The synthesis and structure of a cadmium complex of dimorpholinodithioacetylacetonate and its use as single source precursor for CdS thin films or nanorods

Article abstract of DOI:10.1039/b816909h

A facile method for the preparation of dimorpholides of dithioacetylacetonate is described together with a X-ray single crystal structure of the ligand and of [Cd(msacmsac)₂(NO₃) ₂] (msacmsac = dimorpholinodithioacetylacet

Full text of DOI:10.1039/b816909h

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The synthesis and structure of a cadmium complex of
dimorpholinodithioacetylacetonate and its use as single
source precursor for CdS thin films or nanorods†
Karthik Ramasamy, Mohammad A. Malik, Paul O’Brien* and James Raftery
Received 29th September 2008, Accepted 16th December 2008
First published as an Advance Article on the web 5th February 2009
DOI: 10.1039/b816909h
A facile method for the preparation of dimorpholides of dithioacetylacetonate is described together
with a X-ray single crystal structure of the ligand and of [Cd(msacmsac)2(NO3)2] (msacmsac =
dimorpholinodithioacetylacetonate). The cadmium complex has been used as a single source precursor
for the deposition of the CdS thin films by the aerosol assisted chemical vapour deposition (AACVD)
method or as nanorods by thermolysis in oleylamine. The thin films and nanorods were characterized
by electronic spectra (UV-Vis), photoluminescence (PL), X-ray diffraction (XRD), selected area
electron diffraction (SAED), scanning electron microscopy (SEM), and transmission electron
microscopy (TEM). To the best of our knowledge [Cd(msacmsac)2(NO3)2] is the first complex in its
class to be used as a single source precursor to deposit CdS thin films or nanoparticles.
Introduction
Experimental
Cadmium sulfide is a group II–VI semiconductor with a direct
band gap of 2.42 eV.1 It is well known to be an important device
material as it can be used in solar cells, in light-emitting diodes
for flat-panel display, and other devices.2–4 It has been prepared
by various methods such as chemical bath deposition (CBD),5,6
spray pyrolysis,7,8 solution growth,9,10 and metal organic chemical
vapour deposition (MOCVD).11,12 Amongst these techniques the
MOCVD method is well known and often gives good quality
thin films. A major role in tailoring material properties resides
in the choice of the molecular precursors, whose nature can
strongly affect the morphology and composition of the final
product. In particular, single source precursor containing all the
elements to be deposited in a unique molecule13,14 can be used as
convenient building blocks for materials. CdS nanocrystals have
been prepared using a wide range of synthetic methods.15–20 The use
of single source precursor for CdS as initially reported by Trindade
and O’Brien,21,22 has also provided an efficient route to high qual-
ity crystalline monodispersed nanoparticles of semiconductors.
Various single source precursors have been developed includ-
ing dialkyldithiocarbamates,23 xanthates,24,25 N-alkyl thioureas,26
dithiophosphinates,12 and dithioimidodiphosphinates,27 which
have been used for the preparation of CdS thin films and
nanoparticles. A review by Gleizes gives a detailed account on
the use of single source precursors by CVD method.28 Herein,
we report the synthesis of [Cd(msacmsac)2(NO3)2], single crystal
X-ray diffraction studies for the ligand and complex, and its use
in the deposition of CdS thin films and nanorods.
All preparations were performed under an inert atmosphere of
dry nitrogen using standard Schlenk techniques. All reagents were
purchased from Sigma-Aldrich chemical company and used as
received. Solvents were distilled prior to use. 1H NMR studies were
carried out using a Bruker AC300 FTNMR instrument. Mass
spectra were recorded on a Kratos concept 1S instrument. Ele-
mental analysis was performed by the University of Manchester
micro-analytical laboratory. Melting points were recorded on a
Stuart melting point apparatus and uncorrected.
