Effect of Deposition Time of Sputtering Ag-Cu Thin Film on

Mechanical and Antimicrobial Properties

A. Purniawan1),a), R. Hermastuti1), H. Purwaningsih1), T.M. Atmono2)
1)
Departement of Materials Engineering, Institut Teknologi Sepuluh Nopember, Surabaya, Indonesia
2)
Pusat Sains Teknologi Akselerator - BATAN, Yogyakarta, Indonesia

a)
Corresponding author: agung_pur@mat-eng.its.ac.id

Abstract. Metallic implants are important components in biomedical treatment. However, oftentimes postoperative
infection ensues after installation of implant. Infections on joints installation are usually treated by antibiotics, but it is still
not optimal. Prevention has been undergone by keeping the surgical instruments and implants in a sterile condition.
Nevertheless, this action is not optimal if the utilized material still can attract the bacteria. From material science’s side, it
is developed a type of material which has antibacterial properties or called as antimicrobial material. Silver (Ag) and Copper
(Cu) have antimicrobial properties to prevent infection in bone implants. This research analyzed the influence of deposition
time on Ag-Cu thin film deposition process as antimicrobial material with Physical Vapor Deposition (PVD) RF Sputtering
method. Parameter which is used were time with amount of 10, 15 and 20 minutes in Argon gas pressure around 3 x 10-2
mbar in PVD process. This research will analyze the effect of time deposition parameter. The results of Ag-Cu thin film
deposition was characterized using SEM to analyze morphology of thin film. The result that rise of deposition time will
increase the quality of the thin films that the incomplete of film doesn’t occur. The surface roughness using AFM,
antimicrobial properties using Kirby Bauer Test and adhesion quality using Rockwell C Indentation Test. The result shows
that with the increase in deposition time the roughness of thin film decreased in 15 minutes deposition time. From
indentation test using Rockwell-C, it is obtained that adhesion result of Ag-Cu thin layer is weak and it is not acceptable
according to technical qualification. An antimicrobial assay was then performed using the Disk Diffusion Test Kirby Bauer
method where there was a microbial inhibition area on the Ag-Cu thin film sample.

Keywords—Thin Film, Antimicrobial Coating, Implant, PVD

I. INTRODUCTION

Postoperative infection ensues after installation of implant. Infection in join installation are usually treated by
antibiotics, but it is still note optimal [1]. Prevention has been undergone by kipping the surgical instruments and
implants in a sterile condition. Nevertheless, this action is not optimal if the utilized material still can attract the
bacteria. From material science’s side, it is developed a type of material which has antibacterial properties or called
as antimicrobial material. Silver (Ag) and Copper (Cu) have antimicrobial properties to prevent infection in bone
implants. Silver has the natural antibacterial and biocompatible characteristics. It is used to injury treatment in 20
Century [2]. Some benefit of Silver as the coat of metallic implant is effective to kill the positive, negative gram
bacteria and another kind of bacteria which has resistance to medicine low concentration [3]. Several material
combinations were used such as Ag nanoparticles (Ag NPs)/ chitosan [4], Ag NPs/TiO 2 [5], agar and banana powder
(A/B/NPs) [6], multi-walled carbon nanotubes (MWCNTs) with embedded iron oxide and silver nanoparticles [7].
The copper has been observed as the antimicrobial material that Cu-TiO2 coatings shows antimicrobial properties,
that decreased number of bacterial in the surface and the concentration of the copper content is tolerable in the
physiology condition[8]. PVD (Physical Vapor Deposition) is one of method to deposits to get some improvement
properties of some materials and can control the structure of thin films in atomic scale or nanometer scale. In this
research, deposition of Silver-Copper is using Physical Vapor Deposition RF Sputtering method to fabricate Ag-Cu
thin film as antimicrobial coating.

II. EXPERIMENTAL

Materials

Materials used in this research are Silver (purity 99,9%) and Copper (purity 99,9%) as target and stainless steel
316L and Argon gas from Samator Gas. Other utilities such as abrasive paper, glass slide, metal polish, etc.

Ag-Cu thin film deposition

Stainless Steel 316L plate 3mm thickness were cut by grinding machine to 1 x 1 cm sample, smoothed by abrasive
paper (80 – 2000 grade) until uniform surface roughness were obtained and polished by metal polish. These samples
along with the holders (glass slides) were cleaned with ethanol in petri dish.
After the cleaning process, every 3 samples and sample holder (glass slide) were coated using different variable in
PVD process. The sample along with the sample holder were installed inside PVD chamber. PVD RF Sputtering
BATAN was used to deposit silver thin film and all the parameters and intakes is controlled by RF machine and
BALLZERS equipment.
The chamber were vacuumed and Argon gas were introduced to the chamber until constant gas pressure (3.0 x 10-
2
mbar) and RF machine were turned on to destined power around 68-70 W. The samples were deposited with different
deposition time variable by 10, 15, 20 minutes and done in each three samples.
The samples were extracted from the PVD chamber by turning-off the RF machine and normalized the pressure in
chamber by opening the gas valve sufficiently. The material were extracted chamber after the pressure was low enough
and stored in dry storage with silica gel to absorb humidity.

