We investigated the benefits of using self assembled gold nanoparticles (Au NPs) template for metal electrodepositions. For short electrodeposition time, surface patterning was achieved and a well dense organized structure with nanometre resolution of metallic nanoparticles was prepared. For longer electrodeposition time, different morphologies were obtained. The mechanisms behind the formation of this morphology were analysed and discussed based on the influence of self-assembled Au NPs template in terms of thiol molecules diffusion and adsorption on metallic deposits. Furthermore adjustable wetting properties were obtained through the tuning of electrodeposition time.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3536

Taleb, A.

Yanpeng, X.

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PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 2 No 2, 02FNC21(4pp) (2013)   2304-1862/2013/2(2)02FNC21(4) 02FNC21-1  2013 Sumy State University Why to Use Self Assembled Metallic Nanoparticles Template for Metal Electrodeposition: Metallic Nanostructures with Controlled Morphologies and Adjustable Wetting Properties   A. Taleb*, X. Yanpeng  UPMC –LECIME/ENSCP/Chimie paristech/CNRS7575, 11, Rue P. & M. Curie, 75231 Paris, France  (Received 14 June 2013; published online 31 August 2013)  We investigated the benefits of using self assembled gold nanoparticles (Au NPs) template for metal electrodepositions. For short electrodeposition time, surface patterning was achieved and a well dense or-ganized structure with nanometre resolution of metallic nanoparticles was prepared. For longer electro-deposition time, different morphologies were obtained. The mechanisms behind the formation of this mor-phology were analysed and discussed based on the influence of self-assembled Au NPs template in terms of thiol molecules diffusion and adsorption on metallic deposits. Furthermore adjustable wetting properties were obtained through the tuning of electrodeposition time.   Keywords: Au nanoparticles, Self-assembly, Metal electrodeposition.   PACS numbers: 81.15.Pq, 81.07. – b                                                             *abdelhafed.taleb@upmc.fr 1. INTRODUCTION  For different nanotechnological applications the fabrication of nanostructured materials with a well defined pattern size and shape is a key point [1-4]. In fact, the physical properties associated with such mate-rial depend on the size [5], the morphology and the or-ganization of the pattern [1]. For the preparation of such nanostructures two approaches were used: direct deposition [6] and deposition on modified substrate [7]. Direct deposition approaches, usually achieve disor-dered surface structures because of the preferential nucleation at crystalline defects and step edges [8-10]. To overcome this problem a modified substrate with patterns acting as preferential nucleation sites is pro-posed. However, one of the emerging and promising strategies to create surface patterning and preferential nucleation sites for electrodeposition at a very low scale consists of using a mask made of self-assembled molec-ular film [11-12] or colloidal particles [13-15]. Further-more, a few works deal with the use of the particles as a nucleation sites [16-17].  In this works, we illustrate the ability of self as-sembled Au NPs template to electrocatalyze HOPG surface and to direct electrodeposition of different met-als such as Cu and Ag at nanometer scale. This nanostructuring method provides a promising way to control the electrodeposits growth into ordered struc-ture at nanometer resolution. Additional, we demon-strate that the morphology of metallic electrodeposits can be controlled and different morphologies were ob-tained. Interestingly, these surface morphologies demonstrate adjustable wetting properties.    