Nanostructured dense ZrO2 thin films from nanoparticles obtained by emulsion precipitation

Article abstract of DOI:10.1111/j.1551-2916.2004.01430.x

Nonagglomerated spherical ZrO₂ particles of 5-8 nm size were made by emulsion precipitation. Their crystallization and film-forming characteristics were investigated and compared with nanosized ZrO₂ powders obtained by sol-gel precipitation. High-temperature X-ray diffraction indicated that the emulsion-derived particles are amorphous and crystallize at 500°C into tetragonal zirconia, which is stable up to 1000°C. Crystallite growth from 5-20 nm occurred between 500°-900°C. Films of 6-75 nm thickness were made by spreading, spin coating, and controlled deposition techniques and annealed at 500°-600°C. The occurrence of t-ZrO₂ in the emulsion-precipitated powder is explained by the low degree of agglomeration and the corresponding low coarsening on heating to 500°-800°C, whereas the agglomerated state of the sol-gel precipitate powder favors the occurrence of the monoclinic form of zirconia under similar conditions.

Full text of DOI:10.1111/j.1551-2916.2004.01430.x

J. Am. Ceram. Soc., 87 [8] 1430–1435 (2004)
journal
Nanostructured Dense ZrO2 Thin Films from Nanoparticles
Obtained by Emulsion Precipitation
Fiona C. M. Woudenberg, Wiebke F. C. Sager,† Johan E. ten Elshof,§ and Henk Verweij*,‡
University of Twente, Inorganic Materials Science, MaineSAϩ Research Institute and Department of Science and
Technology, P.O. Box 217, 7500 AE Enschede, the Netherlands
cubic (c-ZrO2) at temperatures Ͼ2400°C.22 The presence of small
amounts of certain ionic species such as sulfate4 may stabilize the
tetragonal phase down to lower temperatures. Garvie23 observed
that t-zirconia is present at room temperature when the particle size
of the tetragonal phase is smaller than a certain critical value.
When the particles grew to be Ͼ30 nm, a complete conversion
from the tetragonal into the monoclinic phase occurred. A simple
thermodynamic model has been proposed to describe the free
energy of an unconstrained spherical crystal, from which the
critical particle radius (rc) for the tetragonal to monoclinic
transformation can be correlated with the phase-transformation
temperature:24,25
Nonagglomerated spherical ZrO2 particles of 5–8 nm size were
made by emulsion precipitation. Their crystallization and
film-forming characteristics were investigated and compared
with nanosized ZrO2 powders obtained by sol–gel precipita-
tion. High-temperature X-ray diffraction indicated that the
emulsion-derived particles are amorphous and crystallize at
500°C into tetragonal zirconia, which is stable up to 1000°C.
Crystallite growth from 5–20 nm occurred between 500°–
900°C. Films of 6–75 nm thickness were made by spreading,
spin coating, and controlled deposition techniques and an-
nealed at 500°–600°C. The occurrence of t-ZrO2 in the
emulsion-precipitated powder is explained by the low degree of
agglomeration and the corresponding low coarsening on heat-
ing to 500°–800°C, whereas the agglomerated state of the
sol–gel precipitate powder favors the occurrence of the mon-
oclinic form of zirconia under similar conditions.
3.79 nm
rc ϭ
(1)
T
1 Ϫ
ͩ ͪ
1448
where T (K) is the transformation temperature. Recent high-resolution
transmission electron microscopy studies on ZrO2 also revealed a
critical upper size for ultrapure tetragonal grains.3,25,26 Aita et al.3
determined a critical layer thickness of 6.2 nm at 564 K for
nanolaminates made from polycrystalline zirconia and amorphous
alumina, which agrees well with the predictions of Eq. (1).
In several other studies, it has been suggested that the pH of the
solution from which the zirconia precursor precipitates determines
the predominant phase. Davis27 investigated zirconia gels, precip-
itated from a zirconyl nitrate solution at pH values between 0–14.
Relatively high fractions of tetragonal ZrO2 were found in calcined
powders synthesized at pH Ͻ5 or Ͼ12. In powders prepared from
nitrate,28 chloride,18 and sulfate4 based zirconia precursors the
tetragonal and monoclinic phases were found to coexist at Ͼ600°C
when the grains had grown larger than 25 nm.
