View Online

COMMUNICATION www.rsc.org/chemcomm | ChemComm

A novel single source precursor: [bis(N,N-diethyl-N 0 -naphthoyl-

selenoureato)palladium(II)] for palladium selenide thin films and
nanoparticlesw
Javeed Akhtar,z Rana Farhat Mehmood, Mohammad Azad Malik, Nasir Iqbal,
Paul O’Brien* and James Raftery
Received 5th August 2010, Accepted 15th November 2010
DOI: 10.1039/c0cc03079a
Published on 07 December 2010 on http://pubs.rsc.org | doi:10.1039/C0CC03079A

We describe for the first time the use of a single source precursor
to deposit thin films and nanocrystals of palladium selenide.

Platinum group metal chalcogenides have applications in

Downloaded by University of Manchester on 08 December 2010

catalysis,1–3 as low resistance ohmic contacts in semiconducting

electronic devices,3 recording films in optical discs and
lithographic films,3 and light image receiving materials with
silver halides.4 Palladium selenide exists in several phases
including PdSe, Pd17S15, Pd7Se4, Pd2.5Se, Pd3Se, Pd7Se, Pd4Se,
Pd4.5Se, Pd8Se and PdSe2. These materials are typically
prepared by heating the two elements in an evacuated sealed
tube followed by annealing at high temperatures for several
days. A single crystal structure of Pd17Se15 has been reported
in three different space groups (Pm3m, P43m, P432) but the
best refinement was obtained in Pm3m.5 PdSe2 has a deformed
pyrite structure.6
A number of relevant organochalcogenolato complexes
including monoselenocarboxylates, benzylselenolates, allyl-
palladium complexes, and palladium/platinum sulfido/seleno
bridged complexes have been prepared by Jain et al.7 They
have investigated the decomposition of such complexes by
pyrolysis. The decomposition of [M2Cl2(m-SenPr)2(PnPr3)2] in
tributylphosphate at 195 1C gave Pd17Se15 residue whereas the
pyrolysis of related allylpalladium complexes in xylene gave
Pd4Se19 residue.8 There are no reports in the literature of using
these types of complexes as single source precursors for the
growth of palladium selenide thin films or nanoparticles.
In another study Pd(acac)2 (or PdCl2) was reacted with
nanowires of trigonal selenium (t-Se, as a template) in refluxing
ethanol to generate Pd17Se15 on the surface of each t-Se
nanowire.9 Although PtS and PdS nanocrystals have been
synthesised in TOPO using a single source precursor,10 to our
knowledge there are no reports in the literature on the use
of a single source precursor for the deposition of palladium
selenide thin films or nanoparticles.
We have synthesized the complex [bis(N,N-diethyl-N 0 -
naphthoylselenoureato)palladium(II)] by slight modification
School of Chemistry and Materials Science Centre, The University of
Manchester, Oxford Road, Manchester M13 9PL, UK.
E-mail: paul.obrien@manchester.ac.uk; Fax: +44 (0)161 275 4598;
Tel: +44 (0)161 275 4653
w Electronic supplementary information (ESI) available: pXRD
pattern, UV/Vis spectrum, TEM image of PdSe nanoparticles, and
method of preparation. CCDC 773721. For ESI and crystallographic
data in CIF or other electronic format see DOI: 10.1039/c0cc03079a
z Present address: Nanoscience and Materials Synthesis Lab, Department
of Chemisty, Qauaid-i-azam university, Islamabad, Pakistan
Fig. 1 Molecular structure of N,N di-ethyl-naphthoyl selenourea (1).
Selected bond distances (Å) and angles C(11)–O(1) 1.218(3),
C(11)–N(1) 1.398(3), C(12)–N(2) 1.326(4), C(12)–N(1) 1.410(4),
C(12)–Se(1) 1.830(3), C(13)–N(2) 1.478(4), O(1)–C(11)–N(1)
121.4(3), O(1)–C(11)–C(1) 122.5(2), N(1)–C(11)–C(1) 116.1(2),
N(2)–C(12)–N(1) 116.2(3), N(2)–C(12)–Se(1) 126.0(2),
N(1)–C(12)–Se(1) 117.8(2).
of the method reported in the literaturey.11 The X-ray single
crystal structure of the ligand (1) was determined (Fig. 1),
repeated attempts to get good quality crystals of the palladium
complex were unsuccessful. The structure of the ligand shows
significantly longer bond length of CQSe (1.824 Å) as
compared to the sulfur analogues (1.67Å).12 There is inter-
molecular hydrogen bonding through carbonyl oxygen and
hydrogen atoms of the naphthoyl ring of neighbouring
molecules. This feature is unusual as compared to previous
reports on related compounds in which hydrogen bonding
is present between selenium atom of one molecule and
selenoamidic hydrogen of adjacent molecule known as
resonance-assisted hydrogen bonding (RAHB).13
The compound [bis(N,N-diethyl-N 0 -naphthoylselenoureato)-
palladium(II)] (2) was used to deposit thin films by AACVD,
using a home made apparatus described previously,14 at
deposition temperatures of 400–500 1C and at an argon flow
rate of 160 sccm for 1 h.
The as-deposited films were analyzed using pXRD which
conclusively showed the formation of the cubic form of
palladium selenide (palladesite Pd17Se15 ICDD: 00-029-1437)
at 400 1C, 450 1C and 500 1C (Fig. 2). The films deposited
showed different morphologies at different growth temperatures.
The palladium selenide thin films obtained at 400 1C consist of
uniformly distributed globular crystallites 700–800 nm in
diameter (Fig. 3(a)). On increasing the growth temperature
to 450 1C (Fig 3(b)) or 500 1C (Fig. 3(c) and (d)), films
consisting of densely packed uniform rods growing upwards
from the substrate were obtained. HRTEM images of the

