J Mater Sci: Mater Electron

DOI 10.1007/s10854-015-3179-9

Surface and interface studies of RF sputtered HfO2 thin films

with working pressure and gas flow ratio
K. C. Das1 • S. P. Ghosh1 • N. Tripathy1 • G. Bose2 • A. Ashok3 • P. Pal3 •

D. H. Kim5 • T. I. Lee4 • J. M. Myoung5 • J. P. Kar1

Received: 20 February 2015 / Accepted: 22 April 2015

Ó Springer Science+Business Media New York 2015

Abstract In this work, hafnium oxide (HfO2) thin films 1 Introduction

were deposited on p-type silicon substrate by radio fre-
quency magnetron sputtering at various working pressure In recent years, there is a great demand for the fabrication
ranging from 4 9 10-3 to 1 9 10-2 mbar and Ar/O2 flow of low cost, portable, low power operated, high efficiency
ratio from 1:4 to 4:1. The morphological and electrical electronic devices [1]. In order to meet these requirements,
properties of the sputtered films were investigated and a scaling down of complementary metal oxide semiconduc-
correlation between the surface and electrical properties of tor (CMOS) technology is highly preferred. However,
the HfO2 films was established with the variation of sput- conventional SiO2 gate dielectric (low-k) has reached the
tering parameters. The evolution of monoclinic structure of maximum operational limit during the downscaling of the
the hafnium oxide thin films was observed by XRD studies. CMOS devices. In order to overcome this problem, con-
The surface of the HfO2 films became rough with the in- siderable research on the growth and characterizations of
crease in grain size at the sputter pressure of 8 9 10-3 high-k dielectric materials such as Ta2O5, TiO2, ZrO2,
mbar and Ar/O2 gas flow ratio of 1:4. The formation of HfO2 are currently under consideration [2–4]. Hafnium
HfO2 bond was seen from FTIR spectra. The oxide charge oxide (HfO2) is considered as a promising candidate be-
density has a lower value for the sputter pressure of cause of its relatively higher dielectric constant, wide
8 9 10-3 mbar and Ar/O2 gas flow ratio of 1:4 due to the bandgap and high temperature stability [5–7]. In addition,
evolution of larger grains. The interface charge density was HfO2 is also found to be a promising candidate for sensor
found to be minimum at a sputter pressure of applications [12]. A portable, low cost, robust electronic
8 9 10-3 mbar. device can be fabricated through the monolithic integra-
tion, where HfO2 film will act as gate dielectric as well as
sensing material. Therefore, a systematic study on the
surface and interface properties HfO2 films with different
growth parameters is utmost important prior to its appli-
& J. P. Kar cations in solid state devices. Various methods such as
karjp@[Link]
Pulsed Laser Deposition [8], Chemical Vapor Deposition
1
Department of Physics and Astronomy, National Institute of [9–11], e-beam evaporation [12] and radio frequency (RF)
Technology, Rourkela 769008, India magnetron sputtering [13–16] are adopted to deposit the
2
Department of Electronics and Instrumentation Engineering, HfO2 film on the silicon substrate. Among them, RF
SOA University, Bhubaneswar 751030, India magnetron sputtering technique has several advantages
3
Department of Physics, Indian Institute of Technology such as low thermal budget, ease of handling, less con-
Hyderabad, Yeddumailaram 502205, India sumption of source materials, nontoxic nature and possi-
4
Department of Bio-Nanotechnology, Gachon University, bility of multi-target processing. During a sputtering
Gyeonggi-do 461701, Republic of Korea process, the sputtering gas is used for knock out of target
5
Department of Materials Science and Engineering, Yonsei atoms, where as reactive gases are used to form the final
University, Seoul 120749, Republic of Korea compound after the reaction with the sputtered species.

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Therefore, the working pressure and sputter gas/reactive

gas ratio has a great impact on the growth kinetics, which
gives rise to the variation in the morphological and elec-
trical properties of the sputtered films. In the present work,
the influence of sputtering pressure and Ar/O2 gas flow
ratio on the morphological and electrical properties of the
HfO2 thin films are systematically investigated and
correlated.

