Materials Research Bulletin 47 (2012) 3052–3055

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Materials Research Bulletin

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Physical/chemical properties of tin oxide thin film transistors prepared using

plasma-enhanced atomic layer deposition
Byung Kook Lee a,b, Eunae Jung a, Seok Hwan Kim a, Dae Chul Moon a, Sun Sook Lee a,
Bo Keun Park a, Jin Ha Hwang b, Taek-Mo Chung a, Chang Gyoun Kim a, Ki-Seok An a,*
a
Thin Film Materials Research Team, Korea Research Institute of Chemical Technology, Yuseong, P. O. Box 107, Daejeon 305-600, Republic of Korea
b
Department of Material Science and Engineering, Hongik University, Seoul 121-791, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: Thin film transistors (TFTs) with tin oxide films as the channel layer were fabricated by means of plasma
Available online 26 April 2012 enhanced atomic layer deposition (PE-ALD). The as-deposited tin oxide films show n-type conductivity
and a nano-crystalline structure of SnO2. Notwithstanding the relatively low deposition temperatures of
70, 100, and 130 8C, the bottom gate tin oxide TFTs show an on/off drain current ratio of 106 while the
device mobility values were increased from 2.31 cm2/V s to 6.24 cm2/V s upon increasing the deposition
temperature of the tin oxide films.
ß 2012 Elsevier Ltd. All rights reserved.

1. Introduction and a low concentration of impurities [19]. Compared to the

Studies of metal oxide semiconductors have widely reported
these types of semiconductors as candidates for optoelectronic
device applications such as light-emitting diodes (LEDs) and thin
film transistors (TFTs) over the last few years [1,2]. Particularly,
transparent TFTs based on transparent metal oxides such as ZnO
[3–5], In2O3 [6], In–Zn–O (IZO) [7,8], In–Ga–Zn–O (IGZO) [9], and
Al–Zn–Sn–O (AZTO) [10] have much attracted due to their
advantages over conventional semiconductors and their good
transparency in the visible range, a low process temperature, good
large-area uniformity, and relatively high carrier mobility [11].
Tin oxide with n-type conductivity due to oxygen vacancies
and/or metal ion interstitials has been widely researched due to its
wide band gap of 3–4 eV, its high optical transparency in the visible
light range, and its good chemical stability [12]. Recently, tin-based
oxide semiconductors have been reported as feasible for use as the
active channel material in the transparent TFTs, light-emitting
diodes, and flexible displays [13,14]. The properties of metal oxide
semiconductor films for optoelectronic applications are strongly
dependent on the thin film deposition process. Tin oxide thin films
have been fabricated by using various methods, such as sputtering
[13], sol–gel methods [15], spray pyrolysis [16], chemical vapor
deposition (CVD) [17], and atomic layer deposition (ALD) [18].
Among them, ALD based on chemical vapor reaction using a metal
precursor and reactant gas has advantages such as good large-area
uniformity, good step coverage, a relatively low deposition process,
* Corresponding author. Tel.: +82 42 860 7356; fax: +82 42 861 4151.
E-mail address: ksan@krict.re.kr (K.-S. An).
conventional ALD process, the plasma-enhanced atomic layer
deposition (PE-ALD) process of ZnO thin films at lower deposition
temperatures may result in a low carrier density because there are
fewer oxygen vacancies [20].
In this study, TFTs are fabricated with tin oxide film as the
channel layer by PE-ALD using the Sn(II) aminoalkoxide precursor,
Sn(dmamp)2 [dmamp = OCMe2CH2NMe2], and an oxygen plasma
reactant. From the film characterizations and device performances,
the low temperature PE-ALD process is expected to be suitable for
use with a flexible substrate for flexible display applications.
2. Experiments
The tin oxide films were deposited onto a thermally grown SiO2
(200 nm) on a highly phosphorous doped Si(0 0 1) by PE-ALD with
Sn(dmamp)2 and oxygen plasma (RF power  150 W) respectively,
at a substrate temperature range of 50–200 8C. The working
pressure was kept at 3 Torr. Ar (80 sccm) was used as the carrier
and purge gas. The pulse time was 1–5 s for the Sn(dmamp)2, 1–5 s
for the oxygen plasma, and 5 s for the Ar purge. The deposited films
were characterized by thickness spectroscopy, X-ray diffraction
(XRD), X-ray photoelectron spectroscopy (XPS), and atomic force
microscopy (AFM). The electrical properties of the films such as the
carrier concentration, resistivity, and carrier mobility were
measured by the Hall measurement method.
To fabricate of the bottom-gate TFTs, the films were processed
for source–drain metal contacts (Al, 50 nm) through a thermal
evaporator. The channel length and width were 200 and 1000 mm,
respectively. The output and transfer characteristics of the tin

