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CERAMICS
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Ceramics International 42 (2016) 138–145
[Link]/locate/ceramint
Evolution of microstructural and electrical properties of sputtered HfO2
ceramic thin films with RF power and substrate temperature
K.C. Dasa, S.P. Ghosha, N. Tripathya, D.H. Kimb, T.I. Leec, J.M. Myoungb, J.P. Kara,n
a
Department of Physics and Astronomy, National Institute of Technology, Rourkela 769008, India
b
Department of Materials Science and Engineering, Yonsei University, Seoul 120749, Republic of Korea
c
Department of Bio-Nanotechnology, Gachon University, Gyeonggi-do 461701, Republic of Korea
Received 24 April 2015; received in revised form 6 August 2015; accepted 7 August 2015
Available online 21 August 2015
Abstract
Hafnium oxide (HfO2) ceramic thin films were deposited on p-type silicon substrate by radio frequency magnetron sputtering at various RF
powers and substrate temperatures. The morphological and electrical properties of the sputtered films were investigated and a correlation between
the surface and interface properties of the HfO2 films was established with the variation of sputtering parameters. The evolution of monoclinic
structure of the hafnium oxide thin films was observed by XRD studies. The surface of the HfO2 ceramic thin films became smooth with the
decrease in grain size for higher power and growth temperature. The characteristic FTIR absorption peaks in the range from 550 cm 1 to
900 cm 1 depicted the formation of Hf–O bond for all the samples. The oxide charge density and leakage current density was found to be
increased with the increase in RF power and substrate temperature, which was mainly due to the evolution of smaller grains. HfO2 thin films,
grown at room temperature with a RF power of 150 W, have shown better electrical properties.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: Hafnium oxide; Ceramic thin films; Sputtering; SEM; C–V
1. Introduction good thermal and chemical stability, high dielectric constant,
low leakage current and excellent mechanical properties
In recent years, tremendous research on the development of [2,6–13]. In addition, HfO2 thin film has ability to reduce
high quality Zirconia (ZrO2), Hafnia (HfO2), Titania (TiO2) the mobility of 2-D semiconductor based transistors due to the
ceramic thin films are under active consideration in order to suppression of both charged impurity scattering as well as
replace the conventional low-k dielectric material such as SiO2 phonon scattering [14–15]. Therefore, an extensive research on
[1–3]. However, ZrO2 thin films are not compatible with the development of high quality HfO2 ceramic thin film is
polysilicon gate electrode because of formation of Zr-silicide, highly required prior to its incorporation into the low-
which in fact gives rise to high leakage current and electrical dimensional semiconductor technology. Various methods such
shorting of the poly/ZrO2 metal oxide semiconductor (MOS) as Pulsed Laser Deposition [16], Chemical Vapor Deposition
capacitors [4]. On the other hand, TiO2 thin films are not [17], e-beam evaporation [18] and radio frequency (RF)
thermodynamically stable with silicon for electronic applica- magnetron sputtering [19] were adopted to deposit the HfO2
tions [5]. Therefore, hafnium oxide (HfO2), a high temperature films on the silicon substrate. Among them, RF magnetron
refractory ceramic material, has drawn great interest in the field sputtering technique has several advantages such as low
of structural ceramics, optics, electronics and electroceramics thermal budget, ease of handling, less consumption of source
due to its high density ( 10 g/cm3), wide bandgap (4 5 eV), materials, nontoxic nature, possibility of multi-target proces-
sing, good reproducibility and ability to produce films of better
n
Corresponding author. Tel.: þ91 661 2462732; fax: þ 91 661 2462721. quality. The electrical properties of the ceramic thin films not
E-mail address: karjp@[Link] (J.P. Kar). only depend on the methods of fabrication, but also mostly
[Link]
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
K.C. Das et al. / Ceramics International 42 (2016) 138–145 139
depend on the growth parameters. Therefore, a systematic force microsope (Asylum research system). Fourier transform
study on the evolution of microstructural properties of HfO2 infrared spectroscopy (FTIR) studies were carried out using
ceramic thin film is utmost important in order to understand its Thermo scientific Nicolet 6700 system in order to get the
electrical behavior. In the present work, microstructural and bonding information. The MOS capacitors were fabricated,
electrical properties of the HfO2 thin films are investigated and through shadow mask, by thermal evaporation technique with
correlated with the variation in the sputtering parameters such Al as top and bottom electrodes. The capacitance–voltage (C–V)
as RF power and substrate temperature. and leakage current density–voltage (J–V) measurements for the