This journal is c The Royal Society of Chemistry 2010 Chem. Commun.


Published on 07 December 2010 on http://pubs.rsc.org | doi:10.1039/C0CC03079A
Fig. 2 pXRD pattern of as-deposited thin films of palladium selenide
Pd17Se15 (ICDD: 00-029-1437) at (a) 400 1C (b) 4501C and (c) 5001C.
Downloaded by University of Manchester on 08 December 2010
Fig. 3 SEM images of the palladium selenide thin film on glass at
(a) 400 1C (b) 450 1C and (c) and (d) 500 1C.
Fig. 4 TEM images of the palladium selenide feathers deposited on
glass at 500 1C.
samples scratched from these films showed flower like structures
as shown in Fig. 4(a) and (b). The length of these rods ranges
from 100–150 nm as estimated from TEM images. EDAX
analysis showed that all deposited films are slightly
selenium rich.
The conductivity of as-deposited palladium selenide thin
films was checked by measuring current–voltage characteristics.
Only the film obtained at 500 1C was found to be conductive
(Fig. 5).
The nanoparticles of palladium selenide were grown by
thermolysis in oleylamine (OA), dodecanethiol (DDTH), or
in 1 : 1 mixture of OA and DDTH. pXRD of the nanoparticles
grown from OA shows the deposition of a mixture of PdSe2
Chem. Commun.
View Online
Fig. 5 I–V characteristic of PdSe films deposited at 500 1C.
(ICDD 01-072-1197) and Pd17Se15 (ICDD 00-029-1437)
nanoparticles with the PdSe2 phase clearly dominant in OA
case (Fig. S1, ESIw). pXRD pattern of the sample deposited
from the DDTH or 1 : 1 mixture showed the growth of the
Pd17Se15 phase only. A UV/Vis spectrum of palladium selenide
nanoparticles obtained from the thermolysis from OA showed
the band edge at 925 nm (Fig. S2, ESIw). TEM images of the
nanoparticles grown from OA show the network of hair like
structures whereas the nanoparticles grown from DDTH show
the formation of spherical structures linked together forming
chains of different lengths (Fig. S3, ESIw). TEM images of the
nanoparticles obtained from the thermolysis of 1 : 1 mixture
of OA and DDSH showed regular crystalline shapes consisting
of cubic and octahedral crystallites (Fig. 6(a), (c) and (d)).
Selected Area Electron Diffraction (SAED) pattern of these
nanocrystals show distinct rings indicating the crystalline
nature of the particles (inset in Fig. 6(b)). Fig. 6(c) and
(d) show HRTEM images of a single hexagonal and cubic
crystal respectively. Fig. 6(e) depicts Fast Fourier Transform
(FFT) image of one of the square shaped nanoparticles.
HRTEM image in Fig. 6(f) shows d-spacing (3.19 Å) which
corresponds to (111) plane.
We have demonstrated for the first time the use of a
palladium complex as a single source precursor for the
Fig. 6 (a) TEM images of palladium selenide nanoparticles prepared
in dodecanethiol (DDSH): oleyl amine (OA) 1 : 1 at 240 1C for 1 hour;
(b) selected area electron diffraction (SAED) pattern; (c) and
(d) HRTEM images of nanocrystals with inset in (c) showing FFT
image. (e) FFT image of cubic nanocrystals; (f) HRTEM image with
d-spacing and FFT inset.
This journal is c The Royal Society of Chemistry 2010

