Journal of The Electrochemical Society, 158 共1兲 H69-H74 共2011兲 H69

0013-4651/2010/158共1兲/H69/6/$28.00 © The Electrochemical Society

Development of ALD HfZrOx with TDEAH/TDEAZ and H2O

X. Shi,a,z H. Tielens,a S. Takeoka,a,c T. Nakabayashi,a,c L. Nyns,a C. Adelmann,a,*
A. Delabie,a,* T. Schram,a L. Ragnarsson,a M. Schaekers,a,* L. Date,a,b
R. Schreutelkamp,a,b and S. Van Elshochta,*
a
IMEC, and bApplied Materials Belgium, Kapeldreef 75, 3001 Leuven, Belgium

In this work we report on the development of the HfZrOx atomic layer deposition 共ALD兲 process with tetrakisdiethylamino
共TDEA兲 hafnium/zirconium 共TDEAH/TDEAZ兲 and H2O. A nanolaminar structure approach is used to grow HfZrOx by alternating
HfO2 and ZrO2 ALD reaction cycles at 250°C. The HfZrOx film thickness increases linearly with the number of ALD cycles.
Compared to the halide based process, the process with TDEA precursors and H2O yields a lower temperature window, an initial
growth insensitive toward the starting surfaces, and a fast film closure on the hydrofluoric acid-last surface. The Zr content,
measured by Rutherford backscattering increases linearly with the cycle ratio of Zr/共Zr + Hf兲. The as-deposited HfZrOx films are
amorphous and crystallize after a 950°C postdeposition anneal. Depending on the film composition a different crystalline phase is
formed, ranging from monoclinic to tetragonal with increasing Zr content. Using H2O instead of O3 not only reduces the
interfacial oxide regrowth during deposition, which allows for a thinner interfacial layer and improves the interfacial oxide
scalability, but also results in a lower C content in the deposited films. Finally, complementary metal oxide semiconductor
transistor using HfZrOx as gate dielectric are fabricated for the evaluation of device performance. These results show that all
considered splits with HfZrOx as gate dielectric yield a similar equivalent oxide thickness-gate leakage current performance and
共low兲 gate current leakage level. The data reported in this paper demonstrates that ALD HfZrOx grown based on TDEAHf/Zr and
H2O is a promising gate dielectric for subnanometer equivalent oxide thickness scaling.
© 2010 The Electrochemical Society. 关DOI: 10.1149/1.3516476兴 All rights reserved.

Manuscript received April 14, 2010. Published November 29, 2010.

Complementry metal oxide semiconductor 共CMOS兲 scaling re-
quires a suitable high dielectric constant 共high-k兲 material to replace
SiON as a gate dielectric to ensure a low transistor leakage current.1
Over the past few years several high-k materials have been investi-
gated, such as hafnium oxide, zirconium oxide, aluminum oxide,
and their silicates. Among these materials, HfO2 is demonstrated to
be a promising high-k gate dielectric due to its relatively high di-
electric constant, larger bandgap, and thermodynamic stability.2-12 In
2007, Hf based high-k gate dielectric was selected as the gate di-
electric for 45 nm technology node.13,14 However, important chal-
lenges remain related to further scaling, e.g., threshold voltage 共Vt兲
instability, degraded carrier mobility, and reliability issues.15,16 Ad-
ditionally, the dielectric constant of HfO2 共 ⬃ 20兲 might not be high
enough for extreme subnanometer equivalent oxide thickness 共EOT兲
scaling.