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http://dx.doi.org/10.1016/j.materresbull.2012.04.120
 B.K. Lee et al. / Materials Research Bulletin 47 (2012) 3052–3055
Fig. 1. (a) Sn 3d, (b) O 1s XPS spectra of tin oxide films, and (c) the peak deconvolution of Sn 3d5/2 core level. (d) Depth-profiling AES of a tin oxide film deposited at 130 8C. The
film thickness is about 100 nm.
oxide TFTs were measured using a semiconductor characterization
system at room temperature in the dark.
3. Results and discussion
Fig. 1(a) and (b) shows the high-resolution XPS Sn 3d and O
1s core level spectra of the film deposited at 130 8C. The binding
energy and line shape of Sn 3d core level spectra before and after
Ar+ ion sputtering were not changed seriously. The binding
energy difference (DBE) between 3d5/2 and 3d3/2 core level was
measured to 8.45 eV. As shown in Fig. 1(c), the peak
deconvolution of Sn 3d5/2 core level shows only a single
component of 486.6 eV. The peak at 485.0 eV with DBE of
8.41 eV corresponds to metallic tin, the peak at 486.6 with DBE
of 8.4 eV to Sn4+ state in SnO2, and the peak at 485.9 eV with DBE
of 8.3 eV to the Sn2+ state in SnO [21–23]. The binding energy
position, DBE, and the peak deconvolution indicate the formation
of SnO2 film without any serious Sn2+ chemical state by the
Sn(dmamp)2-oxygen plasma PE-ALD process. The O 1s core level
was determined to be 530.5 eV with slight surface contamina-
tion at higher binding energy.
Fig. 1(d) shows the AES depth profile of a tin oxide film
deposited at 130 8C. The atomic ratio of tin to oxygen was
estimated to be about 1:1.7  0.3, which indicates an oxygen
deficient environment. Consequently, this shows that PE-ALD tin
oxide films have the possibility of n-type conductivity. In addition, the
low carbon incorporation indicates without any serious reaction of
by-product during the self-limiting PE-ALD process.
Fig. 2(a) shows the AFM surface morphology of a tin oxide
film (16 nm) deposited onto a SiO2(200 nm)/Si substrate at
130 8C. The root-mean-square (RMS) roughness is about
2.248 nm. Small and round-shaped grains in the as-deposited
film can be observed in the AFM image. The surface morphology
3053
of the film suggests that the crystalline phase formed in the as-
deposited film.
Fig. 2(b) shows the XRD pattern of a tin oxide film deposited at
130 8C onto a quartz substrate. The PE-ALD film shows the rutile
polycrystalline structure of SnO2. On the other hand, tin oxide films
deposited at temperatures of 70 and 100 8C show an amorphous
structure, as shown at the inset of Fig. 2(b).
Fig. 3 shows a cross-sectional TEM image of a tin oxide film
deposited at 130 8C. The formation of polycrystalline SnO2 film
with small nm-scale grains is also depicted through the TEM
image. The modulation of the conductivity of metal oxide
semiconductors can be explained by the presence of trapped
charges near the grain boundary. As a trapping site of the free
carrier in each grain, connected to the creation of a depletion layer
near the grain boundary, the grain boundaries can reduce the
carrier concentration (Nd) of the films [24,25]. Therefore, as
increasing the deposition temperature of the tin oxide films, the
trapping sites of free carriers may be decreased because the grain
boundaries of the polycrystalline phase decrease in comparison
with those of the amorphous phase film; moreover, the carrier
concentration of the film can be increased as a result of the
decreased number of carrier traps.
Fig. 4 shows the carrier concentration and resistivity of tin oxide
films deposited at different temperatures according to Hall
measurements. The carrier concentration and resistivity of the
tin oxide films deposited from 70 to 130 8C were not measured due
to the contact error associated with these films. This indicates that
tin oxide films deposited in this deposition temperature range
likely have insulator characteristics, which may affect the
transistor properties because at relatively low carrier concentra-
tion and low conductivity levels, the drain current in the tin oxide
channel can be modulated effectively by the gate voltage.
However, above 130 8C, the carrier concentration increases
drastically to 1019 cm 3. In previous reported ZnO films deposited
3054 B.K. Lee et al. / Materials Research Bulletin 47 (2012) 3052–3055

