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Surface-Energy-Driven Growth of ZnO Hexagonal

Microtube Optical Resonators
Jinxin Zhan, Hongxing Dong,* Shulin Sun, Xiaodong Ren, Jianjun Liu,
Zhanghai Chen, Christoph Lienau, and Long Zhang*

to synthesize tubular structures for non-

A distinct “split and recoalescence” growth mechanism of tubular ZnO micro/ layered materials such as oxides, metals,
nanostructures is observed for the first time. On the basis of experimental and nitrides because of the difficulties of
growth studies and first-principles calculations, it is proposed that H2/H2O controlling their dimensions. In lure of
the excellent properties and tremendous
vapor, added to the traditional carbothermal reduction process, changes the
potential applications of these nonlayered
intrinsic surface energy of ZnO crystal, which affects the ZnO crystal growth materials, great efforts have been made
mode and subsequently controls the geometry of ZnO micro/nanotubes. It is to develop the relevant tubular struc-
shown that these tubular ZnO micro/nanostructures exhibit regular hexagonal tures. Among them, ZnO is of particular
cross sections and smooth outer and inner surfaces. Optical studies of ZnO interest. Because of the wide direct band
micro/nanotubes reveal characteristic coherent intensity modulations of their gap (3.3 eV) and high excitonic binding
energy (60 meV), ZnO has become an
emission spectra which reflect the excitation of either whispering gallery ideal material for efficient short-wave-
modes or wave-guided modes. The specific type of mode can be selected length optoelectronic micro/nanode-
by controlling the microtube geometry, specifically by its wall thickness to vices.[11–15] It has been demonstrated that
diameter ratio, as demonstrated both experimentally by photoluminescence low-dimensional ZnO structures with
spectroscopy, and theoretically by finite-element-method simulations. regular geometrical configuration can be
applied in optical resonators,[16–21] which
commonly sustain two kinds of modes,
whispering gallery (WG) modes and
1. Introduction Fabry–Pérot (FP) modes.[16–18] For WG modes, light wave circu-
lates around in the micro/nanostructure due to multiple total
Tubular micro/nanostructures have gained considerable internal reflection (TIR) at only the outer interface between
interest for both fundamental scientific studies and practical microcavity and air.[17,22] For FP modes, light is reflected back
applications due to their unique and delicate constructions.[1–5] and forth between two opposing parallel facets.[16,18] Compared
Especially, the design and fabrication of novel micro/nanotubes with traditional wire/belt-like ZnO microcavities, tubular ZnO
composed of different materials for future optical device are microcavities have inner and outer surfaces, which introduce
attracting increasing attention. For quite a long time, micro/ additional design flexibilities and may be filled with lumi-
nanotubes had been confined to 2D layered materials like C, nescent or nonlinear optical materials.[23] Such a composite
MoS2, and WS2[5–9] supporting the roll-up mechanism of carbon microcavity would provide an ideal platform to investigate the
nanotube in 1991.[10] Correspondingly, it was quite difficult coupling effect between the matter and light, as well as might

J. X. Zhan, Dr. H. X. Dong, Prof. L. Zhang Prof. Z. H. Chen

Key Laboratory of Materials for High-Power Laser State Key Laboratory of Surface Physics
Shanghai Institute of Optics and Fine Mechanics and Department of Physics
Chinese Academy of Science Fudan University
Shanghai 201800, China Shanghai 200083, China
E-mail: hongxingd@siom.ac.cn; lzhang@siom.ac.cn Prof. C. Lienau
Prof. S. L. Sun Institute of Physics and Center of Interface Science
Department of Optical Science and Engineering and Shanghai Carl von Ossietzky Universität Oldenburg
Engineering Research Center of Ultra-Precision Optical Manufacturing Oldenburg D-26129, Germany
Fudan University Prof. L. Zhang
Shanghai 200433, China IFSA Collaborative Innovation Center
Dr. X. D. Ren, Prof. J. J. Liu Shanghai Jiao Tong University
State Key Laboratory of High Performance Shanghai 200240, China
Ceramics and Superfine Microstructures
Shanghai Institute of Ceramics
Chinese Academy of Sciences
Shanghai 200050, China
DOI: 10.1002/adom.201500442

