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ZnO composite film by magnetron sputtering
Accepted Manuscript Title: Polyester fabric coated with Ag/ZnO composite film by magnetron sputtering Author: Xiaohong Yuan Wenzheng Xu Fenglin Huang Dongsheng Chen Qufu Wei PII: DOI: Reference:
S0169-4332(16)31829-3 http://dx.doi.org/doi:10.1016/j.apsusc.2016.08.164 APSUSC 33913
To appear in:
APSUSC
Received date: Revised date: Accepted date:
23-5-2016 28-8-2016 30-8-2016
Please cite this article as: Xiaohong Yuan, Wenzheng Xu, Fenglin Huang, Dongsheng Chen, Qufu Wei, Polyester fabric coated with Ag/ZnO composite film by magnetron sputtering, Applied Surface Science http://dx.doi.org/10.1016/j.apsusc.2016.08.164 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Polyester fabric coated with Ag/ZnO composite film by magnetron sputtering Xiaohong Yuan1,2, Wenzheng Xu1, Fenglin Huang1, Dongsheng Chen2, Qufu Wei1* (1. Key Laboratory of Eco-Textiles, Ministry of Education, Jiangnan University, Wuxi 214122, Jiangsu, China; 2. Clothing and Design Faculty, Minjiang University, Fuzhou 350121, Fujian,China) E-Mails: [email protected](Q.F.); [email protected](X.H.); [email protected] (W.Z.); [email protected](F.L.); [email protected](D.S.); *E-mail address of corresponding author: [email protected](Q.F.); Tel.: +86-510-85913653;
Highlights
Ag/ZnO composite film was successfully deposited on polyester fabric by magnetron sputtering technique.
Ag film was easily oxidized into Ag2O film in high vacuum oxygen environment, and deposited ZnO film formed directly by RF reactive sputtering on the surface of the fabric previously coated with Ag film could obtain Ag2O/ZnO composite film.
The method was deposited Zn film on the surface of the fabric coated with Ag film before RF reactive sputtering, which not only prepared successfully Ag/ZnO composite film, but also obtained structural color for the polyester fabric.
The anti-ultraviolet and antistatic properties of polyester fabric coated with Ag/ZnO composite film all were better than that of polyester fabric coated with Ag2O/ZnO composite film.
Abstract:
Ag/ZnO composite film was successfully deposited on polyester fabric by using direct
current (DC) magnetron sputtering and radio frequency (RF) magnetron reaction sputtering techniques with pure silver (Ag) and zinc (Zn) targets. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) were used to examine the deposited film on the fabric. It was found that the zinc film coated on Ag film before RF reactive sputtering could protect the silver film from oxidation. Anti-ultraviolet property and antistatic property of the coated samples using different magnetron sputtering methods were also investigated. The experimental results showed that Ag film was oxidized into in Ag2O film in high vacuum oxygen environment. The deposition of Zn film on the surface of the fabric coated with Ag film before RF reactive sputtering, could successfully obtained Ag/ZnO composite film, and also generated structural color on the polyester fabric. Key words: Ag/ZnO composite film; Polyester fabric; Magnetron sputtering; Structural color; Antistatic
1 Introduction In recent years, metal-semiconductor nanocomposites have attracted considerable research attention owing to their great potential applications in a variety of fields
[1-5]
. Metal-semiconductor
nanocomposites can usually provide novel or enhanced chemical and physical properties, for various applications in optics, electronics, magnetics, medicine, chemical sensor, and biomedicine applications [6-9]. Silver/ zinc oxide (Ag/ZnO) nanocomposite was a typical nanocomposite, which has already found a wide application in many fields, because metallic silver has excellent electrical, optical and chemical properties, and zinc oxide with a wide band gap and a large excitation binding
energy has high photocatalytic activity, good thermal and chemical stability, low cost, non-toxicity and environmental friendliness [10-13]. By far, there are many reports about preparation methods of Ag/ZnO nanocomposites, such as chemical bath deposition [14], sol–gel method [17]
[15]
, photoreduction method
[16]
, hydrothermal method
, pulsed laser deposition [18], nonionic polymer assisted thermolysis [19], and so on. However, the
