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Article history:
Received 28 July 2014
Received in revised form 8 December 2014
Accepted 30 March 2015
Available online 6 April 2015
Keywords:
Au lm
HCl-doped polyaniline
Composite
Sputtering
Electrical property
a b s t r a c t
Au lms with a thickness of 14180 nm were sputter-deposited on HCl-doped polyaniline (HCl-PANI) substrates
at 300 K, forming the Au/HCl-PANI composites. The sputter-deposition is discontinuous in order to prevent from
heating the substrate during the deposition. The 14 nm- and 28 nm-thick Au lms have a network structure. The
Au lms with a thickness of 50180 nm have a continuous structure and consist of granular grains. A temperature
dependence of the resistance within 6280 K reveals the complex behavior of the Au/HCl-PANI composite as follows: (1) The composite with the 14 nm-thick Au lm shows the semiconducting behavior. (2) The composite
with the 28 nm-thick Au lm exhibits the metalsemiconductor transition with increasing temperature,
i.e., the composite shows the metallic conduction behavior at temperatures below the transition temperature
and the semiconducting behavior at temperatures over the transition temperature. (3) As the Au lm thickness
reaches and exceeds 50 nm, the composites only exhibit the metallic conduction behavior.
2015 Elsevier B.V. All rights reserved.
1. Introduction
The polymer nanocomposites containing metal nanoparticles were
mostly studied because of their functional applications [1]. Particularly,
the noble metal (Au and Ag) lms grown on polymers have attracted
considerable attention for their potential applications in functional devices, e.g., references [29]. Rufno et al. [2] sputter-deposited Au
lms on polystyrene (PS) and polymethylmethacrylate (PMMA) substrates. They observed that the Au lm evolved from hemispherical
islands to partially coalesced worm-like island, to percolation, and nally to a continuous and rough lm, with increasing deposition time. Furthermore, they annealed the Au and Ag thin lms grown on the PS and
PMMA substrates at temperatures over the glass transition temperature
of the polymer. They found the embedding of the Au and Ag nanoparticles in the PS and PMMA during annealing and obtained the activation
energy for the embedding process [3]. Kaune et al. [4] studied the
growth of the Au lm on the conducting polymer surface and suggested
the growth model. Takele et al. [5] prepared Teon- and Nylon-based
nanocomposite lms consisting of Au and Ag nanoparticles by coevaporating the metal and the polymer. They found that the resistivity
percolation thresholds were 0.42 and 0.32 for Teon- and Nylonbased nanocomposite lms, respectively. Torrisi et al. [6] deposited
Au/polymer multilayers on p-Si substrates to prepare the Schottky device. They found that the Schottky barrier height could be controlled
by the Au/polymer bilayer number. Rufno et al. [7] sputter-deposited
the Au micro-size square patterns on the PMMA layer by xing Cu
Corresponding author. Tel.: +86 10 62333786; fax: +86 10 62332993.
E-mail address: qiuhong@sas.ustb.edu.cn (H. Qiu).
http://dx.doi.org/10.1016/j.tsf.2015.03.069
0040-6090/ 2015 Elsevier B.V. All rights reserved.
lms because it can easily control the composition, structure and physical property of the lms as well as can enhance the adhesion of the lm
to the substrate. Besides, the sputtered atoms have the high energy
when they arrive at the substrate surface or the growing lm surface.
These energetic adatoms can improve the structure of the lm
sputter-deposited at room temperature. Room temperature deposition
can eliminate the thermal stress in the lm and is suitable for the polymer substrates having a low decomposition temperature. Moreover, the
Ni/HCl-PANI composite has been successfully prepared by direct current
magnetron sputtering at room temperature [10]. Thus, in the present
work, Au lms are sputter-deposited on HCl-PANI substrates, forming
the Au/HCl-PANI composites. Structural and electrical properties of
the Au/HCl-PANI composites are studied as a function of the Au lm
thickness.
2. Experimental procedure
All the chemical reagents were purchased from Beijing Chemical
Works and were of analytical grade. Only aniline was doubly distilled
under reduced pressure and stored in refrigerator (at about 4 C) prior
to using. The other chemical reagents were used without further purication. HCl-PANI was chemically synthesized using the well-established
polymerization procedure [17]. The polymerization procedure is summarized as follows: (1) Aniline (0.1 mol) was dissolved in 100 mL aqueous hydrochloric acid (HCl, 1 mol/L) taken in a three-neck ask. The
mixture solution was cooled and stirred at 3 C by a magnetic stirrer.