HfZrOx formed by adding Zr into HfO2 has been extensively
studied as an alternative gate dielectric. HfO2 and ZrO2 have very
similar physical and chemical properties and these materials are
completely miscible in the solid solution.17,18 HfZrOx presents ad-
vantages compared to HfO2, such as higher dielectric constant,
higher level of film structure stability, and improved device
reliability.19
Atomic layer deposition 共ALD兲 is considered as an enabling
technique to deposit thin high-k layers due to its precise thickness
control, low thermal budget, and excellent conformality. Several lit-
erature studies exist on ALD HfO2 and ZrO25,6,20 as well as on ALD
HfZrOx processes with different precursors such as halide based
process 共HfCl4 /ZrCl4兲 with H2O 共Ref. 21兲 and metal-organic pre-
cursors tetrakisethylmethylamino 共TEMA兲 hafnium/zirconium
共TEMAH/TEMAZ兲 with O3.22 The ALD HfZrOx films prepared by
these different processes exhibit comparable physical and electrical
properties. However, there are some limitations related to the above-
mentioned ALD HfZrOx processes: the halide based ALD processes
show a significant growth incubation on hydrofluoric acid 共HF兲-last
共H-terminated兲 surfaces. Additionally, the ALD process using HfCl4
and ZrCl4 generates HCl as a by-product. The strong etching effect
of HCl in the by-product might damage the underlaying structures
and causes additional surface roughening and nonconformality.23
* Electrochemical Society Active Member.
c
Assignee at IMEC from Panasonic, Kapeldreef 75, 3001 Leuven, Belgium.
z
E-mail: xiaoping.shi@imec.be
The ALD process based on TEMA precursors and O3 shows a simi-
lar growth on both OH- and H-terminated surfaces. There are also
no harmful chemicals such as HCl as a by-product. The use of O3 as
an oxidant, however, limits the interfacial oxide 共IFO兲 scalability
due to the strong oxidizing nature of O3. Furthermore, TEMA/O3
based processes have a slightly higher growth per cycle 共GPC兲,
⬃1.0 Å per cycle. A higher GPC impacts the ALD process control,
especially for the sub-nm EOT films.
In this work, we report on the development of an ALD HfZrOx
process with tetrakisdiethylamino hafnium/zirconium 共TDEAH/
TDEAZ兲 and H2O. The ALD HfZrOx process based on the TDEA
precursors and H2O can potentially overcome the growth incubation
observed for the halide based processes on a H-terminated surface.
In addition, the TDEA precursors have a lower decomposition tem-
perature than the halide based precursors because the chemical
bonds between the metal elements and ligands are weaker.24 The
lower decomposition temperature results in a lower temperature
ALD process, which is beneficial for the applications that require a
stringent thermal budget control. The use of H2O instead of O3 is
advantageous for minimizing the interfacial oxide. The developed
process also exhibits a growth rate similar to that of the halide based
process, which ensures a better process control at a sub-nm EOT
scale.
Experimental
The development was done in an Applied Materials 共Santa Clara,
CA兲 300 mm ALD chamber. Precursors and H2O were introduced
into the process chamber separately and sequentially according to
the different ALD pulse settings. A N2 purge was introduced after
each precursor or H2O pulse to remove precursor/H2O residues and
by-products. TDEAH and TDEAZ are highly viscous liquids, stored
in canisters and pushed into vaporizers. Inside the vaporizer,
TDEAH or TDEAZ evaporates into the gas phase. N2 is used as a
carrier gas to transport TDEAH or TDEAZ into the chamber.
Film thickness and uniformity were determined by spectroscopic
ellipsometry 共SE兲 on a KLA-TENCOR 共Milpitas, CA兲 SCD100
ASET F5. A one-layer model with a fixed refractive index 共RI兲 is
used for the SE measurement. X-ray reflectivity 共XRR兲 was done in
a BedeMetrix-L tool 共Jordan Valley Semiconductors Ltd., Austin,
TX兲 with Cu K␣ radiation to determine the HfZrOx layer thickness
by separating the interfacial oxide thickness. Rutherford backscatter-
ing 共RBS兲, done in an RBS400 Endstation system 共Charles Evans
and Associates, Sunnyvale, CA兲 with 1 MeV He+ beam, was applied

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 H70 Journal of The Electrochemical Society, 158 共1兲 H69-H74 共2011兲
Figure 1. The temperature windows for ALD HfO2 and ZrO2 with TDEAH
and TDEAZ, respectively, are shown. The number of cycles is 100 for HfO2
samples, while 50 for ZrO2 samples. The error bar is indicative of film
uniformity.
