Fermi level pinning by defects in HfO

2
-metal gate stacks
J. Robertson
a
Engineering Department, Cambridge University, Cambridge CB2 1PZ, United Kingdom
O. Sharia and A. A. Demkov
Physics Department, University of Texas at Austin, Austin, Texas, 78712, USA
Received 9 August 2007; accepted 7 September 2007; published online 28 September 2007
Various mechanisms for the Fermi level pinning of p-gate metals on HfO
2
are analyzed in detail. It
is found that for Fermi energies below the Si valence band, HfO
2
can oxidize Si by creating
positively charged O vacancies. The band bending due to this vacancy concentration can account for
the observed Fermi level pinning of p metals on HfO
2
. 2007 American Institute of Physics.
DOI: 10.1063/1.2790479
To allow the continued scaling of complementary metal
oxide eld effect transistors FETs, high dielectric constant
K oxides such as HfO
2
will replace SiO
2
as the gate dielec-
tric and metal gates will replace polycrystalline Si as the gate
electrode. HfO
2
was chosen as the gate oxide because it does
not react with Si. The gate metals are chosen so that their
Fermi energies should align with the conduction or valence
band edges of Si, for n-FETs and p-FETs, respectively. How-
ever, it has proved difcult to nd suitable metals to achieve
this and withstand annealing to 1000 C. The gate Fermi
level E
F
tends to shift toward an energy independent of the
metal, near the midgap of Si, a problem referred to as Fermi
level pinning.
16
This is particularly acute for high work
function p metals at low effective oxide thickness EOT
gate.
4
Engineering solutions to some of these problems such
as metals for n-FETs have been found. Nevertheless, the
physical mechanisms for Fermi level pinning and at band
voltage V
FB
shifts are not well understood.
Here, we consider pinning in p-FETs. It was found that
metals deposited at room temperature on HfO
2
with no an-
nealing had unpinned or weakly pinned Fermi levels.
6,7
In
addition, recent calculations showed that the intrinsic varia-
tion of barrier height at HfO
2
-metal interfaces with metal
work function is unpinned.
8
The slope factor S is 1. An-
nealing the metal electrodes to high temperatures causes E
F
to drift toward midgap. This led to interest in refractory
metal alloys such as TiN or TaSiN, but these tend to be
midgap metals. Studies found that high work function metals
such as Pt, Re, or Ru show an instability in oxygen-decient
conditions, and their E
F
moves toward midgap when an-
nealed above 500 C.
2,3
These metals are transparent to oxy-
gen and hydrogen at high temperatures, and the shift could
be reversed by annealing in oxygen. However, the work
function of Pt metal varies little with small oxygen content.
This suggests that pinning is extrinsic and may be related to
oxygen vacancies in the oxide layer.
We therefore consider Fermi level pinning in terms of
oxygen vacancies. These appear to exist in sizable amounts
in HfO
2
lms,
9,10
which allow oxygen transport across the
HfO
2
layer.
11
However, an objection to this mechanism is the
large formation energy of O vacancies, 6.38 eV,
12
so it is
unclear how sufciently large vacancy densities can exist. A
formation energy below 0.7 eV is needed to create enough
vacancies to pin E
F
. Here, we give a detailed description of
various possible vacancy mechanisms, including that of
Shiraishi and co-workers.
13,14
Figure 1 plots the formation energy of the O vacancy
G against the Fermi energy E
F
in the HfO
2
. The formation
energy of a defect G varies with its charge q as
G
1
= G
0
q qE
F
. 1
The calculated formation energy of the neutral vacancy V
0
is
6.38 eV with respect to the O
2
molecule.
12
However, for
lower E
F
, the vacancy becomes V
2+
and the formation energy
now falls rapidly with E
F
. We place the 0/ 2+ vacancy level
at 4.0 eV above the oxide valence band VB edge or at
0.3 eV below the Si conduction band CB edge.
9
The most
recent calculated value for the 0/ 2+ electrical level is 3.9 eV
a
Electronic mail: jr@eng.cam.ac.uk
FIG. 1. Color online a O vacancy formation energy vs Fermi energy in
HfO
2
. b Equivalent model with vacancy electrons falling to the Fermi level
of a metal gate.
APPLIED PHYSICS LETTERS 91, 132912 2007
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above the oxide VB.
15,16
Figure 1 also shows the Si band
edges, with a VB offset of 3.2 eV, a HfO
2
gap of 5.8 eV, a Si
band gap of 1.1 eV, and a Si electron afnity of 4.0 eV. The
energies can be placed on various energy scales, either with
respect to the oxide VB edge, the Si VB edge, or the vacuum
level as used for metal work functions.
17
The formation energy diagram of Fig. 1a is exactly
equivalent to the reaction diagram of Fig. 1b. A neutral
vacancy is created in the HfO
2
, with two electrons in its
vacancy level. These electrons gain energy by falling to the
metal Fermi energy E
F
, with the gate metal setting E
F
in the
oxide. The vacancy concentration is given as
n = n
0
exp G/kT, 2
where n
0
is the oxygen ion density in HfO
2
, n
0
=6.2
10
22
cm
3
, and we assume that the defects are frozen in at
T=1273 K. From Fig. 1a, G is still much too large
5.0 eV at E
F
=E Si VB to create enough charged vacan-
cies to modify the effective work functions.
A second mechanism is to transfer the oxygen atom lib-
erated from the vacancy into the metal electrode M
18
to form
a unit of oxide MO
n
. The overall reaction is
O
O
+ 1/nM = V
O
2+
+ 1/nMO
n
+ 2e

