Journal of Alloys and Compounds 757 (2018) 288e297

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Analysis of the electrical properties and current transportation

mechanism of a metal oxide semiconductor (MOS) capacitor based on
HfGdO gate dielectrics
S.S. Jiang a, G. He a, *, Z.B. Fang b, **, P.H. Wang a, Y.M. Liu a, J.G. Lv c, M. Liu d
a
School of Physics and Materials Science, Radiation Detection Materials & Devices Lab, Anhui University, Hefei 230601, China
b
Department of Physics, Shaoxing University, Shaoxing 312000, China
c
Department of Physics and Electronic Engineering, Hefei Normal University, Hefei 230061, China
d
Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanostructure, Institute of Solid State Physics, Chinese Academy of
Sciences, Hefei 230031, China

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

Article history: The microstructure, optical and electrical properties of sputtering-derived HfGdO high-k gate dielectric
Received 14 November 2017 thin films as a function of the Gd doping content have been systematically investigated. X-ray diffraction
Received in revised form (XRD) measurements have indicated that Gd doping can form a new stable cubic phase. The optical band
7 May 2018
gap of the HfGdO gate dielectrics increases gradually from 5.82 to 6.14 eV as the Gd doping concentration
Accepted 8 May 2018
Available online 9 May 2018
increases. The electrical properties, such as permittivity, oxide trapped charge density, border trap charge
density and leakage current density of samples, are determined using a semiconductor device analyzer.
The formation mechanism of leakage current is also discussed in detail. In addition, the interfacial
Keywords:
High-k gate dielectrics
properties of HfGdO/Si gate satcks were tested to establish the electrical properties. The excellent op-
HfGdO toelectronic properties, such as the optical band gap of 5.95 eV, leakage current density of 8.33
108 A/
Electrical properties cm2 at a bias voltage of 2 V, oxide trapped charge density of 1.06
1012 cm2 and a border trap charge
Metal oxide semiconductor (MOS) density of zero and optimized interfacial properties were observed in the HfGdO thin films with sput-
transistors tering power of 30 W, indicating that it may become a potential high-k gate dielectric in future com-
Leakage current density plementary metal oxide semiconductor (CMOS) devices.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction device performance [10,11], which has strongly stimulated further

research to modify HfO2 and improve its electrical properties for
The continuous scaling down of metal oxide semiconductor potential application in advanced complementary MOS (CMOS)
(MOS) transistors makes it necessary to replace the conventional technology. It has been reported that the microstructure and
gate oxide SiO2 with high dielectric constant (k) dielectric materials electrical properties of high-k dielectric can be improved by
[1,2]. As a high-k dielectric material, HfO2 is widely used because of introducing rare earth metal elements into HfO2. When the intro-
its promising application in MOS field-effect transistors (MOSFET), duced atomic radius is greater than the Hf element, which is
capacitor dielectrics of dynamic random access memory, optical beneficial to the formation of steadily cubic phase of HfO2 at low
devices as well as thermal protective coating [3e6]. However, HfO2 temperatures and the enhancement of dielectric constant. As a rare
suffers from defects in these applications. Guha et al. [7] suggested earth element with an atomic radius greater than Hf, Gd has
that oxygen vacancies are the dominant intrinsic ionic defects in attracted extensive interests, particularly since Gd2O3 has attractive
nanoscaled films of HfO2 on silicon. Oxygen vacancies can degrade features, including comparable dielectric constant (~20) to mono-
the electrical properties by forming defect states [8,9], leading to clinic HfO2 [12], perfect lattice matching to Si [13], and thermo-
the trap-assisted leakage current and the degeneration of the dynamic stability on Si up to 1000  C [14]. In addition, Sementa
et al. [15] reported that the oxygen vacancy of HfO2 could be sup-
pressed by Gd doping. Also, Yim et al. [16] proposed that the flat
* Corresponding author. band voltage Vfb could be shifted negatively by introducing Gd
** Corresponding author. element into HfO2. However, the microstructure, optical and
E-mail addresses: hegang@[Link] (G. He), csfzb@[Link] (Z.B. Fang).