to measure the Hf and Zr content. Time-of-flight secondary ion mass
spectroscopy 共Tof-SIMS兲 was performed in an IONTOF IV
共IONTOF Gmbh, Munster, Germany兲 instrument to study the film
continuity using a Ga+ beam of 15 keV as well as the possible
contaminants in the HfZrOx films with a dual-beam setup 共Xe+ beam
of 500 eV, followed by a beam of 15 keV Ga+ ions兲. Transmission
electron microscopy 共TEM兲, done in a Tecnai F30 TEM system
共FEI, Hillsboro, OR兲, was applied to determine the physical thick-
ness of the interfacial oxide and HfZrOx layers, which were cross
calibrated with the SE measurements. X-ray diffraction 共XRD兲, also
performed in a BedeMetrix-L system, was used to study the film
structure. CMOS transistors with HfZrOx as a gate dielectric and
TiN/TaN as a gate electrode were fabricated to investigate the elec-
trical properties of the HfZrOx films. The EOT of the gate dielectric
and the gate leakage current 共Jg兲 are extracted from device data to
evaluate the HfZrOx device performance.
Results and Discussion
Growth of ALD HfZrOx.— A nanolaminate approach was used
to grow HfZrOx by alternating ALD HfO2 and ZrO2 growth steps.
The temperature windows for ALD HfO2 and ZrO2 with TDEAH
and TDEAZ, respectively, were explored 共Fig. 1兲. The films with
100 HfO2 cycles and 50 ZrO2 cycles were deposited in a tempera-
ture range between 125 and 375°C. The error bars in Fig. 1 are
indicative of the film uniformity. Similar ALD temperature windows
were observed for both ALD HfO2 and ZrO2, ranging from
125 to 300°C. Typical ALD characteristics are shown within this
temperature range: the film thickness decreases with increasing tem-
perature, while the film uniformity remains excellent.5 The GPC
decreases slightly with increasing temperature because the amount
of reactive ALD sites decreases with increasing temperature due to
dehydroxylation. In contrast, the film thickness increases dramati-
cally while the film uniformity degrades above 300°C, which is
indicative of decomposition of the TDEA precursors. Around this
temperature, the reaction regime migrates from ALD to chemical
vapor deposition. The ALD process window is at a lower tempera-
ture for the TDEA based process compared to the halide/H2O based
or TEMA/O3 based processes.5,20-22 This is mainly due to the lower
decomposition temperature of the TDEA precursors compared to the
halide precursors24 as well as the different reaction regime between
the O3 and H2O based processes.25 Related to a lower C content, the
ALD temperature window should be at a higher temperature for
metal-organic based processes. The optimum temperature for ALD
HfZrOx is between 250 and 300°C.
The ALD behavior of the process can be verified by changing the
pulse and purge lengths of HfO2 and ZrO2. For a typical ALD pro-
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Figure 2. Saturation curves are shown for ALD HfO2 共TDEAH兲 and ZrO2
共TDEAZ兲 at 250 and 300°C. The number of cycles used is 100 for HfO2, and
50 for ZrO2, respectively. The error bar is indicative of film uniformity.
cess, the film thickness remains unchanged and the film uniformity
becomes excellent when surface saturation is reached. Figure 2
shows the precursor saturation curves obtained for TDEAH and
TDEAZ at 250 and 300°C, respectively. The error bars in Fig. 2 are
indicative of film uniformity. It is found that the saturation behavior
is very similar for both HfO2 and ZrO2 at 250°C: a pulse length of
2 s 共or longer兲 leads to surface saturation. At 300°C, HfO2 based on
TDEAH exhibits a surface saturation curve similar to that at 250°C.
The slightly lower thickness indicates a slightly reduced GPC,
which is consistent with the results obtained in Fig. 1. At 300°C,
ZrO2 based on TDEAZ, however, does not show a surface self-
limiting process. The ZrO2 thickness increases and the film unifor-
mity degrades slightly with the increase of the TDEAZ pulse length.
This behavior is a clear indication of TDEAZ decomposition. Hence
it can be concluded that the ALD temperature window for TDEAZ is
slightly shifted to a lower temperature compared to that for TDEAH,
in agreement with the results reported in literature.20 As a conse-
quence, 250°C is selected as the optimum temperature for ALD
HfZrOx film development.