Synthesis of msacmsac
Morpholine (26.1 g, 2.9 mmol), sulfur (12.8 g, 3.9 mmol), and allyl
◦
propylether (5 g, 0.4 mmol) were heated to 110 C with stirring
under nitrogen atmosphere and maintained for 5 h. Progress
of the reaction was monitored by TLC. After completion the
reaction mixture was cooled to room temperature followed by
50 ml of methanol. Stirring continued for 15 min, the solid product
was filtered and washed with methanol. Recrystallisation from
acetonitrile yielded colourless needle crystals suitable for single
crystal diffraction. Yield: 3.6 g (26%), mp: 208 ◦C, MS (ES) major
peaks m/z = [M+] 274, [C11H18N2O2S] 241, 1H NMR (200 MHz,
CDCl3): d 3.7–3.9 (m, 12H), 4.3 (m, 4H), 4.38 (s, 2H). Elemental
analysis: Found: C, 48.1; H, 6.8; N, 10.2; S, 22.6%. Calc. for
C11H18N2O2S2: C, 48.2; H, 6.6; N, 10.2; S, 23.3%.
Synthesis of [Cd(msacmsac)2(NO3)2]
Cadmium nitrate (0.281 g 0.9 mmol) was dissolved in 10 ml of
acetonitrile and added dropwise to a stirred solution of msacmsac
(0.5 g, 1.8 mmol) in anhydrous acetonitrile. The resulting solution
was stirred at room temperature for 30 min. The colour of the
solution changed to deep yellow upon stirring. The solution
was allowed to evaporate in room temperature. After 24 h in
room temperature yielded colourless crystals suitable for single
The School of Chemistry and the School of Materials, The University
of Manchester, Oxford Road, Manchester, UK M13 9PL. E-mail: paul.
obrien@manchester.ac.uk; Fax: +44 161 275 4598; Tel: +44 161 275 4653
† Electronic supplementary information (ESI) available: Experimental
details for CdS thin films and CdS nanorods. CCDC reference numbers
685538 and 685540. For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/b816909h
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crystal diffraction experiments. Yield: 0.62 g (87%), mp: 88–90 ◦C,
Synthesis of CdS nanorods
MS (ES) major peaks m/z = [M+] 784.1, [C11H18N2O2S2] 274,
In a three-neck flask [Cd(msacmsac)2(NO3)2] (0.5 g) was dissolved
in 15 ml of oleylamine and heated to 160 ◦C under nitrogen flow.
Heating was continued for 2 h. The solution was cooled to 60 ◦C
and excess of dry methanol was added. The precipitate formed
was centrifuged and clear solution decanted. The precipitate
was washed twice with methanol to remove excess oleylamine.
Reactions were repeated under different conditions to investigate
the changes in size and the shape of the CdS nanorods.
1
[C11H18N2O2S] 241, H NMR (200 MHz, CDCl3): d 3.7–3.9 (m,
12H), 4.3 (m, 4H), 4.38 (s, 2H). Elemental analysis: Found: C, 32.7;
H, 4.7; N, 10.4; S, 15.0; Cd, 13.7%. Calc. for C22H36N6O10S4Cd: C,
33.8; H, 4.6; N, 10.7; S, 16.3; Cd, 14.2%.
Crystal structure determination
Single-crystal X-ray diffraction data for the compounds were
collected using graphite monochromated Mo Ka radiation (l =
Characterization of thin films and nanorods
˚
0.71073 A) on a Bruker APEX diffractometer. The structure was
solved by direct methods and refined by full-matrix least squares
on F2.29 All non-H atoms were refined anisotropically. H atoms
were included in calculated positions, assigned isotropic thermal
parameters and allowed to ride on their parent carbon atoms.
All calculations were carried out using the SHELXTL package.30
CCDC reference numbers 685538 and 685540.†
X-Ray diffraction studies were performed on a Bruker AXS
D8 diffractometer using Cu Ka radiation. The samples were
mounted flat and scanned between 20 to 80 ◦C in a step size
of 0.05 with a count rate of 9 s. Films were carbon coated using
Edward’s E306A coating system before carrying out SEM and
EDAX analyses. SEM analysis was performed using a Philips XL
30FEG and EDAX was carried out using a DX4 instrument.