I. Introduction
IRCONIA coatings are of special interest for several high-
Z
performance applications, such as high-k dielectrics, wear-
resistant insulating coatings, sensors, and electrolytes. Thin homo-
geneous nanocrystalline zirconia films with grain sizes Ͻ20 nm
have been prepared by reactive sputter deposition1–3 and sol–gel
methods.4 Dense layers made by deposition of nonagglomerated
nanoparticle dispersions may lead to systems with substantially
reduced sintering temperature and minimal grain growth.5
Several techniques for the synthesis of nano-ZrO2 have been
reported, such as inert gas condensation,6–8 forced hydrolysis,9–11
alkoxide hydrolysis,12,13 hydrothermal processes14 and other tech-
niques.15–17 ZrO2 nanoparticles obtained by sol–gel-based pro-
cesses are often highly agglomerated,9 whereas more elaborate
methods to obtain monodisperse ZrO2 resulted in particle sizes
Ͼ30 nm.18 ZrO2 precursor particles have also been synthesized in
heterogeneous media, such as emulsions, micellar systems, and
microemulsions.19,20 Typical problems encountered in emulsion
precipitation are particle growth beyond the dimensions of the
aqueous droplets, and strong and uncontrolled aggregation, in
particular during the water-removal step.21
Clearfield29 explained the occurrence of tetragonal ZrO2 at low
temperatures by assuming two precipitation mechanisms, slow and
rapid precipitation. Slow precipitation is thought to dominate at pH
Ͻ2 and Ͼ13, where aqueous tetrameric Zr(IV) species form an
ordered network that acts as a template for the formation of the
tetragonal phase. Rapid precipitation, on the other hand, promotes
the formation of a random network that crystallizes into a mixture
of m- and t-ZrO2 (pH 2–6), or almost pure monoclinic ZrO2 (pH
7–11) on heating.
In the present study, ZrO2 precursor particle dispersions in
decane are made by a modified emulsion precipitation method.
The particle morphology, crystallization behavior and phase evo-
lution on annealing are investigated and compared with similar
sized ZrO2 powders obtained by sol–gel precipitation method.
Three methods are applied to deposit thin films from dispersions of
ZrO2 precursor nanoparticles in decane. The film formation
characteristics, morphology, and phase evolution on annealing are
characterized.
Bulk zirconia has three polymorphs, i.e., monoclinic (m-ZrO2)
at room temperature, tetragonal (t-ZrO2) at 1200°C and higher, and
A. Krell—contributing editor
Manuscript No. 10764. Received December 29, 2003; approved February 27,
2004.
Supported by the Netherlands Technology Foundation and the Priority Program for
Materials.
*Member, American Ceramic Society.
†Present address: Forschungszentrum Ju¨lich, Institut fu¨r Festko¨rperforschung,
D-52425 Ju¨lich, Germany.
II. Experimental Procedures
‡Present address: The Ohio State University, Department of Materials Science and
Engineering, Columbus, OH 43210-1178.
(1) Emulsion Precipitation Synthesis
A 0.02M ZrCl4 (Merck, Darmstadt, Germany) solution was
used as aqueous precursor phase for emulsion precipitation. As
§Author to whom correspondence should be addressed. e-mail: j.e.tenelshof@
utwente.nl.
