Tunneling of holes observed at work function measurements of metal / HfO 2 / SiO 2

/ n-Si gate stacks

J. A. Rothschild, H. Avraham, E. Lipp, and M. Eizenberg

Citation: Applied Physics Letters 96, 122102 (2010); doi: 10.1063/1.3360879

View online: http://dx.doi.org/10.1063/1.3360879
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 APPLIED PHYSICS LETTERS 96, 122102 共2010兲

Tunneling of holes observed at work function measurements

of metal/ HfO2 / SiO2 / n-Si gate stacks
J. A. Rothschild,a兲 H. Avraham, E. Lipp, and M. Eizenberg
Department of Materials Engineering, Technion-Israel Institute of Technology, Haifa 32000, Israel
共Received 4 January 2010; accepted 23 February 2010; published online 22 March 2010兲
The voltage bias that causes a transition from direct tunneling to Fowler–Nordheim tunneling in the
current-voltage characteristic of a metal/ HfO2 / SiO2 / n-Si capacitor was measured. The transition
occurs in the negative gate voltage regime and can be attributed to conduction of electrons from the
metal through a defect level in the HfO2 or to conduction of holes from the Si through the valence
band of the HfO2. The dependence of the determined barrier height on the gate-metal work function
indicates the validity of the latter model. © 2010 American Institute of Physics.
关doi:10.1063/1.3360879兴

A major result of the scaling trend in the micro-
electronics industry is the required replacement of the ther-
mally grown SiO2 gate-oxide and the highly doped polycrys-
talline silicon 共poly-Si兲 gate-electrodes in metal-oxide-
semiconductor 共MOS兲 devices by high-k dielectrics and
metals, respectively.1,2 One of the most important parameters
in determining the device performance is the threshold volt-
age, which depends on the effective work-function of the
gate electrode. The most commonly used technique for
measuring the effective work function is based on extracting
the flatband voltage from capacitance-voltage 共C-V兲
measurements.3 Capacitors of several thicknesses of the ox-
ides are measured in order to eliminate the contributions of
fixed oxide charges. In the case of high-k dielectrics, the
gate stack often consists of two or more dielectric layers,
and the abovementioned procedure becomes much more
complicated. The additional layer and interface increase the
number of measurements needed and assumptions made.
Thus, the C-V method is complicated and its precision is
questionable.4 Other techniques based on photoemission,
such as internal photoemission and x ray-photoemission, are
also used but they require the preparation of special samples
with transparent gate electrodes.
Zafar et al.5–7 proposed a technique to determine the
effective work-function of metal electrodes from current-
voltage 共I-V兲 measurements. In this method, when the domi-
nant conduction mechanism through the dielectric film is
tunneling the transition from direct tunneling 共DT兲 to
Fowler–Nordheim tunneling 共FNT兲 is characterized by a
peak in the d共ln J兲 / dV versus V plot. In their first Paper,5 the
I-V measurements of an n+ poly-Si/ Al2O3 / p-Si stack were
carried out at negative gate voltage 共VG兲 values. In these
voltages, the peak determines the barrier 共⌽BS兲 between the
conduction-band edge of the oxide 共ECO兲 and the Fermi level
of the Si 共EFS兲. The peak is observed at a voltage V p which
depends on the barrier between ECO and EFS at zero bias
共⌽BS0
兲 and the band bending in Si 共⌿Si兲,
eV p = ⌽BS = ⌽BS
0
+ ⌿Si ,
where e is the fundamental charge. An expression for ⌿Si
was derived by Zafar,
a兲
Electronic mail: yonatanr@tx.technion.ac.il.
⌿Si = 共44.4h2/msi兲1/3共5.5e␧ox/␧si兲2/3共VoxEOT兲2/3 , 共2兲
where h is plank’s constant, msi is the effective electron mass
in Si, ␧ox is the permittivity of the oxide, ␧si is the permittiv-
ity of Si, VOx is the potential across the oxide, and EOT is the
equivalent oxide thickness. At the DT-FNT transition, VOx is
equal to the barrier 共⌽BM 兲 between the Fermi level of the
metal 共EFM 兲 and ECO. By determining V p for several differ-
ent values of EOT, both ⌽BS and ⌽BM were found.
In the second Paper,6 a metal/ SiO2 / p-Si stack was stud-
ied by I-V at positive VG values. Now the peak determines
the barrier ⌽BM between EFM and ECO, namely V p = ⌽BM .
Wen et al.8 used this I-V technique in positive VG values and
an n-type substrate and compared the results with the com-
mon C-V technique, showing very similar results. The DT-
FNT transition can also occur in hole-dominated currents
according to the same mechanism, although it was not men-
tioned before.
In our work, n-type Si 共100兲 wafers with a doping level
of 1018 cm−3 were used as substrates for the MOS capaci-
tors. On each substrate a 4 nm thick SiO2 film was thermally
grown by dry oxidation at 810 ° C, and a 4 nm thick HfO2
film was deposited on it using atomic layer deposition
共ALD兲. MOS capacitors were fabricated by depositing either
Pt or Al electrodes through a shadow mask using physical
vapor deposition. Following metal deposition, all the MOS
capacitors were annealed at 400 ° C for 30 min in vacuum.
Electrical measurements were performed in a probe station
sealed from light using an HP 4284A LCR meter. I-V
and C-V measurements were performed on the
metal/ HfO2 / SiO2 / n-Si capacitors at positive and negative
VG scans with steps of 0.05 V.
The d共ln J兲 / dV versus V characteristic of the capacitors
with a Pt electrode and an Al electrode are plotted in Fig. 1.
A pronounced peak was observed at −0.8⫾ 0.1 V for the Pt
electrode and at −2.1⫾ 0.1 V for the Al electrode. However,
no peaks appeared in the positive voltages regime, contradic-
tory to the expected outcome, as will be discussed below.
共1兲 The electronic band structure of the oxide films used in this
study was previously determined by Geppert et al.9 using
XPS measurements. The conduction- and valence-band off-
sets to Si are 2.7 and 1.5 eV, respectively. Therefore accord-
ing to Eq. 共1兲 the expected bias for negative VG which cor-
responds to the DT-FNT transition should be larger than 2.9