The growth behavior of ALD HfZrOx at 250°C is investigated
with different techniques, e.g., SE and RBS. Figure 3a plots the SE
growth curves for ALD HfO2, ZrO2, and Hf0.5Zr0.5O2 on a 10 Å
chemical oxide surface.26 The extracted GPC for ALD HfO2 is
⬃0.67 Å/cycle, which is slightly higher than the ZrO2 GPC
⬃0.63 Å/cycle. These GPC values are very close to the GPC of the
halide based process but lower than that of the TEMA based pro-
cess, ⬃1.0 Å/cycle.27 A lower GPC provides a better process con-
trol for thin films of 2 nm or less, which is essential for sub-nm EOT
scaling. A lower GPC can result from a lack of reactive sites and/or
steric hindrance. The fact that the TDEA/H2O based processes have
a GPC similar to that of the halide/H2O based processes indicates
that the amount of reaction sites might be the dominant factor be-
cause the TDEA ligands are much larger than the halide ligands. The
reaction regime is different for the O3 based process compared to the
H2O based ALD processes,25 which impacts the number of reaction
sites per surface area. This is probably the main reason causing the
higher GPC for the TEMA/O3 based process compared to the
TDEA/H2O based process, even though the TDEA precursors have
larger organic ligands 关e.g., –N共C2H5兲2兴 than the TEMA precursors
共e.g., –NCH3C2H5兲; hence, the steric hindrance is expected to be
more pronounced for the TDEA precursors. For the Hf0.5Zr0.5O2
process, each complete cycle consists of one HfO2 cycle and one
ZrO2 cycle. The GPC for Hf0.5Zr0.5O2 is ⬃1.2 Å/cycle. Figure 3b
shows the growth curves for HfO2, ZrO2, and Hf0.5Zr0.5O2 on
chemical oxide based on RBS analysis. The growth curves are very
 Journal of The Electrochemical Society, 158 共1兲 H69-H74 共2011兲 H71

Figure 3. The growth curves for ALD HfO2, ZrO2, and Hf0.5Zr0.5O2 with
TDEAH and TDEAZ on 10 Å chemical oxide surface at 250°C are shown;
共a兲 SE growth curves, 共b兲 RBS growth curves.

similar to those recorded by SE. The amount of metal atoms depos-

ited per cycle is ⬃1.70 at/nm2 for HfO2 and ⬃1.45 at/nm2 for
ZrO2, which indicates that HfO2 has a slightly higher GPC than
ZrO2. The results further prove that the amount of reaction sites on
the HfO2 surface is slightly higher than that on the ZrO2 surface. Figure 4. The growth behavior is studied with different techniques for ALD
ALD HfO2 and ZrO2 are used to study the initial growth on the ZrO2 with TDEAZ and H2O on different surfaces at 250°C. 共a兲 SE growth
curves, 共b兲 XRR growth curves, and 共c兲 RBS growth curves.
different starting surfaces. Three different surfaces are used: 10 Å
chemical oxide surface 共OH-terminated surface兲, 8 Å thermal oxide
共partly OH-terminated surface兲, and HF-last surface 共H-terminated
surface兲. Three different techniques are applied: SE, XRR, and RBS.
The results obtained for both HfO2 and ZrO2 are very similar. As an H2O versus the measured XRR thickness data. It can be concluded
example, Fig. 4 shows the results of ALD ZrO2. Figure 4a compares that the HF-last surface yields a thinner IFO than the chemical ox-
the SE growth curves on the different starting surfaces and illus- ide. The same methodology is applied for the TEMAH/O3 process27
trates that GPC is very similar on the different substrates. No sig- so that a direct comparison can be made. An IFO thickness of
nificant incubation effect is observed on the HF-last surface, con- 0.9–1.3 nm is extracted for the 2–4 nm HfO2 films compared to an
trary to the observation for halide based processes. Because a one- IFO thickness of 1.4–1.6 nm for the 2–4 nm HfO2 films prepared
layer model with a fixed RI is used in SE measurement, the SE based on a TEMAH/O3 process.27 These data indicate that the
thickness actually includes both IFO and high-k layer. The offset on
the vertical axis relates to the IFO layer. The growth curve on the
HF-last substrate shows the smallest offset, indicative of the thinnest
IFO. XRR was used to determine the ZrO2 layer thickness while
excluding the IFO thickness. Figure 4b shows the XRR growth
curves of ALD ZrO2 on three different surfaces. The ZrO2 high-k
layer thickness data obtained on the different surfaces follow the
same trend line; no differences are observed. These data confirm that
the substrate conditions have hardly an impact on the resulting de-
posited ZrO2 layer thickness. Figure 4c compares the Zr amount on
the different surfaces as measured by RBS. The amount of deposited
Zr is mainly determined by the number of ALD cycles, independent
of substrate. These results also confirm that the initial growth of
ALD ZrO2 based on TDEAZ and H2O is independent of the starting
surface conditions.