[Link]
0925-8388/© 2018 Elsevier B.V. All rights reserved.
 S.S. Jiang et al. / Journal of Alloys and Compounds 757 (2018) 288e297 289

electrical properties of Gd-doped HfO2 dielectric thin films device analyzer (Agilent B1500A; Alltests Instruments Inc., Farm-
deposited using a radio frequency (RF) reactive co-sputtering ingdale, NJ, USA) and Cascade Probe Station (Cascade Microtech,
method with Hf and Gd metal targets have not been investigated USA). All the electrical tests were required to short circuit and open
systemically. Moreover, the effect of Gd doping on the micro- circuit calibration, and carried out at room temperature in a dark
structure, optical band gap and leakage current is not well box. The details of the experimental procedure for Si wafer clean-
understood. ing, HGO films deposition and MOS device fabrication are shown in
In this paper, Gd-doped HfO2 (HGO) dielectric thin films are Fig. 1.
prepared using a RF reactive co-sputtering method. The micro-
structure, optical and electrical properties of the HGO dielectric 3. Results and discussion
thin films are investigated. Also, the effect of the Gd doping con-
centration on the microstructure, optical band gap and electrical 3.1. Crystal microstructure and component analysis
properties is investigated and the formation mechanism of the
leakage current is discussed in detail. The XRD spectra of HGO thin films with different Gd sputtering
powers are shown in Fig. 2. The spectra reveal that the HGO thin
2. Experimental films show the monoclinic phase as the Gd sputtering power is less
than 30 W. Only one diffraction peak centered at 2q ¼ 28 corre-
2.1. Preparation of HGO thin films sponding to the (111) plane of the HfO2 monoclinic phase is
observed. When the Gd sputtering power reaches to 30 W, there are
Quartz glasses and n-type Si(100) wafers with a carrier con- four diffraction peak centered at 2q ¼ 29.7, 34.6, 49.8 and 59.3 ,
centration of 1
1015 cm3 were used as substrates for the prepa- corresponding to the (111), (200), (220) and (311) plane of the cubic
ration of HGO thin films. Prior to the deposition of the HGO thin phase. The peak positions of cubic phase C(111), C(220), C(220) and
films, the substrates was ultrasonically cleaned in ethanol for C(311) of HfO2 gate dielectric films reported in the literature are
10 min at room temperature and then washed at 75  C for 10 min 30.38, 35.2, 50.6 and 60.1, respectively [17]. A small angular de-
using a Radio Corporation of American (RCA) standard cleaning viation of the peak position indicate the introduction of Gd change
procedure to remove organic contamination and metallic impu- the internal structure of HfO2 films. Since the ion radius of element
rities. Subsequently, the substrates were immersed in a diluted Gd (0.09 nm) is slightly larger than the ion radius of element Hf
hydrofluoric acid (HF) solution for 20 s to remove the native oxide (0.071 nm), this structural change is mainly due to Gd3þ replaces
SiO2 and blown dry with high purity nitrogen. The freshly cleaned the position of part Hf4þ. The appearance of cubic phase would
Si and quartz substrates were immediately loaded into the vacuum contribute to the improvement of dielectric constant of HGO
chamber of the magnetron sputtering equipment. Before deposi- dielectric film, which can be matched with the following electrical
tion, the vacuum chamber was evacuated to 3.0
104 Pa. The HGO results. Besides, Singh et al. [18] reported that the cubic (111) plane
films were prepared at room temperature by RF reactive co- has the highest atomic density and such an oriented growth could
sputtering of Hf and Gd metal targets in Ar and O2 ambient at the minimize the total surface energy, which will lead to the improved
flow rates of 50 and 15 SCCM (SCCM denotes cubic centimeter per
minute at STP), respectively. The working pressure was fixed at
0.8 Pa. The Gd doping concentration was adjusted by controlling
the Gd RF sputtering power from 10 to 50 W at a power interval of
10 W, while the RF sputtering power of the Hf target was fixed at
120 W. In addition, the target was pre-sputtered in an argon at-
mosphere for 10 min before the film deposition to remove the
native oxide.