TEM analysis was performed using a cm200 instrument. UV-
Vis spectra were measured using a Helios-BetaThermospectronic
spectrophotometer. Photoluminescence spectra were measured
using a Gilton fluorosens spectroflurometer.
[msacmsac]
C11H18N2O2S2, M = 274.39, colourless needles, monoclinic, space
˚
group C2/c, a = 21.701(4), b = 5.165(9), c = 23.364(4) A, a = 90,
b = 98.890(4), g = 90◦, V = 2587.5(8) A3, Z = 8, D = 1.409 Mg
m-3, T = 100(2) K, reflections collected = 7770/3033, unique
reflections = [Rint = 0.0558], final R indices [I > 2s(I)], R1 =
0.0550, wR2 = 0.0909, R indices (all data) = R1 = 0.1093, wR2 =
0.1062, largest diff. peak and hole = 0.427 and -0.296 e A-3,
GOF = 0.874.
Results and discussion
A schematic diagram for the stepwise synthesis of the ligand, its
cadmium complex and the growth of nanoparticles and thin films
is given in Fig. 1. The ligand was recrystallised from acetonitrile
at room temperature to give transparent needles suitable for X-ray
crystallography. The structure of the ligand shows that the sulfur
atoms are trans to each other. Martin and Stewart31 observed
that the similar SacSac ligand does not exist as uncyclized. In
contrast to this observation we have isolated the linear monomeric
morpholine substituted SacSac ligand (Fig. 2). The reason may be
[Cd(msacmsac)2(NO3)2]
C22H36CdN6O10S4, M = 785.21, yellow plates, triclinic, space group
¯
˚
P1, a = 08.564(2), b = 09.404(2), c = 10.519(3) A, a = 97.480(4),
b = 112.429(3), g = 100.832(4)◦, V = 749.8(3) A3, Z = 1, D =
1.739 Mg m-3, T = 100(2) K, reflections collected = 6436/3376,
unique reflections = [Rint = 0.0345], final R indices [I > 2s(I)],
R1 = 0.0471, wR2 = 0.1283, R indices (all data) R1 = 0.0482,
wR2 = 0.1303, largest diff. peak and hole = 2.813 and -2.132 e
A-3, GOF = 1.059.
Deposition of films by AACVD
In a typical deposition, 60 mg (7.7 ¥ 10-3 mmol) of the precursor
was dissolved in 10 ml mixture of dimethylformamide and
chloroform (1 : 1) in a two-necked 100 ml round-bottom flask
with a gas inlet that allowed the carrier gas (argon) to pass into
the solution to aid the transport of the aerosol. This flask was
connected to the reactor tube by a piece of reinforced tubing. The
argon flow rate was controlled by a Platon flow gauge. Seven glass
substrates (approx. 1 ¥ 3 cm) were placed inside the reactor tube,
which is placed in a Carbolite furnace. The precursor solution
in a round-bottom flask was kept in a water bath above the
piezoelectric modulator of a Pifco ultrasonic humidifier (Model
No. 1077). The aerosol droplets of the precursor thus generated
were transferred into the hot wall zone of the reactor by carrier
gas. Both the solvent and the precursor were evaporated and
the precursor vapor reached the heated substrate surface where
thermally induced reactions and film deposition took place.
Fig. 1 Schematic representation of preparation of ligand, precursor, CdS
thin films and nanorods.
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their chair conformation. The morpholine rings maintain their
chair conformation. Crystal data and refinement parameters
for [Cd(msacmsac)2(NO3)2] are given in the crystal structure
determination section and important bond lengths and bond
angles are given in Fig. 3 caption.
Thin films
CdS thin film depositions were carried out as a function of temper-
ature. Very thin films were obtained at the lowest temperature of
450 ◦C. Thicker films were obtainable at the higher temperatures.