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August 2004
Nanostructured Dense ZrO2 Thin Films from Nanoparticles Obtained by Emulsion Precipitation
1431
precipitation agent, a 0.025M hexamethylenetetramine (HMTA;
Fluka Chemical, Ronkonkoma, NY) solution was used. Thermally
stable (20°–80°C) water in oil emulsions was prepared from 40 g
of one of the above-mentioned aqueous solutions, 60 g decane
(Fluka), 1 g nonyl phenol tetra-ethyleneglycol ether (Arkopal 40;
Hoechst, Frankfort, Germany), and 1 g didodecyl-dimethyl-
ammonium bromide (DiDAB; Fluka). An Ultra-Turrax (IKA T25
basic, Dijkstra Vereenigde, Netherlands) was used to produce
emulsions of the aqueous solutions in decane at a rotation speed of
20 000 rpm. The emulsion containing the precursor solution was
mixed with one of the emulsions containing a precipitation agent,
stirred for 5 min at room temperature, followed by stirring for
10–15 min at 50°–60°C to induce precipitation. The pH during
precipitation was monitored with a pH electrode for emulsions
(Inlab 420, Mettler-Toledo, Highstown, NJ). After precipitation, a
poly-(octadecyl methacrylate) solution (PODMA; 25 wt% solution
in toluene, Aldrich, Milwauke, WI) was added for particle stabi-
lization. The amount of PODMA added was 10 wt% with respect
to the theoretical amount of oxide formed. The water phase was
removed by azeotropic distillation. Because DiDAB is soluble
only at the water/decane interface, the excess of DiDAB not
needed for particle stabilization precipitated after water removal
and was removed with a filter paper. The remaining soluble
surface-active agents were washed out with decane in a cross-flow
filtration device.30
radiation (␭ ϭ 0.15418 nm). The particle dispersions were applied
directly as concentrated films on platinum strips. The spectra were
recorded in the range 2␪ 15°–95° between room temperature and
1300°C (heating/cooling rates 2°C). Every 100°C, the temperature
was kept constant for 1 h to anneal the samples before in situ XRD
spectra were recorded. The average crystallite size D was calcu-
lated using the Scherrer formula D ϭ 0.9␭/Bcos(␪), where B is the
full-peak width at half of the maximum intensity after correction
for instrument broadening contributions.
The morphology of nanoparticles was characterized by high-
resolution transmission electron microscopy (HRTEM; Model
CM30 Twin STEM, Philips; 300 kV, 0.23 nm resolution). TEM
was performed on unfiltered particles, whereas HRTEM was
performed after removal of organic residuals as described above.
Zirconia thin films were characterized by field emission scanning
electron microscopy (FESEM; Model XL30 SFEG-SEM, Philips,
voltage 1–30 kV, 2 nm lateral resolution) and HRTEM on cross
sections of thin films.
III. Results and Discussion
(1) Zirconia Nanoparticles
The yield of ZrO2 precursor particle dispersions was 70%–
80%. These dispersions were stable and could be concentrated
reversibly, whereas the solvent could be exchanged with hexane or
octane. Figure 1(a) shows an HRTEM micrograph of unfiltered
emulsion-derived ZrO2 precursor particles. The particles are not
agglomerated, and some organic residuals are visible in the upper
part of the picture. Most particles have a diameter between 5–8
nm, but some particles with a diameter of up to 12 nm are present
as well. Figure 1(b) shows TEM images of the sol–gel-derived
powder at two magnifications. In contrast to the nonagglomerated
state of the emulsion-precipitated powder, the sol–gel powder
consists of large agglomerates of 50–100 nm or larger size. As
shown in the inset, the primary grain size is 4–9 nm, i.e., in the
same range as the precipitated powder.
(2) Sol–Gel Synthesis
Sol–gel derived ZrO2 nanoparticles were obtained from a 50
mL precursor solution containing 0.4M ZrCl4 and 0.2M HCl
(Merck). Precipitation was induced by adding the precursor
solution dropwise to 80 mL of 25% ammonia (Merck) under
stirring.31 The precipitate was kept in the solution overnight,
collected and washed with doubly distilled water until the chloride
concentration was below the detection limit (tested with AgNO3).
After washing twice with ethanol, the precipitate was dried at 80°C
and calcined in air at 400°C.
The phase evolution of these two types of precursor nanopar-
ticles on heat treatment was investigated with HTXRD. The
emulsion-derived particles made were amorphous and crystallised
into t-ZrO2 after annealing for 1 h at 500°C, as shown in Fig. 2(a).
Line broadening analysis indicated that the initial crystallite size at
500°C is similar to that of the precursor particles. On further
heating the tetragonal phase remained stable till 1000°C. At
1100°C the monoclinic phase formed, although the intensities of
(3) Thin Film Formation
Thin films were deposited by spin coating, spreading, and
controlled deposition of the dispersions on polished [100]-oriented
silicon wafers (76 mm diameter, MEMC Electronic Materials, St.
Peters, MO) under class 1000 clean-room conditions. Before use,
the wafers were chemically etched with concentrated HF.
The spin-coating procedure consisted of covering the substrate
with a few drops of dispersion at low-spinning speed, after which
the rotation frequency was increased to 2000 rpm for ϳ20 s. This
procedure was repeated four times.