2.2. Characterization

HGO thin films, about 60 nm thick, were deposited on n-type

Si(100) substrate for X-ray diffraction (XRD) and energy-dispersive
X-ray spectroscopy (EDS) analysis to probe the microstructure and
the weight percentage of the HGO thin films, respectively. HGO thin
films, about 60 nm thick, were deposited on quartz substrate to test
the optical band gap by UVeVis absorption spectroscopy. About
5 nm HGO thin films were prepared on Si substrate for X-ray
photoelectron spectroscopy (XPS) measurement to abtain the
interfacial information of HGO/Si gate stacks. The spectroscopy
ellipsometry (SC630, SANCO Co, Shanghai) in the spectrum range of
900～1100 nm with a step of 10 nm at an incident angle of 65  C
and 75  C was used to test the thin film thickness. In the process of
fitting, Cauchy-Urbach dispersion model which consists of two
tiers: thickness-fixed si substrate and HGO gate dielectric was
chosed as the fitting mode. In order to explore the electrical
properties, a series of Al/HfGdO/n-Si/Al MOS capacitors were
fabricated by sputtering an Al-top electrode with an area of
3.14
108 m2 through a shadow mask and ohmic contact was
achieved by sputtering Al on the backside of the wafer, followed by
forming-gas (H2 5% þ N2 95%) annealing (FGA) at 300  C for 10 min.
The CeV and J-V curves were obtained using a semiconductor Fig. 1. Schematic flow chart of the HGO thin film synthesized by co-sputtering.
290 S.S. Jiang et al. / Journal of Alloys and Compounds 757 (2018) 288e297

Fig. 2. XRD patterns of Gd-doped HfO2 thin films with various Gd sputtering powers.

performance of the MOS device. The intensity of the diffraction

peaks weakens when the Gd sputtering power increases further
mainly due to the crystallization temperature of HfO2 thin film have
been improved with the increase of the Gd doping concentration.
Additionally, when the Gd sputtering power is greater than 30 W,
the positions of all diffraction peaks are moving in a small angle
direction, which may be due to the increase in the number of Gd3þ
replacement Hf4þ as the Gd sputtering power increases, thus the
lattice constant of the thin film becomes larger, cause the corre-
sponding lattice distortion [19].
The role of the Gd doping concentration on the EDS spectra of
the HGO thin films is illustrated in Fig. 3. It is noted that the main
elemental components of the thin films are Hf, Gd, O and Si, which
results from the Si substrate. The relationship between the Gd
doping power and the specific weight percentages of the films are
summarized in Table 1. The Gd doping percentage is 8.7, 11.1, 22.7,
31.3 and 37.6%, corresponding to the Gd sputtering power of 10, 20,
30, 40, 50 W, respectively.

3.2. Determination of the band gap of the HGO thin films

It is generally known that the insulator optical absorption law is

closely related to energy gap structure. The optical band gap (Eg)
values of the HGO thin films could be obtained by the absorption
spectrum and plotting Oox ¼ Cox ðVfb  fms Þ=Aq versus photon
energy ðhnÞ with the following relation [20]:


ðahnÞ2 ¼ A hn  Eg (1) Fig. 3. EDS spectra of the HGO/Si gate stacks with different Gd sputtering powers.

where a is the absorption coefficient, A is a constant characteristic

Table 1
of the semiconductor, hn is the photon energy and Eg is the apparent
Weight percentage of the components of HGO thin film at various Gd sputtering
optical band gap. The plot of ðahnÞ2 vs ðhnÞ is shown in Fig. 4. The powers.
optical band gap values of 5.82, 5.87, 5.95, 6.04 and 6.14 eV were
Power (W) Hf (wt%) Gd (wt%) Hf:Gd
determined as the Gd sputtering power changed from 10 to 50 W.
Thus, it can be clearly seen that the optical band gap is in the range 10 29.10 2.45 10.47
20 29.95 3.30 8.00
of 5.82e6.14 eV and increases as the Gd doping concentration in-
30 28.07 7.28 3.40
creases. This is mainly attributed to the decrease of oxygen va- 40 29.30 11.8 2.19
cancies in the HGO high-k gate dielectric with the increase of Gd 50 27.90 14.84 1.66
doping concentration. The band gap of the thin film is affected by
the locallized states caused by defects in the energy band, and the
lower locallized states density corresponds to the larger band gap Gd sputtering power, so that the lower the locallized state density
value [21]. The intrinsic defect of HfO2 thin film is mainly oxygen in the band structure, the larger the band gap value. Besides,
vacancy. The oxygen vacancies in HGO thin film decrease with the
 S.S. Jiang et al. / Journal of Alloys and Compounds 757 (2018) 288e297 291