Because the SE thickness data include both IFO and high-k layer
thicknesses and the XRR data only show the high-k layer thickness,
a methodology is developed to extract IFO thickness by subtracting
the XRR thickness from the SE thickness.27 The extracted IFO
thickness can be used to evaluate the effect of starting surface and Figure 5. The extracted IFO thickness of ALD HfO2 is shown vs the XRR
process conditions on initial film growth. As an example, Fig. 5 thickness on the different starting surfaces by subtracting XRR thickness
plots the extracted IFO thickness of ALD HfO2 with TDEAH and from SE thickness.

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 H72 Journal of The Electrochemical Society, 158 共1兲 H69-H74 共2011兲
Figure 6. The normalized Si signal measured by Tof-SIMS is plotted vs the
Hf density measured by RBS to study the surface closure of the HfO2 films
using TDEAH/H2O. The data of HfO2 using HfCl4 are listed as references.
TDEAH/H2O process results in a thinner IFO than the TEMAH/O3
based process. A thinner IFO is essential for further sub-nm EOT
scaling.
RBS and Tof-SIMS are applied to investigate the film continuity
on different starting surfaces, e.g., a chemical oxide and a HF-last
surface. ALD HfO2 and ALD ZrO2 are used for the experiment.
Figure 6 shows only the results for HfO2 because the results are
similar for both HfO2 and ZrO2. The data for HfO2 using
HfCl4 /H2O are listed as references. On a chemical oxide substrate,
the normalized Si signal for HfO2 using TDEAH/H2O decreases at
the same rate as for HfO2 using HfCl4 /H2O. This suggests that on
chemical oxide HfO2 using TDEAH/H2O has an initial growth simi-
lar to that of HfCl4 /H2O. On a HF-last surface, the normalized Si
signal for HfO2 using TDEAH/H2O decreases slightly slower than
on the chemical oxide, indicative of a longer time required to form
a continuous film. In contrast, on a HF-last surface using
TDEAH/H2O results in much faster decrease of the normalized Si
signal than that of HfCl4 /H2O. Based on these results, we can con-
clude that on a HF-last surface there are more reactive sites avail-
able for TDEAH compared to HfCl4. The film growth using TDEAH
on a HF-last surface is two-dimensional, unlike the three-
dimensional 共island兲 growth using HfCl4. The former growth mode
共in-plane, two-dimensional growth兲 is preferable for a better film
quality.
Physical characterization.— The Hf and Zr contents in the
HfZrOx films have been verified based on RBS analysis. In Fig. 7
the Zr content in the resulting HfZrOx film is plotted versus the ALD
Figure 7. Zr content in the HfZrOx films measured by RBS vs the cycle ratio
between ALD HfO2 and ZrO2 Zr/共Hf + Zr兲. The ALD temperature is at
250°C.
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Figure 8. The average amount of Zr and Hf deposited per metal cycle vs the
Zr content in the HfZrOx films.
cycle ratio of HfO2 and ZrO2 共defined as the number of ZrO2 cycles
divided by the total number of HfO2 and ZrO2 cycles兲. It is shown
that the Zr content in the films increases linearly with the ALD cycle
ratio of HfO2 and ZrO2. A good linearity indicates that the growth of
the ALD HfO2 with TDEAH/H2O is not influenced by the incorpo-
ration of the ALD ZrO2 with TDEAZ/H2O and vice versa. As a
consequence, the Zr content in HfZrOx films can be well controlled
by changing the ALD cycle ratio of HfO2 and ZrO2.