Fig. 2 Molecular structure of [msacmsac] with thermal ellipsoids plotted
Characterizations of CdS films
◦
˚
at the 50% probability. Selected bond distances (A) and angles ( ): C5–S1 =
1.665(3), C5–N1 = 1.320(3), C5–C6 = 1.510(3), O1–C2 = 1.472(4),
C6–C5–S1 = 120.5(2), C5–N1–C4 = 120.6(3).
Standard q-2q scans cannot always reliably distinguish (111)-
oriented cubic CdS from hexagonal CdS with (001).33 However, in
this study XRD produced no real evidence for cubic CdS in any
films. The three dominant peaks in most diffraction patterns from
films grown at 450 ◦C can be assigned to the CdS (100), (002), (101)
reflections of hexagonal phase which are also the three strongest
peaks in the powder pattern. Films grown on glass at 500 ◦C show
preferred orientation along the (101) plane (Fig. 4).
the steric hindrance caused by morpholine rings. Both morpholine
rings are disordered and have been modelled so each ring has
one alternative conformation in the ratio of 74 : 26 and 49 : 51
for the rings containing N1 and N2 respectively. Crystal data
and refinement parameters are given in the crystal structure
determination section and important bond lengths and bond
angles are given in Fig. 2 caption.
[Cd(msacmsac)2(NO3)2]
The crystal structure of [Cd(msacmsac)2(NO3)2] is shown in Fig. 3.
The lone pair at the sulfur is responsible for the formation of the six
membered chelate ring with a strong Cd–S bond. Two molecules
of the bidentate msacmsac ligand are coordinated to cadmium
through lone pair of electrons at sulfur atoms equatorially and
axial bonds are formed through the oxygen atoms of nitrate group
to complete the octahedral coordination. The axial compression
˚
of Cd–O (2.385 A) makes the molecule unusually elongated Cd–S
˚
(2.628–2.699 A). The coordination is similar to that observed in
dithiomalonamides of antimony.32 The morpholine rings maintain
Fig. 4 X-Ray diffraction patterns of CdS thin films grown on glass
at (a) 450 ◦C, (b) 500 ◦C. Solid lines representing the hexagonal phase
(JCPDS-0772306).
SEM images given in Fig. 5 exhibit clusters of crystallites for
films deposited at 450 ◦C and 500 ◦C. These films comprise of
different sizes of clusters formed by granular crystallites ranging
from 0.9 to 1.3 mm. The bigger clusters probably grown by fusion
Fig. 3 Molecular structure of [Cd(msacmsac)2(NO3)2] with thermal
˚
ellipsoids plotted at the 50% probability. Selected bond distances (A)
and angles (◦): Cd1–S2 = 2.6286(9), Cd1–S1 = 2.6992(9), Cd1–O4 =
2.385(2), N3–O3 = 1.234(4), N3–O5 = 1.245(3), O4–Cd1–S2 = 91.72(6),
S2–Cd1–S1 = 95.91(2).
Fig. 5 SEM micrographs of CdS thin films grown on glass at (a) 450 ◦
and (b) 500 ◦C. Bar = 1 mm.
C
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of smaller clusters◦. The granular crystallites of CdS grown on glass
substrates at 500 C are considerably larger than those grown at
450 ◦C. EDAX analysis confirms the CdS composition close to
1 : 1 at 450 ◦C (Cd, 53; S, 47%) but sulfur deficient films were
obtained at 500 ◦C (Cd, 55; S, 45%).
CdS nanorods
The shape control of inorganic nanocrystals is topical in
nanoscience.34 The crystalline phase of seeds at the nucleating stage
can be critical in directing the intrinsic shape of the nanocrystals
due to its characteristic unit cell structure. At this stage, the
crystalline phase of the seed can be highly dependent on reaction
environment, especially temperature. The XRD pattern (Fig. 6) of
CdS nanocrystals shows the hexagonal phase (JCPDS-0772306).
The growth at 200 ◦C and 240 ◦C shows that the crystallites
are elongated along the c-axis. In general higher the reaction
temperature stronger and narrower the XRD peaks, concurrent
with the increase in mean size of the nanocrystals.
