Study of amorphous lithium silicate thin films grown by atomic layer

deposition
Jani Hämäläinena)
Laboratory of Inorganic Chemistry, University of Helsinki, P.O. Box 55, FI-00014 Helsinki, Finland
Frans Munnik
Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden–Rossendorf,
P.O. Box 510119, D-01314 Dresden, Germany
Timo Hatanpää, Jani Holopainen, Mikko Ritala, and Markku Leskelä
Laboratory of Inorganic Chemistry, University of Helsinki, P.O. Box 55, FI-00014 Helsinki, Finland
(Received 8 July 2011; accepted 30 August 2011; published 27 September 2011)
Lithium silicate thin films, which are interesting materials for example in lithium ion batteries, were
grown by the atomic layer deposition technique from lithium hexamethyldisilazide [LiHMDS,
Li(N(SiMe3)2)] and ozone precursors. Films were obtained at a wide deposition temperature range
between 150 and 400  C. All the films were amorphous except at 400  C, where partial
decomposition of LiHMDS was also observed. The growth behavior was examined in detail at
250  C, and saturation of growth rates and refractive indices with precursor doses was confirmed,
thereby verifying self-limiting surface reactions. Likewise, the linear thickness dependence of the
films with the number of deposition cycles was verified. Strong dependence of growth rate and film
composition on deposition temperature was also seen. Overall, the amorphous films grown at 250  C
had a stoichiometry close to lithium metasilicate (Li2.0SiO2.9) with 0.7 at. % carbon and 4.6 at. %
hydrogen impurities. The corresponding growth rate and refractive index (n580) were 0.8 Å/cycle
and about 1.55. VC 2012 American Vacuum Society. [DOI: 10.1116/1.3643349]

I. INTRODUCTION films results in good cycling performance and less than

Lithium silicate can form crystalline compounds with var-
ious stoichiometries.1 The ratios between Li2O and SiO2
vary in these stoichiometries; thus resulting in Li2SiO3 (1:1),
Li2Si2O5 (1:2), Li4SiO4 (2:1), and Li8SiO6 (4:1) crystalline
structures. Accordingly, the properties and thus applicability
of the corresponding stoichiometries vary.
Lithium silicates can be applied in lithium ion batteries as
solid state electrolytes.2 At room temperature, amorphous
Li2SiO3 and Li4SiO4 films have quite limited ionic conductiv-
ities of 2.5  108 and 4.1  107 S cm1, respectively, for
lithium ion battery electrolytes.2 However, amorphous
Li2SiO3 thin films have shown about 1–2 orders of magnitude
higher ionic conductivity at elevated temperatures compared
to polycrystalline Li2SiO3.3,4 The ionic conductivity of amor-
phous Li2SiO3 can further be increased by optimizing the film
thickness.3 Also, the substrate material has been reported to
affect the ionic conductivity of amorphous Li2SiO3.4
Li2Si2O5 mixed with carbon black has been suggested as
a cathode material for lithium ion batteries.5 It was found
that Li2Si2O5 nanowires exhibit much higher Li ion charge
capacity compared to 2D or spherical 3D nanostructures.5
Furthermore, Li2Si2O5 nanowires mixed with carbon black
have a higher initial Li ion charge capacity compared to the
conventional Li–Mn–O or Li–Co–O cathode material sys-
tems.5 Also, SiO2/Li cells have been presented, where the
reversible conversion reaction between SiO2 and Li2Si2O5
a)
Author to whom correspondence should be addressed; electronic mail:
jani.hamalainen@helsinki.fi
0.01% per cycle capacity loss during the first 100 cycles.6
This kind of SiO2–Li2Si2O5 conversion system could be an
attractive electrode in lithium ion batteries. Likewise, 2 nm
of amorphous Li2SiO3 on top of LiCoO2 electrode has been
found to enhance the rate performance of the electrode.7
Lithium silicate films consisting of a mixture of Li2SiO3
and Li2Si2O5 on porous silicon may be applied for ozone
detection as well due to the increase of ionic conductivity of
lithium silicates in the presence of ozone.8 The applicability
of lithium silicate electrolytes for CO2 sensors has also been
evaluated.9 It was shown that Li2Si2O5 resists 90% relative
humidity at elevated temperature far better than the other
lithium silicates.9 In addition, Li4SiO4 is unstable against
CO2, forming Li2CO3 in ambient conditions while Li2SiO3
remains stable.2 Li4SiO4 membranes have been suggested
for CO2 separation at high temperatures.10 Furthermore, lith-
ium silicates, Li4SiO4 in particular, are considered as solid
tritium breeding materials in fusion power technology.11
In this study we examine lithium silicate films obtained
using atomic layer deposition (ALD) from lithium hexame-
thyldisilazide [LiHMDS, Li(N(SiMe3)2)] and ozone at a
wide deposition temperature range. The growth rates and re-
fractive indices are reported, as well as the compositional
analysis of the films deposited at various temperatures. The
ALD grown thin films inherently possess good conformality
and uniformity because of the alternating, saturative precur-
sor doses and self-limiting surface reactions.12,13 This results
in accurate thickness controllability and repeatability of the
films. Therefore, films with specific thicknesses can be de-
posited on demanding 3D structures with large surface areas,