៮
the monoclinic (111) and (111) reflections were Ͻ2% of the
intensity of the tetragonal (111) refection. At 1300°C, the mono-
clinic phase was present only in trace amounts. On cooling m-ZrO2
was detected at temperatures Ͻ800°C, and became the predomi-
nant phase at Ͻ400°C. The volume fraction of the tetragonal phase
xt was calculated from the peak intensity ratio,32 i.e.:
Dispersion spreading was done by placing a few droplets of the
dispersion between the polished sides of two wafers and horizontal
sliding of one wafer relative to the other.
The controlled-deposition procedure consisted of attaching the
substrate to a Peltier element (Model L 100, LC-Electronics,
Germany) that was placed under a tilt angle of 9°, and cooling
down the substrate to 10°C. The dispersion was added dropwise to
the top of the substrate, after which the substrate was left for 7 d
in a water vapor-free glove box to allow slow drying.
Any residual organics were removed by subsequent heat treat-
ment for 3 h at 200°C, and oxygen plasma treatment at 45°C for
1.5 h. The oxygen-plasma treatment was conducted with an
(Model ET Plasmafab 508 Electrotech, Ulm, Germany; 49.5
mL/min O2, 0.17 mbar, 250 W rf power). To study the temperature
evolution of the films, samples were annealed in air for 3 h at
different temperatures. The heating rate was 5°C/min between
room temperature and 50°C below the final temperature, and
2°C/min in the last 50°C temperature interval.
I͑111͒
t
xt ϭ
(2)
I͑111͒t ϩ I͑111͒m ϩ I͑111͒
m
where I(abc)x is the intensity of the (abc) reflection of phase “x.”
At room temperature, xt was found to be ϳ35%. Figure 3 shows
the entire HTXRD pattern at 900°C. Although it is assumed that
the amorphous particles crystallize into t-ZrO2, no distinction
between t- and c-ZrO2 can be made by XRD only. However, the
weak (112) reflection at 2␪ 42.6° can be assigned only to t-ZrO2,
which suggests that the material is at least predominantly tetrago-
nal. Samples heated to temperatures Ͻ1000°C remained tetragonal
after cooling down to room temperature. The average crystallite
size of the t-phase remained 5–7 nm until 700°C, and was Ͻ20 nm
until 900°C. Significant growth occurred from 1000°C onward,
reaching an estimated size of ϳ80 nm when the monoclinic phase
appeared. On further heating to 1300°C, further particle growth of
the tetragonal phase to 100–120 nm occurred. When the mono-
clinic phase reappeared from 400°C downward, the particle size of
the tetragonal phase decreased to ϳ30 nm at room temperature.
The average size of the monoclinic phase is also ϳ30 nm. Similar
(4) Characterization
High-temperature X-ray diffraction (HTXRD) measurements
were performed on particle dispersions using a diffractometer
(Model X’pert-MPD, Philips, Eindhoven, Netherlands) with CuK␣

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Journal of the American Ceramic Society—Woudenberg et al.
Vol. 87, No. 8
Fig. 1. (a) TEM image of precipitated 5–8 nm ZrO2 precursor particles. Some organic residuals are also visible; (b) TEM image of sol–gel-derived ZrO2
powder. The inset shows the same powder at higher magnification. The primary particle size is 4–9 nm.
sizes were found when the particles were heated to 1000°C and
subsequently cooled. The decrease in particle size during the
cooling part of the temperature cycle may possibly be explained by
crystal breakup or the formation of hybrid t-ZrO2/m-ZrO2 crystals
from larger tetragonal crystals due to internal stresses.
However, the monoclinic grain size was found to be smaller than
the coexisting tetragonal grain size under various conditions,
which contradicts the assumptions underlying Eq. (1). This sug-
gests that phase development is more strongly related to parame-
ters, such as preparation conditions, material purity, and/or the
influence of constraint effects due to a relatively dense packing of
particles. Especially, the latter effect can explain the observed
differences in the tetragonal/monoclinic compositions of emulsion
and sol–gel-derived powders between 500° and 1000°C. The low
degree of agglomeration and the corresponding low coarsening on
heating to 500°–800°C of the emulsion-precipitated powder ex-
plains the occurrence of t-ZrO2, whereas the high coarsening of the
sol–gel precipitate powder on calcination favors the occurrence of
the monoclinic form of zirconia.
