Thin Solid Films 519 (2011) 6881–6883

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

Improvement of bias stability of indium zinc oxide thin film transistors by the
incorporation of hafnium fabricated by radio-frequency magnetron sputtering
Eugene Chong a,b, Yoon Soo Chun a, Seung Han Kim a,c, Sang Yeol Lee a,b,⁎
a
Electronic Material Center, Korea Institute of Science and Technology, Seoul 136-791, Republic of Korea
b
Nanoelectronics, University of Science and Technology, 113 Gwahangno, Yuseong, Daejeon, 305-333, Republic of Korea
c
Electrical and Electronics Engineering, Chung-Ang University, 221 Heuk Seok-Dong, Seoul 156-756, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Available online 17 April 2011 We report on the fabrication and performance of amorphous oxide thin film transistors with indium zinc
oxide (In2O3:ZnO = 1:1 mol%) and various ratios of hafnium-doped indium zinc oxide (IZO:HfO2 = 2:0, 0.3,
Keywords: 0.7, and 1.1 mol%) deposited at the same deposition conditions for semiconductor channel layer. The carrier
IZO concentration (Ncp) of the HIZO films was further decreased from 7.08 × 1017 to 5.0 × 1016 cm− 3. This
HIZO indicates that Hf metal cations effectively suppress carrier generation due to the high electron negativity (1.3)
Carrier concentration
of Hf. In addition, we compared bias instability of both devices after bias temperature stress (BTS) test under
Stability
on-current state at VDS of 10 V and IDS of 3 μA at 60 °C for 420 min. It was found that the Hf metal cations could
be effectively incorporated in the IZO thin films as a suppressor against both the oxygen deficiencies and the
carrier generation in the ZnO-based system.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Recently, high performance active matrix devices (AMDs) have
been investigated to use for next generation displays. Zinc-based oxide
devices are widely used in displays due to the advantage of good
scalability and a low-cost process because it does not require
crystallization and doping process. However, this technology may not
be sufficient enough to drive functional AMDs because of degradation
of performance due to light sensitivity, and low mobility (~1 cm2/V s)
[1,2]. From the basic review, the minimum TFT properties that are
required for active matrix organic light emitting displays (AM-OLEDs)
and active matrix liquid crystal displays (AM-LCDs) include: a field
effect mobility (μ FE) of at least 5 cm2/V s, on/off ratio of 106 and low
temperature processing for flexible substrates [3]. The requirements for
high mobility and low processing temperatures are easily full-filled
with magnetron sputtered amorphous zinc-based oxide materials.
There have been promising results with zinc-based oxide materials,
which are based on their electrical resistivity tailored (1010–10− 4 Ω
cm) [4]. More recently, the variety of characteristics of zinc-based
materials were investigated by incorporation of metal cations, such as
In, Sn [5,6]. Especially, In–Zn–O (IZO) based thin film transistors (TFTs)
for high performance with room temperature (RT) process have been
reported from lots of researchers [7,8].
In IZO based TFTs, the mobility also increase with increasing carrier
concentration (Ncp), even though the effective carrier concentration
⁎ Corresponding author at: Electronic Material Center, Korea Institute of Science and
Technology, Seoul 136-791, Republic of Korea. Tel.: +82 2 958 5382; fax: +82 2 958 5409.
E-mail address: lsy@kist.re.kr (S.Y. Lee).
of high performance active channel layer is below 1017 cm2/V s [9].
However, the instability under prolonged on-current status is still
critical issue to substitute for Si-based technology. Therefore, multi-
composition IZO-based materials have been suggested with gallium
(Ga), zirconium (Zr), and hafnium (Hf) as suppressor for the oxygen
out-diffusing from channel layer [9–15]. As in the case of a previous
study, Hf is one of the tetravalent groups, which contributes four
valence electrons that can act as oxygen binder to extract from their
electrical properties [12–14]. Additionally, the shallow donor level in
the density-of-states (DOS) of a-HIZO is lower than that of a-GIZO
thin film [12,15]. In our earlier paper, inverted staggered a-HIZO (Hf of
1.1 mol%) TFTs were shown strong binding with oxygen due to
decreased mobility [13]. In this paper, we demonstrated the
compositional dependence of the HIZO TFTs by rf-sputtering process
at RT. In addition, the instability of HIZO-TFTs was compared to that of
IZO-TFT after bias temperature stress (BTS) test under on-current
state at VDS of 10 V and IDS of 3 μA at 60 °C for 420 min. Furthermore,
we suggest the optimized composition of HIZO film for the channel
layer of TFTs.
2. Experimental procedures
Mixed InZnO (In2O3:ZnO = 1:1 mol%) powders were ground with
0 and 1.1 mol% HfO2 powders for 1 h, after which the mixed powders
were compressed at a pressure of 1600 kg/cm2 to form pellets (2 in. in
diameter). The pressed pellets were sintered in nitrogen ambient at
1200 °C for 3 h to yield targets for sputtering. The films of IZO and HIZO
were grown on SiO2/p-Si substrates (200 nm thick SiO2 deposited by
thermal oxidation on highly doped p-type Si (100)). The films were