2. EXPERIMENTAL  A standard three electrode electrochemical configu-ration was used to achieve Cu and Ag electrodeposition. The reference and counter electrodes were respectively Ag/AgCl and a platinum sheet. For Cu electrodeposi-tion experiments a clean (0001) highly oriented pyrolyt-ic graphite (HOPG) surface, which is produced through a cleaving process, was used as a working electrode. The modified HOPG electrode was prepared by deposit-ing a droplet of Au NP solution on the HOPG surface. The area in contact with the solution was fixed at 9 mm2. Cu and Ag were deposited respectively from the aqueous solutions of 10-3 M CuSO4 and 1 M H2SO4 as the supporting electrolyte and from the aqueous solu-tions of 10-2 M AgNO3 and 1 M HCLO4 as the support-ing electrolyte. This solution was deaerated by purified nitrogen for 2 h before use. Copper sulfate pentahy-drate (CuSO4 5H2O) and sulphiric acid (H2SO4) were obtained from Merck whereas Silver nitrate, perchlo-rate acid and dodecanethiol were obtained from fluka. All chemicals used were analytical grade and used without further purification. The electrolytes were pre-pared with water purified by Milli Q system (Millipore, electric resistivity 18.2 M cm).   The 5 nm Au NPs were synthesized using the well known Stucky approach [32]. After synthesis, Au NPs were coated with n-dodecanethiol and presented in a narrow size distribution (6 ). All the experiments of Cu and Ag electrodeposition were performed on Au NPs modified HOPG electrodes. The electrodes were prepared by leaving a dilute droplet of Au NP solution with a concentration of 1.2  10-7 M on the HOPG electrode at ambient temperature. The chronoamperometry was performed at a fixed potential of -0.58 V and -0.3 V versus Ag/AgCl for re-spectively Cu and Ag electrodeposition. All the electro-chemical measurements were performed with an EG&G Princeton Applied Research potenti-ostat/galvanostat model 273 A.  The morphologies of the Cu electrodeposits, Ag elec-trodeposits and Au NPs film were studied using a high-resolution Ultra 55 Zeiss field emission gun scanning electron microscope (FEGSEM).  The chemical compositions of all the samples were determined by X-ray photoelectron spectroscopy (XPS) and for the measurements we used a Kratos Analytical  A. TALEB, X. YANPENG PROC. NAP 2, 02FNC21 (2013)   02FNC21-2 Axis Ultra DLD, using an Al Kα source monochroma-tized at 1486.6 eV.  The wetting properties of our prepared surfaces in terms of static contact angle were determined using a Krüss DSA10 contact angle measuring apparatus equipped with a CCD camera. A 3 l water droplet pu-rified by Milli Q System (Millipore, electric resistivity 18.2 M cm) was used for the static contact angle measurements.  3. RESULTS AND DISCUSSION  In Fig. 1a is shown typical FEGSEM images of Ag electrodeposits on Au NPs modified HOPG substrate over different electrodeposition time.  It is seen that after electrodeposition over 10 s, a small bright spot appears on the modified HOPG electrode corresponding to the formation of Ag NPs. The hexagonal pattern formed by Au NPs is still preserved (indicated by arrow), and Ag deposit is reproducing this structure (indicated by arrow in figure 1(a) and insert) . Similar behavior was observed For Cu electrodeposition in same conditions.   Further confirmation of Ag deposition is provided by XPS experiments (Fig. 1(b)). Theses results evidenced the fact that self assembled Au NPs allows the surface patterning with nanometer resolution which no other techniques can allow [16-18]. By comparing metal elec-trodeposition on bare HOPG and Au NPs modified HOPG electrode, different surface textures were ob-served. On bare HOPG the electrodeposition occurs on step edges and terrace defects according to Volmer We-ber island mechanism whereas atomic flat terrace are inhibited sites [16-18]. However, on Au NPs modified HOPG, metal electrodeposition behavior is completely different and metal deposition takes place on the whole electrode surface including the atomic flat terrace [16-18]. These