Performance and reliability improvement of HfSiON gate dielectrics using chlorine

plasma treatment
Hong Bae Park, Byongsun Ju, Chang Yong Kang, Chanro Park, Chang Seo Park, Byoung Hun Lee, Tea Wan
Kim, Beom Seok Kim, and Rino Choi

Citation: Applied Physics Letters 94, 042911 (2009); doi: 10.1063/1.3078277

View online: http://dx.doi.org/10.1063/1.3078277
View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/94/4?ver=pdfcov
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 APPLIED PHYSICS LETTERS 94, 042911 共2009兲

Performance and reliability improvement of HfSiON gate dielectrics using

chlorine plasma treatment
Hong Bae Park,1 Byongsun Ju,1 Chang Yong Kang,2 Chanro Park,2 Chang Seo Park,2
Byoung Hun Lee,3 Tea Wan Kim,4 Beom Seok Kim,4 and Rino Choi4,a兲
1
Samsung Electronics R&D Center, Republic of Korea
2
SEMATECH, Austin, Texas 78741, USA
3
Gwangju Institute of Science and Technology, Gwangju, Republic of Korea
4
Inha University, 253 Yonghyun-dong, Nam-gu, Incheon 402-751, Republic of Korea
共Received 3 November 2008; accepted 6 January 2009; published online 30 January 2009兲
The effects of chlorine plasma treatment on HfSiON gate dielectrics were investigated with respect
to device performance and reliability characteristics. The chlorine plasma treatment was performed
on atomic layer deposited HfSiON films to remove the residual carbon content. The optimal chlorine
plasma treatment is shown to lower gate leakage current density without increasing equivalent oxide
thickness of the gate stack. Secondary ion mass spectroscopy depth profiling showed that the carbon
residue in HfSiON was reduced by the chlorine plasma treatment. It is demonstrated that an
optimized chlorine plasma treatment improves the transistor Ion-Ioff characteristics and reduces
negative-bias temperature instability. © 2009 American Institute of Physics.
关DOI: 10.1063/1.3078277兴

After 30 yrs of rapid downsizing of transistors, geo-
metrical scaling has clearly reached fundamental material
limits and is now in the era where further scaling can be
realized mainly by new materials and/or device
architecture.1–6 The aggressive scaling of metal-oxide semi-
conductor field effect transistors 共MOSFETs兲 requires metal
gate electrodes and high-k gate dielectrics to replace the con-
ventional polycrystalline silicon gate electrode and SiO2 gate
dielectrics in order to alleviate their excessive gate leakage
current and polycrystalline silicon gate depletion.1–4 Al-
though the gate leakage current was shown to be less than
SiO2, the degradation of carrier mobility and reliability is
still a challenging problem for devices with the high-k/metal
gate stacks.7–9 In addition, impurities such as chlorine and
carbon in high-k films inevitably incorporated during chemi-
cal vapor deposition or atomic layer deposition 共ALD兲 have
negative effects on reliability and device performance.10–13
Specifically, a high carbon content in high-k films was found
to increase both gate leakage current and equivalent oxide
thickness 共EOT兲. Recently, Cho et al.14 showed the effects of
carbon residue in HfO2 films by varying the O3 density in the
oxidation cycles during ALD of HfO2. They reported that a
lower carbon concentration in HfO2 films improved gate
leakage current density and time-dependent dielectric break-
In this study, we introduce an effective way to selec-
tively remove residual carbon in high-k films without in-
creasing the EOT. In addition, we investigated the effects of
chlorine plasma treatment on HfSiON gate dielectrics in
terms of device performance and reliability characteristics.
p-MOSFETs were fabricated on 200 mm wafers using a
conventional complementary metal-oxide semiconductor
process flow. HfSiO film was deposited using ALD, followed
by a postdeposition annealing 共PDA兲 共700 ° C / 30 s at nitro-
gen ambient兲 to incorporate nitrogen in the HfSiO film.
Chlorine plasma treatment was done at various stages of the
high-k deposition process. The control sample did not get
any chlorine plasma treatment. Sample HK was treated by
chlorine plasma after high-k deposition. For sample mid-HK,
the chlorine treatment was performed after the deposition of
approximately one-half of the total HfSiO thickness, fol-
lowed by the deposition of the rest of the high-k film. The
chlorine plasma treatment was performed at low temperature
with no bias power to minimize plasma etching damage.
Subsequently, a very thin ALD Al2O3 capping layer was de-
posited on top of HfSiO to lower the device threshold volt-
0
Capacitance [μF/cm ]

