Obtaining of copper nanoparticles in combined RF+DC discharge plasma

Obtaining of copper nanoparticles in combined RF+DC discharge plasma

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Available online at www.sciencedirect.com

ScienceDirect Materials Today: Proceedings 20 (2020) 329–334

www.materialstoday.com/proceedings

ANM 2018

Obtaining of copper nanoparticles in combined RF+DC discharge plasma Orazbayev S.A. a,b, *, Zhumadylov R.E. b, Zhunisbekov A.T. a, Ramazanov T.S.a, Gabdullin M.Tb. a

b

Institute of Experimental and Theoretical Physics, Al-Farabi Kazakh National University, Almaty, Kazakhstan National Nanotechnology Laboratory of the Open Type, Al-Farabi Kazakh National University, Almaty, Kazakhstan

Abstract Copper nanoparticles attract great attention as a subject of research because of their well-known properties, such as good conductivity, antibacterial and catalytic effects, etc. They are used in many different fields such as medicine, electronics, scientific research, etc. There are various methods for obtaining Cu nanoparticles, chemical, electrochemical, sonochemical, etc. These methods often lead to contamination, including nanoparticles. In this work, a combined HF + DC discharge was used to obtain copper nanoparticles. The optimal plasma parameters for the synthesis of copper nanoparticles were determined. Methods for the synthesis of copper nanoparticles and the dependence of their growth on the plasma parameters and the DC voltage were developed and investigated. The nanoparticles obtained were characterized by scanning electron microscopy (SEM). The synthesized nanoparticles consist of Cu nanoparticles having a spherical shape with a diameter from 60 nm to 300 nm © 2018 Elsevier Ltd. All rights reserved. Selection and peer-review under responsibility of the scientific committee of 11th International Conference on Advanced Nano Materials. Keywords: nanoparticles, copper nanoparticles, nanomaterials, rf plasma, gas discharges.

1. Introduction Studies of nanomaterials have received considerable attention due to their unique properties and numerous applications in different fields [1]. Metallic nanoparticles are of great interest due to their excellent chemical,

* Corresponding author. Tel.: +7 727 377 34 48; fax: +7 727 377 34 48. E-mail address: [email protected] 2214-7853 © 2018 Elsevier Ltd. All rights reserved. Selection and peer-review under responsibility of the scientific committee of 11th International Conference on Advanced Nano Materials.

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physical and catalytic properties. Copper nanoparticles attract much attention because of their well-known properties such as high electrical and thermal conductivity [2], antibacterial and antifungal effects [3], high catalytic activity [4], etc. Cu nanoparticles are considered to be cost-effective compared to noble metals such as Ag, Au and Pt. There are various methods of synthesis of copper nanoparticles, such as chemical reduction, microemulsion method, electrolytic synthesis, Sol-gel method, vacuum vapor deposition, etc. [5]. However, each method has its own drawbacks and limitations. The method of RF discharge plasma [6] belongs to the simplest, but effective method of obtaining nano and microparticles. The simplicity of this method, together with the advantage of obtaining nanoparticles with small size, narrow distribution and weak agglomeration makes it suitable for the synthesis of metallic nanoparticles. The essence of this method: the formation of a plasma in a gas or a mixture of gases at low-pressure in a specific volume using a capacitive discharge. In this work, the main part of the experimental setup is the electrode system, which is located inside the chamber [7,8]. The vacuum part of the experimental setup is represented by a series-connected turbomolecular and forevacuum pumps. The initial removal of the bulk of the air from the working volume of the plant is done by a forevacuum pump through the pipeline up to 10-1 ÷ 10-2 Torr. Further, to obtain a high vacuum (10-5÷10-6 Torr), a diffusion pump is activated. The camera is also equipped with the Bronkhorst MassFlowMeter gas injection system, which is used for filling, gas flow monitoring and operating pressure. One of the electrodes, as well as the camera body is grounded. The high-frequency generator (SEREN), the energy from which is fed to the upper electrode, forms a plasma in the gas mixture in the interelectrode space. In the case of a gas mixture of methane and argon, the carbon atoms and ions produced by the dissociation of methane molecules form carbon nano and microparticles [9,10]. In this paper, a combined RF / DC discharge was used to obtain copper nanoparticles and nanomaterials in a plasma medium. A target made of copper is attached to the upper electrode. In this experiment, an inert argon gas is used to synthesize copper nanoparticles. In our case, the upper electrode in addition to the RF generator was connected to a power source of constant voltage. Adding a constant potential to the upper electrode increases plasma density. Thus, as the constant potential is increased, the process of bombarding the target with electrons and ions is intensified, as a result the target is sprayed, which leads to the rapid formation of particles in the plasma [11-13]. Simplicity and low power consumption of this method ensure good repeatability of the results, confident control of particle size depending on the discharge parameters. The combined (RF+DC) discharge is used for etching various materials, for sterilization, for plasma cleaning of gas-discharge chambers, in plasma chemistry, for pumping gas lasers, etc. [14]. Thus, the aim of this work was to synthesize copper nanoparticles in the combined discharge plasma (RF+DC) and investigate the dependence of particle size on the discharge parameters. 2. Experimental setup For the synthesis of copper nanoparticles in RF/DC plasma discharge was used experimental setup presented in Figure 1 [15]. The experimental setup consists of several parts: power supply system (HF generator with matching device and DC power supply), vacuum system and vacuum chamber. The main part of the experimental setup is the electrode system, which is located inside the chamber. The plasma is ignited between the parallel-parallel electrodes with a diameter of 10 cm. The interelectrode distance is 3 cm. The upper electrode is connected to the RF generator SerenR301 and a DC power source, and the bottom electrode is grounded. The copper target is attached to the upper electrode. The power of the RF discharge ranged from 1 to 40 W, the voltage of the constant power source was 0 ÷ 100 V, and the gas pressure was 0.1 ÷ 1 Torr. As can be seen from the scheme, an additional negative DC voltage is applied to the upper electrode. Synthesis of nanoparticles in this method is also based on ion bombardment of the target. In this case, when a negative voltage is applied, the surface of the upper electrode is charged negatively, thereby increasing the ion bombardment of the copper target. Experiments on the synthesis of nano- and microparticles of copper in RF+DC discharge were carried out at various plasma parameters. As noted earlier, one of the important factors in the synthesis of nanoparticles is the time of their growth, therefore, to determine the time of synthesis, the dependence of the self-displacement voltage on DC at a gas pressure of 0.6 Torr, 20 W discharge power was obtained [16].