0040-6090/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2011.04.044
6882 E. Chong et al. / Thin Solid Films 519 (2011) 6881–6883

deposited at a power density of 1.75 W/cm2, a working pressure of (a)

0.56 Pa, and a gas flow ratio of Ar/O2 = 19:1 by rf-magnetron 10-4
sputtering. The thickness of the active channel layer was fixed at 10-5

Drain Current (A)

35 nm, and the channel width and length were 250 μm and 50 μm,
10-6
respectively. Deposited HIZO film showed same composition ratio with
target that we designed. Ti and Au metals were deposited on the 10-7
patterned channel layer as top source and drain electrodes using 10-8
e-beam and thermal deposition methods, respectively. After fabrication 10-9
of the a-HIZO TFTs, the sample was annealed at 350 °C for 2 h in air 10-10 IZO
ambient. The X-ray diffraction (XRD) and X-ray spectrometer (XPS)
10-11 HIZO (0.3)
measurement have been performed to characterize the role of Hf metal HIZO (0.7)
cations in IZO films with comparison to only IZO films. The composition 10-12
HIZO (1.1)
of HIZO film is analyzed by the Field-emission Scanning Electron 10-13
-10 0 10 20 30
Microscope, Energy-dispersive X-ray (Fe-SEM, EDX) as a function of Hf
concentration in IZO system. Electrical characteristics of devices are
GateVoltage(V)
measured by semiconductor parameter analyzer (EL423, ELECS Co.). A (b)
positive voltage sweep was applied to the bottom gate electrode, while

Sub-threshold Swing (mV/dec.)

Field Effect Mobility (cm2/V.s)
30 200
the top electrodes were occurred the current path formed from the

Carrier Concetration (cm3)

Carrierconcentration
source to the drain through the channel in a driving device. 8.0x1017 Mobility, S.S 25

3. Results and discussions 6.0x1017 20 150

Fig. 1 shows the spectrum of IZO and HIZO thin films as a function of
Hf concentration from 0 to 1.1 mol%. A stick pattern of a hexagonal ZnO
is plotted in the figure for comparison [16]. All peaks of the diffraction
spectrum of the HIZO film correspond well to the amorphous pattern.
For comparison, the microstructure of only IZO films has been reported
to be locally crystallized phase, even though XRD spectrum indicates
amorphous phase. Incorporation of Hf element suppresses the growing
of the columnar structure in HIZO films, which may be due to the
formation of stresses by the difference in ion size between zinc and the
metal cations [17]. On the other hand, the columnar grain growth in
HIZO is strongly related to the Hf element which acted as a crystal
growth and diffusion suppressor [18]. The representative transfer
curves of HIZO TFTs shown in Fig. 2(a) were operated at a drain to
source voltage (VDS) of 10 V. As Hf concentration increases, the
threshold voltage (Vth) was positively shifted and on-current level
was decreased. Fig. 2(b) shows the variation of the SS, Ncp and field
effect mobility (μ FE) as a function of Hf concentration. The Ncp value was
calculated by CiVon/qtC, where the Ci, q, and tC are gate dielectrics
capacitance per area, elementary charge (1.602 × 10− 19), and the
channel thickness, respectively [19]. Hosono et al. have clarified that
mobility increases and subthreshold swing (S.S) value decreases with
20-HIZO
(100) (002)
(d)
Intensity (arbit unit)
15
4.0x1017
10 100
2.0x1017 5
0 50
0.0 0.3 0.6 0.9 1.2
Hf/(Hf+In+Zn) [mol %]
Fig. 2. IZO and a-HIZO TFT characteristics. (a) The transfer curve of HIZO TFTs and (b) the
variation of the S.S, Ncp and uFE as a function of Hf concentrations from 0 to 1.1 mol%.
decreasing Ga ratio, which acts as a carrier generation suppressor and
stabilizer [20]. The behavior of HIZO TFTs is similar to that of previously
reported amorphous Zn-based oxide semiconductors, which the
generation of carriers is suppressed by the Hf 4+ ions in the IZO films.
The exhibiting Ncp dependence on Hf concentration in HIZO (1.1) is
lower than that of HIZO (0.3) after annealing at a temperature of 350 °C
as shown in Fig. 2(b). This implies that higher concentration of Hf in IZO
might be more strongly bound to the oxygen. However, the S.S value
shows maximum value in HIZO (1.1), which may be deducted from
creating non-stoichiometric defect states induced excess of metal
cations or anions [21]. In addition, HIZO (0.7) and (1.1) TFTs exhibited a
significant improvement of on-current stability, showing below 1 V
shift of Vth after the same BTS test as shown in Fig. 3(a). Fig. 3(b) shows
representative transfer curves (plotted log scale) of HIZO (0.3), which
are measured at the initial and after BTS for 420 min. The BTS test result

