Structural, optical and AC conductivity studies on alloy ZnO–Zn2SnO4 (ZnO–ZTO) thin films

Accepted Manuscript Structural, optical and AC conductivity studies on alloy ZnO- Zn2SnO4 (ZnOZTO) thin films R. Dridi, I. Saafi, A. Mhamdi, A. Matri, A. Yumak, M. Haj Lakhdar, A. Amlouk, K. Boubaker, M. Amlouk PII: DOI: Reference:

S0925-8388(15)00417-X http://dx.doi.org/10.1016/j.jallcom.2015.02.009 JALCOM 33383

To appear in:

Journal of Alloys and Compounds

Received Date: Revised Date: Accepted Date:

10 December 2014 30 January 2015 1 February 2015

Please cite this article as: R. Dridi, I. Saafi, A. Mhamdi, A. Matri, A. Yumak, M. Haj Lakhdar, A. Amlouk, K. Boubaker, M. Amlouk, Structural, optical and AC conductivity studies on alloy ZnO- Zn2SnO4 (ZnO-ZTO) thin films, Journal of Alloys and Compounds (2015), doi: http://dx.doi.org/10.1016/j.jallcom.2015.02.009

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Structural, optical and AC conductivity studies on alloy ZnO- Zn2SnO4 (ZnO-ZTO) thin films R. Dridi1, I. Saafi1, A. Mhamdi1, A.Matri2, A. Yumak3, M. Haj Lakhdar1, A. Amlouk1, K. Boubaker*1, M. Amlouk1 1

Unité de Physique des dispositifs à Semi-conducteurs UPDS, Faculté des Sciences de Tunis, Tunis El Manar University, Tunisia. *Actual address : Faculté des Sciences de Bizerte, Carthage university 7021 Zarzouna, Tunisia 2

Laboratoire de Physique des Matériaux, Département de Physique, Faculté des Sciences de Bizerte, Carthage university 7021 Zarzouna, Tunisia 3

Physics Department, Faculty of Arts and Sciences, Marmara University, 34722 Göztepe, Istanbul, Turkey

*corresponding authors: [email protected]

Abstract This work deals with structural and electrical investigations on ZnO-Zn2SnO4 sprayed thin films grown on glass substrates at 460°C. The structural, morphological and optical properties were investigated using X-Ray diffraction (XRD), atomic force microscopy (AFM), and UV-visible spectrophotometry. XRD results describe the existence of the ZnO and Zn2SnO4 phases for various temperatures. AFM micrographs indicate the increase of roughness by increasing temperature. Finally, the electrical conductivity, conduction mechanism, relaxation model of these films was indeed studied by means of the impedance spectroscopy technique in the frequency range 5 Hz –13 MHz at various temperatures (220–280°C). Besides, the frequency and temperature dependence of AC conductivity measurements, as well as Lattice Compatibility Theory (LCT) patterns, have been analyzed under the structural change framework when the annealing process is undertaken.

Keywords: ZnO-Zn2SnO4; thin films; AC and DC conductivity; XRD analysis; Lattice Compatibility Theory (LCT); Spray pyrolysis; 1

1.Introduction Zinc oxide (ZnO) films have been widely studied because of their specific electrical, optical and mechanical properties, low material cost and relatively low deposition temperature. These films can be used in optoelectronic devices as transparent conducting oxide (TCO)[1]. Consequent research and enhancement led recently to more developed ternaries like Zn2SnO4 which is emerged as a new compound belonging to II2-IV-VI4 semiconductors family. It is a very promising material for various potential applications. In particular, the relatively high band gap energy (≈ 3.6 eV) [2] of ZTO renders it as an effective semiconductor material for photocatalytic applications [3,4,5], It finds extensive applications as gas sensors. Indeed, Sbdoped Zn2SnO4 sputtered thin films with spinel-type structure were deposited and showed good sensing characteristics to nitrogen dioxide until 300 ppm at 600°C [6]. Recently, sensors based on

Zn2SnO4/ZnO wire-sheet shape hetero-nanostructures networks have

excellent gas sensing characteristics to hydrogen gas under 1000 ppm concentration below operating temperature of 300 °C [7]. In the same line, an enhanced NO2 sensing property of Zn2SnO4-core/ZnO-shell nanorod sensors less than 5 ppm at 300 °C is reported [8]. This oxide material has been achieved as thin film [2,3,9] and as nano-forms [4,10] by many effective chemical techniques. Among these methods, the spray pyrolysis method is an attractive one due to its simplicity, safety, non-vacuum system of deposition, and inexpensive. Other advantages of this method are that it can be adapted easily for production of large-area films, and to get varying band gap materials during the deposition process.