Fig. 7 TEM image and SAED pattern of CdS nanocrystals synthesized at
(a) 160 ◦C, (b) 200 ◦C and (c) 240 ◦C; (d) HRTEM image of CdS nanorods
at 240 ◦C.
Fig. 6 Powder X-ray diffraction patterns of CdS nanorods grown at (a)
160 ◦C, (b) 200 ◦C and (c) 240 ◦C. Solid lines representing the hexagonal
phase (JCPDS-0772306).
Fig. 8 Absorption spectra (a–c) and photoluminescence spectra (d–f)
(372 nm excitation) for CdS nanorods grown at 160 ◦C, 200 ◦C and 240 ◦C
respectively.
TEM images of CdS nanorods are shown in Fig. 7. The
nanorods grown at 160 ◦C show a mixture of spherical particles,
double armed rods, and single armed rods. As the temperature
increased to 200 ◦C, nanocrystals formed tripods and bipods. At
approximation.37 It is well known that the absorption spectrum can
characterize the dispersivity of the nanoparticles.38 The spectra of
samples grown at 160 ◦C, 200 ◦C and 240 ◦C show clear absorption
peaks. But at higher temperatures the absorption tail is prolonged
suggesting deterioration of the dispersivity with the increase in the
size of nanoparticles. The size of the particles was also investiga◦ted
by using the Wang equation.39 The nanoparticles grown at 160 C,
200 ◦C and 240 ◦C showed only a slight change in size 7.7, 8.0 and
8.2 nm respectively.
◦
240 C the formation of rods dominated and the aspect ratio of
the nanorods decreased. This observation is consistent with earlier
results.35 HRTEM images of the nanorods are shown in Fig. 7(d)
and have lattice fringes with a d-spacing 0.337 nm corresponding
to (002) reflection. SAED pattern consist of broad diffuse rings,
which are indicative of the small size of rods. The diffraction rings
can be indexed to the (002), (110), (103) and (112) planes of the
wurzite phase.
The UV-Vis spectra for as synthesized CdS nanorods are shown
in Fig. 8(a–c). The band edges were close to each other for all the
samples at 160 ◦C (500 nm), 200 ◦C (505 nm) and 240 ◦C (509 nm).
When the size of CdS nanocrystals becomes smaller than the
exciton radius, quantum size effects lead to a size dependent
increase in the band gap and a blue-shift in the absorption onset.36
The increment in band gap is approximately inversely proportional
to the square of the crystal size based on the effective mass
Photoluminescence measurements were carried out at room
temperature with an excitation wavelength 372 nm. Photolumi-
nescence spectra in toluene solution of CdS nanorods are shown
in Fig. 8(d–f). Emission peaks were observed near the band
edge◦s at 492 nm, 484 nm and 496 nm for samples grown at
◦
◦
160 C, 200 C and 240 C respectively. The photoluminescence
appears to increase by the increase in growth temperature. The
highest photoluminescence was observed for the nanorods grown
at 240 ◦C. The nanorods grown at this temperature contain only
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the rods without any mixture of bipods or tripods as observed for
samples grown at 200 ◦C or 160 ◦C.
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The crystal structure of [Cd(msacmsac)2(NO3)2] shows a bidentate
coordination by the sulfur atoms of each ligand. The coordination
geometry around cadmium is close to octahedral. Deposition of
thin films at various temperatures showed the growth of CdS
clusters which were made of granular crystallites. The cluster size
increased by increasing the deposition temperatures. Thermolysis
of the precursor in oleylamine at 160–240 ◦C gave nanorods
with hexagonal phase of CdS. The band edges of the nanorods
grown at different temperature were similar but more intense
photoluminescence was observed for samples grown at 240 ◦C.
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Acknowledgements
KR is grateful to ORS and The University of Manchester for
financial support. The authors also thank EPSRC, UK for the
grants to POB that have made this research possible.
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