Fig. 2. (a) Surface morphology obtained by an AFM image and (b) XRD pattern of a tin oxide film (thickness: 16 nm). The SnO2 films were deposited at 130 8C.

by PE-ALD, the resistivity decreased exponentially within the ALD
temperature window due the loss of impurities [26]. The decrease
in the resistivity led to an increase in the carrier concentration. In
this study, as the growth temperature increased, the carrier
concentration increased to 1019 cm 3 at a temperature of 200 8C. It
may be that the tin oxide films achieved greater crystallization in
the films as the growth temperature increased. At a high carrier
concentration, the current in the film cannot be controlled by the
gate due to the high conductivity caused by the degeneration of the
tin oxide [27].
Fig. 5(a)–(c) shows the drain current–drain voltage (IDS–VDS)
output curves of bottom gate and top-contact tin oxide TFTs
constructed on SiO2(200 nm)/p+-Si at different deposition tem-
peratures of 70, 100, and 130 8C, respectively. The observed TFT
characteristics are typical of n-channel semiconductors, which
show that the positive gate bias modulates the carrier transfer. The
output curves are similar to those of conventional transistor
models with both linear regions at a lower voltage and saturation

Fig. 3. Cross-sectional TEM image of a tin oxide thin film deposited onto SiO2/ Fig. 4. Carrier concentrations and mobilities of tin oxide films deposited at various
Si(0 0 1) substrates at 130 8C. deposition temperatures measured by Hall measurements.
 B.K. Lee et al. / Materials Research Bulletin 47 (2012) 3052–3055
Fig. 5. The output curves of bottom-gate and top-contact tin oxide TFTs constructed on SiO2(200 nm)/p+-Si with different deposition temperatures of (a) 70, (b) 100, and (c)
130 8C and the transfer curves (VDS = 20 V).
regions at high voltages. Pinch-off behavior was also observed in
the output curves. Fig. 5(d)–(f) shows the transfer curves at
VDS = 20 V with different deposition temperatures of 70, 100, and
130 8C, respectively. These figures show the TFT parameters of the
on/off drain current ratio (Ion/off), the threshold voltage (Vth), and
the saturation mobility (msat). The drain current (IDS) was increased
by increasing the positive gate bias. These parameters were
calculated by the following equation: IDS = (mCOXW/
2L)(VGS Vth)2, where COX denotes the capacitance per unit area
of the gate dielectric layer and W and L are the channel width and
length, respectively. Even at the low deposition temperatures of
70, 100, and 130 8C, the Ion/off is about 106. By increasing the
deposition temperature, the threshold voltages of each TFT device
were decreased from 7.465 to 1.88 V and msat values were
increased from 2.31 to 6.24 cm2/V s. Over 130 8C, the TFT devices
did not exhibit appropriate TFT behaviors. This indicates that tin
oxide films deposited at high temperature above 130 8C act as
metallic materials due to the high carrier concentration and
conductivity.
4. Conclusions
We deposited tin oxide thin films by a low-temperature PE-ALD
process and have fabricated bottom-gate TFTs incorporating tin
oxide thin films as a channel layer without any a post-annealing
step. The atomic ratio of tin to oxygen was estimated to be
approximately 1:1.7  0.3, as obtained from the depth-profiling AES.
Even at a low deposition temperature range of 70–130 8C, the Ion/off was
approximately on the order of 106 and the threshold voltages of each
TFT device were from 7.465 to 1.88 V. msat values were increased from
2.31 to 6.24 cm2/V s upon increasing the deposition temperature.
However, the carrier concentration of the tin oxide deposited at
temperatures that exceeded 130 8C was too high to exhibit switching
transistor behavior.
Acknowledgment
This research was supported by the Converging Research Center
Program through the National Research Foundation of Korea (NRF)
3055
funded by the Ministry of Education, Science and Technology
(2011K000611 and 2011K000604).
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