Al/HfO2/Si MOS structures were performed using an Agilent
E4980A precision LCR meter and Keithley 6487 Picoammeter/
2. Experimental Voltage source, respectively.
Hafnium oxide thin ceramic films were deposited by RF 3. Results and discussion
magnetron sputtering technique on p-type silicon [(100),
1–10 Ω cm] wafers using pure hafnium target (99.995%) in Fig. 1(a) shows the XRD patterns of the HfO2 thin films
presence of high purity argon and oxygen gases at a flow ratio deposited at different RF powers on silicon substrates. A weak and
of 3:2. Ceramic thin films were sputtered at 4 10 3 mbar by broad 111 peak is observed for all the samples, which is
varying RF power from 75 W to 300 W. Thereafter, a series of attributed to the monoclinic phase of HfO2 films [20]. Similar
experiments were performed by varying substrate temperature results are obtained by other researchers [21,22]. The broadening
from room temperature to 300 1C. During the entire deposition of weak diffraction peaks signifies the existence of a mixed
process, the substrates were rotated in order to obtain uniform structure of amorphous and crystalline phase in the ceramic thin
ceramic thin films. The thickness of HfO2 films was kept films, where small crystallites being present in an amorphous
around 20 nm. matrix as reported
The structural properties of HfO2 ceramic thin films were by Vargas et al. [21]. The appearance of only
dominated 111 may be due to the lower film thickness, where
investigated by X-ray diffraction system (Rigaku ultima IV), the initial few interfacial Hf–O–Si layer may have amorphous like
whereas the morphological studies were carried out using behavior, which limits the growth of other crystalline phases
scanning electron microscope (JEOL JSM-7001F) and atomic [21,23]. The presence of the anisotropy nature in the crystalline
material is due to the differences in the strain energy densities,
which varies with the variation of the crystalline direction. Hence,
the growth favors such a direction, where the strain energy
becomes minimum [23]. The appearance of 111 orientation of
HfO2 films may be due to the minimizations of the internalstrain-
energy in the film during the film growth. The 111 peak
intensity marginally improved with power, which may be due to
the increase in adatoms energy at higher RF power. Fig. 1(b)
indicates the evolution of HfO2 111 peak at various substrate
temperatures. However, the increase in substrate temperature did
not show any significant improvement on the crystallinity of the
sputtered ceramic films.
The SEM images of HfO2 thin films, deposited at various
RF powers, are shown in Fig. 2. Uniform surface morphology
with homogeneously distributed grains is observed for the
sputtering power of 300 W. SEM micrographs of HfO2 films
with different substrate temperatures are shown in Fig. 3,
where a uniform surface morphology is observed for the films
deposited at higher substrate temperature. The average grain
size was decreased from 30 nm to 24 nm with the increase in
RF power, whereas a reduction in the average grain size from
32 nm to 19 nm is observed for the rise in substrate tempera-
ture. The three dimensional (3-D) surface topography and
atomic structures were examined using atomic force micro-
scopy with a scanning area of 1 μm 1 μm. The AFM
micrographs of the features of HfO2 film deposited by different
RF power and substrate temperature are shown in the Fig. 4
and Fig. 5 respectively. The root mean square (RMS) rough-
ness was estimated by using the standard expression [24]. The
Fig. 1. XRD patterns of the HfO2 thin films deposited at different (a) RF estimated RMS roughness of the ceramic thin films is plotted
powers, and (b) substrate temperatures. in Fig. 6 with different sputtering parameters, where the
140 K.C. Das et al. / Ceramics International 42 (2016) 138–145
Fig. 2. SEM images of HfO2 thin films grown at various RF powers (a) 75 W, (b) 150 W, (c) 225 W, and (d) 300 W. The scale bar represents 100 nm.
Fig. 3. SEM images of HfO2 thin films grown at various substrate temperatures (a) Room temperature, (b) 100 1C, (c) 200 1C and (d) 300 1C. The scale bar
represents 100 nm.
surface roughness is found to be decreased with increase in related to two competitive processes. One is the nucleation of
both RF power and substrate temperature. This result agrees the sputtered particles and another is the growth of the
well with the SEM observation. This phenomenon can be crystallites. When the nucleation is predominant, the sputtered
K.C. Das et al. / Ceramics International 42 (2016) 138–145 141
Fig. 4. 3-D AFM images of HfO2 thin films at various RF powers (a) 75 W, (b) 150 W, (c) 225 W, and (d) 300 W.