problems of high temperature, high pressure, expensive equipments, toxic reagents, or long reaction time limited its application. Thus, a simple and fast route for the preparation of Ag/ZnO nanocomposites is still required to meet economic and industrial needs. Magnetron sputtering technique is a very effective deposition method of a thin film, and can prepare super-hard films, corrosion and friction resistant films, superconducting films, magnetic films, optical films, and nanocomposite films [20-23]. In this article, Ag/ZnO composite film was successfully deposited on the polyester fabric substrate by magnetron sputtering. The method used in this work not only prevented silver film deposited on the textile substrate from oxidization, but also obtained excellent properties and structural color of the fabrics. 2 Experimental 2.1 Materials White plain woven polyester fabrics were cut into 5cm diameter circular samples, and washed by acetone solution to remove impurities. 99.99% silver (Ag) was used as Ag target. 99.99% zinc (Zn) target was chosen in this work because zinc oxide target was fragile. 2.2 Preparation of Ag/ZnO composite films Ag/ZnO composite film was deposited by the sputtering unit (JPG-450 type). The common
preparation process of Ag/ZnO composite film by magnetron sputtering was as follows: silver film was first deposited on the surface of the polyester fabric using silver target by direct current (DC) magnetron sputtering, then, zinc oxide film was further deposited on the surface of the fabric substrate previously coated with silver film using zinc target by radio frequency (RF) reactive sputtering. However, silver film was easy to be oxidized in high vacuum oxygen environment when zinc target was reactively sputtered on the surface of the fabric substrate coated with silver film. Thus, we adopted a method to protect silver film on the surface of fabric substrate from oxidation. That was, the zinc film was deposited on the surface of the fabric substrate previously coated with silver film before RF reactive sputtering. Different samples were prepared by different experimental processes, and the chemical composition, valence state, structure and properties of deposited composite films on the textile substrate were analyzed and tested. Fig.1 shows the samples prepared by different experimental processes. 1# sample (Fig.1a) was coated with silver film using silver target by DC magnetron sputtering. 2# sample was first deposited with silver target by DC magnetron sputtering, then, the baffle plate turned to the position to cover the fabric substrate and the zinc oxide was sputtered into baffle plate in the RF reactive sputtering condition in high vacuum oxygen environment, as illustrated in Fig.1b. 3# sample was first deposited with silver target by DC magnetron sputtering, then, the zinc oxide film was further deposited on the surface of fabric substrate coated with silver film using zinc target by RF reaction sputtering, as shown in Fig.1c. For 4# sample, the silver film was first deposited on the polyester fabric substrate using silver target by DC magnetron sputtering, then, the zinc film was further deposited on the surface of fabric substrate coated with silver film using zinc target by RF magnetron sputtering. Finally, the zinc oxide film was deposited on the surface of fabric substrate
previously coated with silver and zinc film by RF reaction sputtering, as shown in Fig.1d. A base pressure of 1.510-3Pa, a rotating speed of 10r/min, and a working gas pressure of 0.8Pa, the silver film was deposited by DC magnetron sputtering, and Argon (Ar) gas flow rate of 20mL/min, a sputtering power of 64w and for a sputtering time of 10min; the zinc film was deposited by RF magnetron sputtering, and Ar gas flow rate of 20mL/min, a sputtering power of 150w and for a sputtering time of 10min; the zinc oxide film was deposited by RF reactive sputtering using zinc target, gas flow rates of Ar and O2 were set as 20mL/min and 10mL/min respectively, a sputtering power of 300w and for a sputtering time of 10min. 2.3 Characterization The chemical composition and valence state of deposited composite films on polyester fabric substrate were analyzed by X-ray photoelectron spectroscopy (XPS, Escalab 250Xi, England) and X-ray diffraction (XRD) measurements on a Bruker-AXS X-ray diffractometer system with Cu Kα radiation. Scanning range was 2°- 90°(2θ). The color photographs of samples were taken using a digital camera (DCR-HC90E, Sony, Japan). Anti-ultraviolet properties of the coated fabrics were tested by ultraviolet transmittance analyzer (UV-1000F, Lapsphere, America) according to GB/T18830-2009. The samples were stored in standard atmosphere condition（temperature= 20±2 ºC and humidity=65±2%) of experimental environment for 24h to humidify before testing. Solar UV-A spectral transmittance [T(UVA)], solar UV-B spectral transmittance [T(UVB)] and ultraviolet protection factor (UPF) were the evaluation indexes. Each sample was tested five times, and the average values were reported. Antistatic properties of the coated fabrics were tested by static honestmeter (H0110/V1, Shishido electrostatic, LTD, Japan) according to GB/T12703.1-2008. The samples were stored in controlled atmosphere conditions（temperature= 20±2 ºC and humidity=35±5%) of experimental