deposition of palladium selenide thin films or nanoparticles.
Thin films show the deposition of a single phase of palladesite
phase (Pd17Se15) at all growth temperatures. The solution
thermolysis carried out in oleylamine gave predominantly
PdSe2 with some Pd17Se15 whereas nanoparticles grown from
DDSH or 1 : 1 mixture of DDSH and OA gave only Pd17Se15.
The shape and size of nanoparticles was strongly dependent
upon the solvent system.
Notes and references
y All the reactions were performed under nitrogen atmosphere by
using standard Schlenk techniques. All chemicals were bought from
Published on 07 December 2010 on http://pubs.rsc.org | doi:10.1039/C0CC03079A
Sigma-Aldrich. NMR spectra were obtained on CDCl3 using a Bruker
AC300 FTNMR instrument. Element analysis was performed by The
University of Manchester micro-analytical laboratory. Single crystal
X-ray crystallography measurements were made using graphite mono-
chromated Mo-Ka radiation on a Bruker APEX diffractometer. The
Downloaded by University of Manchester on 08 December 2010
structures were solved by direct methods and refined by full-matrix
least-squares on F215 Mo-Ka radiation (l = 0.71073 Å). All non-H
atoms were refined anisotropically. H atoms were placed in calculated
positions by assigned isotropic thermal parameters and allowed to ride
on their parent carbon atoms. All calculations were carried out by
using the SHELXTL package.16 CCDC 773721 (1). N,N diethyl-N 0 -
naphthoylselenourea (1): the preparation of the ligand (1) and its lead
complex (2) was carried out by a modification of the method reported
in the literature.13,14 Instead of selenourea being isolated by addition
of excess of water we used diethyl ether to extract selenourea. Yield,
33%; elemental analysis (found: C, 57.6; H, 5.3; N, 8.3%, calc: C, 57.0;
H, 5.4; N, 8.4%) IR: 3023 n(C–H), 1753 n(CQO), 1198 n(CQSe), 1361
n(C–N) cm1. 1H NMR (d CDCl3, 400 MHz) (400 MHz; CDCl3): 1.42
(t, 3H), 1.30 (t, 3H), 3.6 (q, 2H), 4.18 (q, 2H), 7.85(m, Ar-4H), 7.56
(p, Ar-3H), 8.5 (s, NH), mass (ES, negative scan) m/z 333 (100%),
ligand. [bis(N,N-Diethyl-N 0 -naphthoylselenoureato)palladium(II)] (2)
yield 54%, elemental analysis (found: C 48.30, H 4.0, N 7.0, Pd
14.6%). Calculated: C 50.0, H 4.2, N 7.3, Pd 13.8%. IR: 2977
n(C–H), 1505 n(CQO, coordinated with metal), 914 n(CQSe,
coordinated with metal), 1361 n(C–N) cm1. 1H NMR (d, CDCl3,
400 MHz) (400 MHz; CDCl3): 0.74 (d, 12H), 0.87 (d, 12H), 1.6 (t, 2H),
2.1 (t, 2H), 3.5 (d, 4H), 3.78 (d, 4H), 8.28(m, Ar-8H), (APCI,
acetonitrile) m/z 255(100%) binaphthyl. Crystal data for the ligand:
Mr = 333.28, crystal system triclinic, space group, P1 a = 11.1943(8) Å,
b = 11.2670(8) Å, c = 13.5411(10) Å, a = 72.631, b = 85.291,
g = 66.501. Volume 1493.47(19) Å3, Z = 4, calculated density =
1.482 mg m3. AACVD deposition: AACVD experiments were carried
out at deposition temperatures of 400–500 1C with an argon flow rate of
160 sccm for 1 h under atmospheric pressure. The reactor was