Fig. 5. 3-D AFM images of HfO2 thin films grown at various substrate temperatures (a) Room temperature, (b) 100 1C, (c) 200 1C and (d) 300 1C.
particles on the surface of the growing film is trapped into the enhanced kinetic energy of the incoming species. The surface
nuclei prior to a sufficient diffusion, thus this process will give of the larger nuclei may be simultaneously stroke by the
rise to a large number of newly created smaller grains instead energetic species during the film deposition in order to form
of the growth of the existing crystallites. On the other hand, the smaller grains at higher power. The reduction of surface
deterioration in the grain size with RF power may be due to the roughness with rise in substrate temperature may be explained
142 K.C. Das et al. / Ceramics International 42 (2016) 138–145
Fig. 6. Variation of RMS Roughness as a function of (a) RF powers, and (b)
substrate temperatures.
by the enhancement of adatom mobility as a result of higher Fig. 7. FTIR transmittance spectra of the HfO2 thin films deposited at various
thermal energy. These adotoms with higher mobility move on (a) RF powers, and (b) substrate temperatures.
the surface of the substrate to fill the existing vacant, which in
fact gives rise to the formation of smaller grains instead of distinctly visible, which are formed due to the variation in the hole
agglomeration with the existing grains. Thus, the surface concentrations at the interface with the sweep in bias voltage. The
became smooth at higher temperature with the reduction of negative shift in the C–V curves with the increase in RF power
grain size. indicates an increase in the positive oxide charges density.
FTIR spectroscopy studies were carried out to obtain Hf–O Important electrical properties of HfO2 films such as oxide charge
bond information at various RF powers and substrate tempera- density, HfO2/Si interface state density were evaluated from these
tures. Fig. 7(a) shows the FTIR spectra of HfO2 thin films curves. The oxide charge density (Qox) was calculated from the
grown at different RF power. The spectra were taken between shift in flatband voltage, where as the interface state density (Dit),
500 and 1200 cm 1 as the low wavenumber region is more was calculated from the stretch out of the C–V curves using the
important for detection of Hf–O related bonds. A broad feature Terman method [27]. The estimated Qox and Dit for various RF
corresponding to the vibration modes of Hf–O is appeared powers are plotted in Fig. 9(a). The oxide charge density varied
between 550 cm 1 and 900 cm 1 [25,26]. The distinct broad from 4.5 1011 to 3.79 1012 cm 2 with the increase in RF
and asymmetric peak, observed in the range of 580–630 cm 1, power from 75 W to 300 W. The variation in electrical behavior
is related to the amorphous and crystalline nature of HfO2 can be correlated to the microstructural evolution. The grain
films, whereas rest of the peaks (738 cm 1 and 783 cm 1) boundaries consist of large number of defects such as dangling
correspond to the HfO2 monoclinic phase. These results are bonds and impurities, which generally act as trapping centers.
well agreed with the XRD studies. A broad peak, centered at Ceramic films of smaller grains contain large grain boundaries and
1108 cm 1, corresponds to the stretching mode of Si–O–Si hence more number of trapping centers is available for capturing
bond. Fig. 7(b) shows the similar behavior for the films grown of free carriers. Therefore, there is an enhancement of the oxide
at various temperatures indicating the formation of Hf–O charge density with the rise in RF power. The effect of substrate
bonds. temperatures on the C–V characteristics of HfO2 films are shown
The normalized high frequency (1 MHz) C–V curves of Al/ in Fig. 8(b). There is a marginal negative shift of the C–V curves
HfO2/Si structures are plotted in Fig. 8(a). Three regions of the for higher temperatures. As shown in Fig. 9(b), Qox was found to
C–V graph, namely accumulation, depletion and inversion are be increased with the rise in substrate temperature, which may be
K.C. Das et al. / Ceramics International 42 (2016) 138–145 143
has a lower value for the films deposited at 150 W, which signifies
a better interface between the HfO2 thin film and the silicon
substrate. Annihilation of the dangling bonds, interface defect
densities and/or improvement in the microstructural relaxation at
the interface is the causes for the reduction of Dit values. At lower
RF power, the adatoms may not have sufficient energy to form a
stoichiometric smooth interfacial layer resulting higher Dit. On the
other hand, the increase in Dit values at higher power may be due
to the bombardment of high energetic ionic species with the
substrate surface and produce distorted rough layers during the
very initial stage of the ceramic film growth [29]. On the other
hand, the rise in Dit with substrate temperature may be due to the
incorporation of impurities, thermal mismatch and/or the stoichio-
metric change at the films and the substrates during the initial
stage of film growth (Fig. 9(b)) [29]. In addition, Yu et al has
reported the increase in Dit with substrate temperature is due to the
breaking of interfacial Si–H bond, down diffusion of Hf into SiO2
and high interface roughness [30]. However, a systematic
investigation is required in order to understand the change in
stoichiometry at the initial stage of film growth, which is the scope
of future research.