Electron microscopy and surface chemical analysis (SEM)

The surface and coating morphology and the distribution of silver were analyzed using FEI INSPECT 550 –
Scanning Electron Microscope. Roughness characterization. Roughness of thin films were measured by Atomic Force
Microscopy with a contact probe tip to scan along the surface. Roughness profiles were obtained by examine the Sa
and Sz result in scanning. Sa express the difference in height of each point compared to the arithmetical mean of the
surface. This parameter is used generally to evaluate surface roughness while Sz is defined as the sum of the largest
peak height value and the largest pit depth value within the defined area.

Adhesion quality characterization

Rockwell C Indentation Test were measured at Metallurgy Laboratory Material Engineering Department with 100
kgf as initial load and indentation load 150 kgf. However it was measured qualitatively by examining the delamination
or crack around the indentation area. It represent the adhesion quality oh silver thin film on stainless steel substrate.
Figure 1. Show these failure shape determine which failure is categorized as acceptable or unacceptable failures in
Rockwell-C indentation thin film.
 FIGURE 1. Acceptable or unacceptable failures in Rockwell-C indentation thin film [9]

Antimicrobial characterization

Antimicrobial properties of the deposited coatings was determined using Kirby Bauer Test Method. Cooperating
with Biology Department, Institut Teknologi Sepuluh Nopember (ITS), these test were conducted by measuring
inhibition zone caused by antimicrobial agent. The inhibition zone length will provide quantitative information of
antimicrobial properties.

III. RESULTS AND DISCUSSION

SEM results

Figure 3 shows the image of morphology Ag-Cu thin film. Sample a with 10 minutes deposition time shown the
incomplete area on the surface of coating. By increase of time deposition will cover the substrate and the thickness
of thin film [10].

FIGURE 2. SEM image results of deposition time (a) 10 minutes, (b) 15 minutes (c) 20 minutes.
AFM results

Deposition time from PVD process will likely affected the surface roughness of the material. Figure 3 shows the
AFM results of different deposition time of PVD RF Sputtering process.

FIGURE 4. AFM 3D scanning results of deposition time (a) 10 minutes, (b) 15 minutes (c) 20 minutes.

Qualitatively by examining figure 3. It shows that highest roughness is sample a wiith deposistion time 10
minutes. And the lowest roughness is sample B with 15 minutes deposition time. Appropriate with Sa and Sz data in
Table 1. That roughness can determined with Sa and Sz data. Roughness will increase with increase the number of Sa
and Sz. This data show that the highest Sa is sample a with 10 minutes which has 14.03 nm and Sz is 168.33 nm and
the lowest is sample b which has Sa 8.51 nm and Sz is 131.93 nm. The roughness of sample A due to the roughness
of substrat not same one and another which is affecting the roughness of the surface.

TABLE 1. Surface roughness Sa and Sz data

Deposition time
(minutes) Sa (nm) Sz (nm)
10 14.03 168.33
15 8.51 131.93
20 9.603 173.9

Wettability on the surface material can influenced by the roughness of surface thin film. In previous research, by
increase the roughness number of surface is proportional with increasing the angle of contact between the thin film
and the liquid [10]. So that increase the roughness of the thin film will affect the rate of reaction on the surface. By
lower the number of surface roughness will increase the rate of the surface reaction.

Qualitative Adhesion Test

Adhesion of film to substrate examined by delamination and crack on the coating surface after Rockwell C
Indentation.
FIGURE 4. Rockwell-C indentation after unloading on the thin film surface in constant pressure process P=3 x 10-2
mBar from deposition time a) 10 minutes, b) 15 minutes, c) 20 minutes and d) without Ag-Cu thin film.

In previous research that developed by Heinke, 1995 [10]. That investigated the adhesion properties of the thin film
by indentation with Rockwell-C indentor on TiN and CrN thin films that deposited by Physical Vapor Deposition.
Refers to that research, the adhesion of Ag-Cu thin film in Figure 4. For all sample reveal large delamination area that
represent an unacceptable failure. Delamination and cracks occurred on the thin films not in unacceptable region.
Adhesion of thin film affected by several factor, such as surface cleaning process on the substrat from the impurity.
Cleaning process with the ion bombardment will increase the mechanical bonding between the surface of substrat and
the layer of thin film. Another factor are heating substrat to occur the interdiffusion or the interface alloy between
substrat and layer of thin film [11].

