Microelectronics Reliability 47 (2007) 372–377

www.elsevier.com/locate/microrel

Organic thin film transistors with HfO2 high-k gate dielectric grown
by anodic oxidation or deposited by sol–gel
a,*
J. Tardy , M. Erouel a,b, A.L. Deman a, A. Gagnaire a, V. Teodorescu c,d
,
M.G. Blanchin c, B. Canut c, A. Barau e, M. Zaharescu e
a
Ecole Centrale de Lyon, Laboratoire d’Electronique, Optoélectronique et Microsystèmes (LEOM), 36 Avenue Guy de Collongue,
69134 Ecully cedex, France
b
Ecole Centrale de Lyon, GEGELY, 69134 Ecully cedex, France
c
Université Lyon I, LPMCN, 69621 Villeurbanne, France
d
National Institute of Materials Physics, 077125 Bucharest, Romania
e
Institute of Physical Chemistry ‘‘I.G. Murgulescu’’, 060022 Bucarest, Romania

Received 4 December 2005; received in revised form 28 January 2006

Available online 5 May 2006

Abstract

We report here on pentacene based organic field effect transistors (OFETs) with a high-k HfO2 gate oxide. HfO2 layers were prepared
by two different methods: anodic oxidation and sol–gel. A comparison of the two processes on the electrical properties of OFETs is given.
Ultra thin nanoporous (20 nm) sol–gel deposited oxide films were obtained following an annealing at 450 C. They lead to high mobility
and stable devices (l = 0.12 cm2/V s). On the other hand, devices with anodic HfO2 revealed a little bit more leaky and show some hys-
teresis. Anodization, however, presents the advantage of being a fully room temperature process, compatible with plastic substrates. Sta-
bility and response to a bias stress are also reported.
 2006 Elsevier Ltd. All rights reserved.

1. Introduction erties, it is now recognized that charge transport in OFETs

These last years an increased interest was brought to
organic field effect transistors (OFETs) due to their poten-
tial application in various electronic systems as identifica-
tion tag, active matrix organic luminescent flat panel
driving circuits or sensors and biosensors. All these appli-
cations require devices with suitable performances, among
them a low operating voltage, a high on/off ratio and a
high stability are of prime importance. The control of the
stability and the reliability of OFETs is still an open ques-
tion. The mechanism of bias stress induced drift is, for
example, not yet fully known. Furthermore, organic semi-
conductors suffer from a high sensitivity to oxygen and
water vapor which are both at the origin of a lack of reli-
ability with time. Beyond the semiconductor related prop-
*
Corresponding author. Tel.: +33 4 7218 6065; fax: +33 4 7843 3593.
E-mail address: jacques.tardy@ec-lyon.fr (J. Tardy).
is also largely relying on the nature of the gate dielectric
(polymer or oxide) and on the structural and electrical
properties of the dielectric/organic semiconductor inter-
face. Both influence the growth mode of the organic semi-
conductor layer, the grain size, the structural order and,
consequently, the carrier mobility in the accumulation
channel which is usually as thin as a few organic monolay-
ers. In polycrystalline organic semiconductors, the mobility
is generally low and gate voltage dependent. It was pro-
posed to use high dielectric constant (high-k) gate oxides
to improve the field effect mobility thanks to an increase
of the charge in the channel and of the electric field at
the interface [1]. Since, several high-k insulators were
reported as Si3N4 [2], Al2O3 [3–5], Ta2O5 [6–8] or TiO2
[9,10].
HfO2 thin films were widely investigated as a potential
high-k oxide in replacement of SiO2 in future silicon micro-
electronics [11,12] but, to our knowledge, were not used in