purged with argon for 10 min at the required deposition temperature
before carrying out deposition in order to avoid any in situ oxidation.
Synthesis of nanoparticles: 0.25g (0.32 mmol) of precursor (2) in
This journal is c The Royal Society of Chemistry 2010
View Online
10 ml of oleylamine was heated to 230 1C under nitrogen in a three neck
flask for 1 h. The colour of the mixture changed to red-brown. After
cooling the flask to room temperature and addition of 20 ml of acetone
into the flask gave a brown-black precipitate which was separated by
centrifugation.
1 L. Y. Chiang, J. W. Sioirczeweki, R. Kastrup, C. S. Hsu and
R. B. Upasani, J. Am. Chem. Soc., 1991, 113, 6574.
2 S. Eijsbouts, V. H. J. DeBeer and R. Prins, J. Catal., 1988, 109,
217.
3 S. Dey and V. K. Jain, Platinum Met. Rev., 2004, 48, 16.
4 H. Kyama and T. Iwata, Japanese Patent 08/095, 209, Mitsubishi
Paper Mills Ltd, 1996O. Tanabe, U.S. Patent 5,030,545, Fuji
Photo Film Co Ltd, 1991.
5 S. Geller, Acta Crystallogr., 1962, 15, 713.
6 T. Olsen, E. Roest and F. Groenvolt, Acta Chem., Scand. Ser. A,
1979, 33, 251.
7 A. Singhal, V. K. Jain, R. Mishra and B. Varghese, J. Mater.
Chem., 2000, 10, 1121; B. Liladhar, J. V. Jain, P. P. Phadnis and
M. Nethaji, J. Organomet. Chem., 2007, 692, 1546; S. Dey,
V. K. Jain and B. Varghese, J. Organomet. Chem., 2001, 623, 48;
S. Dey, V. K. Jain, S. Chaudhury, A. Knoedler, F. Lissner and
W. Kaim, J. Chem. Soc., Dalton Trans., 2001, 723; S. Dey,
V. K. Jain, J. Singh, V. Trehan, K. K. Bhasin and B. Varghese,
Eur. J. Inorg. Chem., 2003, 744; B. Liladhar, K. J. Vimal and
B. Varghese, Inorg. Chim. Acta, 2006, 359, 409.
8 S. Dey, S. Narayan, A. Singhal and V. K. Jain, Proc.-Indian Acad.
Sci., Chem. Sci., 2000, 112, 187; V. K. Jain, B. Liladhar, S. Dey and
N. D. Ghavale, Phosphorus, Sulfur Silicon Relat. Elem., 2008, 183,
1003; B. Liladhar, J. K. Vimal, P. P. Phadnis and M. Nethaji,
J. Organomet. Chem., 2007, 692, 1546; B. Liladhar, W. P Amey,
J. K. Vimal, K. Siddharth and M. Nethaji, J. Organomet. Chem.,
2009, 694, 3892.
9 J. Xuchuan, M. Brian, W. Yuliang, C. Bryan and X. Younan,
Chem. Phys. Lett., 2004, 385, 472.
10 M. A. Malik, N. Revaprasadu and P. O’Brien, J. Mater.Chem.,
2002, 12, 92.
11 I. B. Douglass, J. Am. Chem. Soc., 1937, 59, 740; I. B. Douglass
and F. B. Dains, J. Am. Chem. Soc., 1934, 56, 1408.
12 J. C. Bruce and K. R. Koch, Acta Crystallogr., Sect. C: Cryst.
Struct. Commun., 2008, 64, m1; J. Dillen, M. G. Woldu and
K. R. Koch, Acta Crystallogr., Sect. E: Struct. Rep. Online,
2006, 62, 05228.
13 J. Dillen, M. G. Woldu and K. R. Koch, Acta Crystallogr., Sect.
E: Struct. Rep. Online, 2006, 62, 04819; W. Bensch and
M. Schuster, Z. Anorg. Allg. Chem., 1994, 620, 1479.
14 G. Horley, M. Lazell and P. O’Brien, Chem. Vap. Deposition, 1996,
2, 242.
15 G. M. Sheldrick, SHELXL 97 and SHELXS 97, University of
Gottingen, Germany, 1997.
16 SHELTXTL Version 6.10, Bruker AXS Inc., Madison, Wisconsin,
USA, 2000.
Chem. Commun.