Fig. 4. Plots of ðahnÞ2 versus the photon energy hn for the HGO thin films grown on quartz substrate.

Ikarashi and Manabe [22] and Wong and Iwai [23] have reported frequency of 1 MHz, swept from 1 V to 2 V and then swept back.
that the valence band maximum of the transition metal (TM) oxides The accumulation, the depletion and the inversion region are
is provided mainly by the unoccupied O 2pp-states. Accordingly, clearly visible in Fig. 5. As can be seen from Fig. 5, the saturation
the HGO thin films with different Gd doping powers have the same capacitance Cox in the accumulation region does not change linearly
valence band maximum. As a result, the increase in the energy gap with the increase of Gd sputtering power, but increases first and
band as the Gd doping power increases would lead to the constant then decreases, and the Cox value reaches the maximum value
enhancement of the conduction band minimum. when Gd doping power is 40 W. The dielectric constant k always
maintains a positive proportional relationship with Cox, and the k
3.3. Electrical properties analysis values of HGO films extracted from the CeV curves under different
Gd sputtering power are shown in Table 2 as 10.78, 15.91, 16.88,
3.3.1. CeV curves 19.52 and 17.24, respectively, which also increase first and then
To determine the electrical properties of co-sputtering-grown decrease. The k value of pure Gd2O3 gate dielectric is lower than
HGO thin films with different Gd doping concentrations, room- that of pure HfO2 gate dielectric, the reason why the increase in k
temperature CeV and J-V measurements were performed. The value after introducing Gd element into HfO2 is that the doping of
typical CeV characteristics of the Si-MOS capacitors based on HGO Gd atom causes the length of anion-cation bond to become longer
thin films are shown in Fig. 5. All the samples were measured at a and the GdeO bond shortens and shrinks, resulting in the increase
292 S.S. Jiang et al. / Journal of Alloys and Compounds 757 (2018) 288e297