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open up research on the interaction between multiple lumi-
nescence sources and semiconductor microcavities. Thus,
preparing ZnO micro/nanotubes with smooth surface and
high crystal quality employed as optical microcavities is a chal-
lenging but extremely attractive topic.
Generally, the surface stability of the crystal determines the
corresponding structural characteristics, whose effect on the
equilibrium morphology is utilized to design various micro/
nanostructures. ZnO micro/nanotubes have been fabricated by
utilizing some relevant crystal surface characteristics. Hexag-
onal ZnO has three fast growth directions along [0001], [10-10],
[2-1-10], and the [0001] direction has the maximal growth rate.
Thus, the (0001) surface has the highest surface energy, and is
the most unstable crystal surface.[24] Based on these intrinsic
structure characteristics, liquid phase methods have been
adopted to fabricate ZnO nanotubes.[25,26] In this kind of route,
the hexagonal ZnO rods are first obtained, then trhe (0001)
facets are gradually dissolved in the acidic or alkali medium,
finally leading to the successful synthesis of ZnO tubular
structures. Besides, the crystal structural feature of Zn is uti-
lized for growing ZnO micro/nanotubes via the vapor phase
method.[20,27] Similar to ZnO, three fast growth directions of
hexagonal Zn are [0001], [10-10], and [2-1-10]. Nevertheless, its
most stable surface is (0001).[20] In the typical process, vapor-
ized Zn is first deposited into liquid droplets and then the less
stable lateral walls of Zn nanoparticles are oxidized into ZnO
shells. At the same time, the inside Zn at (0001) surface sub-
limates, hence forming the hollow ZnO tubes. It can be seen
that all the established techniques for the ZnO micro/nanotube
growth are based on these intrinsic structural properties. Nev-
ertheless, the uncontrollability of crystal intrinsic properties
leads to that the majority of currently fabricated ZnO tube-like
structures are irregular, entangled, or do not possess smooth
surfaces. These deficiencies greatly hamper their application
as optical resonators. Although Dong et al. reported the ZnO
microtube fabricated through the above traditional growth tech-
nique in 2010,[20] the electric field distribution in the tubular
optical cavity, as well as the dependence of cavity modes on
the size and the morphology of tubes were not provided due
to the limitations of the synthesized products. Therefore, the
development of ZnO micro/nanotube growth techniques to
synthesizing the desired ZnO tubular microcavities is crucial
for further optoelectronic application of tubular ZnO microtube
resonators.
In this paper, we demonstrate the synthesis of ZnO micro-
tubes with regular hexagonal cross sections and smooth sur-
faces through a water-assisted carbothermal reduction process.
The experimental investigations and theoretical calculations
illustrate an interesting split–recoalescence growth mecha-
nism for the first time. In the crystal growth process, H2O/
H2 atmosphere significantly alters the intrinsic ZnO surface
energy and controls the configuration of tubular ZnO micro-
structures with a variety of wall thickness–radius ratios. When
studying the photoluminescence properties of differently
sized ZnO microtubes, distinct whispering gallery mode, and
wave-guided mode, and the dependence of cavity modes on
the ratio of wall thickness to radius were revealed. Our results
are firmly supported by finite-element-method (FEM) simula-
tions and indicate a novel growth route toward the formation of
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tubular microcavity resonators for immediate interest in hybrid
optoelectronics.
2. Results and Discussion
ZnO microtubes with hexagonal cross sections were formed
via a water-assisted carbothermal method. Figure 1a shows the
X-ray diffraction (XRD) pattern of the obtained products. All dif-
fraction peaks can be indexed as hexagonal wurtzite phase ZnO
(JCPDS No. 65-3411) and no impurity peaks are detected, which
