Absolute densities of Cu, Zn, Sn and S atoms in

magnetron sputtering plasmas employing

a Cu2ZnSnS4 target

Nayan Nafarizala,b,∗, Shunya Kikuchia , Koichi Sasakia

a Division of Quantum Science and Engineering, Hokkaido University,
Kita 13, Nishi 8, Kita-ku, Sapporo 060-8628, Japan
b Universiti Tun Hussein Onn Malaysia, Batu Pahat, Johor 86400, Malaysia

Abstract

Absolute densities of Cu, Zn, Sn and S atoms in magnetron sputtering plasmas

were measured using ultraviolet absorption spectroscopy and vacuum ultraviolet
absorption spectroscopy. A single stoichiometric Cu2 ZnSnS4 (CZTS) was used
as target in Ar sputtering discharge. It was found that, at various Ar pressures,
the S density ranges between 2∼8×1010cm−3 , the Cu and Sn densities range
between 0.6∼3×1010cm−3 , and the Zn density ranges between 2∼3×109cm−3 .
The effective depositing flux which was evaluated from the absolute densities
was at comparable order with that evaluated from the deposition rate of CZTS
film. However, the comparison between composition ratios of atomic densities
in gas phase and elements in CZTS films revealed a problematic element compo-
sition in obtaining stoichiometric CZTS films. An altered or non-stoichiometric
CZTS target is required in sputter deposition of ideal CZTS films for solar cell
applications.
Keywords: Cu2 ZnSnS4 , CZTS, magnetron sputtering, absorption
spectroscopy

∗ Correspondingauthor
Email address: nafa@athena.qe.eng.hokudai.ac.jp (Nayan Nafarizal)

Preprint submitted to Journal of LATEX Templates July 7, 2015

 1. Introduction

Cu2 ZnSnS4 (CZTS) is a new compound material that has been proposed
to replace toxic and rare materials used in current CuInGaSe2 (CIGS) and
CdTe thin film solar cells. Several reviews have been published concerning
5 vacuum and non-vacuum approaches that have been attempted for the synthesis
of CZTS thin film [1, 2, 3, 4]. The efficiency of CZTS-based solar cell using both
techniques have shown great improvement. In addition, research effort from the
industrial manufacturer such as IBM and Solar Frontier indicates a huge step
toward the commercialization of CZTS-based solar cell in the near future [5, 6].
10 Magnetron sputtering technique is a simple technique to deposit high qual-
ity thin film with good repeatability [7, 8]. It is a matured technology and
widely used in many major industries such as microelectronics and automotive
industries. Therefore, from an industrial point of view, magnetron sputtering is
a promising technique for commercial production of CZTS thin film. However,
15 main problem during CZTS deposition using magnetron sputtering technique
is to control the stoichiometric of CZTS thin film. This problem is due to high
vapor pressure of sulfur and zinc, which are at 102 and 10−2 Torr at 400 o C,
respectively.
In many reports, CZTS thin film fabrication requires two steps processes
20 [1, 2, 9, 10, 11]. First, the CZTS or CZT thin film is pre-deposited by vacuum
or non-vacuum techniques. Second, the composition of sulfur is alter by post-
annealing treatment in sulfur-containing environment. These methods are com-
plex and some produced toxic by-products during their synthesis. Therefore, a
single-step process using magnetron sputtering technique employing a stoichio-
25 metric CZTS target is a better method to synthesis CZTS thin film. Single-step
process may also reduce the production cost of a commercial CZTS-based solar
cell. For this purpose, it is essential to understand the growth mechanisms of
CZTS thin film in magnetron sputtering process.
In our previous report, we have evaluated the sticking probabilities of Cu,
30 Zn, Sn and S atoms sputtered from a stoichiometric CZTS target. We found

2
 that the sticking probability of S was less than that of Cu, Zn and Sn. Therefore,
the result suggests a difficulty in obtaining stoichiometric CZTS film from single
target. In the present report, we investigate the CZTS sputtering plasmas in
more details. We measure the absolute ground state densities of Cu, Zn, Sn and
35 S atoms sputtered from a stoichiometric CZTS target. Cu, Zn, and Sn atoms
were measured by using ultraviolet absorption spectroscopy (UVAS), whereas
S atoms was measured using vacuum ultraviolet absorption spectroscopy (VU-
VAS). Then, we evaluate the effective depositing fluxes of Cu, Zn, Sn and S
atoms from their absolute densities and sticking probabilities. We compared
40 the effective depositing fluxes with the fluxes evaluated from the deposition of
CZTS films.