doping concentration would lead to the decrease of oxygen va-

cancies and thus a less flat band voltage shift can be observed in
HGO thin films as revealed by the CeV curves. The oxide trapped
charge density Qox was calculated with the following equation
Oox ¼ Cox ðVfb  fms Þ=Aq [27], where Øms is the work-function
difference between the Al electrode and Si substrate, A is the Al
electrode area. The values of Oox have been obtained from the CeV
curves, as shown in Table 2. According to the above analysis, the
negative oxide trapped charge density of all the samples mainly
reflect the relative quantity of negative oxygen vacancies. Besides,
the border trapped oxide charge density (Nbt) can be calculated
through the anticlockwise hysteresis DVfb using the following
expression: Nbt ¼ ðCmax DVfb Þ=qA [28]. The synchronous change of
the border trapped oxide charge density and the hysteresis were
detected and are shown in Table 2. The DVfb and the Nbt values of
the HGO gate dielectric deposited at the 30 W doping power are the
lowest, which is almost zero, mainly due to less and less defect
charge in the film. However, the Nbt and DVfb values are increased
Fig. 5. Capacitance-voltage (C-V) characteristics curves for the HGO gate dielectric when Gd sputtering power is higher than 30 W, which may be due
MOS capacitors as a function of the Gd sputtering power. to the increase of defect density caused by lattice distortion when
Gd sputtering power is higher than 30 W of XRD result. This in-
crease of defect density may be due to the increase of shake-up
of molecular polarizability am [24]. According to the Clausius- peak in XPS Gd 3d spectrum [29] (Fig. S1). The shake-up peak is
Mossotti relationship [25]:k ¼ ð1 þ 8pam =3Vm Þ=ð1  4pam =3VÞ, located at about 10 eV at the high binding energy of 3d5/2 main
the dielectric constant k of HGO thin film increases as the molecular peak. It comes from the charge transfer between the outer electrons
polarizability am increases. In addition, the appearance of the cubic of the ligand atoms and the empty 4f orbitals of the rare earth metal
phase structure of the thin film also plays a role in increasing the atoms [30]. When Gd sputtering power is higher than 30 W, the
dielectric constant. When Gd sputtering power is 50 W, namely Gd crystal structure of HGO thin film present worsening lattice
doping concentration was 37.6%, the Cox and k values decrease distortion, resulting in more charge transfer, and thus the density of
because the pure Gd2O3 has a lower k value than the pure HfO2, and defective charges increases, corresponding to larger DVfb and the
when Gd is doped to a certain extent, the dielectric constant k of Nbt values. Besides, the significant increase of interfacial component
the HGO film begins to decrease. Also, the flat band voltage Vfb can SiOx and Sillicate SieHf(Gd)eO (seen from Fig. S2) also contribute
be obtained, which are 0.48, 0.34, 0.28, 0.28, 0.10 V for Gd doping to the increase of DVfb and the Nbt values as Gd sputtering power
power from 10 to 50 W. The positive flat band voltage shift indicates higher than 30 W. The XPS Hf 4f spectrum also presented in sup-
the presence of negative trapped charges in the HGO thin films and/ porting information. Additionally, it can be noted from Fig. S2 that
or at the interface. Oxygen vacancy is the origin of the inherent the HGO thin film with 30 W Gd sputtering power possesses a good
shallow electron traps in the pure HfO2 thin films. It has been re- interface quality with lower SiOx and Sillicate.
ported by Tse and Robertson that those oxygen vacancies could trap The CeV characteristics at different Gd doping powers and
one or two electrons to form negative oxygen vacancies V or V2, various frequencies for the Al/HGO/n-Si MOS capacitors are shown
thus leading to the positive flat band voltage shifts [26]. The in Fig. 6. For the HGO films with a 10 W doping power, there is an
forming process can be expressed as follows: obvious frequency dispersion in the accumulation region, which
reveals that the amount of interface trap charges exist in the high-k
VO
þ e4VO (2) and interface. At lower frequencies, the interface states can follow
the alternating current signal. However, at the high frequency limit
(f > 500 kHz), the interface states cannot follow the applied signal,
VO
þ 2e4VO2 (3) which will cause an obvious difference in the accumulation
Thus, the more positive flat band voltage in the CeV curve is capacitance [31]. Moreover, it is evident that a larger flat band shift
mainly due to the presence of oxygen vacancies. The electronega- in the voltage transition region occurs as a function of the fre-
tivity of elements Hf, Gd and O is 1.3, 1.2 and 3.44, respectively. quency, implying the existence of trace amounts of oxide charge
Therefore, the difference in electronegativity between Gd and O is [32]. Compared to the film with a 10 W Gd doping power, the small
larger than that between Hf and O. It is well-known that the larger frequency dispersion and flat band shift for the Gd doping powers
the difference, the ion bond between the two elements becomes from 20 to 50 W is significant. The frequency dispersion percentage
stronger. Accordingly, compared to HfO2, introducing Gd into HfO2 are calculated by [C1M/C0.5M-C1M]
100% with the capacitance value
makes the escape of the element O from HGO films harder and thus at 2 V. The calculated frequency dispersions are 34.58%, 3.06%,
restrains the formation of oxygen vacancy. To sum up, the higher Gd 2.31%, 3.02% and 0% for the Gd doping powers from 20 to 50 W. The

Table 2
Parameters of the MOS capacitors extracted from the CeV curves.