environment for 24h to humidify before testing. Applied voltage was 10kV. The evaluation indexes of anti-ultraviolet properties were static half period and instantaneous electrostatic voltage. Each sample was tested six times, and the average values were used. 3 Results and Discussion 3.1 XPS analysis To verify the oxidation of the silver film deposited in high vacuum oxygen environment and that the zinc film deposited on the surface of fabric substrate coated with silver film before RF reactive sputtering could protect the silver film from oxidation, the surface components, chemical states of 2#sample and 4#sample were investigated by XPS respectively, and the corresponding experimental results are shown in Figs.2 and 3. Figs.2a, 2b and 2c are full spectrum, Ag3d peak and O1s peak of 2# sample respectively. It can be seen that there have characteristic peaks of three elements from the full spectrum, and they were Ag, O and C, and the appearance of C peak came mainly from the fabric. It could be concluded that Ag was oxidized in high vacuum oxygen environment. Combination of Ag and O may take many forms, and familiar ones were Ag2O, AgO, Ag2O3, Ag3O4, and others. The position of Ag 3d5/2 peak and Ag 3d3/2 peak respectively were 368.10 eV and 374.10 eV, and the O1s peak was 531.21 eV, which illustrated that Ag existed in high oxidation states, and proved the formation of Ag2O on the surface of polyester fabric substrate [24]. The high-resolution XPS spectra of full spectrum, Ag3d, O1s and Zn2p in the Ag/ZnO composite film of 4# sample are illustrated in Figs.3a, 3b, 3c and 3d respectively. All of the peaks in Fig.3a can be ascribed to Ag, Zn, O, and C elemrnts and no obvious peaks for other elements are observed. The peaks of Zn element in Fig 3(a) includes the Zn2p peaks, Zn3s peaks, Zn3p peaks, Zn3d peak, and it can be seen that the Zn2p peaks as the characteristic peaks
were the strongest peaks. The peaks centered at 1022.00, 1044.10 eV (Fig.3d) and 529.74 eV (Fig. 3c) can be attributed to Zn 2p3/2, Zn 2p1/2, and O 1s respectively, which confirmed that in 4# samples, Zn element existed in the form of ZnO
[24]
. The peaks observed at 367.25 and 373.35eV
corresponded to the Ag 3d5/2 and Ag 3d3/2 states of the metallic silver, which proved the formation of elemental silver on the surface of polyester fabric substrate [24]. Compared Fig.2b and Fig.3b, it can be seen that the spectrum peak area of Ag 3d for 2# sample was much bigger than that of 4# sample, and proved that Ag film in 4# sample was covered under the ZnO film. 3.2 XRD analysis Fig.4 illustrates the X-ray diffraction (XRD) patterns of 1#-4# samples. 1# sample was the fabric only coated with silver film, and it can be clearly observed that the shape of diffraction peaks was pointed and narrow, which indicated that the sample had a high degree of crystallinity. The peaks appeared at 38.15°, 44.25°, 64.59°, 77.43° and 81.59° of 2θ corresponded respectively to the (111), (200), (220), (311) and (222) crystal plane of Ag (JCPDS Card File No.04-0783) except for the diffraction peaks of fabric substrate in Fig.4a. The XRD pattern of 4# sample in Fig.4d was similar with the pattern of 1# sample, and 4# sample was the fabric coated with Ag/ZnO composite film. It can be seen that the strongest diffraction peak appeared at 38.71°, 44.89°, 64.99°, 77.81° and 82.23° of 2θ also corresponded respectively to the (111), (200), (220), (311) and (222) crystal plane of Ag (JCPDS Card File No.04-0783) in Fig.4d. Compared with the shape and area of diffraction peak, it can be seen that the crystallinity degree of Ag in 4# sample was lower than that of Ag in 1# sample, because the Ag film in 4# sample was under the ZnO film, which was well consistent with the XPS results in Fig.3. However, the diffraction peak of ZnO was not found. This was because ZnO film did not form
crystalline structure in the process of RF reactive sputtering. 2# sample was the fabric coated with silver film and then, it was exposed in high vacuum oxygen environment. It can be clearly seen that Ag film was completely oxidized. The strongest diffraction peak appeared at 32.91°, 38.17°, 55.47° and 65.41° of 2θ corresponded respectively to the (111), (200), (220) and (311) crystal plane of Ag2O (JCPDS Card File No.41-1104) also except for the diffraction peaks of textile substrate in Fig.4b. The result was well consistent with the XPS results in Fig.2. 