01A106-1 J. Vac. Sci. Technol. A 30(1), Jan/Feb 2012 0734-2101/2012/30(1)/01A106/5/$30.00 C 2012 American Vacuum Society
V 01A106-1

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01A106-2 Hämäläinen et al.: Study of amorphous lithium silicate thin films
which could effectively increase the energy storage capacity
in battery applications.14–16
The development of ALD processes for Li containing
films is currently under a growing interest for the 3D all-
solid-state lithium ion batteries. Lithium lanthanum titanate
thin films were deposited by introducing lithium into the
films using LiOtBu–H2O subcycles.17 On the other hand,
lithium lanthanate films were grown combining Lithd–O3
and La(thd)3–O3 processes.18 The Lithd–O3 combination by
itself leads into Li2CO3 films,18 which also can be obtained
by using LiOtBu, H2O, and CO2.19 In addition, lithium phos-
phates can be grown using either LiOtBu or LiHMDS
[Li(N(SiMe3)2)] with trimethyl phosphate.20 Also, the depo-
sitions of LiFePO4 and Li1.6Al1.0Oz have been presented
recently.21,22 As the overall number of ALD processes for
lithium containing materials is quite small, there is still a
need for developing straightforward, simple, and robust
ALD processes that could eventually be applied for lithium
ion batteries. In the following study, LiHMDS will serve
both as an Li and Si source when combined with ozone,
which breaks not only the Li–ligand bond but partially also
the ligand itself. Because LiHMDS serves as a precursor for
two elements, the overall process is simplified from that usu-
ally required for ternary oxides.
II. EXPERIMENT
Thin films were grown in a commercial cross-flow F-120
ALD reactor (ASM Microchemistry Ltd.) equipped with a
quartz cassette substrate holder under a nitrogen pressure of
about 10 mbar. Nitrogen was produced with a Domnick
Hunter G2100E nitrogen generator and used as a carrier and
a purging gas in the ALD reactor. Two 5  5 cm2 silicon
(111) substrates were used in most of the depositions, while
a soda lime glass also was applied in some experiments in
place of an Si substrate. The films were grown using lithium
hexamethyldisilazide [LiHMDS, Li(N(SiMe3)2), also known
as lithium bis(trimethylsilyl)amide] and ozone as precursors.
LiHMDS (Aldrich, 97%) was sublimed from an open source
boat held inside the reactor at 60  C and pulsed with inert
gas valving. Some LiHMDS was also synthesized in-house
according to the literature.23 Ozone was produced with a
Wedeco Ozomatic Modular 4 HC Lab ozone generator from
oxygen (99.999%, Linde Gas) and pulsed from the main
ozone flow line into the reactor through a needle valve and a
solenoid valve.
Film thicknesses and refractive indices at a wavelength of
580 nm were evaluated from reflectance spectra measured
mostly between 190 and 1100 nm by a Hitachi U-2000 spec-
trophotometer.24 Crystallinity of the films was determined
with a PANalytical X’Pert Pro x-ray diffractometer in grazing
incidence mode (GIXRD). Adhesion of the films to Si was
tested with a common Scotch tape test. Electric resistivity of
the films was confirmed with a four-point probe technique.
Elemental compositions of the films were determined
with elastic recoil detection analysis (ERDA) using a 35
MeV Cl7þ ion beam. The recoil ions were detected with a
Bragg ionization chamber using a full energy detection cir-
J. Vac. Sci. Technol. A, Vol. 30, No. 1, Jan/Feb 2012
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01A106-2
cuit and a fast timing circuit to obtain a Z dependent signal
to separate different ions. Hydrogen and lithium were
detected simultaneously with a separate solid state detector
preceded by either a Mylar or an Al foil to stop other scat-
tered and recoiled ions. The ERDA spectra and the RBS
spectrum from Cl scattering were fitted simultaneously using
the program NDF.25
III. RESULTS AND DISCUSSION
LiHMDS is a trimeric compound in the solid state
(Fig. 1)26–28 and dimeric in the gas phase.29 The LiHMDS
melts at 71–72  C and is thus a solid at the used precursor
temperature. Despite the oligomeric structure of LiHMDS
the volatility is quite good compared to many other lith-
ium compounds.20 Good volatility is also indicated by the
low precursor temperature (60  C) that was used in the
ALD.
Lithium silicate films were deposited using LiHMDS and
ozone as precursors. Figure 2 presents growth rates and
refractive indices of the films as a function of LiHMDS pulse
length at 250  C. The growth rate is about 0.7 Å/cycle with
LiHMDS pulse length of 2 s or less and stabilizes to 0.8–0.9