In the sol–gel-derived powders m-ZrO2 already formed at much
lower temperatures, i.e., 600°–700°C, as illustrated in Fig. 2(b). At
1100°C, the volume fraction of t-ZrO2 was ϳ37%. At higher
temperatures, the monoclinic phase diminished and disappeared
completely at 1300°C. On cooling the powder remained tetragonal
until the monoclinic phase re-emerged below 1000°C. Initially, the
initial crystallite size of the sol–gel powders was ϳ9 nm, as
estimated from line broadening analysis, and they had grown to
12–15 nm when the monoclinic phase started to form. The crystal
size of the monoclinic phase was similar. The crystallites of both
phases grew to ϳ70 nm at 1200°C. During cooling the monoclinic
phase reappeared at 900°C with crystal sizes of ϳ70 nm. The
shape of the tetragonal peak during cooling was highly asymmetric
between 900° and 500°C, which may be explained by strain
occurring during phase transformation.33 As the volume fraction of
the monoclinic phase increased, the monoclinic crystal size de-
creased until it reached values of ϳ55 nm at room temperature.
The crystalline phase that forms from both types of amorphous
powders is the metastable low-temperature t-zirconia phase that is
often observed in nanopowders.23 A special feature of the powder
prepared by emulsion precipitation is that the tetragonal phase
remains stable in a broad temperature range up to 1000°C.
Powders prepared by other techniques such as sol–gel synthesis
form a mixture of m- and t-ZrO2 already at much lower tempera-
tures.34,35 The martensitic transition from the monoclinic to the
high-temperature tetragonal phase at 1200°–1300°C exhibited by
both types of powders is also observed in conventional bulk
zirconia.22,36
(2) ZrO2 Thin Films
When the nanoparticle dispersions were deposited as thin films,
very similar results were obtained for the spin coating and
spreading techniques. Both methods led to thin layers with
thicknesses of 6–30 nm. This corresponds roughly to 1–5 layers of
grains. The coated wafers became transparent after heat treatment
in air at 500°C or higher. The TEM image in Fig. 4(a) shows a
cross section of a spin-coated ZrO2 film after annealing at 500°C
for 3 h. A smooth and continuous ZrO2 layer with a thickness of
6–10 nm that is attached to an amorphous SiOx layer can be seen.
Although the native oxide layer of the wafer had been removed by
chemical etching before film deposition, it reappears during
annealing. The spin-coated film shown in Fig. 4(b) was annealed
at 1000°C. The thickness of 9–10 nm is similar to the thickness
before annealing, but the grains appear to have become flatter. The
SiOx layer in between the zirconia film and the silicon wafer grew
considerably to a thickness of ϳ130 nm, and was found to be
independent of the thickness of the zirconia layer.
The usual layer thickness obtained with spin coating was 4–8
nm, which corresponds to 1–2 monolayers. HRTEM measure-
ments were performed on cross sections of samples after annealing
at 200°–600°C for 3 h to study the structural development of these
layers on heat treatment. The coatings shown in Fig. 5 (annealed at
200, 400° and 600°C, respectively) appeared dense even below the
crystallization temperature, and showed no signs of significant
shrinkage. A native silicon oxide layer formed between the silicon
Partial transformation to m-ZrO2 occurs between
1000°–1100°C and 500°–600°C in both the emulsion and sol–gel-
derived powders, respectively. According to Eq. (1), these tem-
peratures correspond with critical particle radii rcϳ31 nm
(1000°C) and ϳ8 nm (500°C). Although the experimental data did
not show a distinct transformation temperature above which only
the monoclinic phase is stable, these calculated values correspond
well with the experimental tetragonal particle sizes of 32 and 6.3
nm that are found in these two systems at the same temperatures.

August 2004
Nanostructured Dense ZrO2 Thin Films from Nanoparticles Obtained by Emulsion Precipitation
1433
៮
Fig. 2. Temperature evolution of the t-(111), m-(111), and m-(111) reflections by HTXRD: (a) emulsion-derived ZrO2 particles; (b) sol–gel-derived ZrO2
particles.
wafer and the zirconia film as a result of the high-temperature
treatment. Between 200° and 500°C the ZrO2 layers are mainly
amorphous, although they have some crystalline grains with
visible lattice fringes. The latter grains probably developed under
the electron beam. Coatings annealed between 200° and 500°C are
very similar to the coating shown in Figs. 5(a) and (b). A fully
crystallized layer is formed at 600°C, as shown in Fig. 5(c). The
crystallites are randomly orientated with sizes of 5–12 nm.
