Effect of solvent in the synthesis of colloidal copper

nanoparticles by pulse laser ablation method

Inayah Mumpuni Budiati1, Fatkhiyatus Sa’adah1, Nabila Dyah Rifani2, Ali

Khumaeni1
1
Department of Physics, Faculty of Science and Mathematics, Diponegoro University
2
Departement of Dentist, Faculty of Medicne, Diponegoro University
Jl. Prof. Soedharto, SH, Tembalang, Semarang 50275, Indonesia

*) Corresponding author: khumaeni@fisika.undip.ac.id (Ali Khumaeni)

Abstrak

In this experiment, Cu nanoparticle produced using Nd: YAG laser method with
wavelength, energy and pulse width used consecutively is 1064 nm, 45mJ, and 7 ns.
Repetition of the laser pulse is 10 Hz, blazed on pure Cu plate (99,99%) in a petri dish
that is filled with liquid as a medium. Variation of liquids has been used in the making
of CuNPs. Based on Ultraviolet-visible (UV-Vis) test, shows that in aquadest as a
medium wavelength is at 292 nm, PVP 0.5 millimolar is at 302 nm, PVP 5 millimolar
is at 296 nm and PVP 10 millimolar is at 306 nm.

1. Inroduction
Cuprum or copper is a yellow metal like gold, whose willingness to experience is quite abundant
and its size is quite cheap [1]. Copper is a good conductor of heat and electricity after silver. The
physical properties of copper in bulk are relatively unreactive so that they are corrosion resistant,
easy to hold and easily formed. In nano size, these particles are very reactive, easily oxidized and
aggregated so it needs stabilizer [2]. Cu Nanoparticle has a different color characteristic because of
the size variation and the shape result from synthesis depends on the stabilizer concentration on
medium [3]. Cu Nanoparticle has a potential for application and can be used widely in biomedical
fields such as drug prescribing, antibacterial coating in medical devices, synthetic bone,
antibacterial paint, water and cloth cleaner and antibacterial bandage. Copper ion plays a crucial
part in healing burns and prevents injuries caused by infection and help in bone matrix making [4].
Cu Nanoparticle is a commonly used metal because of antibacterial characteristic, lower bacterial
resistance and cheaper than other types of copper. When it is in nano size, it has a lower toxicity for
human [5]. CuNP can be synthesized using a chemical reduction method or polyol method by
reducing the use of copper acetate hydrate [6]. Laser ablation method uses low energy Nd:YAG
laser to ablaze the surface for the sample, resulted in high purity nanoparticle. This is caused by the
fact that the particle purity is based on the purity of the target and the media (gas or liquid) without
contamination from reactant whereas NP colloids produced through chemical processes are usually
contaminated by reducing compounds [6].
Nanoparticle synthesis using laser ablation method in liquid medium known as laser ablation in
liquid mechanism (LAL). The mechanism of LAL in outline is the generation, transformation, and
condensation of plasmic mass. Mechanism of nanoparticle colloid-forming [7]. The shape of the
nanoparticles can be controlled by liquid medium and laser parameters [8].
Laser ablation method uses low energy of Nd:YAG laser to burn the surface of the sample,
resulting in nanoparticle with high purity. This is caused by the fact that the purity of a particle is
based on the purity of the target and the media (gas or liquid) without contamination from the
reactant, meanwhile, NP colloid that formed from chemical process usually contaminated by
reduction molecule [9].
2. Method
Sample preparation to make ablation medium. 3 grams of Polyvinyl Pyrrolidone (PVP) is weighed
and mixed with 20 ml aquadest resulting in 5 millimolar Polyvinyl Pyrrolidone (PVP) medium.
The mixture is mixed using magnetic stirrer for 3 hours until homogenized. 10 ml PVP liquid is
poured into petri dish along with Cu (copper) plate sided 15 mm x 15 mm that has been cleaned by
70% alcohol and washed with aquadest. The rest of 10 ml is used as a background in UV-Vis
characteristic test and also as a reservation. Repeat this process for other liquid medium variation
(10 ml PVP, 0.5 PVP, and aquadest).

Cu plates measuring
1 cm x 1 cm Cu plates are placed on Addition of 10 mL of distilled
the petri dish water into a petri dish

Figure 1. Skema Preparasi Sampel

Cu nanoparticle synthesis is done by blazing Nd: YAG laser (1064nm) on 99,99% Cu plate
placed in 10 ml of medium for 180 minutes. In this study, Nd: YAG laser has 40 mJ energy with
a pulse width of 7 ns. The synthesis is also done in other variation of PVP concentration medium
and aquadest.
In the synthesis process, the laser beam will be deflected by mirrors toward convex-focused lens
with a focal length of 3 cm in order that the laser beam directly hit the sample. During the
ablation process, the petri dish containing a Cu plate is moved slowly to obtain homogenized
nanoparticle. The experimental set-up is shown in the figure below.

Silver Silver
mirror mirror

Laser
beam

lens Nd:YAG
Laser
Liquid

Cu plate

PC

Figure 2. experimental set up

CuNPs that has been successfully synthesized went through characterization test. Characterization
test includes Ultraviolet Visible Light Spectroscopy Test (UV-Vis) to understand the spectrum
and the absorbance degree of Cu nanoparticle colloid. X-Ray Diffraction Test is done to
understand the crystallization phase and other oxides contained in Cu nanoparticle.
 Scanning Electron Microscopy (SEM) Test is done to understand the morphology of Cu
nanoparticle in aquadest. SEM Test is done by dropping Cu nanoparticle colloid on Silicone plate
with a size of 0.5 x 0.5 cm. Silicone plate is dried using a microwave for 10 minutes. Image result
from SEM then processed using ImageJ software to find the size of the Cu nanoparticle made.