10
J[A/cm ]
2

-2
down. However, reducing carbon residue by a higher O3 den- 2.0 10
-4
sity or oxygen plasma treatment increases the EOT due to 10
-6
10
accelerated interfacial oxidation. 1.5 -8
10 -3 -2 -1 0
Another way of reducing the residual carbon from the Gate Voltage [V]
dielectrics is chlorine plasma because chlorine can easily re- 1.0
act with carbon to form CCl4. With chlorine plasma treat-
ments, therefore, it is expected that the carbons incorporated 0.5 Control
HK
in the high-k layer diffuse out of the dielectric resulting in Mid-HK
the formation of CCl4 as a reaction by-product,15 0.0
-2 -1 0 1 2
Gate voltage [V]
C + 4Cl → CCl4共⌬H f = − 95.7 Kcal/mol兲.
FIG. 1. 共Color online兲 C-V curves of HfSiON with and without chlorine
plasma treatment. The chlorine plasma-treated samples show lower EOT
a兲
Author to whom correspondence should be addressed. Electronic mail: and lower gate leakage current density 共inset兲 at the same time. The EOTs of
rino.choi@inha.ac.kr. Tel.: 82-32-860-7529. FAX: 82-32-862-5546. the control, HK, and mid-HK samples are 2.2, 2.0, and 1.9 nm, respectively.

0003-6951/2009/94共4兲/042911/3/$25.00
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is copyrighted as indicated in the article. Reuse of AIP content © 2009 American InstituteDownloaded
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 042911-2 Park et al. Appl. Phys. Lett. 94, 042911 共2009兲

3
10
Vdd = -1.2V
Control HK Mid-HK 10
2

Ioff [nA/μm]
10
TaCN
0
Al2O3 10
HfSiO
-1 Control
10
HK
10
-2 Mid-HK
204 255

10 nm 0 100 200
Ion [μA/μm]
300 400

FIG. 4. 共Color online兲 Ion-Ioff characteristics of each sample measured at

FIG. 2. HRTEM images of high-k gate stacks. Amorphous silicon was de-
Vdd = −1.2 V. Note the improved Ion-Ioff characteristics with chlorine plasma
posited on top of TaCN gate electrode and has been crystallized during
treatment.
postannealing. No physical thickness change was observed with and without
chlorine plasma treatment.