results show clearly that Au NPs deposited on the HOPG electrode activate the inhibited sites of atomic flat terrace. The mechanism behind this activation can be understood by taking into account the strain effects of Au NPs on the electronic properties of HOPG electrode [18-19]. For longer electrodeposition time and low deposition temperature (18 C), the FEGSEM images depicted in Fig. 2 show dendrite particles [20-21]. This kind of growth is mainly diffusion controlled locally and accompanied by preferential growth directions [21-22]. Furthermore in the pure diffusion limited aggregation (DLA), the solid growth occurs as random walkers diffuse of metal ion (Ag  or Cu2  in our case) into contact with the growing aggregate [23-24]. This mechanism explains the random orientation of growing silver dendrites. However, with Cu dendrites oriented and dense superstructures were observed. From the FEGSEM experiments it is evidenced that the self assembled Au NPs pattern plays a crucial role in the formation of the observed Cu dendrites’ superstructure [21]. In fact the crack defects of the Au NPs template allow micrometer patterning for Cu electrodeposition. A combination of self assembled Au NPs pattern and the aggregation of Cu electrodeposits has been shown to be behind the observed Cu superstructure formation mechanism.  For high electrodeposition temperature of 62 C, different other morphologies were obtained [21]. The results are depicted in Fig. 2. It can be seen that by increasing the temperature more faceted particles were obtained. Ag deposits form plate particles [25] whereas Cu particles are of polyhedral morphology[21]. These results can be understood in terms of dodecanethiol molecules diffusion from Au NPs into the metal deposits surface in which it is adsorbed. Furthermore, dodecanethiol was found to adsorb strongly on the (111) crystallographic facets. As a consequence the growth of this facet slow down through the formation of a dense layer which slow the metal ion reduction on their surface allowing the growth of crystallographic planes in perpendicular directions. This growth anisotropy results in the formation of different observed faceted morphologies. The wetting properties of electrodeposited silver den-dritic film were characterized by the measurement of water contact angles (CAs) [20]. The results are depicted in Fig. 3 and it should be observed that the CA depends on the electrodeposition time. The observed wetting properties are governed by the continuous increase of dendritic surface roughness during the electrodeposition time and the rate coverage of adsorbed dodecanethiol molecules. Thus by varying the silver electrodeposition time adjustable wetting properties can be obtained and a transition between Wenzel and Cassie Baxter state can be induced.    Fig. 1 – (a) FEGSEM images of the electrodeposited silver nanoparticles onto Au NP-modified HOPG electrode at electrodeposition time of 10 s and from an aqueous solution containing 10-2 M AgNO3 and 1 M HClO4 at potential deposition of -0.3 V. Insert is the TEM image of Au NP monolayer (b) XPS core level spectra of Ag 3d acquired from electrodeposited silver on a Au NP modified HOPG electrode over different electrodeposition times 0s and 10 s.  WHY TO USE SELF ASSEMBLED METALLIC NANOPARTICLES TEMPLATE … PROC. NAP 2, 02FNC21 (2013)   02FNC21-3    Fig. 2 – FEGSEM images of the electrodeposited silver particles onto Au NP-modified HOPG electrode from an aqueous solution containing 10-2 M AgNO3 and 1M HClO4 at potential deposition of -0.3 V and temperature of 18 C (a) and 62 C (b). FEGSEM images of the electrodeposited Copper particles onto Au NP-modified HOPG electrode from an aqueous solution containing 10-3 M CuSO4 and 1 M H2SO4 at potential deposition of -0.58 V and temperature of 18 C (c) and 62 C (d).    