3. Result and Discussion

Successfully synthesized Cu in different variation of liquid medium. The nanoparticle synthesis

result on aquadest, PVP 0,5 millimolar concentration, 5 millimolar concentration, and 10
millimolar concentration consecutively is shown in figure 3.

aquadest
PVP 0,5 mM PVP 5 mM PVP 10 mM

Figure 3. Koloid CuNPs pada 10 larutan variasi akuades, pvp konentrasi 0.5 Mm, 5 mM, dan
10 mM

CuNP's absorbed spectrum is shown in figure 4. CuNPs spectrum is taken using UV-Vis
Spectroscopy. The result shows that single adsorption for aquadest as a medium is at wavelength
292 nm. For PVP millimolar as a medium is at wavelength 302 nm. For PVP 5 millimolar as a
medium is at wavelength 296 nm and for PVP 10 millimolar as a medium is at 306 nm. Based on
those result, 292nm - 306 nm wavelength indicator of nanoparticle distribution is detected. This
result is strongly supported by the result of XRD test in figure 5.
 Gambar. Spektrum absorbansi pada CuNPs variasi medium

The biggest single absorption is in aquadest medium, followed by PVP with 5 millimolar
concentration, PVP with 10 millimolar concentration and the smallest is in PVP with 0.5 millimolar
concentration. Variation of liquid medium for ablation influence the interaction between the laser
and the plat when ablation so it influences the result of the amount of particle made from ablation.
It also takes a role as a stabilizer agent on the nanoparticle made to maintain the condition of Cu
nanoparticle so it doesn't easily agglomerate.

Figure 5. Intensitas fasa kristal CuO

Analytical result of XRD shows that there are a few peaks that can be identified as the CuO phase.
XRD Peaks outcome is located on degree 20 between 44.930, 65.270, and 78.360 that shows as a
diffraction pattern by plane 111, 200 and 220. This result is corresponding to the second standard
of JCPDS Number 04-0836. The value 20 from those three peaks is corresponding with JCPDS.
The existence of diffraction peaks shows that CuO nanoparticles produced in this study contain
CuO molecule [10].
 Figure 6. Foto SEM CuO pada medium aquades

Figure 6. Shows the morphological image of NPS CuO in aquades according to SEM photos.
Based on the visible image the nanoparticles have a spherical shape. Morphological photos of the
CuNPs produced are shown in figure 6, enlargement of 3000 for 10 mL of CuNPs produced was
dropped on a plate and then heated in an oven at 1000C for about 10 minutes. The dry Si plate is
then scanned using SEM. Based on the picture it appears that the particles produced have varying
sizes. Furthermore, the size of the nanoparticles and size distribution is calculated from SEM
images using imageJ software. The size distribution of CuO NPs can be seen in Figure 7. In the
graph the distribution of the size of CuO NPs on the Awuades medium at a 10 Hz repetition rate
obtained an average diameter of 243.2783 nm with standard deviation of 432, 0494.

4. Conclution
Synthesis of copper oxide nanoparticle (CuO NPs) colloid with laser ablation method was
successfully carried out. Variation of aquades solution, pvp 0.5 mM, 5 mM, and 10 Mm obtained
the most stable colloid at a concentration of 5 Mm. Based on the results of the ultraviolet visible
(UV-Vis) test in the 292 nm -306 nm spectrum, it shows the presence of CuNPS, but it has a
different peak of adsorbance. The results of XRD analysis The presence of diffraction peaks shows
that CuO nanoparticles produced in this study contain CuO compounds.
5. References
[1] Bogdanović U., Lazić V., Vodnik V., Budimir M., dkk. (2014). “Copper nanoparticles with
high antimicrobial activity”. Materials Letters 128, 75–78.
[2] Saito, M., Yasukawa, K., Umeda, T., and Aoi, Y. (2008). “Copper nanoparticles fabricated by
laser ablation in polysiloxane”. Optical Materials 30, 1201–1204.
[3] Kwon, Y.T., Lim, G.D., Kim, S., dkk. (2017). “Effect of localized surface plasmon resonance
on dispersion stabilityof copper sulfide nanoparticles”. Applied Surface Science (2017).
[4] Sahidi, S., Rashidian, M., Dorranian, D.(2018). ”Preparation of antibacterial textile using laser
ablation method”. Optics and Laser Technology 99, 145–153
[5] Khan, I., Saeed K., dan Khan I., 2017, Nanoparticle: Properties, applications and toxicities,
Arabian Journal of Chemisty.
[6] Ramyadevi, J., Jeyasubramanian, K., Marikani, A., Rajakumar, G., and Rahuman, A.A. (2012),
“Synthesis and antimicrobial activity of copper nanoparticles”. Materials Letters 71, 114–116
[7] Xiao, J., Liu, P., Wang, C.X., dan Yang G. W. (2017). “External Field-Assisted Laser Ablation
in Liquid: An Efficient Strategy for Nanocrystal Synthesis and Nanostructure Assembly”.
Progress in Materials Science, 87, 140-220.
[8] Tsuji, T., Iryo, K., Watanabe, N., and Tsuji, M. (2002). “Preparation of silver nanoparticles by
laser ablation in solutionninfluence of laser wavelength on particle size”. Applied Surface
Science 202 (2002) 80–85.
[9] Kim, M., Osone, S., Kim, T., Higashi, H. dan Seto, K. 2016. Synthesis of Nanoparticles by
Laser Ablation. KONA powder and particle journal. Volume 34: 80-90
[10] Theivasanthi, T and Algar, M. 2010. X-Ray Diffraction Studies of Copper Nanopowder.
Scholar Research Labortory. 1 (2) : 112 - 117