. 3
The reaction energy of Eq. 3 is G
1
plus the free energy of
MO
n
per O atom,
G
2
= G
1
+ G1/nMO
n
. 4
We take the experimental free energy of bulk MO
n
. We can
then calculate the modied vacancy formation energy Eq.
4 for this mechanism Fig. 2b. We nd that G
2
is still
too large for Pt, Ru, or Re to allow enough vacancies to
have an effect.
To see why, Fig. 2a plots the experimental free energy
of oxides per O against the work function of the pure
metal.
19,20
Noble metals with larger work function have
smaller oxide free energies. Thus, the two terms in Eq. 4
oppose each other. Interestingly, while Fig. 2a shows a
clear trend that high work function metals have less stable
oxides, there is considerable scatter. Oxides of Si and Al are
more stable than expected from their electronegativity alone.
The mechanism which will cause E
F
pinning involves a
reaction with the Si channel, as proposed by Akasaka et al.
13
The high temperature annealing allows oxygen to diffuse
through the SiO
x
interfacial layer under the HfO
2
layer and
to react with the Si channel. The overall reaction is
O
O
+
1
2
Si = V
O
2+
+
1
2
SiO
2
+ 2e

. 5
Oxygen from the vacancy reacts with Si from the channel,
while its two electrons fall to the gates Fermi level. The
reaction energy of Eq. 5 is
G
3
= G
1
+ G
1
2
SiO
2
= G
1
4.73 eV. 6
G is now lowered by 4.73 eV per O free energy of SiO
2
,
a substantial energy gain. Figure 3a shows the net vacancy
formation energy in HfO
2
vs E
F
Eq. 6. G is much lower
than in Eq. 1, and G becomes negative for E
F
below an
energy E
p
. E
p
0.02 eV below the Si VB or a gate work
function of 5.12 eV. Thus, whereas HfO
2
is stable against
oxidation of Si in normal conditions, Si can actually reduce
FIG. 2. Color online a Experimental free energy of bulk metal oxide
MO
n
per O. b Energy of reaction 3.
FIG. 3. Color online a O vacancy formation energy vs Fermi energy in
HfO
2
on a Si substrate, with the reaction allowed. b Band bending due to
charge vacancies.
132912-2 Robertson, Sharia, and Demkov Appl. Phys. Lett. 91, 132912 2007
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HfO
2
to form vacancies if E
F
0.02 V with respect to Si
VB.
Two further effects occur. First, a charged vacancy is
attracted by its image charge in the metal.
21
This lowers G
1
as the vacancy approaches the metal by 0.10.3 eV. Second,
many vacancies are formed. When charged, these cause an
upward band bending of V toward the gate which opposes
charge transfer Eqs. 1 and 5 Fig. 3b,
G = G
0
q qE
F
V. 7
For simplicity, assume that the charged vacancies, instead of
being uniformly distributed, lie in a plane at d=1 nm physi-
cal thickness from the metal so V=eNd
2
/
0
K, where N is
the volume density of vacancies. We take K=20 for HfO
2
.
The solution to Eqs. 2, 6, and 7 is found numerically.
Figures 4a and 4b plot the vacancy concentration and
depletion voltage V vs E
F
.
We see that this model can give small vacancy formation
energies and large vacancy densities, and thus account for
pinning. The model involves reaction at oxide-Si interface
and band bending at the metal oxide interface. The need for
O diffusion through the SiO
2
interface layer accounts for the
observed temperature dependence
3
and the fact that it only
occurs at small EOT, the V
t
roll-off.
4
The mechanism ac-
counts for the observed oxidation of Si by O passing from
the gate metal.
11,22
The fact that G can approach zero al-
lows even HfO
2
monolayers to provide pinning.
1
The model
accounts for the high vacancy density seen in HfO
2
lms on
Si even without metal overlayers,
10
which otherwise is dif-
cult to understand. HfO
2
can oxidize Si when E
F
is low,
whereas normally SiO
2
oxidizes Hf. The pinning effect can
be inhibited by reoxidation of vacancies at a low enough
temperature that it does not cause thickening of the SiO
2
interlayer. It appears in some cases that the oxidation of a Ru
electrode can also contribute to the V
FB
shifts.
5
However, the
generality of pinning behavior suggests that this is not the
main cause. Additionally, dipole layers at the HfO
2
SiO
2
interface could arise, but a vacancy model is a natural
mechanism.
Akasaka et al.
13
obtained a pinning energy higher than
here by taking the V
O
defect level above the Si CB.
Experiment
9
suggests that the V
O
level is deeper. Neverthe-
less, this does not affect the models validity; the exact pin-
ning energy depends on numerical details such as image
potentials.
J.R. acknowledges the J. Tinsley Oden Faculty Fellow-
ship from UT Austin. A.D. acknowledges support by the Na-
tional Science Foundation under Grant No. DMR-0548182.
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FIG. 4. Color online a Calculated effective work functions and depletion
layer potential vs vacuum work function of gate metal. b Calculated va-
cancy density.
132912-3 Robertson, Sharia, and Demkov Appl. Phys. Lett. 91, 132912 2007
Downloaded 31 Dec 2009 to 163.13.111.50. Redistribution subject to AIP license or copyright; see http://apl.aip.org/apl/copyright.jsp