Power（w） Cox(pF) K Vfb(V) Qox(cm2) DVfb(V) Nbt(cm2) J(A/cm2)

10 149 10.78 0.48 1.34
1012 0.02 5.93
1010 5.89
105
20 208 15.91 0.34 1.28
1012 0.05 2.07
1011 3.19
105
30 212 16.88 0.28 1.06
1012 0 0 8.33
108
40 218 19.52 0.28 1.43
1012 0.02 8.68
1010 4.65
106
50 183 17.24 0.10 2.54
1011 0.14 5.10
1011 1.19
104
 S.S. Jiang et al. / Journal of Alloys and Compounds 757 (2018) 288e297 293

Fig. 6. C-V characteristics measured at different frequencies ranging from 0.5 to 1 MHZ for the HGO gate dielectrics with different Gd sputtering powers.

30 W and 50 W doping powers have a relatively small frequency All the samples were measured at room temperature and swept
dispersion, but the films with a 50 W doping power have a larger from 3 V to 3 V. With the increase of Gd doping power, the leakage
flat band shift, larger hysteresis and larger border trapped oxide current density J decreases first and then increases. At 30 W, the
charge density. Based on above CeV curves analysis, the HGO thin lowest leakage current density is 8.33
108 A/cm2 at 2 V, and then
film with a 30 W doping power (Hf:Gd ¼ 3.4:1) has a good interface the leakage current density increases significantly. The reasons for
quality with suitable dielectric constant, relatively lower oxide the decrease of leakage current density are as follows: (1) The
trapped charge density, without any border trapped oxide charge optical bandgap of the HGO gate dielectric film increases with the
density and a lower frequency dispersion. increase of the Gd doping power, so that the conduction band offset
DEc and the conduction band minimum increase. In the case of
positive bias, electrons are inject from that substrate to the gate
3.3.2. J-V curves
(called substrate injection), and the barrier height is DEc; when
The gate leakage current density versus gate voltage (J-V) curves
under a negative bias, electrons are injected from gate to substrate
for the HGO thin films are presented in Fig. 7. The JeV curves
(called gate injection), and the height of the barrier is equal to the
revealed that the leakage current density J under a negative bias
value of the conduction band minimum minus the fermi energy
voltage (gate injection) is higher than that under a positive bias
level of the metal. Thus, that barrier height increases both in sub-
voltage (substrate injection) at the same absolute voltage value.
strate injection and gate injection, thus contribute to the decrease
These results may be attributed to the different carrier under the
in leakage current density [35]; (2) The oxygen vacancy in the HGO
different injection mode [33] and different materials properties and
film decreases with the increase of the Gd sputtering power, and
conduction mechanism in the Al/HGO and HGO/Si interface [34].
294 S.S. Jiang et al. / Journal of Alloys and Compounds 757 (2018) 288e297

power is greater than 30 W, the one possible reason for the increase
of leakage current is that the increase in the number of Gd3þ
replacement Hf4þ, and lattice distortion seriously affects the
leakage performance of the device. Another possible reason for the
increase of leakage current is the increase of interfacial component
SiOx and Sillicate. Combined the results of XRD, EDS, UVevis and
electrical measurements, the properties of HfO2 thin films can be
improve by doping the Gd element with approximately 22%
concentration.

3.3.3. Current transportation mechanisms analysis

In order to analyze the current transportation mechanisms of
the HGO thin films, the Gd doping power dependence of the gate
leakage current were systematically investigated. The current
mechanisms of Ohmic conduction, Schottky emission and direct
tunneling were investigated and evaluated under the substrate
injection in the present work. The conduction mechanisms can be
divided into two types, namely the electrode-limited conduction
Fig. 7. Leakage current density-gate voltage (J-V) characteristics curves for the HGO
gate dielectric MOS capacitors as a function of the Gd sputtering power. mechanism, which depends on the electrical properties at the
electrode-dielectric contact, and the bulk-limited conduction
mechanism, which depends on the electrical properties of the
the trap charge-assisted leakage current is reduced; (3) The lower dielectric itself. The Schottky emission and direct tunneling are
electronegativity (1.2) and larger ion radius (0.09 nm) of Gd connected to the electrode-limited conduction mechanism, while
element contribute to the decrease of leakage current of HGO thin the Ohmic conduction belong to the bulk-limited conduction
film [36]; (4) The content of interfacial SiOx and Sillicate decrease mechanism.
with increasely Gd sputtering power. When the Gd sputtering The current density of Ohmic conduction can be described as