2. Experimental apparatus

Figure 1 shows the experimental apparatus. A magnetron sputtering source

was inserted from the top of a cylindrical vacuum chamber. The diameter and
45 the height of vacuum chamber were 160 mm and 180 mm, respectively. The
magnetron source was a conventional one with cylindrical permanent magnets.
A stoichiometric CZTS target had a diameter of 50 mm and was bonded on the
water-cooled copper surface of the magnetron source. The target holder was
connected to an rf power supply at a frequency of 13.56 MHz via a matching
50 circuit. The sputtering cathode was surrounded by a grounded shield with a
diameter of 80 mm, which worked as the anode of the magnetron discharge. A
substrate holder was placed at a distance of 50 mm from the target surface.
The diameter of the substrate holder was 100 mm. The base pressure of the
vacuum chamber was less than 1 × 10−6 Torr. After the evacuation to the base
55 pressure, we introduced Ar into the chamber. The Ar pressure was monitored
using a capacitance manometer and was controlled using a gate valve near the
pumping unit.
The ground state Cu, Zn, and Sn densities in CZTS sputtering plasmas
were evaluated by UVAS using hollow cathode Cu, Zn, and Sn lamps as the

3
60 light sources. The light from the hollow cathode lamp was launched into the
sputtering plasma and the emission transmitted through the plasma was de-
tected using an ICCD camera via a monochromator, as schematically shown in
Fig. 1. The absorption wavelengths from excited state to ground state for Cu,
Zn, and Sn were 324.75 nm (4p 2 P3/2
o
−4s 2 S1/2 ), 213.86 nm (4s4p 1 P1o −4s2 1 S0 )
65 and 286.33 nm (5p6s 3 P1o −5p2 3 P0 ), respectively. Since the absorption measure-
ment in the discharge phase did not succeed due to the strong optical emission
from the sputtering plasma, the absorption was measured after the termination
of the rf power. The on- and off-periods of the rf power were 90 and 10 ms,
respectively. The repetition frequency was 10 Hz and the instantaneous rf power
70 was 80 W in all the experimental conditions.
On the other hand, the absolute S density was evaluated by VUVAS. The
details have been described in our recent report[12]. In brief, an electron cy-
clotron resonance (ECR) plasma using SF6 +Ar gases was produced as the light
source for measuring the absolute S atom density. The absorption wavelength
75 was 147.39 nm (4s 3 D3o − 3p4 3 P1 ). The off-period was set at 20 ms while the
on-period was 80 ms. The light from the ECR plasma passed through the MgF2
window and the centre of the magnetron sputtering plasma. Then it was de-
tected using a secondary electron multiplier tube via a VUV monochromator.
The absorption after the termination of the rf power was measured at various
80 Ar gas pressures.

3. Results and discussion

3.1. Absolute densities and fluxes

Figure 2(a) shows the emission spectrum from Cu hollow cathode lamp and
Cu absorption in the wavelength range from 322.5 to 325.0 nm. It is clearly
85 shown in Fig. 2(a) that the intensities of the resonant transition transmitted
through the plasma at various times after the termination of rf power are weaker
than the original intensity of Cu lamp. On the other hand, the intensities of the
other emissions are not weakened by the plasma. The absolute density of Cu

4
 atom was calculated from the absorptions using conventional theory[14], assum-
90 ing a temperature of 400 K for Cu atoms in plasmas. The relation between the
absorption ratio and the ground state density of Cu atom is shown in Fig. 2(b).
The absorption length was set as 100 mm, which was considered from the size
of bright plasma region in front of the sputter target.
Figure 3 shows the temporal variations of absolute Cu density in the after-
95 glow of magnetron sputtering plasmas at various discharge pressures. The rf
power was 80 W. As shown in Fig. 3, the absolute Cu density decreased ex-
ponentially in the afterglow. The absolute Cu density in the discharge phase
was evaluated from the intercept of Fig. 3, which is the extrapolated density at
the termination of the rf power. We found that the absolute Cu densities at
100 discharge pressures of 25, 50 and 100 mTorr were 6.4×109, 1.4×1010, 1.6×1010
cm−3 , respectively.
The absolute densities of Zn, Sn and S were evaluated using a similar man-
ner. Figure 4(a) shows the absolute densities of Cu, Zn, Sn and S at various
discharge pressures. The absolute densities of Cu, Sn and S increased with in-
105 creasing discharge pressure from 25 to 100 mTorr. The absolute densities of Cu
and Sn were almost at the same range of 6×109 ∼ 3×1010cm−3 , while the abso-
lute density of S was higher, between 2∼8×1010cm−3 . On the other hand, the
absolute density of Zn was not influenced by the discharge pressure and it was
significantly low, between 2∼3×109cm−3 . Since the sputtering yields of Cu, Zn
110 and Sn atoms by Ar ions at 200 eV are given as 1.0, 3.0, 0.5, respectively [13],
these results suggest that the absolute densities of metal atoms in CZTS sput-
tering plasmas were not the same as expected from CZTS stoichiometry and
sputtering yields. So far, we found no report on the sputtering yield of S by low
energy Ar ions.
115 Then, we evaluated the effective depositing flux from the absolute densities
in Fig. 4(a). The effective depositing fluxes of Cu, Zn, Sn and S atoms are given
by the product of sticking probability and thermal flux of each species, which

