Characteristics of colloidal copper particles prepared by using Polyvinyl pyrrolidone (PVP) and Polyethylene glycols (PEG) in chemical reduction

method
Chinh Dung Trinh1, Dung My Thi Dang1, Tuyet Thu Thi Le1, Eric Fribourg-Blanc2, Hoang Ba Le Tran1 and Chien Mau Dang1 Laboratory for Nanotechnology, Vietnam National University, Ho Chi Minh City, Community 6, Linh Trung Ward, Thu Duc District, Ho Chi Minh City, Vietnam; Email: dtmdung@vnuhcm.edu.vn 2 CEA-LETI, MINATEC Campus, 17, rue des Martyrs, 38054 Grenoble Cedex 9, France
Abstract A simple chemical reduction method is used to prepare colloidal copper nanoparticles. In this method we use polyethylene glycols (PEG) and polyvinyl pyrrolidone (PVP) as stabilizer, size controller and capping agents, and NaBH 4 as the reducing agent .The obtained copper nanoparticles were characterized by powder x-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-visible spectrophotometry (UV-vis). The main purpose of this paper is to report about the large improvement in replacing PEG by PVP in the reduction synthesis of copper nanoparticles. From the TEM results we found that colloidal copper nanoparticles prepared by using PVP and PEG are well-dispersed, and from the UV-vis results surface plasmon peak is very stable over time at 561 nm whereas when using (PEG) the peak shifts from 561 to 572 nm. This comparison also shows that copper nanoparticles in the solution using (PVP) have smaller size and the uniformity of their distribution in particle size is better. Then it is observed that the oxidation time of copper nanoparticles at room temperature for solution using (PVP) is over twenty days while solution using (PEG) takes place in two days. The protection level provided by PVP is therefore much higher than with PEG.
1

Keywords: copper nanoparticle, inert gas protection, solvents, chemical synthesis

1. Introduction

In recent years, metallic and semiconductive nanoparticles have been widely investigated. In nanostructure form, materials exhibit specific properties not present in their form. Nanoparticles are studied for a long time and almost all monoatomic materials including gold [14], silver [13] or copper

[16-17] due to their potential applications as optical sensors [11], biological labels [19, 20] or conducting deposits [21]. Nowadays according to the new trend of electronic industry, metallic nanoparticles are used to make conductive inks [10] that can be used to

print electrical paths on different types of substrates. There have been many successful studies on inks based on silver (Ag) as metallic nanoparticles. Silver nanoparticles have many special characteristics that are of great advantage to make and preserve ink. However, the limitation of silver nano ink is of having a high cost makes it difficul in developping widespread products. Therefore, we have been studying the replacement of Ag nanoparticles by copper nanoparticles in order to reduce the production cost of ink. There are many methods for copper nanoparticles synthesis including chemical reduction [2, 3], thermal decomposition [4, 5], polyol [1, 6], laser ablation [7], electron beam irradiation [8] and in situ chemical synthetic route [9]. We have succeeded in making copper nanoparticles with an average diameter of less than 10 nm by chemical reduction method. However, making copper nanoparticles for use in conductive ink presents many difficulties, which stem from peculiar properties of copper, such as: easy agglomeration, fast oxidation in atmosphere and low stability of copper nanoparticles in solution. Therefore, following our previous study [ref] we modified the capping agent (PEG) for PVP in the chemical reduction synthesis in order to study its effect on the properties of copper nanoparticles. 2. Experimental 2.1 Material All chemicals were analytical grade as purchased and used without further purification. Copper (II) sulfate pentahydrate salt, CuSO4.5H2O, with 98.0 102.0 % in purity (Merck), was

dissolved in deionized water. Polyethylene glycol 6000 (PEG 6000 Merck) and Polyvinyl pyrrolidone (PVP, average molecular weight of 40 000) were used as the capping agent. Sodium borohydride (NaBH4 - Reagent Plus 99%, Sigma-Aldrich) was used as the main reducing agent while ascorbic acid (99.7%, Prolabo) was used as antioxidant of colloidal copper. Sodium hydroxide NaOH (> 98%, China) was also used to adjust the pH and accelerate the reduction reaction in water. 2.2 Synthesis nanoparticles of copper