0026-2714/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.microrel.2006.01.012
 J. Tardy et al. / Microelectronics Reliability 47 (2007) 372–377
OFETs so far. HfO2 dielectric constant is nominally close
to that of Ta2O5 (er  22–25 for high temperature pro-
cessed materials) but the energy band gap is higher
(Eg = 5.7 eV for HfO2 versus Eg = 4.5 eV for Ta2O5).
This paper aims at evaluating HfO2 as gate oxide for
OFETs. Two different methods of deposition were com-
pared: sol–gel deposition and anodization of an evaporated
Hf film. The first method is not strictly speaking a low tem-
perature method as often claimed since the formation of a
dense film needs a moderate annealing step of the deposited
film. As a rule, the quality of sol–gel films is excellent (low
surface roughness, homogeneity, bulk-like physical proper-
ties). On the other hand, anodization revealed to be a well
adapted method to grow high-k oxides at low temperature
compatible with OFETs processing on plastic substrates.
These two methods are promising for the development of
OFETs technology.
2. Experimental details
In order to grow anodic HfO2 gate insulators, Hf films
were deposited by e-beam evaporation onto highly doped
Si-p++ substrates. The evaporation rate and the final thick-
ness were respectively 2.2 Å/s and 250 nm. Anodization
was carried out in a so-called AGW solution, i.e., a mixture
of acid, glycol and water. A solution of tartaric acid (0.1 M)
buffered with NH4OH to a pH = 6 was mixed with ethylene
glycol in a 1:5 vol ratio. The solution was thoroughly stirred
and a flow of nitrogen was bubbling in before and during the
anodization process. Ammonium hydroxide increases the
density of charge carriers in the solution which in turn
enables a sufficient electrical conduction of the electrolyte.
Ethylene glycol increases the viscosity of the solution. The
decrease of ion mobility improved lateral homogeneity of
the oxidation process. The anodization process was carried
out at constant current density up to an anodization voltage
VA in the 25–100 V range. In this voltage range, the Hf film is
not entirely oxidized and Hf gate metal in remaining. The
current density is maintained at 0.2 mA/cm2.
Sol–gel films were deposited from hafnium tetra-ethox-
ide (Hf(OC2H5)4) dissolved in ethanol and stirred for 1 h
at 100 C in a water vapor free atmosphere. Then acetyl-
acetone and ethanol were added to the solution which is
then hydrolyzed under water saturated atmosphere at
100 C. The final concentration of HfO2 is 60 g/l. Thin films
were obtained by spinning the solution at 5000 rpm, then
drying at 100 C for 10 min and annealing under nitrogen
flux for 1 h at 450 C. The final film thickness is 20 nm.
Oxide films were characterized by spectroscopic ellipso-
metry to determine the thickness of the oxide, the refractive
index and the absorption coefficient. Capacitors were pro-
cessed by evaporation of top Al electrodes of various area
and the dielectric constant er was deduced from impedance
measurements carried out at 1 kHz and 10 mV modulation
voltage with a HP 4284 A impedance analyzer.
OFETs in a top contact configuration were processed by
vacuum evaporation of 80 nm thick pentacene layer on
373
Fig. 1. Device structures with either anodically grown (a) or sol–gel
deposited HfO2 (b).
HfO2 at a rate of 0.02 nm/s. The process is completed by
the deposition of gold source and drain electrodes on the
pentacene. Two set of devices were processed with different
gate length L and width W, either a standard geometry
with L = 120 lm and W = 1 mm or an interdigited struc-
ture with L = 115 lm and W = 19 mm. The devices were
characterized in ambient atmosphere on a probe station
with two Keithley 2400 Source-meters driven under Lab-
view environment. Fig. 1 reports the device structure with
anodic (a) and sol–gel (b) HfO2. In the case of sol–gel oxi-
des, it is noticeable that a very thin SiO2 layer was present
at the interface between Si and HfO2 resulting from Si oxi-
dation during the post deposition annealing process of
HfO2. The influence of this layer on device leakage will
be discussed further.
3. Results and discussion
3.1. Anodically grown HfO2
Fig. 2 reports the evolution of the anodization voltage as
a function of time for a constant current density (0.2 mA/
cm2). The thickness of HfO2 films for VA = 25 and 50 V is
shown. The anodization ratio is found to be 1.8 nm/V
between 25 and 50 V in accordance with results of the
120
HfO2 in 0.1M tartaric acid + ethylene glycol
I = 0.2 mA/cm2
100
Anodization Voltage (V)
80
60
85.6 nm
40
40.1 nm
20
0
0 2 4 6 8 10 12
Time (min)
Fig. 2. Time–voltage evolution in the electrochemical cell during the
anodic growth of HfO2 in a 0.1 M tartaric acid solution. The thickness of
two HfO2 layers used in this study are reported for given anodization
voltages of respectively 25 and 50 V.
374 J. Tardy et al. / Microelectronics Reliability 47 (2007) 372–377

Table 1
Thickness, refractive index, gate capacitance and dielectric constant of
-0.03
HfO2 films for two values of anodization voltage VA (25 and 50 V) Vg = -1.5V
VA (V) 25 50
d (nm) 40.1 85.6 -0.02