Figure 8 plots the average amount of metal atoms deposited per
metal cycle 共Zr/Zr cycle and Hf/Hf cycle兲 versus the Zr content in
the HfZrOx films. It is found that the average amount of Zr depos-
ited per Zr cycle 共Zr/Zr cycle兲 decreases with Zr content; a similar
trend is found for Hf 共from 1.75 to 1.45 at/nm2 for Zr and from
1.7 to 1.4 at/nm2 for Hf兲. The above-mentioned RBS results 共Fig.
3b兲 already indicated that the amount of reaction sites on a ZrO2
surface is slightly lower than that on a HfO2 surface. In other words,
the Hf atoms yield more ALD reaction sites than the Zr atoms.
Therefore, by incorporating Zr into a HfO2 film, the number of
reaction sites also slightly decreases. Hence, the incorporation of Zr
into the film leads to the decrease of the number of deposited Hf per
Hf cycle and Zr per Zr cycle. With the same Zr content, the Zr/Zr
cycle is slightly higher than Hf/Hf cycle, although the difference is
very small, ⬃0.1 at/nm2. This suggests that Zr atoms are more eas-
ily absorbed on a HfO2 surface than do Hf atoms on a ZrO2 surface.
TEM was applied to investigate the physical thickness for IFO
and high-k layers. The samples with 20 cycles of HfO2 and ZrO2
and 10 cycles of Hf0.5Zr0.5O2 were prepared on a chemical oxide as
well as a thermal oxide substrate. All the samples were capped with
a dual metal gate stack and poly-Si layer. The results are similar for
all the samples, regardless of the Zr content and oxide substrate. As
an example, Figure 9 shows two cross-sectional TEM pictures for
films based ten cycles of Hf0.5Zr0.5O2 prepared on chemical and
thermal oxides, respectively. Both samples demonstrate smooth in-
terfaces between substrate/IFO, IFO/high-k, and high-k/metal gate.
A thin IFO ⬃7 Å is observed under a 14 Å high-k layer. No IFO
regrowth is observed during the gate stack deposition. The images
demonstrate that the ALD HfZrOx with the TDEA precursors and
H2O delivers a well-controlled, ultrathin IFO, which benefits
sub-nm EOT scaling.
XRD was used to study the HfZrOx film structure. Samples with
HfZrOx layers as thin as 4 nm were used, representative of a gate
dielectric film structure in sub-nm EOT devices. The 4 nm HfZrOx
layers yield a sub-nm EOT. Figure 10 shows the XRD results ob-
tained on the 4 nm HfO2, Hf0.5Zr0.5O2, Hf0.1Zr0.9O2, and ZrO2 films.
As-deposited films exhibit an amorphous structure 共only HfO2 and
ZrO2 are shown兲. All samples crystallize after a postdeposition an-
neal treatment at 950°C for 30 s. The HfO2 film shows the most
intense diffraction peak at 28.5°, corresponding to the monoclinic
共111兲 phase. All other samples containing Zr, including Hf0.5Zr0.5O2,
 Journal of The Electrochemical Society, 158 共1兲 H69-H74 共2011兲
Figure 9. Cross-sectional TEM pictures of the ALD Hf0.5Zr0.5O2 films
grown on different surfaces based on 10 ALD cycles: 共a兲 on chemical oxide,
共b兲 on thermal oxide. The samples are capped with a dual metal gate stack
and poly-Si.
Hf0.1Zr0.9O2, and ZrO2, show the most dominant diffraction peak at
30.4°, indicative of the tetragonal 共111兲 phase. These results confirm
that adding Zr into HfO2 helps to stabilize the tetragonal phase.21,22
For HfZrOx films, the tetragonal phase usually has a higher k value
than the monoclinic phase.17,18 A higher k value benefits sub-nm
EOT scaling further.