3# sample was the fabric coated with silver film and then was further deposited with ZnO film by RF reactive sputtering. It also can be clearly seen that the silver film on the surface of fabric substrate was oxidized, and the peaks appeared at 32.91°, 38.33°and 65.73° of 2θ corresponded respectively to the (111), (200) and (311) crystal plane of Ag2O (JCPDS Card File No.41-1104) in Fig.4c. However, the diffraction peak appeared at 44.49°of 2θ corresponded to the (200) crystal plane of Ag (JCPDS Card File No.04-0783), which indicated that silver film was not completely oxidized. Therefore, it can be included that there were mainly Ag2O in the composite film. As for the 4# sample, the structure of ZnO in Ag/ZnO composite film was non-crystalline structure. 3.3 Color analysis The color photographs of samples are displayed in Fig.5. From Fig.5, it can be seen that the color of 1# sample looked silver, 2# and 3#sample appeared a little black, and 4# sample was blue-green. The photographs indicated that there was silver film on the surface of 1#sample, and the silver films on the surfaces of 2# and 3# samples were oxidized, thus resulting in a little black of 2# and 3# samples, and the results were well consistent with the XPS and XRD results in Figs.2, 4b and 4c. The structural color was obtained for 4# sample because
of thin-film interference principle
[25]
, and the result also was well consistent with the XPS and
XRD results in Figs.3 and 4d. 3.4 Anti-ultraviolet property Table 1 shows the anti-ultraviolet properties of 1#-4# samples. The smaller the values of T(UVA) and T(UVB), the anti-ultraviolet property is better. Conversely, the greater the ultraviolet protection factor (UPF), the anti-ultraviolet property is higher. From Table 1, it can be seen that the anti-ultraviolet property of 1# sample was the best, followed by 4# sample because of the effect of Ag film. The anti-ultraviolet property of 2# and 3# sample was a little lower because of metallic oxide on the surface of fabric substrate. The result of anti-ultraviolet property was well consistent with the above experimental results. 3.5 Antistatic property Table 2 shows antistatic properties of 1#-4# samples. Higher static half period value means higher antistatic property, and the value of the instantaneous electrostatic voltage is the opposite. As shown in Table 2, it was observed that the antistatic property of 1# sample coated with silver film was the best, followed by 2# sample because Ag2O film also had good electrical conductivity. The antistatic property of the fabric coated with Ag/ZnO composite film was better than that of the fabric coated with Ag2O/ ZnO composite film, and poorer than the fabric coated with coated with Ag2O film. This was because that the electrical conductivity of Ag2O film was better than that of ZnO film. The result of antistatic property also was well consistent with the above experimental results. 4 Conclusions In summary, Ag/ZnO composite film was successfully deposited on polyester fabric by
magnetron sputtering technique. According to XPS and XRD analyses, Ag nanoparticles on the surface of polyester fabric was oxidized into Ag2O nanoparticles in high vacuum oxygen environment, and the deposited ZnO film formed directly by RF reactive sputtering on the surface of the fabric previously coated with Ag film could obtain Ag2O/ZnO composite film. Zn nanoparticles on the surface of Ag film could protect the Ag nanoparticles from oxidation in RF reactive sputtering process. The method that deposited Zn film on the surface of the fabric coated with Ag film before RF reactive sputtering, which not only prepared successfully Ag/ZnO composite film, but also obtained structural color for the polyester fabric. The anti-ultraviolet and antistatic properties of polyester fabric coated with Ag/ZnO composite film all were better than that of polyester fabric coated with Ag2O/ZnO composite film. Therefore, this green method can be an effectively route to design and fabricate novel metal/metal oxide nanocomposites for further application. In addition, the polyester fabrics coated with Ag/ZnO composite films were structurally-colored and multi-functional textiles that can be applied widely in various areas, such as functional clothing, home textiles and technical textiles.
Acknowledgments This work was financially supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions, the Natural Science Foundation of Jiangsu Province (BK20150155), Six talent peaks project in Jiangsu Province (2014-XCL001), the Fundamental Research Funds for the Central Universities (JUSRP51621A, JUSRP51505), and the Technical Plan Project of Fuzhou City (2016-G-77).
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Figure captions
Fig.1 Samples prepared by different experimental processes: (a) 1# sample; (b) 2# sample; (c) 3# sample and (d) 4# sample
Fig.2 X-ray photoelectron spectroscopy of 2#sample: (a) Full spectrum; (b) Ag3d peak and (c) O1s peak.
