NANO

LETTERS

One-Step Synthesis and Assembly of

Copper Sulfide Nanoparticles to
Nanowires, Nanotubes, and
Nanovesicles by a Simple Organic
Amine-Assisted Hydrothermal Process

2002
Vol. 2, No. 7
725-728

Qingyi Lu, Feng Gao, and Dongyuan Zhao*

Molecular Catalysis and InnoVatiVe Materials Lab, Department of Chemistry,
Fudan UniVersity, Shanghai 200433, P. R. China
Received March 12, 2002; Revised Manuscript Received May 23, 2002

ABSTRACT
A simple organic amine-assisted hydrothermal process has been proposed to simultaneously realize the synthesis and assembly of copper
sulfide nanoparticles at low temperature (90 110 C). Nanowire-like aggregates (average diameter of 120 nm and length of 2 m) assembled
by digenite phase copper sulfide nanoparticles have been synthesized with triethylenediamine (TEDA) as a linking agent. Nanotube-like aggregates
(diameter ranging from 40 to 200 nm and length from 400 nm to 4 m) and nanovesicle-like aggregates (size ranging from 50 to 180 nm),
assembled by djurleite phase copper sulfide nanoparticles, have also been obtained by substituting tramethylethylenediamine (TMEA) and
di-n-butylamine (DBA) for TEDA, respectively.

The study of semiconductor nanoparticles is one of the most

active areas due to their interesting properties which are far
from those of bulk substances.1 Because of their distinguished
optical and electronic properties, the control of the size and
morphology of chalcogenide nanocrystals has been a primary
focus.2 However, the realization of technologically useful
nanoparticle-based materials depends not only on the quality
of the nanoparticles (e.g., size and shape) but also on their
spatial orientation and arrangement.3 The development of
practical strategies for the assembly of inorganic nanoparticles into well-defined arrays is thus an area of considerable
current interest, because it offers opportunities to exploit their
unique optical and electronic properties and possibilities to
probe new, potentially collective phenomena.3,4 Nevertheless,
compared with the synthesis of discrete nanoparticles, the
assembly of nanoparticles into well-defined superstructures
remains a challenge and usually requires the initial synthesis
of spherical nanoparticles, followed by further processing
such as evaporation of hydrophobic colloids,5 molecular
cross-linking in colloidal aggregates,6 or template-directed
synthesis using porous protein crystals of bacterial superstructures.7 Many efforts focus on the formation of organized
two-dimensional (2-D) and 3-D arrays of nanoparticles,8 and
just a few reports have appeared regarding the synthesis of
1-D nanoparticle systems or hollow structures including 1-D
strands of iron oxide and CdS nanoparticles with biomol10.1021/nl025551x CCC: $22.00
Published on Web 06/05/2002

2002 American Chemical Society

ecules as linking agents,9 1-D Au- or Ag-polymer

nanochains with pores of Al2O3 or polymer membranes as
templates,10 and inorganic-organic nanotube composites
with tobacco mosaic virus as guide.11
Herein, we propose a simple organic amine-assisted
hydrothermal process for the one-step synthesis and assembly
of copper sulfide nanoparticles with CuCl and thiourea as
the reactants at low temperature (90 110 C). With
triethylenediamine (TEDA) as a linking agent, nanowirelike aggregates (average diameter of 120 nm and length of
2 m) assembled by digenite phase copper sulfide nanocrystals have been synthesized. By using tramethylethylenediamine (TMEA) and di-n-butylamine (DBA) as the linking
agents instead of TEDA, respectively, nanotube-like aggregates (diameter ranging from 40 to 200 nm and length
from 400 nm to 4 m) and nanovesicle-like aggregates (size
ranging from 50 to 180 nm) assembled by djurleite phase
copper sulfide nanocrystals have also been obtained.
The synthesis and assembly of copper sulfide nanoparticles
were carried out under hydrothermal conditions at low
temperature. In a typical preparation, 1.4 mmol TEDA was
dissolved into 50 g of 0.055 M (2.8 mmol) thiourea solution
and then the TEDA-thiourea solution was transferred into
a Telfon bottle, then 5.0 mmol CuCl was added into the
bottle. After the bottle was heated at 90 110 C for 40 h,
a black precipitate with yield higher than 90% was collected,

Figure 1. XRD patterns of the semiconductor copper sulfide

samples prepared under low-temperature hydrothermal conditions
with (a) TEDA (1.4 mmol), (b) (1,12)-dodecyl-diamine, (c) TEDA
(14 mmol), (d) TMEA, (e) DBA.