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 122102-2 Rothschild et al.
FIG. 1. Peaks of Pt/ HfO2 and Al/ HfO2 observed on a plot of d ln J / dV
vs V.
V in absolute value. However, all the peaks measured in the
current work are at a smaller absolute value than 2.7 V, in-
dicating that they originate from a different mechanism.
Therefore, there are two remaining options which can
explain the peaks.10 The first option is that there is a defect
level 共ED兲 inside the HfO2 共SiO2 is assumed to be defect
free兲 and the peaks determine the electron barrier 共⌽SD兲 be-
tween ED and EF,Si, as illustrated in Fig. 2共a兲. Defect-induced
trap levels have already been observed in HfO2 using an
electron spectroscopic technique.11 These traps have been at-
FIG. 2. The two possible mechanisms in the metal/ HfO2 / SiO2 / n-Si stack
for peaks at VG ⬍ 0. 共a兲 The DT-FNT transition through a defect layer in
HfO2.is共b兲
This article The DT-FNT
copyrighted as transition
indicatedwith holes
in the as charge
article. Reusecarriers.
of AIP content is subject to the terms at:Very similar results were obtained byDownloaded
193.61.135.80 On: Mon, 15 Dec 2014 12:03:52
Appl. Phys. Lett. 96, 122102 共2010兲
tributed mainly to oxygen vacancies and the energetic posi-
tion of several kinds of defects has been calculated.12 Trap
assisted tunneling is a well known model for explaining
leakage current in high-k materials13 which was previously
used in order to model tunneling currents in Hf-based gate
stacks.14
Under this assumption the peak in the HfO2 / SiO2 stack
is determined in a similar manner to Eq. 共1兲, with the addi-
tion of the voltage which is applied on the SiO2 film 共VSiO2兲,
eV p = ⌽SD = ⌽SD
0
+ ⌿Si + eVSiO2 , 共3兲
where ⌽SD 0
is the barrier between ED and EFS at zero bias.
The other terms can be calculated according to the applied
voltage. We assume that ⌽SD 0
is a bulk property and does not
depend on the metal deposited. As shown in Fig. 2共a兲, the
applied voltage on the HfO2 layer at the DT-FNT transition
point is equal to the barrier between EFM and ED, i.e.,
eVHfO2 = ⌽ MD. Since the thickness of the HfO2 and SiO2 lay-
ers are equal, the ratio between the applied voltages on the
SiO2 layer and the HfO2 is VSiO2 / VHfO2 = ␧HfO2 / ␧SiO2.15
Therefore, according to Eq. 共2兲, ⌿Si is proportional to ⌽MD.
Consequently, electrodes with higher work-function values
共⌽ M 兲 are expected to exhibit a DT-FNT transition at a higher
absolute voltage. However, the peak in the I-V of the Pt
electrode, which has a higher ⌽ M than the Al electrode, is
actually observed at a lower absolute voltage.
The second option is that the tunneling charge carriers
are holes, rather than electrons. In this case, the barrier for
hole conduction 共⌽BH兲 is between EFM and EV,HfO2, as illus-
trated in Fig. 2共b兲. As can be seen, the peak is expected to
appear at a voltage exactly identical to the value of ⌽BH. It
should be noted that the transport of minority carriers was
already observed by Zafar et al.,6 who used p-type Si and
analyzed the electron conduction. The conduction of holes in
HfO2 was directly observed by hole trapping experiments
made by Afanas’ev and Stesmans.16 Hou et al.17 used it for
modeling the leakage current in HfO2 based MOS capacitors
for both p-type substrates and n-type substrates. This model
had good agreement with experimental results for a capacitor
with a HfO2 layer which had a conduction- and valence-band
offset of 1.91 and 2.22 eV, respectively.18,19 For our system,
the dominant current is in the valence band, since the valence
band offset is much smaller than the conduction band offset.
The effective work function of the metal can then be
determined by,
M = ␹HfO2 + EG,HfO2 − 兩⌽BH兩 = ␹Si + EG,Si + ⌬VB
⌽eff
− 兩⌽BH兩, 共4兲
where ␹ is the electronic affinity, EG is the energy gap, and
⌬VB is the valence band edge offset between HfO2 and Si.
Using Eq. 共4兲, the effective work-function value of Pt on
HfO2 is ⌽Pt eff
= 5.8⫾ 0.1 eV and the effective work-function
of Al is ⌽Al eff
= 4.5⫾ 0.1 eV. According to these values and
confirmed by C-V measurements, the flatband voltage is lo-
cated near 1.4 and 0.1 V for Pt and Al, respectively, meaning
that the observed peaks are located at a voltage in which the
n-type Si is in inversion or very close to inversion, resulting
in holes being generated near the SiO2 / Si surface. The effec-
tive work-function values are very close to 5.7 and 4.5 eV,
which are the vacuum work-function values of Pt and Al,
20
respectively.
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 122102-3 Rothschild et al. Appl. Phys. Lett. 96, 122102 共2010兲