Fig.3 X-ray photoelectron spectroscopy of 4# sample: (a) Full spectrum; (b) Ag3d peak; (c) O1s peak and (d) Zn2p peak
Fig.4 XRD patterns of different samples: (a) 1# sample; (b) 2# sample; (c) 3# sample and (d) 4# sample
Fig.5 Color photographs of all the samples: (a) 1# sample; (b) 2# sample; (c) 3# sample and (d) 4# sample
Table 1 Experimental result of anti-ultraviolet property T(UVA) /%
T(UVB) /%
UPF
Samples
Average value/%
Standard deviation/%
Average value/%
Standard deviation/%
Average value
Standard deviation
1#
3.52
0.02
2.69
0.05
35.26
0.61
2#
4.36
0.43
3.67
0.18
26.70
1.64
3#
3.94
0.07
3.55
0.14
27.68
1.21
4#
3.86
0.24
3.21
0.01
30.37
0.20
Table 2 Experimental result of antistatic property Samples
Static half period/s
Instantaneous electrostatic voltage /V
Average value/s
Standard deviation/s
Average value/V
Standard deviation/V
1#
0.510
0.23
188
9.83
2#
4.658
0.39
380
8.94
3#
70.34
10.42
565
5.48
4#
25.83
3.58
315
5.48
S0169-4332(16)31829-3 http://dx.doi.org/doi:10.1016/j.apsusc.2016.08.164 APSUSC 33913
To appear in:
APSUSC
Received date: Revised date: Accepted date:
23-5-2016 28-8-2016 30-8-2016
Please cite this article as: Xiaohong Yuan, Wenzheng Xu, Fenglin Huang, Dongsheng Chen, Qufu Wei, Polyester fabric coated with Ag/ZnO composite film by magnetron sputtering, Applied Surface Science http://dx.doi.org/10.1016/j.apsusc.2016.08.164 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Polyester fabric coated with Ag/ZnO composite film by magnetron sputtering Xiaohong Yuan1,2, Wenzheng Xu1, Fenglin Huang1, Dongsheng Chen2, Qufu Wei1* (1. Key Laboratory of Eco-Textiles, Ministry of Education, Jiangnan University, Wuxi 214122, Jiangsu, China; 2. Clothing and Design Faculty, Minjiang University, Fuzhou 350121, Fujian,China) E-Mails: [email protected](Q.F.); [email protected](X.H.); [email protected] (W.Z.); [email protected](F.L.); [email protected](D.S.); *E-mail address of corresponding author: [email protected](Q.F.); Tel.: +86-510-85913653;
Highlights
Ag/ZnO composite film was successfully deposited on polyester fabric by magnetron sputtering technique.
Ag film was easily oxidized into Ag2O film in high vacuum oxygen environment, and deposited ZnO film formed directly by RF reactive sputtering on the surface of the fabric previously coated with Ag film could obtain Ag2O/ZnO composite film.
The method was deposited Zn film on the surface of the fabric coated with Ag film before RF reactive sputtering, which not only prepared successfully Ag/ZnO composite film, but also obtained structural color for the polyester fabric.
The anti-ultraviolet and antistatic properties of polyester fabric coated with Ag/ZnO composite film all were better than that of polyester fabric coated with Ag2O/ZnO composite film.
Abstract:
Ag/ZnO composite film was successfully deposited on polyester fabric by using direct
current (DC) magnetron sputtering and radio frequency (RF) magnetron reaction sputtering techniques with pure silver (Ag) and zinc (Zn) targets. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) were used to examine the deposited film on the fabric. It was found that the zinc film coated on Ag film before RF reactive sputtering could protect the silver film from oxidation. Anti-ultraviolet property and antistatic property of the coated samples using different magnetron sputtering methods were also investigated. The experimental results showed that Ag film was oxidized into in Ag2O film in high vacuum oxygen environment. The deposition of Zn film on the surface of the fabric coated with Ag film before RF reactive sputtering, could successfully obtained Ag/ZnO composite film, and also generated structural color on the polyester fabric. Key words: Ag/ZnO composite film; Polyester fabric; Magnetron sputtering; Structural color; Antistatic
1 Introduction In recent years, metal-semiconductor nanocomposites have attracted considerable research attention owing to their great potential applications in a variety of fields
[1-5]
. Metal-semiconductor
nanocomposites can usually provide novel or enhanced chemical and physical properties, for various applications in optics, electronics, magnetics, medicine, chemical sensor, and biomedicine applications [6-9]. Silver/ zinc oxide (Ag/ZnO) nanocomposite was a typical nanocomposite, which has already found a wide application in many fields, because metallic silver has excellent electrical, optical and chemical properties, and zinc oxide with a wide band gap and a large excitation binding
energy has high photocatalytic activity, good thermal and chemical stability, low cost, non-toxicity and environmental friendliness [10-13]. By far, there are many reports about preparation methods of Ag/ZnO nanocomposites, such as chemical bath deposition [14], sol–gel method [17]
[15]
, photoreduction method
[16]
, hydrothermal method
, pulsed laser deposition [18], nonionic polymer assisted thermolysis [19], and so on. However, the