2.2.1 Using PVP 40000 Copper (II) sulfate pentahydrate salt, CuSO4.5H2O (0.01 M) is first dissolved in deionized water to obtain a blue colored solution. Then polyvinyl pyrrolidone (PVP) 40000 (0.003M) is dissolved in water and added to the aqueous solution containing the copper salt while vigorously stirring. Ascorbic acid (0.02 M) and sodium hydroxide (0.1 M) are dissolved in water in a separate beaker and added to the synthesis solution. Color change occurres in the aqueous phase from white to yellow. This solution was stirred for 90 minutes. Finally, a solution of NaBH4 (0.1 M) in deionized water was prepared and added to the solution under continuous rapid stirring. An instant color change occurred in the aqueous phase from yellow to violet. The mixture was further stirred rapidly for around 10 minutes at ambient atmosphere, to allow the reaction to complete. 2.2.2 Using PEG 6000

We prepared ascorbic acid solution by dissolving 8.8 mg of PEG in 5 ml of deionized water. At the same time, a solution of copper (II) sulfate pentahydrate CuSO4 5H2O (0.01 M) in deionized water was prepared separately and added to the solution of ascorbic acid under strong magnetic stirring. PEG 6000 was then poured followed by the dropwise addition the solution of NaOH (0.1 M) in deionized water to adjust the pH up to 12. The mixture was stirred at room temperature for about 15 minutes. Then a solution of NaBH4 (0.1 M) in deionized water was added to the mixture under continuous strong stirring for about 10 min in order to complete the reaction. 2.3 Characterization Synthesized samples were studied by UV-vis absorption spectroscopy from a double-beam spectrophotometer (Varian Cary 100) in the wavelength range from 190 to 1100 nm. Particle size was studied by using Transmission Electron Microscopy (TEM). Samples for TEM measurements were suspended in ethanol and ultrasonically dispersed. Drops of the suspensions were placed on a copper grid coated with carbon. 3. Results and discussion 3.1. Stability UV-vis absorption spectra of copper nanoparticles are shown in gure 1 (PEG capping) and 2 (PVP capping). The plasmon absorption band for copper nanoparticles has been reported to be in the range of 500600 nm [12]. In the present study, we have been able to prepare surface capped copper nanoparticles and it is shown that the

surface plasmon resonance can be maintained over time. The spectra were measured immediately after synthesis, then after 1 day, 2 days and 3 days from sample preparation. For the PVP case the spectra were measured immediately after synthesis, and after 1 day, 2 days, 3 days and 20 days from sample preparation.

2.5

Immediately After 2 days

After 1 day After 3 days

Absorbance (a.u)

1.5

0.5

0 450

500

550

600

650

700

750

Wavelength (nm)

Fig.1 The UV-vis spectra of colloidal copper nanoparticles synthesized in solution prepared with (PEG) at different times.
1.5 1.2

1.5 1.2 Absorbance (a.u) 0.9

Absorbance (a.u)

After 20 days
0.9

Immediately After 1 day After 2 days After 3 days

0.6

0.3 0 400

450

500 550 600 Wavelength (nm)

650

700

0.6 0.3 0 400

450

500

550

600

650

700

750

Wavelength (nm)

Fig.2 The UV-vis spectra of colloidal copper nanoparticles synthesized in solution prepared with (PVP) at different times. The insert is the UV-vis spectra of the colloidal copper nanoparticles after 20 days. Table 1. Plasmon resonance of colloidal copper nanoparticles synthesized in solution prepared with (PEG) at different times. Immediately after synthesis Colloidal copper nanoparticles prepared with PEG after 1 day after 2 days after 3 days