Current density–voltage (J–V) studies of hafnium oxide thin
films on silicon substrate with different power are plotted in
the Fig. 10(a). Leakage current of all the samples initially is
increased rapidly with an increase in applied gate voltage up to
Fig. 8. Capacitance–voltage characteristics of HfO2 films grown at various (a) 2 V, thereafter it increased very slowly with the applied gate
RF powers, and (b) substrate temperatures. voltage. This ‘quasi-saturation’ nature of the current density
may be due to the charge trapping, which leads to the creation
of an internal electric field. This internal electric field opposes
the applied electric field and subsequently limits the carrier
conduction [31]. The leakage current density is found to be
maximum at higher RF power of 300 W, which may be due to
the generation of additional interface defect densities as a
result of high energetic ion bombardments with the substrate
surface. In addition, the evolution of smaller grains at higher
RF powers may be one of the reasons behind the higher
leakage current, where smaller grain boundaries provide
additional conduction paths for the enhancement of leakage
current. As shown in Fig. 10(b), the J–V characteristics of Al/
HfO2/Si structures have shown similar trend with variation in
substrate temperature.
4. Conclusion
A preliminary study has been carried out to correlate the
electrical properties of HfO2 ceramic films with its morphology
by varying sputtering parameters. The evolution of monoclinic
structure of the HfO2 thin films was observed by XRD studies.
The formation of Hf–O bond was seen from FTIR spectra. The
surface and interface investigation of the films were carried out
for using SEM and C–V measurements. The surface roughness
as well as average grain size of the HfO2 films was decreased
Fig. 9. Variation of oxide and interface charge densities of HfO2 films with (a)
with the decrease in grain size for both high power and high
RF powers, and (b) substrate temperatures.
temperature growth. The oxide charge density, interface trap
due to the reduction in grain size. On the other hand, the stretch density and leakage current density was found to be maximum
out of the C–V curves at the accumulation–inversion region for high power and high growth temperature, which was
determines the interface properties [28]. As shown in Fig. 9(a), Dit mainly due to the evolution of smaller grains. The smaller
144 K.C. Das et al. / Ceramics International 42 (2016) 138–145
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This work was supported by the Department of Science and 700–705.
Technology (DST), India sponsored Indo-Korea project (INT/ [19] Flora M. Li, Bernhard C. Bayer, S. Hofmann, J.D. Dutson,
Korea/P-16/2013) and partly supported by DST Science and S.J. Wakeham, M.J. Thwaites, W.I. Milne, A.J. Flewitt, High-k
Engineering Research Board (SERB) project (SR/FTP/PS-099/ (k ¼30) morphous hafnium oxide films from high rate room temperature
2012) under Fast Track Scheme for Young Scientist. This deposition, Appl. Phys. Lett. 98 (2011) 252903.
[20] J. Aarik, A. Aidla, H.M. andar, V. Sammelselg, T. Uustare, Texture
research was also supported by the International Research & development in nanocrystalline hafnium dioxide thin films grown by
Development Program of the National Research Foundation of atomic layer deposition, J. Cryst. Growth 220 (2000) 105.
Korea (NRF) funded by the Ministry of Science, ICT & Future [21] M. Vargas, N.R. Murphy, C.V. Ramana, Tailoring the index of refraction
Planning (Grant number: 2012K1A3A1A19038371). of nanocrystalline hafnium oxide thin films, Appl. Phys. Lett. 104 (2014)
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