Moreover, ac electrical investigations under structural change in such oxide occurring in some circumstances owing to experimental conductions (presence of defaults, dislocation, presence of binary phases such as ZnO and SnxOy) remains the object of further investigations. To address possible ways to control the structural as well as electrical conductivity in ZnOZTO sprayed thin films material, some works still pay attention to the possible causes of the change of its electrical behavior by using appropriate heat treatment under air atmosphere.

2

The present work aims at providing some structural and electrical investigations on alloy ZNO-ZTO thin films by means of AC conductivity measurements in terms of both temperature and frequency. This may be of great interest in some optoelectronic applications as well as in sensitivity tests as recently mentioned above. 2 . Experimental conditions

Zinc stannic oxide thin films were deposited on glass substrates at 460° C using appropriate mixture of two alcohol starting solutions (S1 and S2) containing Zn+2 and Sn+4 ions with 2:1 as ratio between molarities (S1: 2 x10-1M ; S2: 10-1M). This substrate temperature as well as the precursor composition solutions is selected according to protocols achieved previously in our laboratory [11, 12]. Nitrogen was used as the carrier gas (0.35 bar) through a 0.5 mmdiameter nozzle. As reported previously, the nozzle-to-substrate plane distance was fixed at the optimal value of 27 cm. During the deposition process, the precursor mixture flow rate was taken constantly at 4 mL/min. To make the Electrical measurements we made contact with a platinum wire deposited on both side in a thin layer of ~1.5 cm ² surface. These electrodes were painted on the two extremities of the sample using silver paste (Fig1). The measurements were carried out in the temperature range of 220–280 °C by using a tube furnace (Vecstar FURNACES) and the electrical conductivity was measured by HP4192A impedance for high frequency and Autolab PGSTAT30 for low frequency. Both devices are controlled by programs that allow received and safeguard measures. 3. Results and investigations

3.1. Structural properties

Figure 2 shows the XRD patterns of alloy (Zno- Zn2SnO4) as deposited sprayed thin film grown on glass substrate at 460°C and annealed thin films during 1 hour in air at 500 and 530°C. The observed indexed peaks in these XRD patterns are fully matched with the corresponding hexagonal würtzite structure ZnO and cubic structure Zn2SnO4 ( PDF number: 24-1470) but the crystalline phase dominate is Zn2SnO4 . The XRD results indicate that all the films have

3

the polycrystalline structure. It is also seen that Zn2SnO4 exhibit preferential orientation of crystallites along (311) direction. The average crystallite sizes of all Zn2SnO4 thin films are estimated from (311) principal peak by using the Debye- Scherrer formula [13].

=

(1)

Where l = 1.5418 Å for Cu radiation, θ is the diffraction angle, K = 0.9, and β is the full width at half maximum FWHM with

−

=

, where βe is measured from the film

and is the full width at half maximum related to the instrument [13, 14]. The calculated values of crystallite size are presented in table 1. We note that the crystallites size increases by increasing annealing temperature, which results in the decrease of the grain boundaries. The microstrain εs is calculated using the following relation[15] :

=

(2)

This parameter increases by increasing annealing temperature due to the appearance of undesirable ZnO secondary phase with no negligible amount.

3 .2 Optical study:

The optical transmission and reflectance spectra of( Zno-ZTO) films in the wavelength region of 250-2500 nm are shown in Figures (3) . It can be seen that the interference fringe patterns are absent in transmittance and reflectance spectra due to weak multiple reflections at the interface. These film show a high transparency within the visible range with an average transmittance lying between 80-90%. The fundamental absorption edge of the films corresponds to transitions of electrons from the valence band to the conduction band edge and this can be used to calculate the difference in the optical band gap of the films. The absorption coefficient can be expressed by [16]:

4

a=

1 1- R ln( ) d T

(3)

Where d=0.5 μm is the thickness of the prepared thin film. In the case of a direct transition the absorption coefficient and optical band gap are related by the following relation which corresponds to the direct band gap [17]:

a hn =

A( hn - E g )

(4)

where A is a constant, hν is the photon energy and Eg is the optical band gap. Figure 4 shows the plot of [α.(hν)]2 versus the photon energy hν which yields in the sharp absorption edge for the high quality films by a linear fit it is clearly observed two band gap The first is ZnO Eg = 3.3eV and the Second is ZTO Eg = 3.7eV.This result is consistent with the XRD results.