10-HIZO is well agreed with the results of chemical bonding analysis by XPS
spectra. The intensity and the peak of O 1s are increased and shifted to
(c) lower binding energy level due to adapted Hf metal cations in IZO
5-HIZO system, which is well agreed with the reduction of oxygen vacancy by
Hf metal cations as shown in Fig. 4 [13]. The peaks position at
~529.9 eV, ~531.4 eV and ~531.7 eV can be related to oxygens in oxide
(b)
without oxygen vacancy, with oxygen vacancy and hydrogen, respec-
InZnO tively. The oxygen vacancy and hydrogen related peak of 531.5 eV affect
the Vth shift due to the environment effects [22]. Fig. 4 shows that the O
1s peak of IZO films has higher binding energy than a-HIZO film.
(a) Furthermore, from the XPS data, we can explain that the a-HIZO film
25 30 35 40 has been strongly oxidized with minimal oxygen vacancy and
2θ (deg.) hydrogen. This indicates that lower O 1s binding energy in HIZO films
can expect high stability with less affect by oxygen vacancy and OH\.
Fig. 1. Diffraction spectra from XRD measurement with a 2theta configuration for
We investigated the properties of Hf incorporated IZO thin films as
annealed films at 350 °C for 1 h depending on different Hf concentration incorporated channel layer in our previous work [13]. However, here, we focus on the
in IZO films. effect of different Hf concentration to obtain highly stable and high
 E. Chong et al. / Thin Solid Films 519 (2011) 6881–6883 6883

(a) strong oxygen binding ability. Additionally, the Hf metal cations

12 induced suppressing columnar grain growth to grown HIZO films as
amorphous phase. Those might be a key role of enhanced stability.

Vth variation (V) 9

IZO
4. Conclusions
HIZO (0.3)
6 HIZO (0.7)
HIZO (1.1)
In conclusions, Hf incorporated IZO thin films were prepared for
TFTs in this paper via RF-sputtering at RT. The influence of Hf metal
3
cations on the crystal structure and electrical properties of the films
was investigated. HIZO films show clear amorphous phase structure
0 independent of Hf concentration. The electrical properties of the
0 100 200 300 400 fabricated a-HIZO TFTs strongly depend on the Hf concentration in the
films. Incorporated Hf in IZO films significantly affected the S.S and μFE,
Stress Time (min)
which are strongly related to defect states and Ncp, respectively. The
(b) comparison of prolonged bias stability for IZO and a-HIZO TFTs
10-3 revealed the trade off between mobility and stability. It is indicated
that the characteristics of Hf ions suppress the formation of oxygen
10-4
vacancy and stabilize the film's atomic structure and electrical
10-5
Drain Current (A)

properties. This is consistent with the discussion in which the

10-6 0h incorporation of Hf into an IZO system is necessary to obtain good
10-7 420m controllability and stability in electrical properties (or electron
10-8 density) of a-HIZO films. These findings could be useful to achieve
10-9 high stability of oxide TFTs in various applications.
10-10
10-11 Acknowledgment
10-12
10-13 This work is supported by the IT R&D program of MKE/IITA
-20 -10 0 10 20 30 [KI002182, TFT backplane technology for next generation display].
Gate Voltage(V)
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