2 Experimental works

Hafnium oxide thin films were prepared by RF magnetron

sputtering process using pure hafnium target (99.995 %) at
different sputtering pressures ranging from 4 9 10-3 to
1 9 10-2 mbar and Ar/O2 flow ratio varying from 1:4 to
4:1. P-type silicon (100) wafers (q * 1–10 X cm) were
used as substrate material. During the entire deposition
process, the sputtering power was kept at 150 W. The
thickness of the films was found to be around 20 nm.
The structural properties of HfO2 thin films were studied
by X-ray diffraction system (Rigaku ultima IV). The
morphological studies of the sputtered films were carried
out by scanning electron microscope (JEOL JSM-7001F)
and atomic force microscope (Asylum research system). In
order to get the bonding information, fourier transform
infrared spectroscopy (FTIR) studies were carried out using
Thermo scientific Nicolet 6700 system. Thermally
evaporated aluminum metal dots of 1 mm diameter were
deposited through shadow mask technique to realize the Fig. 1 XRD patterns of the HfO2 thin films deposited at different
top electrodes in Al/HfO2/Si (MOS) structure. The ca- a sputtering pressure, and b Ar/O2 gas flow ratio
pacitance–voltage (C–V) and leakage current density–
voltage (J–V) measurements for the Al/HfO2/Si MOS flow ratio. This can be explained by the variation of
structures were performed by an Agilent E4980A precision sputtering rate with the gas flow ratios. The sputtering rate
LCR meter and Keithley 6487 Picoammeter/Voltage of HfO2 films for Ar/O2 flow ratio of 1:4 and 4:1 were 0.44
source, respectively. and 0.7 nm/min, respectively. At lower argon concentra-
tion, the deposition rate is slower due to the ejection of less
amount of hafnium atoms from the metallic target. In this
3 Results and discussion case, Hf atoms get enough time to react with oxygen due to
the time interval between the arrivals of sputtered species is
The X-ray diffraction (XRD) patterns of HfO2 films at longer. Thus, the adatoms get sufficient time to orient
different sputtering pressures are shown in Fig. 1a. The themselves in a preferred direction [18]. On the other hand,
broadening of diffraction peaks signifies that the thin films the evolution of additional diffraction peaks at higher argon
have a mixed structure of amorphous and crystalline phase. concentration may be due to the higher sputter rate, where
 Þ and (020) broad peaks are ascribed to the evo-
The ð111 the adatoms would not get enough time to orientation
lution of monoclinic phase of HfO2 [17]. Similar structural themselves in a preferred direction.
behavior is also observed for all the films grown at other The SEM images HfO2 thin films as a function of
working pressures. On the other hand, the films grown with sputtering pressure are shown in Fig. 2. As the sputtering
higher Ar/O2 ratio shows a different XRD pattern with the pressure increased from 4 9 10-3 to 8 9 10-3 mbar, the
 Þ, (111), (002), (211),
evolution of (110), ð111  (220), (221) average grain size was increased from 22 to 35 nm, re-

peaks (Fig. 1b). The evolution of ð111Þ and (020) broad spectively and it reduced with further increase in sputtering
peaks were observed for the films grown at a lower Ar/O2 pressure up to 1 9 10-2 mbar. The enhancement of the

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Fig. 2 SEM images of HfO2

thin films grown at various
sputtering pressures
a 4 9 10-3 mbar,
b 6 9 10-3 mbar,
c 8 9 10-3 mbar, and
d 1 9 10-2 mbar. The scale bar
represents 100 nm

Fig. 3 SEM images of HfO2

thin films grown at various Ar/
O2 gas flow ratios a 1:4, b 2:3,
c 3:2, d 4:1. The scale bar
represents 100 nm

grain size can be understood by analyzing the kinetics of mean free path. The sputtered species, having higher mean
the sputtered species during the plasma deposition. At free path, possess higher kinetic energy during their arrival
lower sputtering pressure, less amount of both sputtering at the silicon surface. The nuclei, initially formed at the
gas (Ar) and reactive gas (O2) are available in the sput- substrate surface, are stroked by the incoming energetic
tering chamber, which in fact results the enhancement in species during the film deposition. However, a complete

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Fig. 4 Variation of RMS roughness as a function of a sputtering

pressure, and b Ar/O2 gas flow ratio
Fig. 5 FTIR transmittance spectra of the HfO2 thin films deposited at
investigation on the atomic layer depositions of the HfO2 various a sputtering pressure, and b Ar/O2 gas flow ratio
thin films may explain the exact mechanism for variation in
the microstructural properties during the initial stage of the argon. Therefore, excess numbers of sputtered species
sputtering, which is the scope of future research. The rise in are readily available to the initially formed nuclei for their
the grain size with the increase of pressure up to 8 9 10-3 further growth. The average grain size of the sputtered thin
mbar may be due to the decrease in the mean free path of films grown at Ar/O2 gas flow ratio of 1:4 and 4:1 are
the sputtered species and kinetic energy get reduced as a estimated as 27 and 40 nm, respectively. The RMS surface
result of multiple collisions. On the other hand, as the roughness, measured at an area of 1 9 1 lm, is plotted in
sputtering pressure is increased beyond 8 9 10-3 mbar, the the Fig. 4. The surface roughness is followed the similar
mean free path was further decreased because of enormous trend as the variation of the grain sizes. The HfO2 thin
random collisions between the sputtered particles. There- films, deposited at the sputtering pressure of 8 9 10-3
fore, the deposition rate at 1 9 10-2 mbar has a lower mbar and Ar/O2 concentration of 4:1, has shown higher
value of 0.49 nm/min, where as the deposition rate at surface roughness, which agreed well with the SEM
4 9 10-3 mbar was found to be maximum (0.93 nm/min). studies.
Due to these random collisions, reduction in the kinetic Figure 5 shows the FTIR spectra of HfO2 thin films with
energies of the sputtered species takes place and as a result various sputtering pressures and the Ar/O2 flow ratio. The
deterioration in the grains size is occurred [19]. The SEM spectra were taken between 500 and 1200 cm-1 since the
images HfO2 thin films as a function of Ar/O2 flow ratio are low wavenumber region is more important for detection of
shown in Fig. 3. Rough granular surface morphology is hafnium-oxide-related bonds. A broad feature correspond-
observed with the evolution of the larger grains at higher ing to HfO2 film is appeared between 500 and 900 cm-1,
argon concentration. This may be due to the enhancement which corresponds to the vibration modes of Hf–O
in the sputter rate of hafnium with higher concentration of [20, 21]. FTIR spectra of all the samples show similar