problems of high temperature, high pressure, expensive equipments, toxic reagents, or long reaction time limited its application. Thus, a simple and fast route for the preparation of Ag/ZnO nanocomposites is still required to meet economic and industrial needs. Magnetron sputtering technique is a very effective deposition method of a thin film, and can prepare super-hard films, corrosion and friction resistant films, superconducting films, magnetic films, optical films, and nanocomposite films [20-23]. In this article, Ag/ZnO composite film was successfully deposited on the polyester fabric substrate by magnetron sputtering. The method used in this work not only prevented silver film deposited on the textile substrate from oxidization, but also obtained excellent properties and structural color of the fabrics. 2 Experimental 2.1 Materials White plain woven polyester fabrics were cut into 5cm diameter circular samples, and washed by acetone solution to remove impurities. 99.99% silver (Ag) was used as Ag target. 99.99% zinc (Zn) target was chosen in this work because zinc oxide target was fragile. 2.2 Preparation of Ag/ZnO composite films Ag/ZnO composite film was deposited by the sputtering unit (JPG-450 type). The common
preparation process of Ag/ZnO composite film by magnetron sputtering was as follows: silver film was first deposited on the surface of the polyester fabric using silver target by direct current (DC) magnetron sputtering, then, zinc oxide film was further deposited on the surface of the fabric substrate previously coated with silver film using zinc target by radio frequency (RF) reactive sputtering. However, silver film was easy to be oxidized in high vacuum oxygen environment when zinc target was reactively sputtered on the surface of the fabric substrate coated with silver film. Thus, we adopted a method to protect silver film on the surface of fabric substrate from oxidation. That was, the zinc film was deposited on the surface of the fabric substrate previously coated with silver film before RF reactive sputtering. Different samples were prepared by different experimental processes, and the chemical composition, valence state, structure and properties of deposited composite films on the textile substrate were analyzed and tested. Fig.1 shows the samples prepared by different experimental processes. 1# sample (Fig.1a) was coated with silver film using silver target by DC magnetron sputtering. 2# sample was first deposited with silver target by DC magnetron sputtering, then, the baffle plate turned to the position to cover the fabric substrate and the zinc oxide was sputtered into baffle plate in the RF reactive sputtering condition in high vacuum oxygen environment, as illustrated in Fig.1b. 3# sample was first deposited with silver target by DC magnetron sputtering, then, the zinc oxide film was further deposited on the surface of fabric substrate coated with silver film using zinc target by RF reaction sputtering, as shown in Fig.1c. For 4# sample, the silver film was first deposited on the polyester fabric substrate using silver target by DC magnetron sputtering, then, the zinc film was further deposited on the surface of fabric substrate coated with silver film using zinc target by RF magnetron sputtering. Finally, the zinc oxide film was deposited on the surface of fabric substrate
previously coated with silver and zinc film by RF reaction sputtering, as shown in Fig.1d. A base pressure of 1.510-3Pa, a rotating speed of 10r/min, and a working gas pressure of 0.8Pa, the silver film was deposited by DC magnetron sputtering, and Argon (Ar) gas flow rate of 20mL/min, a sputtering power of 64w and for a sputtering time of 10min; the zinc film was deposited by RF magnetron sputtering, and Ar gas flow rate of 20mL/min, a sputtering power of 150w and for a sputtering time of 10min; the zinc oxide film was deposited by RF reactive sputtering using zinc target, gas flow rates of Ar and O2 were set as 20mL/min and 10mL/min respectively, a sputtering power of 300w and for a sputtering time of 10min. 2.3 Characterization The chemical composition and valence state of deposited composite films on polyester fabric substrate were analyzed by X-ray photoelectron spectroscopy (XPS, Escalab 250Xi, England) and X-ray diffraction (XRD) measurements on a Bruker-AXS X-ray diffractometer system with Cu Kα radiation. Scanning range was 2°- 90°(2θ). The color photographs of samples were taken using a digital camera (DCR-HC90E, Sony, Japan). Anti-ultraviolet properties of the coated fabrics were tested by ultraviolet transmittance analyzer (UV-1000F, Lapsphere, America) according to GB/T18830-2009. The samples were stored in standard atmosphere condition（temperature= 20±2 ºC and humidity=65±2%) of experimental environment for 24h to humidify before testing. Solar UV-A spectral transmittance [T(UVA)], solar UV-B spectral transmittance [T(UVB)] and ultraviolet protection factor (UPF) were the evaluation indexes. Each sample was tested five times, and the average values were reported. Antistatic properties of the coated fabrics were tested by static honestmeter (H0110/V1, Shishido electrostatic, LTD, Japan) according to GB/T12703.1-2008. The samples were stored in controlled atmosphere conditions（temperature= 20±2 ºC and humidity=35±5%) of experimental