3.3. Surface morphology The surface morphology of ZnO-(ZTO) thin films as deposited at 460 °C and those annealed at temperatures of 500 and 530 °C was examined by an atomic force microscope (AFM). The threedimensional (3D) images of AFM micrographs are shown in Figure 5 . These micrographs reveal

that all films surfaces are rough. These perturbed surfaces are probably due to very small droplets, resulting from the mini-spray pyrolysis technique, which vaporize above the glass to form clusters with various dimensions. For a scanning area (5 µm x 5 µm), the root-mean squares (RMS) of average surface roughness are : 78.9 , 77.9 and 100.3 nm for (ZnO-ZTO) unannealed , and those annealed thin films at 500 °C and annealed at 530 °C respectively. As expected, the surface roughness changes when the annealing temperature increased, this is in agreement with the XRD and optic results and confirms that the increase in temperature may change the thin film structure.

4 . Impedance analysis 5

In this section, the conductivity in terms of both temperature and frequency has been carried out to probe the conducting state in ZnO-Zn2SnO4 thin films. Indeed, complex impedance curves of Z " as a function of Z ' in temperature range (220-280°C) are displayed in (Fig. 6) . The analysis of experimental data of these samples show that the semicircles are depressed and their centers are shifted down to the real axis indicating distribution of relaxation time. In the present study, the equivalent circuit (Fig 6) is modeled by Cole–Cole function [18]: Z=

R [1 + ( jwt )a ]

(5)

Where ω is angular frequency, τ = RC is the relaxation time and α is a parameter which characterizes the distribution of the relaxation time. The real and imaginary parts of the impedance are given by:

p ù é R ê1 + (wt )a sin((1 - a ) ) ú 2 û ë Z'= p é a 2a ù êë1 + 2(wt ) sin(1 - a ) 2 + (wt ) úû

(6)

p ù é R ê (wt )a co s((1 - a ) ) ú 2 û ë Z"= p é 2a ù a êë1 + 2(wt ) sin(1 - a ) 2 + (wt ) úû

(7)

The variation of real part Z’ with frequency at different temperatures is plotted in (Fig. 7). It is still remarkable that Z’ decreases with increasing temperature as well as frequency, which indicates a semiconductor behavior. Figure 7 depicts the experimental values of imaginary part Z″ versus frequency at different temperatures. We note that the imaginary part Z″ increases with frequency reaching a maximum peak Z″max then decreases as the temperature increases. On the other hand, it is noted that Z″max decreases as the temperature increases, in the same line the position of relaxation peak shifts to higher frequencies. Continuous line in Figure 7 and Figure 8 represents best fit to experimental data according to equations 4 and 5.The values of the fit parameters have been listed in table 2. In Fact, the relaxation frequency obeys to Arrhenius law:

6

wm = w0 exp(-

Ea ) k BT

(8)

We note an activation energy value of about 0.88 ev.

Z" w ) plots at different temperatures are shown in Figure 9. The matching of versus ln( Z"max wmax curves at various temperatures into a single curve indicates that the dynamical processes occurring at different frequencies are independent of temperature. 4.1 Dependence of AC conductivity on frequency and temperature AC conductivity measurements have been widely investigated to reach the conduction mechanisms of the charge carriers. Figure 10 shows the variation of total conductivity ( s t ) as a function of applied frequency. At low frequency, s t has a small variation with frequency then it increases with increasing frequency. The AC conductivity is described by the Jonsher law as :

s ac = s t - s dc = Aw s

(9)

Where A is a constant dependent on temperature, ω is the angular frequency, σdc is the DC conductivity and the frequency exponent 0
assumed to hop between the sites over a potential barrier separating them. The expression for s(T) according the CBH model is given by:

s = 1-

6KT (Wm )