filing of a poly-Si/ TaCN/ Al2O3 / HfSiON/ SiO2 / Si gate

age due to dipole formation.16 A thin ALD TaCN layer was
used as a metal gate, followed by a polycrystalline silicon
cap layer. A spike activation annealing was employed for the
source/drain activation, followed by a forming gas annealing.
Capacitance-voltage 共C-V兲 measurements were performed at
a frequency of 100 kHz. The EOT was extracted using the
NCSU CVC program with quantum corrections. For depth
profiling of the poly-Si/ TaCN/ Al2O3 / HfSiON/ SiO2 / Si gate
stack, secondary ion mass spectroscopy 共SIMS兲 was per-
formed.
High frequency C-V curves of HfSiON with and without
chlorine plasma treatment are plotted in Fig. 1. The chlorine
plasma-treated samples exhibit higher capacitance 共lower
EOT兲 than the nontreated sample. In addition, the chlorine
plasma-treated samples show a lower gate leakage current
density as shown in the inset of Fig. 1. More importantly, the
mid-HK sample shows a significant reduction in EOT and
gate leakage current density. This demonstrates that a well-
tuned plasma treatment can significantly reduce both EOT
and gate leakage current density. High resolution transmis-
sion electron microscopy 共HRTEM兲 images of the samples
are shown in Fig. 2. No apparent physical thickness change
was observed in the high-k and interfacial SiO2 layers be-
tween the samples with and without chlorine plasma treat-
ments, indicating the chlorine plasma does not cause plasma
damage in high-k gate stacks.
To analyze the residual carbon content in high-k gate
stacks after chlorine plasma treatment, the SIMS depth pro-
5
10
stack was performed 共Fig. 3兲. The 12C peak in the
Al2O3 / HfSiON/ SiO2 dielectric stacks gradually decreases
with the chlorine plasma treatment, which means that chlo-
rine plasma under well-controlled conditions such as tem-
perature, pressure, and no bias power is an effective method
of removing the residual carbon content incorporated in the
HfSiON films during ALD of HfSiO. A mid-HK sample
shows the lowest carbon peak level throughout the gate di-
electric stacks, indicating that this process for the chlorine
plasma treatment is preferable. Figure 4 shows the Ion-Ioff
characteristics of each sample measured at Vdd = −1.2 V. The
chlorine plasma-treated samples demonstrate improved
Ion-Ioff characteristics compared to the nontreated sample.
Furthermore, the mid-HK samples show significantly im-
proved Ion-Ioff characteristics, over 25%, due to the reduced
EOT and improved quality of the gate stacks with reduced
residual carbon content. In addition, transconductance in the
devices with the chlorine plasma treated gate stacks was bet-
ter than the nontreated sample 共not shown here兲. The effec-
tive mobility of the chlorine plasma treated samples was al-
most identical with the nontreated samples. Therefore, the
primary reason of the improved on-current is believed to be
the reduced EOT.
Figure 5 shows the negative-bias temperature instability
共NBTI兲 characteristics as function of stress time measured on
the W / L = 10/ 1 ␮m p-MOS transistors. The threshold volt-
age 共Vt兲 shift after the 10 000 s stress in the mid-HK sample
100
∆Vt [mV]

Control 10
HK
1
Counts/sec._12C

Mid-HK Vg-Vt=-1.6V
0.1 Control
100 HK
4
10 Mid-HK
∆Vt [mV]