Fig. 3 – Water contact angle measured on the surface of a Au NP-modified HOPG electrode as a function of silver electrodeposi-tionn time at E  -0.3 V versus Ag/ AgCl and from a solution of 10-2 M AgNO3 and 1 M HClO4. The insert correspond to the water droplet shape for the indicated conditions  4. CONCLUSIONS Different advantages of using self assembled Au NPs template for metal electrodeposition were illus-trated. It is evidenced that self assembled Au NPs al-lows the surface patterning with nanometer resolution which no other techniques can achieve. It have been demonstrated that the temperature and applied poten-tial are the key parameters for controlling the mor-phology of prepared films. Importantly, there exists significant preferential crystal growth during the elec-trodeposition processes leading to uniform particle morphology. The morphology changes during the elec-trodeposition process are attributed to thiol molecules’ diffusion favored by the increase in the temperature and their preferential adsorption on the (111) crystal-lographic plane of silver and copper.  Furthermore, this work offers new opportunities for functionalized nano-particles to assist shape selective synthesis of electro-deposited material using modified electrodes by con-venient surfactant covered metallic nanoparticles. The present method also offers a new and simple way for large scale synthesis of millimeter scale films.  Other-wise, the morphology of the particles in the film should be independent of the conducting substrate nature.   By varying the silver electrodeposition time adjustable wetting properties can be obtained  AKNOWLEDGEMENTS  Authors are grateful to Pierre Dubot at the Institut de chimie et des matériaux Paris Est UMR 7181 for acquiring and discussing the XPS spectra.    A. TALEB, X. YANPENG PROC. NAP 2, 02FNC21 (2013)   02FNC21-4 REFERENCES  1. R. Walters, J. Biteen, H. Atwater, G. Bourianoff, Laser Focus World 40, 70 (2004) 2. Y. Niquet, G. Allan, C. Delerue, M. Lannoo, Appl. Phys. Lett. 77, 1182 (2000). 3. N.W. Dashiell, U. Denker, C. Muller, G. Costantini, K. Kern, O.G. Schmidt, Appl. Phys. Lett. 80, 1279 (2002). 4. M. Law, L.E. Greene, L.C. Johnson, R. Saykally, P. Yang, Nature Mater. 4, 455 (2005). 5. A. Taleb, C. Petit, M.P. Pileni, J. Phys. Chem. B, 102, 2214 (1998). 6. G.E. Engelmann, J.C. Ziegler, M.D. Kolb, Surf. Sci. 401, L420 (1998). 7. B.C. Bunker, P.C. Rieke, B.J. Tarasevich, A. Campbell, G.E. Fryxell, G.L. Graff, J. Song, J. Liu, J.W. Virden, Sci-ence, 264, 48 (1994). 8. R. Ullmann, T. Will, D.M. Kolb, Chem. Phys. Lett. 209, 238 (1993). 9. H. Ling, L. Eun-Sung, K. Kwang-Bum, Colloids Surf. A 262, 125 (2005). 10. H. Liu, F. Favier, K. Ng, M.P. Zach, R.M. Penner, Electro-chim. Acta 47, 671 (2001). 11. O. Azzaroni, M.H. Fonticelli, G. Beniter, R.L. Schilardi, R. Gago, I. Caretti, L. Vazquez, R.C. Salvarezza, Adv. Ma-ter, 16, 405 (2004).  12. M. Zhang, S. Lenhert, M. Wang, L. Chi, N. Lu, H. Fuchs, N. Ming, Adv. Mater. 16, 409 (2004). 13. D. Ito, M.L. Jespersen, J.E. Hutchison, ACS Nano 2, 2001 (2008). 14. J. Huang, A.R. Tao, S. Connor, R. He, P. Yang, Nano Lett., 6, 524 (2006). 15. C. Li, G. Hong, P. Wang, D. Yu, L. Qi, Chem. Mater. 21, 891 (2009). 16. A. Taleb, C. Mangeney, V. Ivanova, J. Electrochem. Soc. 158 No2, K28 (2011). 17. M.G. Montes de Oca, D.J. Fermin, Electrochim. Acta 455, 8986 (2010). 18. A. Taleb, X. Yanpeng, P. Dubot, J. Electroanal. Chem. 693 60 (2013). 19. M. Zhou, A. Zhang, Z. Dai, Y.P. Feng, C. Zhang, J. Phys. Chem. C 114, 16541 (2010). 20. A. Taleb, C. Mangeney, V. Ivanova, Nanotechnology,22, 205301 (2011). 21. A. Taleb, X. Yanpeng, Electrochimica Acta 2013, in press. 22. C. Yan, D. Xue, Crystal Growth Design 8, 1849 (2008) 23. A.A. Aviziens, C.M. Olmos, H.O. Sillin, M. Aono, J.K. Gimzewski, A.Z. Stieg, Crystal Growth Design 13, 465 (2013). 24. M. Matsushita, M. Sano, Y. Hayakawa, H. Honjo, Y. Sawada, Phys. Rev. Lett. 53, 286 (1984). 25. A. Taleb, X. Yanpeng, S. Munteanu, F. Kanoufi, P. Dubot, Electrochimica Acta 88, 621 (2013). 