environment for 24h to humidify before testing. Applied voltage was 10kV. The evaluation indexes of anti-ultraviolet properties were static half period and instantaneous electrostatic voltage. Each sample was tested six times, and the average values were used. 3 Results and Discussion 3.1 XPS analysis To verify the oxidation of the silver film deposited in high vacuum oxygen environment and that the zinc film deposited on the surface of fabric substrate coated with silver film before RF reactive sputtering could protect the silver film from oxidation, the surface components, chemical states of 2#sample and 4#sample were investigated by XPS respectively, and the corresponding experimental results are shown in Figs.2 and 3. Figs.2a, 2b and 2c are full spectrum, Ag3d peak and O1s peak of 2# sample respectively. It can be seen that there have characteristic peaks of three elements from the full spectrum, and they were Ag, O and C, and the appearance of C peak came mainly from the fabric. It could be concluded that Ag was oxidized in high vacuum oxygen environment. Combination of Ag and O may take many forms, and familiar ones were Ag2O, AgO, Ag2O3, Ag3O4, and others. The position of Ag 3d5/2 peak and Ag 3d3/2 peak respectively were 368.10 eV and 374.10 eV, and the O1s peak was 531.21 eV, which illustrated that Ag existed in high oxidation states, and proved the formation of Ag2O on the surface of polyester fabric substrate [24]. The high-resolution XPS spectra of full spectrum, Ag3d, O1s and Zn2p in the Ag/ZnO composite film of 4# sample are illustrated in Figs.3a, 3b, 3c and 3d respectively. All of the peaks in Fig.3a can be ascribed to Ag, Zn, O, and C elemrnts and no obvious peaks for other elements are observed. The peaks of Zn element in Fig 3(a) includes the Zn2p peaks, Zn3s peaks, Zn3p peaks, Zn3d peak, and it can be seen that the Zn2p peaks as the characteristic peaks
were the strongest peaks. The peaks centered at 1022.00, 1044.10 eV (Fig.3d) and 529.74 eV (Fig. 3c) can be attributed to Zn 2p3/2, Zn 2p1/2, and O 1s respectively, which confirmed that in 4# samples, Zn element existed in the form of ZnO
[24]
. The peaks observed at 367.25 and 373.35eV
corresponded to the Ag 3d5/2 and Ag 3d3/2 states of the metallic silver, which proved the formation of elemental silver on the surface of polyester fabric substrate [24]. Compared Fig.2b and Fig.3b, it can be seen that the spectrum peak area of Ag 3d for 2# sample was much bigger than that of 4# sample, and proved that Ag film in 4# sample was covered under the ZnO film. 3.2 XRD analysis Fig.4 illustrates the X-ray diffraction (XRD) patterns of 1#-4# samples. 1# sample was the fabric only coated with silver film, and it can be clearly observed that the shape of diffraction peaks was pointed and narrow, which indicated that the sample had a high degree of crystallinity. The peaks appeared at 38.15°, 44.25°, 64.59°, 77.43° and 81.59° of 2θ corresponded respectively to the (111), (200), (220), (311) and (222) crystal plane of Ag (JCPDS Card File No.04-0783) except for the diffraction peaks of fabric substrate in Fig.4a. The XRD pattern of 4# sample in Fig.4d was similar with the pattern of 1# sample, and 4# sample was the fabric coated with Ag/ZnO composite film. It can be seen that the strongest diffraction peak appeared at 38.71°, 44.89°, 64.99°, 77.81° and 82.23° of 2θ also corresponded respectively to the (111), (200), (220), (311) and (222) crystal plane of Ag (JCPDS Card File No.04-0783) in Fig.4d. Compared with the shape and area of diffraction peak, it can be seen that the crystallinity degree of Ag in 4# sample was lower than that of Ag in 1# sample, because the Ag film in 4# sample was under the ZnO film, which was well consistent with the XPS results in Fig.3. However, the diffraction peak of ZnO was not found. This was because ZnO film did not form
crystalline structure in the process of RF reactive sputtering. 2# sample was the fabric coated with silver film and then, it was exposed in high vacuum oxygen environment. It can be clearly seen that Ag film was completely oxidized. The strongest diffraction peak appeared at 32.91°, 38.17°, 55.47° and 65.41° of 2θ corresponded respectively to the (111), (200), (220) and (311) crystal plane of Ag2O (JCPDS Card File No.41-1104) also except for the diffraction peaks of textile substrate in Fig.4b. The result was well consistent with the XPS results in Fig.2. 3# sample was the fabric coated with silver film and then was further deposited with ZnO film by RF reactive sputtering. It also can be clearly seen that the silver film on the surface of fabric substrate was oxidized, and the peaks appeared at 32.91°, 38.33°and 65.73° of 2θ corresponded respectively to the (111), (200) and (311) crystal plane of Ag2O (JCPDS Card File No.41-1104) in Fig.4c. However, the diffraction peak appeared at 44.49°of 2θ corresponded to the (200) crystal plane of Ag (JCPDS Card File No.04-0783), which indicated that silver film was not completely oxidized. Therefore, it can be included that there were mainly Ag2O in the composite film. As for the 4# sample, the structure of ZnO in Ag/ZnO composite film was non-crystalline structure. 3.3 Color analysis The color photographs of samples are displayed in Fig.5. From Fig.5, it can be seen that the color of 1# sample looked silver, 2# and 3#sample appeared a little black, and 4# sample was blue-green. The photographs indicated that there was silver film on the surface of 1#sample, and the silver films on the surfaces of 2# and 3# samples were oxidized, thus resulting in a little black of 2# and 3# samples, and the results were well consistent with the XPS and XRD results in Figs.2, 4b and 4c. The structural color was obtained for 4# sample because
