2,13,14 CuInSe2,14a CuGaS2,15 due to their
adjustable band gap energies and having promise for photovol-
taic applications,14a but also can promote the exploitation of
Although the principle of seed-assistant growth is easy to
understand, the fabrication of single-crystal heterostructures is
highly difficult in experiment, because the self-nucleation of
the second material is difficult to be completely avoided. And
also, accurately controlling the surface states of seed, which is
suitable for epitaxial growth of the second materials, is also
difficult. The try and error method was adopted to search the
optimum experiment parameters such as temperature, concentra-
tion of the precursors, surfactants (including the types, concen-
trations, and often rigorous combination of two or more different
ones), feeding way, and so on, which is tremendously trivial
and tedious.2,9
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