568

567

570

unidentified

Table 2. Plasmon resonance of colloidal copper nanoparticles synthesized in solution prepared with (PVP) at different times. Immediately after synthesis Colloidal copper nanoparticles prepared with PVP 570 after 1 day after 2 days after 3 days

561

562

561

Fig. 1 and Table 1 show that colloidal copper nanoparticles in solution prepared with PEG absorbed at 568 nm, 567 nm and 570 nm wavelength for the 3 measurements. On the third day, peaks of the spectra disappeared. This means that colloidal copper nanoparticles in solution prepared with PEG are only protected within 2 days. From the third day they are almost oxidized completely as seen by a black agglomerate at the bottom of the container. Fig 2 shows that the aborption of copper nanoparticles synthesized with PVP as capping agent display a broadband behavior especially toward smaller wavelengths. As shown in table 2, the plasmon peak is stable one day after synthesis at 561 nm. According to the attached chart in Fig 2, there still

is an absorbing peak at 572 nm wavelength on the twentieth day despite less pronounced. This proves that colloidal copper nanoparticles prepared using PVP as capping agent present much better stability over time. With PVP acting as a capping agent [18], copper nanoparticles seem to be protected against oxidization over time. Fig.1 also shows that the intensity of the spectra peaks tends to decrease over time. This means the number of absorption center (colloidal copper nanoparticles) decreases over time; it also means that colloidal copper nanoparticles prepared with PEG are only well protected at the beginning but quickly start to modify in solution. In Fig.2, the intensity of the spectra peaks increases over time in the first days after

synthesis. This might be related to a slow evolution of the nanoparticles which are not completely stabilized after synthesis. This is then followed by a decrease of the intensity of the plasmon
20 18 16

peak which we think is slowly weakened by oxidation of copper nanoparticles. 3.2 Uniformity and dispersity

Size distribution (%)

14 12 10 8 6 4 2 0 0 10 20 30 40 50

Particle size (nm)

Figure 3 Transmission electron micrographs of Cu nanoparticles synthesized in solution using PEG

30 25 20

Figure 4 Transmission electron micrographs of Cu nanoparticles synthesized in solution using PVP In figure 4 the copper nanoparticle particularly are rather defined. But on the opposite the particles in figure 3 cluster together to become hardly distinguishable. The size distribution diagram was determined manually by defining by hand the nanoparticles from the TEM picture using contrast. From the above observation, we see that the di stribution of copper nanoparticles in solution using PVP is better than in solution using PEG. This is an interesting improvement to the application of copper nanoparticles in the future manufacture of conductive ink. From the two diagrams of particle size distribution of Figure 3 and 4 it can be extracted that the copper nanoparticles in solution using PEG and PVP have an average diameter of of 27 nm and 12 nm respectively. Furthermore the particle size distribution of nanoparticles in the sample using PVP is narrower than the sample using PEG. From diagrams in Figure 3 and 4 we can see that there is well-uniform in copper nanoparticles in the two samples. The dispersity in sample using PVP is better than in sample. In sample using (PVP), the amount of particles having size at 10nm, 12nm, 14nm and 16nm mainly, whereas particles with different sizes hold insignificant portion. In the sample

Size distr ibut ion (%)

15 10 5 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

Particle size (nm)

using (PEG) as capping agent the size of particles is more diversified and uneven than in sample using (PVP). We can conclude that in sample using (PVP) copper nanoparticles have better dispersity than in sample using (PEG). 4. Conclusion In this paper, copper nanoparticles were successfully synthesized by chemical reduction method with 2 different capping molecules, namely PEG and PVP. Using PVP as a capping agent showed an interesting improvement in the stability over time in solution at ambient atmosphere and in dispersity. Compared to PEG capped nanoparticles, the PVP copper nanoparticles show a ten-fold improvement in time stability . Despite this can not be considered enough for a real world application in conductive ink synthesis, it lays the ground for future development towards a better control on copper nanoparticles synthesized by chemical reduction. Acknowledgment The authors appreciate the nancial support of Vietnam National University in Ho Chi Minh City. References
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