Id (μA)
n (at k = 700 nm) 1.99 1.92
Cox (nF/cm2) 469.4 217.2 -0.01
er 21.3 22.2 Vg = -1V

0.00
Vg = 0 and -0.5V
literature with H3PO4 and H2SO4 based solutions [13]. In
0.01
the same reference, a decreased anodization ratio is found
above 50 V attributed to crystallization with oxygen evolu- 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4 -1.6
tion and accumulation of stress in the films (sometimes up (a) Vd (V)
to breakdown). Table 1 summarizes the optical and electri-
cal properties of HfO2 films grown at VA = 25 and 50 V. 0.18 0.1

The refractive index is in the range 1.99–1.92 and seems

Log Drain current (µA)

0.16 0.01

to decrease with the thickness as previously observed on 1E-3

0.14
anodic Ta2O5 [14]. This could be explained by an increased 1E-4
0.12
porosity with film thickness. This is however not corrobo-

IIdI1/2 (μA1/2 )
1E-5
0.0 -0.4 -0.8 -1.2 -1.6
0.10
rated by the C–V measurements which gives higher er at Gate voltage (V)

0.08 Vd = -1V
50 V. This point is still somewhat unclear but could be μ = 0.022 cm2/V.s
related to the fact that anodic Ta2O5 is generally amor- 0.06

phous whereas anodic HfO2 is known to be crystalline. 0.04

At increasing oxide thickness, some structural changes
might occur in HfO2 films leading to modified optical char-
acteristics. The refractive index also seems to be strongly
dependent on the nature of the electrolyte. For instance,
lower n (n = 1.82–1.85 for HNO3 1 M) and higher n
(n = 2.07 in H3PO4 and H2SO4 1 M) were reported [13].
Fig. 3 gives typical output characteristics (a) and the
transfer
pffiffiffiffiffi characteristics (b). This latter is plotted as
I D ¼ f ðV G Þ in the saturation regime to estimate the
mobility l and the threshold voltage VT according to the
standard expression: I D ¼ lC ox 2L W
ðV G  V T Þ2 , where W
and L are the gate width and length respectively and
VD  (VG  VT). It must be mentioned that l is
strongly gate voltage dependent in polycrystalline OFETs
which
p ffiffiffiffiffi is not taken into account in a determination from
I D ¼ f ðV G Þ. Fig. 3(a) shows that OFETs with HfO2 insu-
lators operate at a voltage as low as 1 V. The characteristics
were recorded by ramping the gate voltage up then down to
evidence instabilities in devices. We observe a limited but
unavoidable hysteresis. This is often observed in OFETs
with high-k oxides. From the transfer characteristics
(Fig. 3(b)), we deduce a threshold voltage VT = 0.75 V
and a maximum mobility l ffi 2.2 · 102 cm2/V s. In insert
is reported the same characteristics in semilog representa-
tion which shows that the onset voltage is 0.5 V and the
on–off ratio is higher than 103. The mobility is lower than
generally observed for pentacene on anodic high-k oxides
[3,7] and could be related to properties of pentacene/
HfO2 interface. Recent results indeed show that pentacene
on anodic HfO2 is poorly organized as assessed from the
low intensity of XRD diagrams [15]. Furthermore, the
oxide surface roughness is pretty high (2 nm) as com-
pared to what obtained on anodic Ta2O5. A perturbed
growth of pentacene is also known to produced traps at
0.02
0.00
0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4 -1.6
(b) Vg (V)
Fig. 3. Output (a) and transfer characteristics (b) for a pentacene OFETs
with HfO2 oxide grown by anodic oxidation at VA = 25 V (close
symbol = ramp up, open symbol = ramp down).
the interface. Work is in progress towards a deeper under-
standing of the relationship between the surface properties
of anodic HfO2 and the morphological and structural
properties of evaporated pentacene.
3.2. Sol–gel HfO2
Fig. 4 reports a RBS spectrum of a 20 nm thick HfO2
film. Rutherford backscattering was carried out with
2 MeV He+ ions. The spectrum shows two important fea-
tures corresponding to peak deformation at the back side
of the Hf peak and at the Si edge. Porosity of the film is
thought to be the reason of these spectra deformations.
From the area of Hf peak we can deduce the total number
of atoms/cm2 and as we know the film thickness from
ellipsometry spectroscopy, the density of the HfO2 film
can be easily deduced. It is found that the film density is
about 40% of that of bulk material. This result is in excel-
lent agreement with the measure of the dielectric constant,
er = 11, from admittance spectroscopy. After correction for
a 2.5 nm thick SiO2 interfacial layer, this value is corre-
sponding to that of an effective medium made of 45%
HfO2 and 55% air. The film porosity is clearly evidenced
on cross section transmission electron microscopy (XS-
TEM) photographs shown in Fig. 5. The photograph
 J. Tardy et al. / Microelectronics Reliability 47 (2007) 372–377 375