filtered, washed with distilled water and absolute alcohol

several times, and dried at room temperature.
Figure 1a shows the X-ray diffraction (XRD) pattern of
the sample prepared with TEDA as linking agent (1.4 mmol)
under low temperature (90 110 C) hydrothermal conditions, recorded on a Rigaku D/Max-IIA using filtered Cu
KR radiation. All diffraction peaks can be indexed as digenite
phase copper sulfide with lattice parameters comparable to
that of JCPDS card (23-962). No XRD peaks arising from
impurities can be detected. The relatively broad XRD peaks
reveal the small size of copper sulfide crystals, and according
to the Scherrer diffraction formula the average particle size
is approximately 12 nm. Transmission electron microscopy
(TEM) images (Figure 2a,b) of this sample were obtained
using Japan JEOL JEM2011 high-resolution transmission
electron microscopy, revealing that fibrous aggregates with
average width of 120 nm and length of 2 m have been
obtained. The diffraction rings in the selected area electron
diffraction (SAED) pattern (inset in Figure 2b) can be
indexed as (555), (10100), and (5515) reflections, respectively, associated with pseudo cubic structure, indicating that
these copper sulfide nanowires are composed of polycrystals
of digenite phase copper sulfide. The sample has also been
embedded in resin and then sliced up for TEM observation.
A TEM image of the embedded sample (Figure 2c) can
reveal the section morphology of the nanowires, clearly
showing that these nanowires are assembled by dozens of
nanoparticles with average size of 15 25 nm. The highresolution TEM image (inset in Figure 2c) shows that these
nanoparticles are single crystals with interplanar distance of
3.21 , corresponding to the (555) direction of digenite phase
copper sulfide. In our experiments, almost all of the copper
salt reactants can be transformed into copper sulfides under
the hydrothermal conditions, and the yield for the copper
sulfide solids is very high (>90%). It should be noted that
based on TEM observation, the fraction of the nanowirelike aggregates is calculated to be about 60% and the remnant
726

Figure 2. TEM images and the selected area electron diffraction

(SAED) patterns of the copper sulfide samples prepared with
different concentration TEDA under low-temperature hydrothermal
conditions with (a) (b) (c) 1.4 mmol TEDA and (d) 14 mmol TEDA
(inset b,d, showing the SAED pattern). For TEM image (c), the
sample was embedded in the resin and sliced up for TEM
observation (inset c showing TEM image with large magnification).

consists of discrete nanoparticles that compose the nanowirelike aggregates.

To the contrary, without the addition of organic amine,
copper sulfide nanocrystals cannot be formed under our
experimental conditions because the interaction between
CuCl and thiourea is too strong to decompose, confirmed
by an XRD pattern (not shown). The sample prepared with
(1,12)-dodecyl-diamine as a linking agent is also digenite
phase copper sulfide (Figure 1b). TEM images (not shown)
reveal that this sample consists of discrete digenite phase
copper sulfide nanocrystals with average size about 15 nm.
Figure 3 shows the UV-vis absorption spectra of the
samples prepared with different organic amines, recorded
with an Agilent 8453 spectrophotometer. Copper sulfide
nanoparticles prepared with (1,12)-dodecyl-diamine display
an absorption maximum at 515 nm (Figure 3a), which might
be assigned to the optical transition of the first excitonic
state.12 With TEDA (1.4 mmol) as linking agent, the product
has an absorption peak at 555 nm (Figure 4b). The red shift
of the maximum is associated with the formation of aggregated nanowire-like structures with TEDA as linking
agent.13
The interaction between a metal ion and an organic amine
molecule is an important factor to the structure and morNano Lett., Vol. 2, No. 7, 2002

Figure 3. UV-vis absorption spectra of the copper sulfide samples

prepared under low-temperature hydrothermal conditions with (a)
(1,12)-dodecyl-diamine, (b) TEDA (1.4 mmol).

Figure 4. TEM images and the SAED patterns of the samples

prepared under low-temperature hydrothermal conditions with (a)
(b) TMEA and (c) (d) DBA. (inset a,d showing the SAED pattern).
For TEM image (b), the sample was embedded in the resin and
sliced up for TEM observation (inset c showing TEM image with
large magnification).

phological controls of the product.14 In our experiment,

TEDA is of importance not only in the synthesis and
assembly of copper sulfide nanoparticles but also in the
morphological control of copper sulfide nanocrystals. To
optimize the reaction conditions to get maximum fraction
of nanowire-like aggregates, we adjusted the used amount
of TEDA. We found that with proper concentration of
TEDA, the nanowire-like aggregates are the dominating
product and the maximum fraction is about 60%. At low
concentration of TEDA (such as 0.5 mmol) just a few
Nano Lett., Vol. 2, No. 7, 2002