Kirby-Bauer test (disk diffusion test)

As shown in Figure 5. all samples with Ag-Cu thin film shows inhibition zone tested on E. coli medium. And the
sample without Ag-Cu thn film did not inhibit the growth of E. coli. It concluded that every samples have
antimicrobial properties against E. coli Figure 5. Inhibition area of Ag-Cu thin film in deposition time a) 10 minutes
b) 15 minutes c) 20 minutes d) without Ag-Cu thin film. It proved that Ag-Cu thin film can inhibit the growth of
bacteria in surround it. The number of inhibition area shown in Figure 6.

0,4
Inhibition length (cm)

0,3

0,2

0,1

0
10 15 20
Time (minutes)

Figure 6. Graphic of inhibition area Ag-Cu thin film

Figure 6 shown the optimal inhibition of Ag-Cu thin film is sample with 15 minutes deposition time. Nevertheless,
deposition time on PVD process did not affecting directly toward antimicrobial ability. But this variation shown the
difference of the surface roughness of Ag-Cu thin film affecting the antimicrobial properties. The lowest number of
roughness increase the antimicrobial ability due to the lowest contact angle increase the rate of reaction and also the
antimicrobial ion such as Ag+ and Cu2+ due to the ion activation with NaClO. The result of AFM test, sample b which
is 15 minutes deposition time, reveal the lowest roughness so that increase the rate of reaction to release Ag + and Cu2+
ions which is appropriate with largest inhibition area.

CONCLUSSION

The result that rise of deposition time will increase the quality of the thin films that the incomplete of film doesn’t
occur Deposition time in Ag-Cu thin film process did not directly affecting to the roughness and the adhesion of the
Ag-Cu thin film. Nevertheless, The roughness of the thin film affecting the antimicrobial ability. The lowest roughness
is 15 minutes deposition time shown good antimicrobial properties. All sample shown large delamination area. It is
obtained that adhesion result of Ag-Cu thin layer is weak and it is not acceptable according to technical qualification.

ACKNOWLEDGEMENT

This work had financially supported by Material Engineering Departement of Institut Teknologi Sepuluh
Nopember. We also thank National Nuclear Energy Agency (BATAN), Yogyakarta, Indonesia for fabication
assistance and Laboratory of Microbiology and Biotechnology, Biology Department, Institut Teknologi Sepuluh
Nopember for Antimicrobial Test assistance.

REFERENCES

1. D.P Lew, Waldvogel FA (2004,): Osteomyelitis. Lancet 364(9431):369-379

2. J.W. Alexander (2009). History of the medical use of silver. Surgical Infections, 10, 289-292
3. M. Bosetti, Massè A, Tobin E, Cannas M. (2002) Silver coated materials for external fixation devices: in vitro
biocompatibility and genotoxicity. Biomaterials; 23:887–92.
4. M.D. Perli, V. Karagkiozakia,, F. Pappaa, I. Moutsiosa, L. Tzounisa, A. Zachariadisa, C. Gravalidisa, A.
Laskarakisa, S. Logothetidisa J.D. Miller, Veeramasuneni, J. Drelich, dan Yalamechili M.R 2017, Synthesis
and Characterization of Ag Nanoparticles for Orthopaedic applications, 13th International Conference on
Nanosciences & Nanotechnologies & 9th International Symposium on Flexible Organic Electronics, Materials
Today: Proceedings 4 (2017) 6889–6900
5. D.Guitoume, S.Achour, N.Sobti, M.Boudissa, N.Souami, Y.Messaoudi, (2017). Structural, optical and
photoelectrochemical properties of TiO2 films decorated with plasmonic silver nanoparticles, Optik -
International Journal for Light and Electron Optics
6. A. Orsuwan, Shiv Shankar, Long-Feng Wang, Rungsinee Sothornvit, 2017, Preparation of antimicrobial
agar/banana powder blend films reinforced with silver nanoparticles, Food Hydrocolloids 60 (2016) 476-485
7. Q.Ali, Waqar Ahmed, Sham Lal, Tapas Sen (2017), Novel Multifunctional Carbon Nanotube Containing Silver
and Iron Oxide Nanoparticles for Antimicrobial Applications in Water Treatment, Materials Today:
Proceedings 4 (2017) 57–64
8. F.C. Fang, (1997). Perspectives series: host/pathogen interactions. Mechanisms of nitric oxiderelated
antimicrobial activity. Journal of Clinical Investigation, 99, 2818.
9. PVD Coating Characterization. Manual P&P Thin Film Advanced Technologies. Badizolle, Italy
10. M. Sin, Mamat, M, H., dan Rusop M. (2013). Effect of Deposition Time on Properties Nanostructure ZnO
Thin Film Deposited by RF Magnetron Sputtering. Advance Material Research : Malaysia
11. W. Heinke, Leyland A., Mtthews A., Berg G., Fredrich C., Broszeit E (1995). Evaluation of PVD nitrtide
Coating, using impact, scractch and Rockwell Cadhesion test. RCSE: Germany