Fig. 8. Ohmic conduction plots for the Al/HGO/n-Si MOS capacitor at different Gd sputtering powers for substrate injection.
 S.S. Jiang et al. / Journal of Alloys and Compounds 757 (2018) 288e297 295

[37]: obtained, the electrons in the gate will overcome the energy barrier
to the dielectric layer. The results presented in Fig. 9 show that the
 
ðEc  EF Þ plot of ln(J/T2) versus the E1/2 is a good linear fitting. The refractive
J ¼ sE ¼ nqmE; n ¼ Nc exp (4)
kT index n and εr can be calculated from the expression as follows:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
where s is the electrical conductivity, E is the applied electric filed, q3
n is the number of electrons in the conduction band, m is the slope ¼ (6)
4pεr ε0
electron mobility, T is the absolute temperature, and Nc is the
effective density states of the conduction band. The forming
mechanism of Ohmic conduction is that a small number of carriers εr ¼ n2 (7)
are stimulated to the conduction band from the valence band and/
or from the impurity level. The plot of J versus E for the HGO film at The corresponding n and εr values of the substrate injection are
low electric field is presented in Fig. 8, where a linear behavior was presented in Fig. 9. The n values of the 10 W, 20 W and 30 W Gd
found, indicating that Ohmic conduction is a predominant con- doping HGO films deviate from those of the other report [39],
duction mechanism in the lower electric field. which suggested that only the 40 W and 50 W Gd doping HGO films
Besides, as the applied electric field further increases, the cur- exist in the current mechanism of Schottky emission at medium
rent conduction mechanism of the HGO film may be converted into electric field.
Schottky emission expressed as follows [38]: In a high enough electric field, direct tunneling becomes
dominant. The plot of E lnðJ=E2 Þ versus the E3=2 is shown in Fig. 10,
" pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi# where the good linear fitting indicates that the electrons could
* 2 qð4B  qE=4pε0 εr direct tunneling to the oxide layer.
JSE ¼ A T exp (5)
kB T

where A* is the effective Richardson constant, 4B is the Schottky 4. Conclusions

barrier height, εr and ε0 are the dynamic dielectric constant and the
vacuum dielectric constant, respectively. When enough energy is The microstructure, optical band gap, composition and electrical

Fig. 9. Schottky emission (SE) plots for the Al/HGO/n-Si MOS capacitor at different Gd sputtering powers for substrate injection.
296 S.S. Jiang et al. / Journal of Alloys and Compounds 757 (2018) 288e297

Fig. 10. Direct tunneling (DE) plots for the Al/HGO/n-Si MOS capacitor at different Gd sputtering powers for substrate injection.

properties of co-sputtering HGO thin films were systematically Acknowledgments

investigated by XRD, UVevis, EDS and a semiconductor device
analyzer. The XRD analysis results revealed that the stable cubic The authors acknowledge the support from the National Natural
phases were present as the Gd sputtering power increase to 30 W. Science Foundation of China (51572002,11774001,11474284), the
The optical band gap of the HGO thin films increase from 5.82 eV to Technology Foundation for Selected Overseas Chinese Scholar,
6.14 eV with the increase of the sputtering power. The electrical Ministry of Personnel of China (J05015131), Anhui Provincial Nat-
measurements of the Al/HGO/Si MOS capacitor indicate that the ural Science Foundation (1608085MA06).
HGO thin film with a sputtering power of 30 W possesses the
suitable permittivity, the smaller frequency dispersion and the Appendix A. Supplementary data
smallest leakage current. These results can be attributed to the
better interface quality with smaller oxide trapped charge density Supplementary data related to this article can be found at
and zero border trapped oxide charge density. The current trans- [Link]
portation mechanisms for substrate injection were also analyzed.
The current transportation of HGO thin films are the ohmic con-
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