nanoparticles can assemble to form copper sulfide nanowires,

and many discrete copper sulfide nanoparticles are observed
in the product. On the other hand, high concentration of
TEDA also does not increase the fraction of nanowire-like
aggregates and especially, 14 mmol TEDA leads to the
formation of copper sulfide single-crystal nanorods. The
XRD pattern (Figure 1c) shows that the sample prepared with
high concentration TEDA (14 mmol) is also digenite phase
copper sulfide, but the diffraction peaks are relatively sharp,
indicating large crystal size of the sample. TEM image
(Figure 2d) shows that the product is copper sulfide nanorods
with nonuniform diameter in the range from 40 to 180 nm
and length in the range from 500 nm to 3 m, and the
inserted SAED pattern confirms that these copper sulfide
nanorods are single crystals with (111) growth direction.
For comparison, other organic amines have also been used
as linking agents for the synthesis and assembly of copper
sulfide nanocrystals. Figure 1d,e shows the XRD patterns
of the samples prepared with TMEA and DBA as linking
agent. All diffraction peaks can be indexed as djurleite phase
copper sulfide with lattice constants comparable to those of
JCPDS card (34-660). These results indicate that with TMEA
and DBA as linking agent, djurleite phase instead of digenite
phase copper sulfides are formed, which may be due to
different interactions between copper ions and different
amines.14 By the Scherrer diffraction formula, the average
crystal sizes of the samples prepared with TMEA and DBA
as linking agent are both calculated to be about 10 nm. Like
the sample prepared with TEDA as linking agent, the yields
of copper sulfides prepared with TMEA and DBA as linking
agent are also very high (>90%). TEM image (Figure 4a)
shows that the sample prepared with TMEA has a special
tube-like morphology. These nanotubes with diameters in
the range from 40 to 200 nm and lengths from 400 nm to
4 m are open-ended and not very uniform. The diffraction
rings in the SAED pattern (inserted in Figure 4a) can be
indexed as (811), (333), (433), (821), (802), (424), (514),
(1312), (835) and (1242) reflections, respectively, associated
with orthorhombic phase copper sulfide, indicating that these
nanotubes are assembled by polycrystals of djurleite phase
copper sulfides. The sample has also been embedded in resin
and then sliced up for TEM observation. TEM image of the
embedded sample (Figure 4b) shows the cross sections and
vertical sections of nanotubes, confirming that these nanotubes are assembled by nanoparticles with average size of 8
20 nm. The thickness of nanotube wall is about 10 50
nm and the inner diameter is about 20 100 nm. Its highresolution TEM image (inset in Figure 4b) displays that these
nanoparticles are single crystals with interplanar distance of
2.82 , corresponding to the (424) (or (514)) direction of
djurleite phase copper sulfide. On the other hand, by using
DBA as a linking agent, copper sulfide nanovesicles with
size ranging from 50 to 180 nm are formed (Figure 4c,d).
The SAED pattern (inset in Figure 4d) indicates that these
nanovesicles are also assembled by polycrystals of djurleite
phase copper sulfide, in agreement with the results from XRD
measurement. The fractions of both nanotube-like and
nanovesicle-like aggregates are about 40% from the TEM
727

observation. In the sample prepared with DBA as linking

agent, the remnant consists of discrete nanoparticles. In
contrast, in addition to discrete nanoparticles, there are also
some nanowire-like and nanovesicle-like aggregates observed
in the sample obtained with TMEA as linking agent, but the
fractions of those nanowire-like and nanovesicle-like aggregates are both lower than 10%.
The organic amines such as ethylenediamine, diethylenediamine, (1,3)-propyl-diamine, and (1,4)-dodecyl-diamine
can also be used as linking agents. In the case of ethylenediamine, the interaction between CuCl and ethylenediamine
is very strong and the complex of ethylenediamine with
copper is formed, instead of copper sulfide, under lowtemperature hydrothermal conditions.15 For diethylenediamine, (1,3)-propyl-diamine, and (1,4)-dodecyl-diamine, only
discrete copper sulfide nanoparticles or short nanochains
(400 nm in length) can be obtained. The assembly functions
of different organic amines may be related to their coordination abilities and molecular structures.16,17 The reaction
temperature is also a key factor to the formation and
assembly of the copper sulfide nanoparticles. When hydrothermal temperature is lower than 70 C, copper sulfide
nanocrystals cannot be formed, since the copper-amine
complex may be stable enough at this temperature that it
does not decompose to copper sulfide nanoparticles. High
hydrothermal temperatures such as 170 C lead to the further
growth of the nanoparticles and are unfavorable to the
assembly of nanoparticles, resulting in the formation of
discrete copper sulfide nanoparticles.
In summary, we have demonstrated that a simple organic
amine-assisted hydrothermal process can be employed to
achieve the synthesis and assembly of copper sulfide
nanoparticles in one step. Nanowire-like aggregates with
average diameter of 120 nm and length of 2 m, nanotubelike aggregates with diameters ranging from 40 to 200 nm
and lengths from 400 nm to 4 m, and nanovesicle-like
aggregates with sizes ranging from 50 to 180 nm have been
synthesized at 90 110 C with TEDA, TMEA, and DBA
as the linking agents, respectively. This method is very
simple and can be easily extended to the synthesis and
assembly of other inorganic nanocrystals.
Acknowledgment. The work was supported by the
National Natural Science Foundation of China, (Grant

728

29925309 and 20101002), Education Ministry of China,

Shanghai Science Foundation (00JC14014), State Key Basic
Research Program of PRC (2001CB610505), and Chinese
Post-Doctor Foundation.
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