Why to Use Self Assembled Metallic Nanoparticles Template for Metal Electrodeposition: Metallic Nanostructures with Controlled Morphologies and Adjustable Wetting Properties

We investigated the benefits of using self assembled gold nanoparticles (Au NPs) template for metal electrodepositions. For short electrodeposition time, surface patterning was achieved and a well dense or-ganized structure with nanometre resolution of metallic nanoparticles was prepared. For longer electro-deposition time, different morphologies were obtained. The mechanisms behind the formation of this mor-phology were analysed and discussed based on the influence of self-assembled Au NPs template in terms of thiol molecules diffusion and adsorption on metallic deposits. Furthermore adjustable wetting properties were obtained through the tuning of electrodeposition time

A. Taleb

X. Yanpeng

CiteSeerX

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  
NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 2 No 2, 02FNC21(4pp) (2013) 
 
 
2304-1862/2013/2(2)02FNC21(4) 02FNC21-1  2013 Sumy State University 
Why to Use Self Assembled Metallic Nanoparticles Template for Metal Electrodeposition: 
Metallic Nanostructures with Controlled Morphologies and Adjustable Wetting Properties  
 
A. Taleb*, X. Yanpeng 
 
UPMC –LECIME/ENSCP/Chimie paristech/CNRS7575, 11, Rue P. & M. Curie, 75231 Paris, France 
 
(Received 14 June 2013; published online 31 August 2013) 
 
We investigated the benefits of using self assembled gold nanoparticles (Au NPs) template for metal 
electrodepositions. For short electrodeposition time, surface patterning was achieved and a well dense or-
ganized structure with nanometre resolution of metallic nanoparticles was prepared. For longer electro-
deposition time, different morphologies were obtained. The mechanisms behind the formation of this mor-
phology were analysed and discussed based on the influence of self-assembled Au NPs template in terms of 
thiol molecules diffusion and adsorption on metallic deposits. Furthermore adjustable wetting properties 
were obtained through the tuning of electrodeposition time.  
 
Keywords: Au nanoparticles, Self-assembly, Metal electrodeposition. 
 
 PACS numbers: 81.15.Pq, 81.07. – b 
 
 
                                                          
*abdelhafed.taleb@upmc.fr 
1. INTRODUCTION 
 
For different nanotechnological applications the 
fabrication of nanostructured materials with a well 
defined pattern size and shape is a key point [1-4]. In 
fact, the physical properties associated with such mate-
rial depend on the size [5], the morphology and the or-
ganization of the pattern [1]. For the preparation of 
such nanostructures two approaches were used: direct 
deposition [6] and deposition on modified substrate [7]. 
Direct deposition approaches, usually achieve disor-
dered surface structures because of the preferential 
nucleation at crystalline defects and step edges [8-10]. 
To overcome this problem a modified substrate with 
patterns acting as preferential nucleation sites is pro-
posed. However, one of the emerging and promising 
strategies to create surface patterning and preferential 
nucleation sites for electrodeposition at a very low scale 
consists of using a mask made of self-assembled molec-
ular film [11-12] or colloidal particles [13-15]. Further-
more, a few works deal with the use of the particles as 
a nucleation sites [16-17].  
In this works, we illustrate the ability of self as-
sembled Au NPs template to electrocatalyze HOPG 
surface and to direct electrodeposition of different met-
als such as Cu and Ag at nanometer scale. This 
nanostructuring method provides a promising way to 
control the electrodeposits growth into ordered struc-
ture at nanometer resolution. Additional, we demon-
strate that the morphology of metallic electrodeposits 
can be controlled and different morphologies were ob-
tained. Interestingly, these surface morphologies 
demonstrate adjustable wetting properties.   
 