Considerably thicker ZrO2 layers were prepared using the
controlled deposition technique. Typically, the thickness of a
single layer was 40–50 nm, although the final films did not have
a similar thickness over the entire substrate. Further layer buildup
by multiple deposition steps without detectable boundaries be-
tween layers was possible, provided that each layer was heat-
treated before deposition of the next layer. Up to four deposition
steps were applied. Samples for HRTEM characterization were
usually taken from the thinnest part of the coating.
Figure 6 displays a cross section and a planar view of a singly
coated film after annealing at 600°C. The surface of the coating
appears to be very smooth and the thickness is ϳ45 nm. The
densely packed grains have a random orientation and are 5–10 nm
in size, as estimated from their lattice fringes. A thin film is visible
on top of the coating in Fig. 6(a) that is due to thickness variations
of the layer.
IV. Conclusions
Nonagglomerated spherical ZrO2 particles of 5–8 nm size were
made by an emulsion-precipitation method. The precipitated nano-
particles are amorphous and crystallize at 500°C into tetragonal (t)
zirconia, which is the only phase present up to 1000°C. In other
studies on zirconia nanoparticles reported to date, the monoclinic
(m) and tetragonal phases were found to coexist already at

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Journal of the American Ceramic Society—Woudenberg et al.
Vol. 87, No. 8
Fig. 3. HTXRD pattern of emulsion-derived ZrO2 at 900°C. The marked reflections can be attributed to the tetragonal phase.
temperatures of 100°–150°C above the amorphous-to-tetragonal
phase transition temperature. Sol–gel-derived ZrO2 nanoparticles
that were investigated for the sake of comparison, were partly
monoclinic at 600°C and higher temperature. Both types of
powders exhibit the well-known martensitic transition from the
monoclinic to the high-temperature tetragonal phase at Ͼ1200°C.
The crystallites obtained by emulsion precipitation grew slightly
from 5–20 nm between 500° and 900°C, and grew significantly from
1000°C onward to ϳ100 nm at 1300°C. The low degree of agglom-
eration and the corresponding low coarsening on heating to 500°–
800°C of the emulsion-precipitated powder explains the occurrence of
t-ZrO2, whereas the high coarsening of the sol–gel precipitate powder
on calcination favors the occurrence of the monoclinic form of
zirconia. Because of the enhanced thermal stability of the low-
temperature tetragonal phase, the particle size at the onset of the
tetragonal-to-monoclinic phase transition was much larger than re-
ported elsewhere. On cooling the tetragonal crystals transformed into
monoclinic, yielding a final size of ϳ30–40 nm at room temperature
for both the t- and m-ZrO2 grains. This suggests that the crystals either
broke up during cooling, or that hybrid t-ZrO2/m-ZrO2 crystals were
Fig. 4. Cross-sectional images of ZrO2 films prepared by spin-coating.
(a) TEM image of layer after annealing at 500°C; (b) HRTEM images of
layer after annealing at 1000°C.
Fig. 5. Thermal evolution of the microstructure of ZrO2 layers prepared
via spin-coating; (a) annealed at 200°C; (b) annealed at 400°C; (c)
annealed at 600°C.

August 2004
Nanostructured Dense ZrO2 Thin Films from Nanoparticles Obtained by Emulsion Precipitation
1435
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Thin films were prepared by spreading, spin coating, and
controlled deposition and annealed at 500°–600°C. Spreading and
spin coating led to thin layers with a thickness of 6–30 nm.
Deposition by controlled deposition led to films with an average
thickness of 45–75 nm. After annealing the densely packed grains
were randomly orientated and were only 5–10 nm in size. HTXRD
and HRTEM showed that the powders and films were tetragonal
up to at least 1000°C, although the presence of cubic zirconia
cannot be excluded.
Homogeneous mono- or multilayers of nanocrystalline zirconia
with grain sizes Ͻ20 nm have been made so far only by reactive
sputter deposition and sol–gel methods. In particular, the latter
method yields very similar zirconia films to those obtained here.
However, layer deposition from premade particle dispersions
offers the advantage of milder deposition conditions and may
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