13000 -16 Vg= -2.4 V

line: ramp up
12000 annealing at 450°C Hf
-14 squares: ramp down
11000
10000 -12
deformation
Counting yield (a.u.)

9000 -10
of Si peak

Id (μA)
8000 O
-8
7000
deformation -6
6000 Vg= -1.6 V
of Hf peak
5000 -4
4000
-2
3000 Si Vg= -0.8 V
2000 0
Vg= 0 V
1000 2
0 0.0 -0.5 -1.0 -1.5 -2.0
200 300 400 500 600 700 800 900 (a) Vd (V)
Channel number

Fig. 4. Rutherford backscattering (RBS) spectrum of a 2 MeV He+ ions

on a 20 nm thick HfO2. The porosity of the film is clearly evidenced from 1E-5
the Si edge and the shape of the Hf peak. VD = -1.5 V

1E-6

Log ID (μA)
1E-7

1E-8
Von

0.0 -0.5 -1.0 -1.5 -2.0 -2.5

(b) VG (Volts)

Fig. 6. Output (a) and transfer (b) characteristics of OFETs with a 20 nm

thick sol–gel deposited HfO2 gate oxide. The transfer characteristics is
recorded in the saturation regime.

Fig. 5. XS-TEM image of a spun on 20 nm thick HfO2 film. The

crystallites size is less than 10 nm and the pores are 2–4 nm dia (average: dependence of the mobility in the linear regime
2.4 nm). (VD = 0.2 V) is reported in Fig. 7. The mobility is
deduced from the relation:

reveals a nanoporous material with pore diameter between

2 and 4 nm, with an average at 2.4 nm. The size of the crys-
tallites is 10 nm at most. An enlarged view (not shown) can
reveal that some grains are crystalline. 0.14
Fig. 6 shows output (a) and transfer (b) characteristics VD = -0.2V
0.12
of OFETs with a HfO2 insulator deposited by sol–gel.
Mobility μ (cm 2 / V.s)

The operating voltage of that OFET is very low (about 0.10

1 V). The gate leakage current at low voltage (determined
relatively to a normalized to the maximum drain current) 0.08

is also observed to be much smaller than that with anodic 0.06

HfO2. Furthermore, the characteristics do not show any
hysteresis when VD is ramped up and down. The thin 0.04

SiO2 layer at the interface with Si-p++ substrate may 0.02

account for by this improved gate leakage. Fig. 6(b) reports
the transfer characteristics in a semilog plot in the satura- 0.00
tion regime. The on–off ratio is limited to about 5 · 103 0.0 -0.5 -1.0 -1.5 -2.0
because of leakage either due to the use of a very thin VG (Volts)
HfO2 oxide but also to a not optimized device design. A
threshold voltage of 0.3 V is observed. The gate voltage Fig. 7. Gate voltage dependence of the hole mobility in the linear regime.
376 J. Tardy et al. / Microelectronics Reliability 47 (2007) 372–377

gm L 0.5
l¼ where gm is the transconductance given by bias stress: VG = -2V
WC i V D
  0.4
bias stress: VG = +2V
oI DS 

gm ¼   . 0.3 VD = -0.2V

Threshold voltage shift (V)

oV  G V DS ¼C ste
0.2
The data are not corrected for the contact resistance which 0.1
may be the cause of l leveling at high VG [16]. The highest
0.0
mobility is 0.13 cm2/V s. This is similar to that previously
observed with a 80 nm thick evaporated Ta2O5 [8] under -0.1