2. EXPERIMENTAL 
 
A standard three electrode electrochemical configu-
ration was used to achieve Cu and Ag electrodeposition. 
The reference and counter electrodes were respectively 
Ag/AgCl and a platinum sheet. For Cu electrodeposi-
tion experiments a clean (0001) highly oriented pyrolyt-
ic graphite (HOPG) surface, which is produced through 
a cleaving process, was used as a working electrode. 
The modified HOPG electrode was prepared by deposit-
ing a droplet of Au NP solution on the HOPG surface. 
The area in contact with the solution was fixed at 
9 mm2. Cu and Ag were deposited respectively from the 
aqueous solutions of 10-3 M CuSO4 and 1 M H2SO4 as 
the supporting electrolyte and from the aqueous solu-
tions of 10-2 M AgNO3 and 1 M HCLO4 as the support-
ing electrolyte. This solution was deaerated by purified 
nitrogen for 2 h before use. Copper sulfate pentahy-
drate (CuSO4 5H2O) and sulphiric acid (H2SO4) were 
obtained from Merck whereas Silver nitrate, perchlo-
rate acid and dodecanethiol were obtained from fluka. 
All chemicals used were analytical grade and used 
without further purification. The electrolytes were pre-
pared with water purified by Milli Q system (Millipore, 
electric resistivity 18.2 M cm).   
The 5 nm Au NPs were synthesized using the well 
known Stucky approach [32]. After synthesis, Au NPs 
were coated with n-dodecanethiol and presented in a 
narrow size distribution (6 ). All the experiments of 
Cu and Ag electrodeposition were performed on Au NPs 
modified HOPG electrodes. The electrodes were 
prepared by leaving a dilute droplet of Au NP solution 
with a concentration of 1.2  10-7 M on the HOPG 
electrode at ambient temperature. 
The chronoamperometry was performed at a fixed 
potential of -0.58 V and -0.3 V versus Ag/AgCl for re-
spectively Cu and Ag electrodeposition. All the electro-
chemical measurements were performed with an 
EG&G Princeton Applied Research potenti-
ostat/galvanostat model 273 A.  
The morphologies of the Cu electrodeposits, Ag elec-
trodeposits and Au NPs film were studied using a high-
resolution Ultra 55 Zeiss field emission gun scanning 
electron microscope (FEGSEM).  
The chemical compositions of all the samples were 
determined by X-ray photoelectron spectroscopy (XPS) 
and for the measurements we used a Kratos Analytical 
 A. TALEB, X. YANPENG PROC. NAP 2, 02FNC21 (2013) 
 
 
02FNC21-2 
Axis Ultra DLD, using an Al Kα source monochroma-
tized at 1486.6 eV.  
The wetting properties of our prepared surfaces in 
terms of static contact angle were determined using a 
Krüss DSA10 contact angle measuring apparatus 
equipped with a CCD camera. A 3 l water droplet pu-
rified by Milli Q System (Millipore, electric resistivity 
18.2 M cm) was used for the static contact angle 
measurements. 
 