(2) 51.5 mL ammonium persulfate solution (2.4 mol/L) in a constant
pressure funnel was slowly added into the mixture solution for 1 h in
order to avoid heating the reaction mixture. The reaction proceeded at
3 C for 8 h. (3) The nal solution was ltered. (4) The protonated
precipitate was washed with deionized water, acetone and ethanol
until the washing water, acetone and ethanol became colorless and
the pH was equal to 7. (5) The powder was dried at 50 C in oven for
two days. The HCl-PANI powder was obtained.
The HCl-PANI powder was compacted to pellets with 0.4 mm in
thickness and 13 mm in diameter. The HCl-PANI pellets were used as
the substrates. Au lms were deposited on the HCl-PANI substrates at
300 K by using a direct current sputtering system SCB-12 (KYKY) [18,
19]. The Au target (99.99% in purity) with 50 mm in diameter faced
the substrate. The distance between the target and the substrate was
40 mm. Prior to deposition, the working chamber was evacuated to a
pressure of 2 Pa by using the rotary pump. The sputtering was started
at an Ar gas (99.9995% in purity) pressure of 4 Pa and the sputtering
power applied to the target was xed at 1000 V 4 mA. The sputterdeposition is discontinuous in order to prevent from heating the substrate during the deposition. After the Au lm was sputter-deposited
for 10 s, the sputtering paused for 10 s and then continued to start.
The 10-second sputter-deposition and the 10-second pause were one
preparation cycle. The Au lm preparation required several cycles to obtain the desired lm thickness. The lm thicknesses ranging from 50 nm
to 180 nm were measured using eld emission scanning electron microscopy. The relationship between the lm thickness d and the deposition time t exhibits a linear dependence having a linear correlation
coefcient of 0.98. The deposition rate, which was obtained from the
dt relationship, was 9.4 nm/min. The lm thicknesses below 50 nm
were obtained by controlling the deposition time. The relative error in
the lm thickness came mainly from the surface roughness of the lm
and was around 10%.
Field emission scanning electron microscopy (FE-SEM) of SUPRA55
(Zeiss) was used to observe the structure of the Au lms. The acceleration voltage of electron beam was 10 kV. The electron beam did not inuence the surface morphology of the Au/HCl-PANI composite during
the FE-SEM observation. X-ray diffraction (XRD) of D/Max-RB (Rigaku)
was used to analyze the structure of the lms. The XRD measurements
were performed in a standard 2 scan using a Cu K radiation ltered
by a crystal monochromator (wavelength = 0.15406 nm). A
159
resistance of the Au/HCl-PANI composite was measured in the temperature range of 6280 K using the Cryogen-Magnet system of CFM-5TH3-CFVTI-1.6K-24.5 with the four-point probe (Cryogenic Inc.).
200nm
b
Fig. 1. FE-SEM microphotographs of the Au lms sputter-deposited on the HCl-PANI substrates; (a) 14 nm-thick lm and (b) 28 nm-thick lm.
160
200nm
100nm
100nm
200nm
Fig. 2. FE-SEM microphotographs of the Au lms sputter-deposited on the HCl-PANI substrates; (a, b) 50 nm-thick lm, (c, d) 100 nm-thick lm, and (e, f) 180 nm-thick lm.
600
500
HCl-PANI
I (cps)
400
Au(111)
300
200
Au(200)
Au(220) Au(311)
100
0
10
20
30
40
50
60
70
80
90
2 (deg)
Fig. 3. XRD pattern of the 50 nm-thick Au lm sputter-deposited on the HCl-PANI
substrate.
0.40733 nm, which is almost equal to the lattice constant of the Au bulk
(0.40790 nm).
Fig. 4 shows a temperature dependence of the resistance of the Au/
HCl-PANI composites with different lm thicknesses. In Fig. 4, the resistance R at each temperature is normalized to the resistance R6 at 6 K.
The relative error in the resistance is mainly determined by the accuracy
of current control and voltage measurement and is below 1%. As can be
seen from Fig. 4, only the composite with the 28 nm-thick Au lm exhibits the metalsemiconductor transition with increasing temperature.
The transition temperature is around 70 K. The composite shows the
metallic conduction behavior at temperatures below the transition temperature and the semiconducting behavior at temperatures over the
transition temperature. The composite with the 14 nm-thick Au lm
exhibits the semiconducting behavior whereas the composites with
the 50 nm-, 100 nm- and 180 nm-thick Au lms show the metallic conduction behavior in the temperature range from 6 K to 280 K. A
1.20
0.007
0.006
0.005
0.004
0.003
0.002
0.001
0.000
1.00
0.80
0.60
0.40
Table 1
The values of the Au lms with a thickness dF of 28180 nm at Tb = 10 K.