(10)

where T is the temperature, k is the Boltzmann constant and Wm is the polaron binding energy. We note a value of Wm equal to 3.23eV. 4.2 Temperature dependence of DC conductivity DC conductivity measurement σdc for ZnO-ZTO thin films plotted versus 1000/T are shown in figure 11. The linearity of the plot indicates that the conductivity exhibits a thermally activated behavior [20.21] in accordance with the Arrhenius relation [22]:

s dc = s 0 e

-

Ea KT

(11)

Where σ0 is the pre-exponential factor, k the Boltzmann constant and Ea is the activation energy for the hops. The parameter σ0 was determined from the intersection of linear parts of the function with the ordinate axis (T→∞), and the activation energy Ea was obtained from its slope.

The

value

of

the

activation

energy

Ea

is

equal

to

0.89

eV.

The activation energy calculated from equation (11) is almost identical to the activation energy obtained from the angular relaxation frequency suggesting a hopping mechanism.

4.3 Dielectric study In a solid material, the dielectric response can be described by expression of the complex relative dielectric constant as a amount consists of a real part and an imaginary component expressed as:

e (w ) = e '(w ) - je "(w )

(12)

where e ' and e " are respectively the real and imaginary part of dielectric constant, representing the amount of energy stored in a dielectric material as polarization and the energy loss , while applying an electric field. In addition, the σac conductivity originates from the bound and free charges and can be expressed

in

terms

of

the

absolute

8

permittivity

ɛ0

and

the

dissipation:

s ac = ewe "(w ) s ac = e 0e '(w )w tg (d )

(13)

The dielectric loss is given by [23]:

tg(d ) =

Z' e" = Z" e'

(14)

As shown in Figure 12 the dielectric loss increases by increasing temperature at constant frequency. This behavior can be attributed to the fact that at low temperatures, the conduction loss is minimal, when the temperature increases the conduction loss increases too which may be due to the increase in conductivity. On the other hand, the variations of the real part of dielectric constant e ' (ω) with the frequency at different temperature of ZnO-ZTO thin films are shown in (Fig. 13). It can be seen that the dielectric constant e ' (ω) decreases with the frequency of the applied field at constant temperature, while it shows an increase by increasing temperature at constant frequency. The decrease of the dielectric constant with frequency can be assigned to the fact that at higher frequencies, the variation in the field is rapid. The dipoles cannot align themselves and the contribution of the polarization to the dielectric constant e ' (ω) becomes negligible. On the other hand, the increase of the dielectric constant e ' (ω) with temperature, as shown in (Fig. 13), can be explained by the fact that the bound charge carriers get gradually an amount of thermal excitation energy to be able to respond to the change in the external field more easily. This in turn enhances their contribution to the polarization leading to an increase of the real part of the dielectric constant. The dependence of the imaginary part of the dielectric constant e " (ω) on the frequency at different temperatures of ZnO-ZTO thin films is illustrated in (Fig. 14) e " (ω) decreases by increasing frequency, at constant temperature and increases by increasing temperature at constant frequency. Dielectric constant consists of two contributions: one from the DC conduction at low frequency and the other from the dielectric polarization processes at high frequency. 5. Modulus study For more information regarding the relaxation process, we have adopted the formalism of electrical modulus. The electric modulus M is expressed in the complex modulus formalism by: 9

M =

1 = M '+ jM " e

(15)

Where M ' and M " are the real and imaginary parts of the modulus spectrum giving by: e' ì ïï M ' = [(e ' ) 2 + (e " ) 2 ] í e" ïM "= ïî [(e ' ) 2 + (e " ) 2 ]

(16)

Figure 15 shows the variation of M " versus M ' the shape of this curve is not a circular arc, which shows that not a single phase of Zn2SnO4 but alloy ZnO-Zn2SnO4 Figure 16 shows the variation of M ' as a function of frequency at different temperatures. It is seen that at low frequency M ' value approaches zero. This observation can be explained by a lack of force which governs the mobility of charge carriers under the influence of an electric field [24]. Moreover, an increase in the value of M ' with increasing frequency at different temperatures is also observed which supports the conduction phenomena due to short-range mobility of charge carriers. The variation of M " with frequency at different temperatures is plotted in (Fig.17). It is still remarkable that M " increases with frequency and reaches a maximum value then decreases along with the temperature. Furthermore, the relaxation peak position shifts to higher frequencies with increasing temperature. This means that the relaxation rate for this process increases with the temperature. Figures 18 and 9 shown the variation of both

ZnO-Zn2SnO4 thin films,

M" Z" and as a function of ln(w ) . For M "max Z "max

M" Z" and peaks do not overlap. This behavior confirms the M "max Z "max

presence from both long range and localized relaxation for our films [25].