3. RESULTS AND DISCUSSION 
 
In Fig. 1a is shown typical FEGSEM images of Ag 
electrodeposits on Au NPs modified HOPG substrate 
over different electrodeposition time.  It is seen that after 
electrodeposition over 10 s, a small bright spot appears 
on the modified HOPG electrode corresponding to the 
formation of Ag NPs. The hexagonal pattern formed by 
Au NPs is still preserved (indicated by arrow), and Ag 
deposit is reproducing this structure (indicated by arrow 
in figure 1(a) and insert) . Similar behavior was observed 
For Cu electrodeposition in same conditions.   
Further confirmation of Ag deposition is provided by 
XPS experiments (Fig. 1(b)). Theses results evidenced 
the fact that self assembled Au NPs allows the surface 
patterning with nanometer resolution which no other 
techniques can allow [16-18]. By comparing metal elec-
trodeposition on bare HOPG and Au NPs modified 
HOPG electrode, different surface textures were ob-
served. On bare HOPG the electrodeposition occurs on 
step edges and terrace defects according to Volmer We-
ber island mechanism whereas atomic flat terrace are 
inhibited sites [16-18]. However, on Au NPs modified 
HOPG, metal electrodeposition behavior is completely 
different and metal deposition takes place on the whole 
electrode surface including the atomic flat terrace [16-
18]. These results show clearly that Au NPs deposited on 
the HOPG electrode activate the inhibited sites of atomic 
flat terrace. The mechanism behind this activation can 
be understood by taking into account the strain effects of 
Au NPs on the electronic properties of HOPG electrode 
[18-19]. 
For longer electrodeposition time and low deposition 
temperature (18 C), the FEGSEM images depicted in 
Fig. 2 show dendrite particles [20-21]. This kind of 
growth is mainly diffusion controlled locally and 
accompanied by preferential growth directions [21-22]. 
Furthermore in the pure diffusion limited aggregation 
(DLA), the solid growth occurs as random walkers 
diffuse of metal ion (Ag  or Cu2  in our case) into 
contact with the growing aggregate [23-24]. This 
mechanism explains the random orientation of growing 
silver dendrites. However, with Cu dendrites oriented 
and dense superstructures were observed. From the 
FEGSEM experiments it is evidenced that the self 
assembled Au NPs pattern plays a crucial role in the 
formation of the observed Cu dendrites’ superstructure 
[21]. In fact the crack defects of the Au NPs template 
allow micrometer patterning for Cu electrodeposition. A 
combination of self assembled Au NPs pattern and the 
aggregation of Cu electrodeposits has been shown to be 
behind the observed Cu superstructure formation 
mechanism.  
For high electrodeposition temperature of 62 C, 
different other morphologies were obtained [21]. The 
results are depicted in Fig. 2. It can be seen that by 
increasing the temperature more faceted particles were 
obtained. Ag deposits form plate particles [25] whereas 
Cu particles are of polyhedral morphology[21]. These 
results can be understood in terms of dodecanethiol 
molecules diffusion from Au NPs into the metal 
deposits surface in which it is adsorbed. Furthermore, 
dodecanethiol was found to adsorb strongly on the (111) 
crystallographic facets. As a consequence the growth of 
this facet slow down through the formation of a dense 
layer which slow the metal ion reduction on their 
surface allowing the growth of crystallographic planes 
in perpendicular directions. This growth anisotropy 
results in the formation of different observed faceted 
morphologies. 
The wetting properties of electrodeposited silver den-
dritic film were characterized by the measurement of 
water contact angles (CAs) [20]. The results are depicted 
in Fig. 3 and it should be observed that the CA depends 
on the electrodeposition time. The observed wetting 
properties are governed by the continuous increase of 
dendritic surface roughness during the electrodeposition 
time and the rate coverage of adsorbed dodecanethiol 
molecules. Thus by varying the silver electrodeposition 
time adjustable wetting properties can be obtained and a 
transition between Wenzel and Cassie Baxter state can 
be induced. 
 
 
 
Fig. 1 – (a) FEGSEM images of the electrodeposited silver nanoparticles onto Au NP-modified HOPG electrode at electrodeposition 
time of 10 s and from an aqueous solution containing 10-2 M AgNO3 and 1 M HClO4 at potential deposition of -0.3 V. Insert is the 
TEM image of Au NP monolayer (b) XPS core level spectra of Ag 3d acquired from electrodeposited silver on a Au NP modified HOPG 
electrode over different electrodeposition times 0s and 10 s. 
 WHY TO USE SELF ASSEMBLED METALLIC NANOPARTICLES TEMPLATE … PROC. NAP 2, 02FNC21 (2013) 
 
 
02FNC21-3 
 
 
 
Fig. 2 – FEGSEM images of the electrodeposited silver particles onto Au NP-modified HOPG electrode from an aqueous solution 
containing 10-2 M AgNO3 and 1M HClO4 at potential deposition of -0.3 V and temperature of 18 C (a) and 62 C (b). FEGSEM images 
of the electrodeposited Copper particles onto Au NP-modified HOPG electrode from an aqueous solution containing 10-3 M CuSO4 
and 1 M H2SO4 at potential deposition of -0.58 V and temperature of 18 C (c) and 62 C (d). 
 