et al.,21 who did not anneal the stack. On the other hand,
Shaeffer et al.,22 who annealed the stack at 1 000 ° C found
strong Fermi level pinning. The effective work-function dif-
ference ⌬⌽eff = 1.3⫾ 0.1 eV is within the experimental error
of the vacuum work-function difference ⌬⌽vac = 1.4 eV. The
slight shift in work-function cannot be explained by the con-
ventional metal-induced gap states23 model since according
to it ⌬⌽eff is expected to be noticeably smaller than ⌬⌽vac.
The shift can be explained by an interface dipole at the
HfO2 / SiO2 interface as proposed by Kirsch et al.24 to ex-
plain the flatband voltage shift in stacks with lanthanides.
Charbonnier et al.25 observed this interface dipole for a sys-
tem without lanthanides.
The reason that no peaks are observed at positive volt-
ages is that non-tunneling conduction mechanisms are of
larger magnitude and screen the tunneling currents at volt-
ages above 2.7 eV. Otherwise, another peak would be ex-
pected to be observed at higher voltages.
In summary, the peaks that we observed are due to a
transition from DT to FNT with holes as the dominant
charge-carriers. This mechanism is similar to the phenom-
enon reported in the past for electronic currents with the
exception that the barrier for holes becomes smaller and not
larger as the effective work function increases. Therefore,
when analyzing the I-V characteristics of MOS it is impor-
tant to first know the electronic structure of the high-k di-
electric in order to be able to decide which mechanism is
observed.
We acknowledge the support of the Russel Berrie Nano-
technology Institute at Technion, Y. Shneider from Micro-
electronics Research Center at the Technion for helpful dis-
cussions regarding oxidation, A. Bavin from AVIZA Inc. for
the ALD deposition, and Dr. G. Frant from Materials Engi-
neering Department at Technion for sputtering the metals.
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