5
 is, r
n 8kT
ΓEf f ec. = αΓ = α , (1)
4 πM
where α, n, T , M and k being the sticking probability, the absolute density, the
120 temperature, the atomic mass and the Boltzmann constant, respectively. Since
the temperature of an Ar metastable state measured by diode laser-induced flu-
orescence spectroscopy was approximately 400 K [15], we assumed TCu/Zn/Sn/S
= TAr = 400 K. In our recent report, we evaluated the sticking probabilities
for Cu, Zn and Sn atoms as unity and the sticking probability for S atom as
125 0.7. From these results, Fig. 4(b) shows the calculated depositing fluxes of
Cu, Zn, Sn and S at various Ar discharge pressures. The total depositing flux
increased slightly with increasing discharge pressure and was in the range be-
tween 3∼8×1014 cm−2 s−1 . From characteristic of depositing flux of S atom in
Fig. 4(b), we understood that S atom, which is the species with highest density,
130 dominates the total depositing flux.
For comparison, the depositing flux was also evaluated from the deposition
rate of CZTS film. The sample films were deposited at various discharge pres-
sures for 30 minutes and no heating was applied during deposition. The film
thickness was evaluated from the cross-sectional image observed using JEOL
135 JSM-7001FA field emission scanning electron microscope (FE-SEM). We found
that the thickness of the deposited films varied between 1.5∼2.5 µm, which is
corresponding to deposition rate of approximately 50∼80 nm/min. Accordingly,
the flux was estimated by,

Rd ρ
ΓDepo. = , (2)
MCZT S

where Rd is the deposition rate, ρ is the film density (ρ = 4.6 gcm−3 ) [26], and
140 MCZT S is the molecular mass of CZTS (MCZT S = 7.3 × 10−22 g). As shown
in Fig. 4(b), we found that the depositing fluxes evaluated from the CZTS films
were at comparable order with the total depositing fluxes of Cu, Zn, Sn and S
in the gas phase.

6
 3.2. Composition ratios
145 The major issue in CZTS deposition is to control the growth CZTS film at its
stoichiometry. For that purpose, we compared the composition ratio of atoms in
CZTS sputtering plasmas with elements in CZTS films, as shown in Fig. 5. The
compositions of deposited films were analysed using energy dispersive spectrom-
eter (EDS) equipped in JEOL FE-SEM. The structural, crystalline and optical
150 properties of the deposited films will be discussed in details in separate paper.
Figure 5 shows that the composition ratios of Sn/Zn and S/(Cu+Zn+Sn)
in CZTS films were slightly lower than the stoichiometry of CZTS. The Sn
and S deficiencies may be attributed to the desorption of Sn and S from CZTS
films[20]. On the other hand, the density ratios of Sn/Zn and S/(Cu+Zn+Sn) in
155 the gas phase indicates that the absolute densities of Sn and S were significantly
high. On the other word, the absolute density of Zn was significantly low in
comparison with the stoichiometry of CZTS. The result in Fig. 5 indicates that
there is an inconsistency between the composition of atoms in the gas phase
of CZTS sputtering plasmas and the composition of elements in CZTS films.
160 We suggest two reasons for this phenomenon. First, the sputtered species from
compound CZTS target may not only in the form of atoms, but may also in
the form of molecules. Several reports and our previous work have described
the existence of molecules in sputtering plasmas[16, 17, 18, 19]. The sputtered
molecules could significantly contribute to the growth of stoichiometric CZTS
165 films. Further work to measure these molecules in the gas phase of CZTS
sputtering plasmas is necessary. Second, tin sulfide (SnS) has been reported
as species with high vapor pressure and of interest in several publications[20,
21, 22, 23]. It has been reported that the SnS evaporated from CZTS films at
temperature above 350 o C [20]. Therefore, Sn and S atoms could goes back to
170 the gas phase from desorption and decomposition mechanisms in plasmas.
Finally, we propose that one could obtain stoichiometric CZTS film by in-
creasing the composition of Zn in CZTS target. As clearly understood from
Fig. 4(a), if the Zn density was at the range of 1010 cm−3 , stoichiometric CZTS
in the gas phase is possibly obtained. This finding is consistent with the re-

7
175 ports from literatures [27, 28, 29], whereby they deposited ideal CZTS films
under Zn-rich conditions. In addition, it is worthy to note that Cu-poor and
Zn-rich CZTS film is essential to achieved high conversion efficiency of CZTS
solar cell [30].