14nm Au
dF (nm)
104 (K1)
0.20
50
0.00
0
50
100
150
200
250
300
161
350
1.10
28
7.1
50
8.1
100
8.5
180
9.2
where F is the resistivity of the Au lm, S is the resistivity of the HClPANI substrate, dF is the Au lm thickness and dS is the HCl-PANI
substrate thickness. A constant value of 3.31 is determined by the
four-point probe instrument. As it is well known, a temperaturedependence of resistivity of the metallic lm is linear and can be
expressed as
F b 1 TTb
28nm Au
R/R6
0.88
where b is a reference resistivity of the lm at a reference temperature
Tb. is a temperature coefcient of resistance of the lm, also related to
Tb. T is a temperature. On the other hand, for the HCl-PANI substrate, the
carrier transport mechanism is three-dimensional variable range
hopping and a temperature-dependence of resistivity follows the
relation [2022]
0.66
1.03
1.02
0.44
1.01
1.00
0.22
0.99
0
20
40
60
80
0.00
0
50
100
150
1.80
200
250
300
350
180nm Au
" 1 #
T0 =4
S 0 exp
T
1.60
100nm Au
1.40
RC
50nm Au
1.20
b 1 TTb 0 exp
1
T0 =4
T
1 :
=
3:31 dS b 1 TTb d F 0 exp TT0 4
5
1.00
50
100
150
200
250
300
350
T (K)
Fig. 4. Temperature dependence of the resistance of the Au/HCl-PANI composites. The
arrow represents the transition temperature.
R F RS
R F RS
F S
3:31 dS F d F S
1.40
1.30
RC/RC10
0.80
180nm Au
100nm Au
50nm Au
1.20
1.10
28nm Au
1.00
0.90
100
200
300
400
T (K)
Fig. 5. Calculated RT relationship of the Au/HCl-PANI composites with a Au lm thickness
of 28180 nm. The arrow represents the transition temperature.
162
50 nm-, 100 nm- and 180 nm-thick Au lms show the metallic conduction behavior. The calculated RT relationship is in qualitative agreement with the experimental RT relationship. Thus it is considered
that the simple parallel resistor model could be used to qualitatively
explain the temperature dependence of the resistance for the Au/HClPANI composites. The difference between the experimental RT relationship and the calculated RT relationship could be attributed to
these two facts: (1) the parameters used in Eq. (5) is inaccurate,
and (2) the current does not distribute throughout the thickness
of the lm/substrate sample during the RT measurement [24]. For
example, the and b values are related to the lm preparation condition. Therefore, these parameters used in Eq. (5) are different from the
practical parameters of the Au lms prepared in this work, resulting in
the difference between the calculated resistance and the measured
resistance.
As shown in Fig. 4, the TCR value increases with increasing lm
thickness in the temperature range of the metallic conduction. The
TCR of the metallic lm can be given by [25]
c 0
c v i g
Acknowledgment
The authors would like to thank Prof. J. P. He of the State Key Laboratory for Advanced Metals and Materials for FE-SEM observations. The nancial support from the Fundamental Research Funds for the Central
Universities No. 8220 is gratefully acknowledged.
References
[1] F. Faupel, V. Zaporojtchenko, T. Strunskus, M. Elbahri, Metalpolymer nanocomposites for functional applications, Adv. Eng. Mater. 12 (2010) 1177.
[2] F. Rufno, V. Torrisi, G. Marletta, M.G. Grimaldi, Growth morphology of nanoscale
sputter-deposited Au lms on amorphous soft polymeric substrates, Appl. Phys. A
103 (2011) 939.
[3] F. Rufno, V. Torrisi, G. Marletta, M.G. Grimaldi, Effects of the embedding kinetics on
the surface nano-morphology of nano-grained Au and Ag lms on PS and PMMA
layers annealed above the glass transition temperature, Appl. Phys. A 107 (2012)
669.
[4] G. Kaune, M.A. Ruderer, E. Metwalli, W. Wang, S. Couet, K. Schlage, R. Rohlsberger,
S.V. Roth, P. Muller-Buschbaum, In situ GISAXS study of gold lm growth on
conducting polymer lms, Appl. Mater. Interfaces 1 (2009) 353.
[5] H. Takele, S. Jebril, T. Strunskus, V. Zaporojchenko, R. Adelung, F. Faupel, Tuning of
electrical and structural properties of metalpolymer nanocomposite lms prepared
by co-evaporation technique, Appl. Phys. A 92 (2008) 345.
[6] V. Torrisi, F. Rufno, G. Isgro, I. Crupi, G.L. Destri, M.G. Grimaldi, G. Marletta, Polymer/metal hybrid multilayers modied Schottky devices, Appl. Phys. Lett. 103
(2013) 193117.