 
 
Fig. 3 – Water contact angle measured on the surface of a Au NP-modified HOPG electrode as a function of silver electrodeposi-
tionn time at E  -0.3 V versus Ag/ AgCl and from a solution of 10-2 M AgNO3 and 1 M HClO4. The insert correspond to the water 
droplet shape for the indicated conditions 
 
4. CONCLUSIONS 
Different advantages of using self assembled Au 
NPs template for metal electrodeposition were illus-
trated. It is evidenced that self assembled Au NPs al-
lows the surface patterning with nanometer resolution 
which no other techniques can achieve. It have been 
demonstrated that the temperature and applied poten-
tial are the key parameters for controlling the mor-
phology of prepared films. Importantly, there exists 
significant preferential crystal growth during the elec-
trodeposition processes leading to uniform particle 
morphology. The morphology changes during the elec-
trodeposition process are attributed to thiol molecules’ 
diffusion favored by the increase in the temperature 
and their preferential adsorption on the (111) crystal-
lographic plane of silver and copper.  Furthermore, this 
work offers new opportunities for functionalized nano-
particles to assist shape selective synthesis of electro-
deposited material using modified electrodes by con-
venient surfactant covered metallic nanoparticles. The 
present method also offers a new and simple way for 
large scale synthesis of millimeter scale films.  Other-
wise, the morphology of the particles in the film should 
be independent of the conducting substrate nature.   
By varying the silver electrodeposition time adjustable 
wetting properties can be obtained 
 
AKNOWLEDGEMENTS 
 
Authors are grateful to Pierre Dubot at the Institut 
de chimie et des matériaux Paris Est UMR 7181 for 
acquiring and discussing the XPS spectra. 
 
 
 A. TALEB, X. YANPENG PROC. NAP 2, 02FNC21 (2013) 
 
 
02FNC21-4 
REFERENCES 
 
1. R. Walters, J. Biteen, H. Atwater, G. Bourianoff, Laser 
Focus World 40, 70 (2004) 
2. Y. Niquet, G. Allan, C. Delerue, M. Lannoo, Appl. 
Phys. Lett. 77, 1182 (2000). 
3. N.W. Dashiell, U. Denker, C. Muller, G. Costantini, 
K. Kern, O.G. Schmidt, Appl. Phys. Lett. 80, 1279 (2002). 
4. M. Law, L.E. Greene, L.C. Johnson, R. Saykally, P. Yang, 
Nature Mater. 4, 455 (2005). 
5. A. Taleb, C. Petit, M.P. Pileni, J. Phys. Chem. B, 102, 2214 
(1998). 
6. G.E. Engelmann, J.C. Ziegler, M.D. Kolb, Surf. Sci. 401, 
L420 (1998). 
7. B.C. Bunker, P.C. Rieke, B.J. Tarasevich, A. Campbell, 
G.E. Fryxell, G.L. Graff, J. Song, J. Liu, J.W. Virden, Sci-
ence, 264, 48 (1994). 
8. R. Ullmann, T. Will, D.M. Kolb, Chem. Phys. Lett. 209, 
238 (1993). 
9. H. Ling, L. Eun-Sung, K. Kwang-Bum, Colloids Surf. A 
262, 125 (2005). 
10. H. Liu, F. Favier, K. Ng, M.P. Zach, R.M. Penner, Electro-
chim. Acta 47, 671 (2001). 
11. O. Azzaroni, M.H. Fonticelli, G. Beniter, R.L. Schilardi, 
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English

http://nap.sumdu.edu.ua/index.php/nap/nap2013/paper/download/1249/482/

Why to Use Self Assembled Metallic Nanoparticles Template for Metal Electrodeposition: Metallic Nanostructures with Controlled Morphologies and Adjustable Wetting Properties

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