Tof-SIMS was applied to investigate the C impurity in the
HfZrOx films. Figure 11 plots the normalized C impurity depth pro-
files for the ALD HfO2 films prepared with TDEAH/H2O at 150 and
250°C. The results prove that a higher deposition temperature yields
a lower C impurity. A lower C impurity is preferred because a higher
C content may lead to a higher leakage level. For comparison, the C
impurity depth profile for the ALD HfO2 film prepared with
TEMAH/O3 at 285°C is also listed. Although the reference sample
is prepared at 285°C, it shows a C impurity level similar to that for
the sample prepared with TDEAH/H2O at 150°C. In other words, at
a similar C impurity level, the TDEAH/H2O based process yields a
much lower ALD temperature than the TEMAH/O3 based process.
It has already been discussed that H2O as oxidant is more efficient
to remove C than O3 due to the fact that H2O can more easily break
Figure 10. XRD results of the 4 nm HfZrOx films with different Zr contents.
The films are grown on top of a thin chemical oxide surface.
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H73
Figure 11. Tof-SIMS depth profiles of C impurities in the ALD HfO2 films
grown using TDEAH/H2O at 150 and 250°C. The results of TEMAH/O3 at
285°C are listed as references.
the amine ligands than O3.25 The TDEA/H2O based process is there-
fore more efficient to yield a lower C impurity than the TEMA/O3
based process.
Device performance.— CMOS transistors with HfZrOx as the
gate dielectric were fabricated to investigate the electrical properties
of ALD HfZrOx with TDEA based precursors. A TiN/TaN metal
gate is used as the gate electrode. The EOT is extracted from the
device current–voltage curves, while the Jg is measured at a gate
voltage 共Vg兲 of 1.1 V. Figure 12 shows the EOT-Jg performance for
n-type metal oxide semiconductor 共nMOS兲 devices. All the HfZrOx
splits considered in this work result in a similar EOT-Jg perfor-
mance. The process splits based on pure ZrO2 show a slightly higher
gate leakage. A promising device result is achieved with a gate
leakage of 1 A/cm2 共at Vg = 1.1 V兲 at 11 Å EOT. The results can
be benchmarked with the device data achieved with ALD HfZrOx
based on the halide precursors as reported in literature.15,19 The
current results show that ALD HfZrOx based on TDEA precursors
and H2O can be a promising gate dielectric for sub-nm EOT scaling.
Conclusion
The development of ALD HfZrOx with TDEA based precursors
and H2O is reported. Compared to the halide based ALD process,
the developed ALD HfZrOx process exhibits a similar GPC, a lower
ALD temperature window, less growth sensitivity to the starting
surface conditions, as well as a fast film closure on a HF-last sur-
face. Compared to the TEMA/O3 based process, the process shows
a lower GPC, a thinner interfacial oxide, as well as a lower C im-
Figure 12. EOT-Jg performance for nMOS devices with HfZrOx as the gate
dielectric and TiN/TaN as the metal gate is shown.
 H74 Journal of The Electrochemical Society, 158 共1兲 H69-H74 共2011兲
purity level. The combinations result in the following advantages:
共1兲 a lower GPC would benefit the control of process in the sub-nm
EOT range; 共2兲 a lower ALD temperature can be beneficial for the
applications that require stringent thermal budget control, e.g., ALD
on Ge or graphene; 共3兲 a thin interfacial layer can improve the
interfacial oxide scalability; and 共4兲 a lower C impurity benefits
device gate leakage. RBS results show that the Hf and Zr contents in
the films can be well controlled by the cycle ratio of ALD HfO2 to
ZrO2. XRD studies show that the as-deposited films are amorphous.
During a 950°C anneal, the films crystallize into different crystalline
phases, ranging from the monoclinic to tetragonal phase, with the
increase of Zr content. CMOS devices using HfZrOx as the gate
dielectric and TiN/TaN as the dual metal gate stack exhibit an ex-
cellent EOT-Jg performance 关e.g., a gate leakage of 1 A/cm2 共at
Vg = 1.1 V兲 at 11 Å EOT兴. The current results demonstrate that
ALD HfZrOx based on TDEA based precursors and H2O is a prom-
ising gate dielectric for sub-nm EOT scaling.
IMEC assisted in meeting the publication costs of this article.
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