of thin-film interference principle
[25]
, and the result also was well consistent with the XPS and
XRD results in Figs.3 and 4d. 3.4 Anti-ultraviolet property Table 1 shows the anti-ultraviolet properties of 1#-4# samples. The smaller the values of T(UVA) and T(UVB), the anti-ultraviolet property is better. Conversely, the greater the ultraviolet protection factor (UPF), the anti-ultraviolet property is higher. From Table 1, it can be seen that the anti-ultraviolet property of 1# sample was the best, followed by 4# sample because of the effect of Ag film. The anti-ultraviolet property of 2# and 3# sample was a little lower because of metallic oxide on the surface of fabric substrate. The result of anti-ultraviolet property was well consistent with the above experimental results. 3.5 Antistatic property Table 2 shows antistatic properties of 1#-4# samples. Higher static half period value means higher antistatic property, and the value of the instantaneous electrostatic voltage is the opposite. As shown in Table 2, it was observed that the antistatic property of 1# sample coated with silver film was the best, followed by 2# sample because Ag2O film also had good electrical conductivity. The antistatic property of the fabric coated with Ag/ZnO composite film was better than that of the fabric coated with Ag2O/ ZnO composite film, and poorer than the fabric coated with coated with Ag2O film. This was because that the electrical conductivity of Ag2O film was better than that of ZnO film. The result of antistatic property also was well consistent with the above experimental results. 4 Conclusions In summary, Ag/ZnO composite film was successfully deposited on polyester fabric by
magnetron sputtering technique. According to XPS and XRD analyses, Ag nanoparticles on the surface of polyester fabric was oxidized into Ag2O nanoparticles in high vacuum oxygen environment, and the deposited ZnO film formed directly by RF reactive sputtering on the surface of the fabric previously coated with Ag film could obtain Ag2O/ZnO composite film. Zn nanoparticles on the surface of Ag film could protect the Ag nanoparticles from oxidation in RF reactive sputtering process. The method that deposited Zn film on the surface of the fabric coated with Ag film before RF reactive sputtering, which not only prepared successfully Ag/ZnO composite film, but also obtained structural color for the polyester fabric. The anti-ultraviolet and antistatic properties of polyester fabric coated with Ag/ZnO composite film all were better than that of polyester fabric coated with Ag2O/ZnO composite film. Therefore, this green method can be an effectively route to design and fabricate novel metal/metal oxide nanocomposites for further application. In addition, the polyester fabrics coated with Ag/ZnO composite films were structurally-colored and multi-functional textiles that can be applied widely in various areas, such as functional clothing, home textiles and technical textiles.
Acknowledgments This work was financially supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions, the Natural Science Foundation of Jiangsu Province (BK20150155), Six talent peaks project in Jiangsu Province (2014-XCL001), the Fundamental Research Funds for the Central Universities (JUSRP51621A, JUSRP51505), and the Technical Plan Project of Fuzhou City (2016-G-77).
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Figure captions
Fig.1 Samples prepared by different experimental processes: (a) 1# sample; (b) 2# sample; (c) 3# sample and (d) 4# sample
Fig.2 X-ray photoelectron spectroscopy of 2#sample: (a) Full spectrum; (b) Ag3d peak and (c) O1s peak.
Fig.3 X-ray photoelectron spectroscopy of 4# sample: (a) Full spectrum; (b) Ag3d peak; (c) O1s peak and (d) Zn2p peak
Fig.4 XRD patterns of different samples: (a) 1# sample; (b) 2# sample; (c) 3# sample and (d) 4# sample
Fig.5 Color photographs of all the samples: (a) 1# sample; (b) 2# sample; (c) 3# sample and (d) 4# sample
Table 1 Experimental result of anti-ultraviolet property T(UVA) /%
T(UVB) /%
UPF
Samples
Average value/%
Standard deviation/%
Average value/%
Standard deviation/%
Average value
Standard deviation
1#
3.52
0.02
2.69
0.05
35.26
0.61
2#
4.36
0.43
3.67
0.18
26.70
1.64
3#
3.94
0.07
3.55
0.14
27.68
1.21
4#
3.86
0.24
3.21
0.01
30.37
0.20
Table 2 Experimental result of antistatic property Samples
Static half period/s
Instantaneous electrostatic voltage /V
Average value/s
Standard deviation/s
Average value/V
Standard deviation/V
1#
0.510
0.23
188
9.83
2#
4.658
0.39
380
8.94
3#
70.34
10.42
565
5.48
4#
25.83
3.58
315
5.48