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Fig. 1. Scheme of setup for RF/DC discharge.

3. Results and discussion Thus, in this paper, copper nanoparticles were obtained by a combined discharge method, in particular in an RF discharge using an additional negative voltage. As a result of the experimental work carried out at various negative voltages, appropriate samples were obtained, which were studied on the basis of SEM. Figure 2 shows the SEM image and the chemical composition of the resulting sample.

Fig. 2. SEM image of synthesized cooper nanoparticles and chemical composition.

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SEM analysis of samples and their chemical composition indicates the presence of copper nanoparticles. Experimentally it was found that the growth of particles in the plasma depends on the value of DC voltage. By controlling the DC voltage, it is possible to investigate the growth and concentration of nanoparticles. Figure 3 shows SEM images of copper nanoparticles obtained under different DC voltage conditions (0 V, -50 V, 80 V, -100 V), while other parameters such as working gas pressure p=0.6 Torr and power of the RF generator P=20 W remained constant. It was determined that the change in the DC voltage significantly affects the growth of particles in the plasma.

(a)

(b)

(c)

(d)

Fig. 3. SEM images of copper nanoparticle samples obtained at different voltage values Vdc: (a) 0 V, (b) -50 V, (c) -80 V, (d) -100 V.

Figure 4 shows the dependence of the synthesis time on the self-bias voltage at different plasma parameters (gas pressure and discharge power). As can be seen from the graph, the voltage of the constant power supply ranged from 0 V to 100 V, RF discharge power and gas pressure remained unchanged P=20 W p=0.6 Torr. It was determined that the time of particle synthesis decreases with increasing DC voltage. This is explained by the fact that the addition of a negative potential to the upper electrode increases the plasma density. Thus, as the negative potential increases, the process of bombarding the target with electrons and ions is amplified, as a result of which the target is sprayed, which leads to the rapid formation of particles in the plasma.

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P=20 W; p=0,6 mbarr; Vdc=0 P=20 W; p=0,6 mbarr; Vdc= - 25 B P=20 W; p=0,6 mbarr; Vdc= - 50 B P=20 W; p=0,6 mbarr; Vdc= - 75 B P=20 W; p=0,6 mbarr; Vdc= - 100 B

0 -25 -50

Vdc

-75 -100 -125 -150 -175 0

10

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Time of synthesis, m

Fig. 4. Dependence of synthesis time on self-bias voltage at different plasma parameters.

4. Conclusion This paper presents experimental results on the production of copper nanoparticles by plasma method in RF+DC discharge. As the result of the experimental work, it was found that the synthesis of copper nanoparticles by this method is influenced by various parameters such as discharge power, working medium pressure, constant power supply voltage, etc. The obtained samples were examined by scanning electron microscopy (SEM). Dependences of the synthesis time on the self-displacement voltage at different plasma parameters (gas pressure and discharge power) were obtained. So, we can conclude that as the voltage Vdc increases, the density of ions and electrons in the plasma increases, which leads to a decrease in the synthesis time of the particles. References [1] W.T. Lai, C.J. Hwang, A.T. Wang, J.C. Yau, J.H. Liao, L.H. Chen, K. Adachi and S. Okamoto, Proc. Int. Symp. on Dry Process (2006) 109. [2] Muhammad Imran Din & Rida Rehan (2017) Synthesis, Characterization, and Applications of Copper Nanoparticles, Analytical Letters, 50:1, 50-62. [3] Galletti, A. M. R., C. Antonetti, M. Marracci, F. Piccinelli, and B. Tellini. 2013. Novel microwavesynthesis of Cu nanoparticles in the absence of any stabilizing agent and their antibacterial and antistatic applications. Applied Surface Science 280:610–18. [4] Suramwar, N. V., S. R. Thakare, and N. T. Khaty. 2012. One pot synthesis of copper nanoparticles at room temperature and its catalytic activity. Arabian Journal of Chemistry 4:1–6. [5] Easom, K. A., K. J. Klabunde, C. M. Sorensen, and G. C. Hadjipanayis. 1994. Nanoscale magnetic particles. New methods to surface protected metallic and immiscible bimetallic clusters/particles. Polyhedron 13 (8):1197–223. [6] Shiratani M., Kawasaki H., Fukuzawa T., Yoshioka T., Ueda Y., Singh S. and Watanabe Y. Simultaneous in situ measurements of properties of particulates in rf silane plasmas using a polarization‐sensitive laser‐light‐scattering method // J. Appl. Phys. – 1996. – Vol. 79. – P. 104. [7] S. A. Orazbayev, Y. A. Ussenov, T. S. Ramazanov, M. K. Dosbolayev, A.U. Utegenov //Contributions to Plasma Physics. – 2015. – Т. 55, №. 5. – С. 428-433.

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