otherwise identical transistor process conditions. -0.2

The stability of the devices has been assessed upon -0.3
applying a gate voltage bias stress. The threshold voltage
-0.4
shift upon application of a gate bias stress in organic tran-
sistors was previously reported [17,18]. The way the -0.5
0 2 4 6 8 10
organic semiconductor is deposited [19] or the oxide sur- Stress time (minutes)
face is functionalized [20] were also shown to influence
the threshold voltage by modifying the trap states at the Fig. 9. Shift of the threshold voltage as a function of stress time for
interface. The experiment is conducted as follows: a trans- positive and negative gate bias stress.
fer characteristics ID  VG is first recorded with a low drain
bias (VD = 0.2 V) so as to remain in the linear regime. Then and positive (VG = +2 V) stress biases were investigated
the device is biased at a constant gate voltage for a deter- and stress periods span from 1 to 10 min.
mined period of time, after which a transfer characteristics The application of a negative stress is shown in Fig. 8(a).
is recorded from VG = 0 to 2 V. Negative (VG = 2 V) We can observe that the mobility is remaining almost con-
stant upon bias stress, besides an unexplained increase after
2 min stress. The threshold voltage is negatively shifted
-2.5 upon stress indicating of some charge trapping. The local-
Stress Voltage VG = -2V:
2
initial µ = 0.12 cm /V.s ization of traps is not known at the moment. They may be
-2.0 2
2 min µ = 0.25 cm /V.s located either at the interface between the oxide and the
2
5 min µ = 0.12 cm /V.s
pentacene or in the oxide. Traps may also be resulting from
Drain current (µA)

-1.5 2
10 min µ = 0.14 cm /V.s
reversible structural change in pentacene as pointed out in
Ref. [2]. In this latter, the threshold voltage shift was more
-1.0 VD = -0.2V pronounced after a positive bias than after a negative one.
This not observed in this work, where the magnitude of the
shift is about the same whatever the sign of the gate stress
-0.5
is. The time dependence of the threshold voltage shift is
reported in Fig. 9 for positive and negative stress. The shift
0.0 follows a time dependence of the form: jDVTj / tc where
0.0 -0.5 -1.0 -1.5 -2.0
c ffi 0.15 for positive or negative stress. In Ref. [2], the c fac-
(a) Gate voltage (V) tor was reported to be 0.06 and 0.22 for negative and posi-
tive stress respectively. Fig. 8(b) shows a positive threshold
VD = -0.2V
voltage shift. This would indicate that charges initially
-2.0
trapped at the interface could be released and participate
Stress at VG = +2V for various time periods: to the drain current upon applying a positive gate voltage
stress. The mobility is not changed in the process. The ori-
Drain current (μA)

-1.5 initial: µlin = 0.125 cm2/V.s

1 min µlin = 0.13 cm2/V.s gin of these trapped charges is not known so far and more
5 min µlin = 0.136 cm 2/V.s detailed investigations are needed to unveil the origin of
-1.0
10 min µlin = 0.13 cm2/V.s traps so as to improve of the stability and the reliability
of organic FETs.
-0.5
VT shift
4. Conclusions

0.0 This paper reported recent results on HfO2 as gate oxide

0.0 -0.5 -1.0 -1.5 -2.0 for organic FETs. HfO2 was either grown by anodic oxida-
(b) Gate voltage (V) tion of an evaporated Hf film or deposited by the sol–gel
Fig. 8. Evolution of the transfer characteristics upon bias stress at VG =
method. The latter process leads to nanoporous films. Elec-
2 V (a) and VG = +2 V (b). The drain voltage is kept at VD = 0.2 V trical performances of devices have been shown to be
and the characteristics are recorded in the linear regime. dependent on the oxide deposition process. Anodization
 J. Tardy et al. / Microelectronics Reliability 47 (2007) 372–377
leads to device showing some lack of stability attributed to
charge trapping due to polarization effect because of the
high dielectric constant of the insulator. Nanoporous sol–
gel processed HfO2 films exhibit a dielectric constant
er = 11 after annealing at 450 C and the performances of
the devices are excellent. Nevertheless, this is not really a
low temperature process and this technology is restricted
to glass substrates and cannot be compatible with a all
plastic process. To our knowledge, this is the first report
of HfO2 for OFETs applications. Bias stress effect was
investigated on pentacene transistors with sol–gel HfO2
gate oxide. Long term trapping was evidenced in agreement
with previously published data. Work is in progress to a
more exhaustive understanding of the drift mechanisms
and stability in OFETs.
Acknowledgements
This work is partly supported by the French Ministry of
Research through a project ACI, #ECD-121. One of us
(M.E.) thanks the French Ministry for a PhD grant-
in-aid. Mr. B. Devif is acknowledged for ellipsometry
measurements.
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