4. Conclusions

180 In conclusion, we have measured the absolute densities of Cu, Zn, Sn and
S sputtered from stoichiometric CZTS target. From the absolute densities and
sticking probabilities of atoms, we evaluated the total depositing fluxes and
compared it with those evaluated from the deposition rate of CZTS films. De-
positing fluxes evaluated from both methods were consistent, indicating that
185 the ground state Cu, Zn, Sn and S atoms were successfully measured. However,
since the composition ratios of elements were not at CZTS stoichiometry, we
suggest that an altered or non-stoichiometric CZTS target is necessary to ob-
tain stoichiometric CZTS film. We have showed that higher ratio of Zn element
in CZTS target is required for this purpose. Therefore, we believe that the
190 present results are helpful to optimize the composition of CZTS sputter target
and eventually to achieved high conversion efficiency of CZTS solar cell.

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12
 Figure captions

290 Fig. 1 Experimental setup for absorption spectroscopy measurements.

Fig. 2 (a) Emission from a hollow cathode Cu lamp and Cu absorption spec-
trum at 10, 100 and 500 µs after the termination of rf power. (b) Calcu-
lated relation between Cu absorption at 324.75 nm and the ground state
Cu atom density.

295 Fig. 3 Temporal variations of absolute Cu density in the afterglow of mag-

netron sputtering plasmas at various discharge pressures. The rf power
was 80 W.

Fig. 4 (a) Absolute densities and (b) depositing fluxes of Cu, Zn, Sn and S
atoms at various discharge pressures. The rf power was 80 W.

300 Fig. 5 Comparison between the composition ratio of elements in CZTS sput-
tering plasmas and CZTS films.

13
 Cooling Matching RF Power Trig.
Ar gas water box supply
inlet

CZTS target
Delay
pulser
Lens
Monochromator
Hollow
cathode
lamp ICCD
z TMP camera

y Controller
x

Computer

Figure 1: Experimental setup for absorption spectroscopy measurements.

14
 1
(a)
RF power: 80 W
0.8 Ar pressure: 25 mTorr
Intensity (a.u.)

0.6 HCL
HCL CuCulamp
lamp
10 µ
10 µs
s
100 µµs
100 s
0.4
500 µµs
500 s

0.2

0
323.5 324 324.5 325
Wavelength (nm)

1
(b)
0.8
Cu 324.75 nm
Absorption (100%)

0.6

0.4

0.2

0
107 108 109 1010 1011 1012
Absolute density (cm-3)

Figure 2: (a) Emission from a hollow cathode Cu lamp and Cu absorption spectrum at 10, 100
and 500 µs after the termination of rf power. (b) Calculated relation between Cu absorption
at 324.75 nm and the ground state Cu atom density.

15
 1011
Ar pressure
25 mTorr
50 mTorr
Cu density (cm -3)

100 mTorr

1010

109
0 100 200 300 400 500
Delay after rf off ( µs)

Figure 3: Temporal variations of absolute Cu density in the afterglow of magnetron sputtering

plasmas at various discharge pressures. The rf power was 80 W.

16
 1011
(a)
Cu
Absolute density (cm -3)

Zn

Sn
10
10
S

109
0 20 40 60 80 100 120
Ar pressure (mTorr)

Cu
(b) Zn
1015
Sn
Depositing flux (cm -2s-1)

S
Total
Deposition
1014

1013
0 20 40 60 80 100 120
Ar pressure (mTorr)

Figure 4: (a) Absolute densities and (b) depositing fluxes of Cu, Zn, Sn and S atoms at various
discharge pressures. The rf power was 80 W.

17
 CZTS plasma
Sn/Zn
10 Cu/(Sn+Zn)
S/(Cu+Zn+Sn)
Composition ratio

CZTS thin film

Sn/Zn
Cu/(Sn+Zn)
S/(Cu+Zn+Sn)
0.1
0 20 40 60 80 100 120
Ar pressure (mTorr)

Figure 5: Comparison between the composition ratio of elements in CZTS sputtering plasmas
and CZTS films.

18