6. Lattice Compatibility Theory investigation

The Lattice Compatibility Theory, is a theory which is based on the interaction of dopingelement lattice behavior versus host edifice, as mentioned in some recent studies [26-29], and as associated to Simha-Somcynsky principles [30].

10

Preludes to this theory have been established by Petkova et al. [26] and Boubaker et al. [2729] in the context of analysing stability of some doped compounds. An original formulation of the Lattice Compatibility Theory [29] has been established as following: “The stability of doping agents inside host structures is favorized by geometrical compatibility, expressed in terms of matching patterns between doping agent intrinsic lattice and those of the host”.

In this study, the nature of the highest occupied bands, and bonds configuration have been demonstrated to be determinant. In this context, fundamental geometrical observations concerning the structure of intrinsic Zinc oxide lattice along with that the host matrix Zn2SnO4 (Fig. 19), were interpreted in terms of conventional lattice-linked parameters (lattice parameters, angles and bond spatial extent). Particularly, main Z-O bond lengths in the perpendicular direction to c-plane show obvious incompatibility (a versus a1, a2, a3 and a4) which is likely to forbid, in terms of LCT, the stability of ZnO intrinsic structures within Zn2SnO4 as a host matrix. This irregularity has been evoked earlier by Asokan al. [31] and Peiteado et al. [32]. 7. Discussion From dielectric investigations, the contributions have been classified as DC conduction at low frequency-related and high frequency-related dielectric polarization. These two items enrich the possibilities of using alloy ZNO-ZTO thin films as gas sensing (Methanol..). Nonetheless, the Lattice Compatibility Theory LCT gave plausible and scientifically founded explanations to the dominancy of Zn2SnO4 crystalline phase within

polycrystalline ZnO-

Zn2SnO4 films as confirmed earlier by XRD analysis (§3.1). This dominancy pleas also in favor of gas-sensing performance of the as grown compounds.

8. Conclusion: In this work, ZnO-Zn2SnO4 sprayed thin films have been grown at 460°C on glass substrate using an appropriate aqueous solution. XRD analysis show that ZnO-Zn2SnO4 films are polycrystalline nature but dominant crystalline phase is Zn2SnO4 . The electrical study, the conduction mechanism has been studied in terms of both temperature and frequency. The study of ac conductivity via frequency showed a universal power law s dependence. Its 11

behavior has been explained by the correlated barrier hopping CBH model. This study seems so interesting since a simple and cost effective spray pyrolysis method has been used to prepare alloy ZnO-ZTO thin films. Thin films of ZnO-ZTO can be very promising and are subsequently a great potential in the field of optoelectronic. Efforts are ongoing to test such films as TCO in photovoltaic solar cells as well as in gas sensors devices.

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13

List of figures Fig. 1.Configuration of substrate/ZnO-Zn2SnO4 thin film/Ag samples for the electrical measurements. Fig. 2: XRD patterns ofZnO- Zn2SnO4 thin films deposited at different substrate temperatures Fig 3: Transmission and reflection spectra of ZnO- Zn2SnO4 thin films . Fig 4 : Plots of [α.(hν)]2 versus hν for the ZnO-Zn2SnO4 thin films Fig.5: Zn2SnO4 (ZTO) surface topography Fig 6 : complex impedance spectra at various temperatures Fig 7 : Frequency dependence of Z’ at different temperatures Fig 8 : Frequency dependence of Z” at different temperatures Fig 9 : Variation of Z”/Z”max with Ln(ω/ωmax) at different temperatures Fig.10: Angular frequency dependence of AC conductivity for ZTO thin films at different temperatures Fig 11 : temperature dependence of Dc conductivity Fig 12: variation of tg(δ) at different temperature Fig.13 Dependence of dielectric constant, e ' , on angular frequency for zno-zn2sno 4 thin films Fig.14 Dependence of dielectric constant, e " , on angular frequency for zno- zn2sno 4 thin films Fig 15 :. Complex modulus spectrum at different temperatures Fig 16 : Frequency dependence of M ' at different temperatures. Fig 17: Frequency dependence of M″ at different temperatures. Fig 18: Variation of M " with ln(ω/ωmax) at different temperatures of ZnO-ZTO M "max