[7] F. Rufno, V. Torrisi, G. Marletta, M.G. Grimaldi, Patterning of templatedconned nanoscale Au lms by thermal-induced dewetting process of a
poly(methylmethacrylate) underlying layer, J. Appl. Phys. 112 (2012) 124316.
[8] H. Takele, A. Kulkarni, S. Jebril, V.S.K. Chakravadhanula, C. Hanisch, T. Strunskus, V.
Zaporojtchenko, F. Faupel, Plasmonic properties of vapour-deposited polymer composites containing Ag nanoparticles and their changes upon annealing, J. Phys. D.
Appl. Phys. 41 (2008) 125409.
[9] T. Peter, M. Wegner, V. Zaporojtchenko, T. Strunskus, S. Bornholdt, H. Kersten, F.
Faupel, Metal/polymer nanocomposite thin lms prepared by plasma polymerization and high pressure magnetron sputtering, Surf. Coat. Technol. 205 (2011) S38.
[10] Z.W. Yang, H. Qiu, B. Hu, G.S. Zou, Structural and electrical properties of Ni lms
sputter-deposited on HCl-doped polyaniline substrates, Vacuum 99 (2014) 192.
[11] S.Y. Qiu, Z.W. Yang, H. Qiu, Theoretical analysis on resistance-temperature characteristic of Ni/HCl-PANI composites, Adv. Mater. Res. 852 (2014) 142.
[12] M. Sheffer, D. Mandler, Control of locally deposited gold nanoparticle on polyaniline
lms, Electrochim. Acta 54 (2009) 2951.
[13] M. Guerra-Balczar, D. Morales-Acosta, F. Castaneda, J. Ledesma-Garca, L.G. Arriaga,
Synthesis of Au/C and Au/PANI for anode electrodes in glucose microuidic fuel cell,
Electrochem. Commun. 12 (2010) 864.
[14] C. Liu, K. Hayashi, K. Toko, Au nanoparticles decorated polyaniline nanober sensor
for detecting volatile sulfur compounds in expired breath, Sensors Actuators B 161
(2012) 504.
[15] Y. Ali, V. Kumar, R.G. Sonkawade, A.S. Dhaliwal, Effect of swift heavy ion beam irradiation on Aupolyaniline composite lms, Vacuum 90 (2013) 59.
[16] E. Spain, T.E. Keyes, R.J. Forster, Vapour phase polymerized polyanilinegold nanoparticle composites for DNA detection, J. Electroanal. Chem. 711 (2013) 38.
[17] P.N. Adams, P.J. Laughlin, A.P. Monkman, A.M. Kenwright, Low temperature synthesis of high molecular weight polyaniline, Polymer 37 (1996) 3411.
[18] Y. Huang, H. Qiu, F.P. Wang, L.Q. Pan, Y. Tian, P. Wu, Effect of annealing on the characteristics of Au/Cr bilayer lms grown on glass, Vacuum 71 (2003) 523.
[19] Y. Huang, H. Qiu, H. Qian, F.P. Wang, L.Q. Pan, P. Wu, Y. Tian, X.L. Huang, Effect of annealing on the characteristics of Au/Ni80Fe20 and Au/Ni30Fe70 bilayer lms grown on
glass, Thin Solid Films 472 (2005) 302.
[20] M. Ghoshi, A. Barman, A.K. Meikap, S.K. De, S. Chatterjee, Hopping transport in HCl
doped conducting polyaniline, Phys. Lett. A 260 (1999) 138.
[21] J. Li, K. Fang, H. Qiu, S.P. Li, W.M. Mao, Micromorphology and electrical property of
the HCl-doped and DBSA-doped polyanilines, Synth. Met. 142 (2004) 107.
[22] R.C. Liu, H. Qiu, H. Li, H. Zong, C.Y. Fang, Fabrication and characteristics of composite
containing HCl-doped polyaniline and Ni nanoparticles, Synth. Met. 160 (2010)
2404.
[23] Z.Q. Sun, J.G. Lv, X.P. Song, Microstructure and electrical properties of ultrathin gold
lms prepared by DC sputtering, Vacuum 85 (2010) 297.
[24] Y. Cao, R.Y. Huang, B. Hu, H. Qiu, J.P. He, Structural and electrical properties of Ag
lms sputter-deposited on HCl-doped and undoped polyaniline substrates, Mater.
Chem. Phys. 143 (2014) 788.
[25] X.B. Chen, H. Qiu, P. Wu, F.P. Wang, L.Q. Pan, Y. Tian, Characteristics of Ni6Fe94 lms
deposited on SiO2/Si(100) by an oblique target co-sputtering, Thin Solid Films 515
(2006) 2786.