Å/cycle between 3 and 6 s. The refractive index is 1.54–1.55
with pulse lengths of 2 s or more. With 1 s LiHMDS pulse
the refractive index seems to be slightly higher (1.56). Simi-
lar results are obtained when varying the ozone pulse length
(Fig. 3). The growth rate is around 0.8 Å/cycle with ozone
pulses of 2 s or more; although the growth rate seems to
increase still slightly with increasing ozone pulse length.
The use of 1 s ozone pulse lengths results in a small decrease
in growth rate; however the films are still uniform across the
substrate. The films deposited with 1 s ozone pulses also
have a somewhat higher refractive index (1.57) compared to
the films obtained with longer ozone exposures (1.55). Over-
all, the results on both precursor pulse lengths indicate that
the process is well controllable and follows the basic princi-
ples of self-limiting growth as characteristic in ALD.
Next, the effect of the number of deposition cycles on
film thickness and refractive index was examined at 250  C.
FIG. 1. (Color online) Molecular structure of [Li(N(SiMe3)2)]3. Thermal
ellipsoids are drawn on the 50% level and hydrogen atoms are omitted for
clarity.
01A106-3 Hämäläinen et al.: Study of amorphous lithium silicate thin films
FIG. 2. Growth rate and refractive index of the lithium silicate films at
250  C as a function of LiHMDS pulse length. The pulse length for ozone
was 2 s. All the purges were 1 s each. One-thousand cycles were applied in
each deposition.
As characteristic for ALD oxide processes, the film thickness
is related to the number of deposition cycles applied without
any noticeable incubation delay (Fig. 4). The refractive
index also remains constant between 1.55 and 1.56, which is
in good agreement with the refractive indices obtained with
varying precursor pulse lengths (Figs. 2 and 3).
The LiHMDS–ozone process seems to comply with the
general characteristics of ALD with respect to constant
growth rate due to saturative precursor doses and self-
limiting surface reactions (Figs. 2 and 3), and the linear
dependence of film thickness with increasing number of
deposition cycles at 250  C (Fig. 4). However, the growth
rate of the process was found to be strongly dependent on
the deposition temperature (Fig. 5). The growth rate
increases quite linearly with increasing deposition tempera-
ture from 0.3 Å/cycle at 150  C up to 1.7 Å/cycle at 400  C.
This means that the LiHMDS–ozone process is lacking the
so-called ALD temperature window found in most ALD ox-
ide processes. The refractive indices of the films on the other
FIG. 3. Growth rate and refractive index of the lithium silicate films at
250  C as a function of ozone pulse length. The pulse length for LiHMDS
was 4 s. All the purges were 1 s each. One-thousand cycles were applied in
each deposition.
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01A106-3
FIG. 4. Thickness and refractive index of the lithium silicate films deposited
at 250  C as a function of number of deposition cycles. The pulse lengths
for LiHMDS and ozone were 4 and 2 s, respectively, with 1 s purges.
hand have a constant value over a large deposition tempera-
ture range. A plateau for refractive index (1.55) is found
between 225 and 275  C, and in a deposition temperature
range between 150 and 300  C the refractive index variation
is still within the experimental error margins. The refractive
index seems to slightly decrease between 275 and 350  C,
which may indicate compositional changes in the films
grown at higher temperatures. The sudden increase in refrac-
tive index at 400  C is most likely related to the partial
decomposition of LiHMDS, observed also as a darker shade
in the hot end of the precursor tube after deposition. How-
ever, this was not detrimental to the film uniformity and did
not result in increased carbon contamination in the film (to
be discussed later).
The films are x-ray amorphous when deposited between
150 and 350  C (Fig. 6); however, an unidentifiable peak is
visible in the pattern of a film deposited at 400  C. As
noticeable decomposition was observed at this deposition
temperature, it may be suggested that this crystallinity is
FIG. 5. Growth rates and refractive indices of lithium silicate films as a func-
tion of deposition temperature. The pulse lengths for LiHMDS and ozone
were 4 and 2 s, respectively, with 1 s purges. One-thousand cycles were
applied for all depositions, except at 150  C where 2000 cycles were used.
01A106-4 Hämäläinen et al.: Study of amorphous lithium silicate thin films 01A106-4