10

1
Al2O3 o
@125 C, 10/1μm Vg-Vt=-1.0V
TaCN SiO2 Si 0.1
3 /HK 0.1 1 10 100 1000 10000
10 Stress Time [s]
0 5 10 15 20
Depth [nm]
FIG. 5. 共Color online兲 NBTI as a function of stress time measured at
FIG. 3. 共Color online兲 The SIMS depth profiling of a 125 ° C. The improved NBTI for the optimal chlorine plasma treatment
poly-Si/ TaCN/ Al2O3 / HfSiON/ SiO2 / Si gate stack. The carbon peaks in indicates that chlorine plasma treatment on HfSiON shows defect-curing
high-kis gate
This article stacks decrease
copyrighted with chlorine
as indicated plasma Reuse
in the article. treatment. effects
of AIP content is subject on terms
to the high-k at:
gate 1 ␮m.
stacks. The gate length of the samples isDownloaded
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 042911-3 Park et al.
shows much less degradation compared to the nontreated
sample, indicating that the reduced carbon concentration can
improve device reliability and our postchlorine treatment can
be exploited to enhance device performance and reliability
characteristics.
In summary, the effects of the chlorine plasma treatment
on HfSiON were investigated. A well-controlled chlorine
plasma treatment of HfSiON is shown to improve the elec-
trical characteristics of HfSiON gate stacks; in particular, it
reduces both EOT and gate leakage current density. The
depth profile by SIMS shows that the residual carbon content
in HfSiON was reduced by the chlorine plasma treatment.
More importantly, the chlorine plasma treatment can improve
transconductance, drive current, and NBTI reliability in
p-MOSFETs. One may conclude that the chlorine plasma
treatment of HfSiON is an effective way to remove the re-
sidual carbon content in HfSiON gate dielectrics, leading to
enhanced device performance and reliability characteristics.
This work was supported by Inha University Research
Grant 共Grant No. INHA-38190兲.
1
G. D. Wilk, R. M. Wallace, and J. M. Anthony, J. Appl. Phys. 89, 5243
共2001兲.
2
Z. Xu, M. Houssa, S. De Gendt, and M. Heyns, Appl. Phys. Lett. 80, 1975
共2002兲.
3
S. J. Lee, H. F. Luan, W. P. Bai, C. H. Lee, T. S. Jeon, Y. Senzaki, D.
Roberts, and D. L. Kwong, Tech. Dig. - Int. Electron Devices Meet.
2000, 31.
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
160.36.178.25 On: Sat, 20 Dec 2014 03:40:47
Appl. Phys. Lett. 94, 042911 共2009兲
4
J.-H. Lee, Y.-S. Kim, H.-S. Jung, J.-H. Lee, N.-I. Lee, H.-K. Kang, J.-H.
Ku, H. S. Kang, Y.-K. Kim, K.-H. Cho, and K.-P. Suh, Dig. Tech. Pap. -
Symp. VLSI Technol. 2002, 84.
5
S. M. Kim, E. J. Yoon, M. S. Kim, M. Li, C. W. Oh, S. Y. Lee, K. H. Yeo,
S. H. Kim, D. U. Choe, S. D. Suk, D.-W. Kim, and D. Park, Journal of
Semiconductor Technology and Science 6, 22 共2006兲.
6
W. Y. Choi, J. D. Lee, and B.-G. Park, Journal of Semiconductor Technol-
ogy and Science 6, 43 共2006兲.
7
A. S. Oates, Tech. Dig. - Int. Electron Devices Meet. 2003, 923.
8
M. S. Akbar, J. C. Lee, N. Moumen, and J. Perterson, Appl. Phys. Lett.
88, 082901 共2006兲.
9
H. R. Harris, H. Alshareef, H. C. Wen, S. Krishnan, K. Choi, H. Luan, D.
Heh, C. S. Park, H. B. Park, M. Hussain, B. S. Ju, P. D. Kirsch, S. C.
Song, P. Majhi, B. H. Lee, and R. Jammy, Tech. Dig. - Int. Electron
Devices Meet. 2006, 633.
10
K. Endo, T. Tatsumi, Jpn. J. Appl. Phys., Part 2 42, L685 共2003兲.
11
S. Van Elshocht, M. Baklanov, B. Brijs, R. Carter, M. Caymax, L. Car-
bonell, M. Claes, T. Conard, V. Cosnier, L. Daté, S. De Gendt, J. Kluth, D.
Pique, O. Richard, D. Vanhaeren, G. Vereecke, T. Witters, C. Zhao, and M.
Heyns, J. Electrochem. Soc. 151, F228 共2004兲.
12
M. Cho, R. Degraeve, G. Pourtois, A. Delabie, L.-A. Ragnarsson, T.
Kauerauf, G. Groeseneken, S. D. Gendt, M. Heyns, and C. S. Hwang,
IEEE Trans. Electron Devices 54, 752 共2007兲.
13
Y. W. Kim, Y. Roh, J.-B. Yoo, and H. Kim, Thin Solid Films 515, 2984
共2007兲.
14
M. Cho, J. H. Kim, C. S. Hwang, H.-S. Ahn, S. Han, and J. Y. Won, Appl.
Phys. Lett. 90, 182907 共2007兲.
15
D. R. Lide, CRC Book of Handbook of Chemistry and Physics, 82nd ed.
共CRC, Boca Raton, FL, 2001兲 pp. 5–26.
16
H.-C. Wen, S. C. Song, C. S. Park, C. Burham, G. Bersuker, K. Choi, M.
A. Quevedo-Lopez, B. S. Ju, H. N. Alshareef, H. Niimi, H. B. Park, P. S.
Lysaght, P. Majhi, B. H. Lee, and R. Jammy, Dig. Tech. Pap. - Symp.
VLSI Technol. 2007, 160.