unannealed Fig 19: Lattice Compatibility Theory synoptic scheme for ZnO and Zn2SnO4 lattices

List of tables Table 1 : Lattice parameters, Grain size, dislocation density and micro strain for different samples . Table 2 : Values of Cole–Cole fitting parameters of ZnO-ZTO unannealed.

14

Fig. 1.Configuration of substrate/ZnO-Zn2SnO4 thin film/Ag samples for the electrical measurements

15

Fig. 2 XRD patterns of ZnO-Zn2SnO4 thin films deposited at different substrate temperatures

16

Fig 3: Transmission and reflection spectra of ZnO- Zn2SnO4 thin films .

17

Fig 4 : Plots of [α.(hν)]2 versus hν for the ZnO-Zn2 SnO4 thin films

18

Fig 5: ZnO-Zn2SnO4 surface topography

19

Fig 6 : complex impedance spectra at various temperatures of (ZnO-ZTO) unannealed

20

Fig 7 : Frequency dependence of Z’ at different temperatures of ZTO unannealed

21

Fig 8 : Frequency dependence of Z” at different temperatures of ZnO-ZTO unannealed

22

Fig 9 : Variation of Z”/Z”max with Ln(ω/ωmax) at different temperatures of ZnO-ZTO

unannealed

23

Fig.10: Angular frequency dependence of AC conductivity for ZnO-ZTO thin films at different temperatures

24

Fig 10 : temperature dependence of Dc conductivity of ZnO- ZTO unannealed

25

Fig 12 : variation of tg(δ) at different temperature of ZnO-ZTO unannealed

26

Fig.13 Dependence of dielectric constant, e ' , on angular frequency for zno-zn2sno 4 thin films

27

Fig.14 Dependence of dielectric constant e " on angular frequency for zno- zn2sno 4 thin films

28

Fig 15 :. Complex modulus spectrum at different temperatures of ZnO-ZTO unannealed

29

Fig 16 : Frequency dependence of M ' at different temperatures of ZnO-ZTO unannealed

30

Fig 17: Frequency dependence of M″ at different temperatures.

31

Fig 18: Variation of M " with ln(ω/ωmax) at different temperatures of ZnO-ZTO M "max

unannealed

32

Fig 19: Lattice Compatibility Theory synoptic scheme for ZnO and Zn2SnO4 lattices

33

2θ (°) β d(311) a (Å) D (nm) ε (10-3)

ZnO-Zn2SnO4 T=460°C 34.49 0.167 2.600 8.62 49.85 0.23

ZnO-Zn2SnO4 T=500°C 34.46 0.117 2.602 8.63 71.14 1.6

ZnO-Zn2SnO4 T=530°C 34.45 0.115 2.602 8.63 71.19 1.6

Table 1 : Lattice parameters, Grain size, dislocation density and micro strain for different

samples .

34

Temperature(°C) 220 230 R(Ω) 880320.96 500162.14 346806.31 611690.03 wMAX

240 260 270 280 318296.21 118073.32 93149.95 99475.24 920199.40 2309633.85 2860057.17 2976483.57

α (for Z Cole–Cole)

0.94501

0.99041

0.96745

0.85608

0.86131

Table 2 : Values of Cole–Cole fitting parameters of ZnO-ZTO unannealed.

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0.91507

Graphical Abstract The graphical abstract:

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Highlights

ü AC conductivity is consistent with model of correlated barrier hopping (CBH). ü Relaxation processes are described by the Cole–Cole model. ü Value of the maximum barrier height Wm is in good agreement with CBH theory as suggested by Elliott in case of chalcogenide glasses. ü The relaxation phenomenon describes the same mechanism at various temperatures.

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