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Fig. 6 Capacitance–voltage characteristics of HfO2 films grown at

various a sputtering pressure, and b Ar/O2 gas flow ratio. The inset of Fig. 7 Variation of oxide and interface charge densities of HfO2
a shows the schematic diagram of MOS structure films with a sputtering pressure, and b Ar/O2 gas flow ratio

characteristics except the films grown at the Ar/O2 flow (Fig. 7a). This may be due to the variation of the grain sizes.
ratio of 4:1. The broad peak, observed in the range of The trap centers such as defects, voids, unsaturated bonds,
580–640 cm-1, was significantly suppressed at higher ar- impurities are generally present at the grain boundaries
gon concentration indicating the reduction of Hf–O bonds. [23]. Films of smaller grains have large grain boundary
This may be due to the unavailability of sufficient amount surfaces and hence, more number of trapping centers is
of oxygen for the complete oxidation of the hafnium atoms available for capturing of free carriers. Annihilation in the
during the Ar/O2 flow ratio of 4:1. The peak became dis- surface area of the grain boundaries takes place with the
tinct for lower argon flow rate indicating the enhancement increase of granular dimensions and therefore, the defect
of Hf–O bonds. A broad peak, centered around 1108 cm-1, densities reduces with the increase in the average grain
corresponds to the stretching mode of Si–O–Si. sizes. Therefore, there is a reduction of the oxide charge
The normalized high frequency (1 MHz) C–V curves of density with the rise in sputtering pressure up to 8 9 10-3
Al/HfO2/Si (MOS) structures are plotted in Fig. 6, where mbar. Similar variation in the Qox is observed for different
HfO2 thin films are deposited at different sputtering pres- gas flow ratio due to the increase in grain sizes (Fig. 7b).
sure and gas flow ratio. The inset of Fig. 6a shows the The Qox is found to be increased beyond the pressure of
schematic diagram of MOS structure. The oxide charge 8 9 10-3 mbar, which may be due to the reduction in the
density (Qox) was calculated from the shift in flatband grain size. A abrupt increase in the Dit was observed for
voltage, whereas the interface state density (Dit) was cal- higher sputtering pressure and argon flow ratio. The en-
culated from the stretch out of the C–V curves using Ter- hancements of dangling bonds, interface defect densities,
man method [22] and plotted in Fig. 7. The oxide charge and/or interfacial stress at the HfO2/Si interface are the
density is found to be decreased with the increase in the causes of higher Dit. XRD and FTIR studies has shown that
sputtering pressure from 4 9 10-3 to 8 9 10-3 mbar there is some abrupt change in the structural properties of

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were grown on Si substrates by RF reactive magnetron

sputtering method at various working pressure ranging from
4 9 10-3 mbar to 1 9 10-2 mbar and different Ar/O2 gas
flow ratio varying from 1:4 to 4:1. The evolution of
monoclinic structure of the hafnium oxide thin films was
observed by XRD studies, where as the formation of HfO2
bond was seen from FTIR spectra. The broad peak, observed
in the range of 580–640 cm-1, was significantly suppressed
at higher argon concentration indicating the reduction of
Hf–O bonds. The surface and interface investigation of the
films were carried out for using SEM and C–V measure-
ments. The surface roughness of the HfO2 films was
decreased with the decrease in grain size. The oxide charge
density was maximum for lower working pressure and lower
Ar/O2 ratio, which was mainly due to the evolution of
smaller grains. HfO2 films have shown a lower interface
charge density at Ar/O2 flow ratio of 3:2.

Acknowledgments This work was supported by the DST, India

sponsored Indo-Korea Project (INT/Korea/P-16/2013) and partly
supported by SERB Project (SR/FTP/PS-099/2012). This work also
supported by the International Research and Development Program of
the National Research Foundation of Korea (NRF) funded by the
Ministry of Science, ICT and Future Planning (Grant number:
2012K1A3A1A19038371).

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