1=2 Li NðSiMe3 Þ2 2 ðgÞ þ X OHðsÞ


! Li NðSiMe3 Þ2 1X ðsÞ þ XHNðSiMe3 Þ2 ðgÞ;


Li NðSiMe3 Þ2 1x ðsÞ þ YO3 ðgÞ ! LiSi22x O4:54x ðsÞ
þ X OHðsÞ þ COx ðgÞ þ O2 ðgÞ þ H2 OðgÞ
þ other possible by-products

It should also be emphasized that no N could be detected in

any analyzed ERDA sample above the detection limit of
about 0.2 at. %.
The densities of the films were calculated from the film
thicknesses obtained from the reflectance measurements
(nm) and the areal densities obtained from the ERDA meas-
urements (atoms/cm2) (Table I). The film densities increase
FIG. 6. GIXRD pattern of lithium silicate films deposited at various temper-
from 2.26 to 2.39 g/cm3 between 200 and 350  C. The
atures. The deposition parameters are the same as in Fig. 4.
slightly higher densities at 150 and 400  C are most likely
results of substantially higher Li/Si ratios in the films; how-
caused by a CVD component in the film growth process. The
ever at 150  C higher carbon and hydrogen impurity contents
films were electrically resistive according to the four-point
also may have contributed. Overall, the films deposited at
probe measurements. Only the films deposited at the lowest
250  C show a stoichiometry of Li2.0SiO2.9, which is in good
temperatures showed faint electrical conductivity, which
agreement with the stoichiometry of lithium metasilicate
could not, however, be determined reliably.
(Li2SiO3). The film deposited at 300  C is already showing
The elemental compositions of the films deposited at vari-
slightly decreased Li and O contents (Li1.7SiO2.8) compared
ous temperatures are presented in Table I. The film deposited
to Li2SiO3. Also, an additional ERDA measurement was car-
at 150  C shows considerable carbon (about 4 at. %) and
ried out from a lithium silicate film deposited at 300  C on
hydrogen (about 9 at. %) impurity contents. The carbon con-
top of about 150 nm thick Ta2O5. The analyzed 360 nm
tent decreases with increasing deposition temperature being
less than 1 at. % in all the films deposited at 200  C and
above. Also, the hydrogen content decreases with increasing
temperature; however, the film deposited at 250  C contains
still 4.6 at. % hydrogen. The composition of the films varies
as a function of deposition temperature. The Li/Si ratio
decreases with increasing temperature from 2.8 (150  C) to
1.6 (350  C). The O/Si ratio shows a similar tendency,
decreasing from 4.0 to 2.7. The higher Li/Si and O/Si ratios
at 400  C are likely a result of a partial decomposition of
LiHMDS. It is worth noting that in the LiHMDS precursor
the Li/Si ratio is 0.5, i.e., much less than in any of the films.
This means that only part of the ligands is combusted by
ozone. Most likely during the LiHMDS pulse some of the
ligands are released as HN(SiMe3)2 in exchange reactions
with surface hydroxyl groups, and only the remaining
ligands are combusted during the following O3 pulse:

TABLE I. Elemental compositions of the lithium silicate thin films as meas-

ured with ERDA.

Deposition temperature

150  C 200  C 250  C 300  C 350  C 400  C

Li (at. %) 31.8 29.8 32.5 30.8 30.0 37.5

Si (at. %) 11.2 13.9 16.1 17.7 18.5 15.1
O (at. %) 44.2 48.7 46.3 48.6 49.6 45.9
C (at. %) 3.94 0.96 0.65 0.32 0.14 0.15
H (at. %) 8.78 6.63 4.60 2.70 1.71 1.29
Thickness (nm) 62 62 86 120 140 172
Density (g/cm3) 2.48 2.26 2.32 2.36 2.39 2.5
Li:Si:O ratio 2.8:1:4.0 2.1:1:3.5 2.0:1:2.9 1.7:1:2.8 1.6:1:2.7 2.5:1:3.0 FIG. 7. (Color online) Photographs of the soda lime glass substrate after
ALD lithium silicate film deposition at 300  C.

J. Vac. Sci. Technol. A, Vol. 30, No. 1, Jan/Feb 2012

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01A106-5 Hämäläinen et al.: Study of amorphous lithium silicate thin films
thick film showed substantially lower lithium content
(Li1.0SiO2.9) compared to the film grown on Si in Table I
(Li1.7SiO2.8). The reason for this lithium content reduction is
currently unknown. However, as lithium is known as an eas-
ily moving ion due to its small size, lithium might have
migrated into Ta2O5. In fact, the lithium ionic conductivity
of lithium silicates has been shown to increase in the pres-
ence of ozone.8 Also, the soda lime glasses used in some
growth experiments suffer from quite dramatic cracking
after the lithium silicate deposition (Fig. 7), which is most
likely caused by the lithium ion migration into the glass. An
efficient lithium ion barrier such as TiN (Ref. 30) could be
able to prevent the glass cracking.
IV. SUMMARY
In conclusion, lithium silicate films were successfully
deposited between 150 and 400  C from LiHMDS and ozone.
The films deposited at 250  C were shown to be grown in a
saturative and controllable manner as expected in ALD. The
growth rate of the LiHMDS–O3 process was strongly depend-
ent on the deposition temperature and increased from 0.3 up
to 1.7 Å/cycle between 150 and 400  C. Also the stoichiome-
tries of the films changed with deposition temperature. The
amorphous films deposited at 250  C had a growth rate of
0.8 Å/cycle, refractive index of about 1.55 (n580), and a stoi-
chiometry close to lithium metasilicate (Li2SiO3). The carbon
and hydrogen contents were 0.7 and 4.6 at. %, respectively.
ACKNOWLEDGMENT
Financial support from ASM Microchemistry Ltd. is
gratefully acknowledged.
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