indicate that the samples are pure ZnO with good crystalline
quality. From scanning electron microscopy (SEM) images of
these ZnO microtubes in Figure 1b–d, we can see that the ZnO
tubular structures have a highly regular hexagonal cross section
and smooth surfaces. Among all the as-grown products, ZnO
microtubes can be classified into three categories by the ratio,
d/R, of wall thickness, d, to outer radius, R, of the tubes, which
locate in different positions on the substrate (see Figure S1,
Supporting Information). The ZnO microtubes with small
hollow cores (large ratio of wall thickness, d, to outer radius, R)
as depicted in Figure 1b are deposited in the central zone of the
substrate. These tubular structures have outer radii of 2–3 µm,
wall thicknesses of about 2 µm, and lengths of 20–40 µm. In
addition, it is surprising to find some special microtubes with
extremely large hollow cores (small ratio of d/R) deposited in
the edge zone as shown in Figure 1d. Their lengths span a
range of 100–200 µm. The wall thicknesses of 0.5–1 µm and
outer radii of 10–40 µm generate a quite small ratio value of
d/R, ≈1/40. For ZnO, such high-quality tubular structure with
regular geometry, microsize, and smooth surfaces is quite
rarely reported, which may exhibit some unique microcavity
performances. Besides, some other scaled ZnO tubular struc-
tures given in Figure 1c are also obtained in the middle zone.
Their radii are 5–6 µm, wall thicknesses are around 1–2 µm,
and the lengths are in the range of 40–60 µm. The diversity of
the obtained ZnO microtubes makes it particularly interesting
to further study the optical properties of these low-dimensional
tubular optical microcavities. Figure 1e shows the SEM image
of a typical ZnO microtube. The results of energy dispersive
X-ray spectroscopy (EDS) elemental mapping measurements in
Figure 1f,g illustrate the uniform distribution of Zn and O ele-
ments along the entire microtube.
To understand the formation of such high-quality ZnO
microtubes, the growth mechanism was studied by monitoring
the morphology evolution during the entire reaction process.
Figure 2 shows SEM images of products obtained at different
time delays after beginning the deposition process. The results
clearly illustrate the ZnO tubular crystal growth process. As
reported in previous works,[20,27,28] the reaction process of carbo-
thermal reduction occurs as depicted in Equations (1) and (2).
First, ZnO powder is reduced by graphite into metal
ZnO + C → Zn + CO (1)
At high temperature, the Zn vapor then condenses on the
substrate and simultaneously is reoxidized as follows
2Zn + O2 → 2ZnO (2)
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Figure 1. a) XRD pattern of the obtained samples deposited on the whole substrate. SEM images of the synthesized ZnO microtubes collected from
b) the central zone, c) the middle zone, and d) the edge zone of the substrate. e) SEM image of a typical ZnO microtube. f,g) EDS mappings of Zn
and O, respectively.
From the point of crystal growth mode, ZnO material
has hexagonal wurtzite crystal structure and four common
low-index faces of (0001), (000-1), (10-10), and (11-20). The
(0001) facet has the highest surface energy, and is the most
unstable crystal surface. Its theoretical growth form is the
hexagonal columnar structure. Thus, the ZnO crystal nuclei
are first deposited on the substrate, forming the ZnO micro-
rods exposing both {0001} and {01-10} facets as shown in
Figure 2a. When the reaction time is prolonged to 1 min, the
microcolumn continues to grow and develops a clear hexagonal
cross-sectional profile. Simultaneously, however, obvious cracks
emerge and the lateral walls appear to be splitting to several
irregular hexagonal nanorods as illustrated in Figure 2b. This
reveals the formation of a primary ZnO hollow structure
instead of a solid hexagonal construction. Such interesting
growth phenomenon is rarely reported in ZnO nanocrystals
growth. As the deposition time increases, the splitting tendency
sustains and becomes even more pronounced. Hence, irregular
rods persistently grow and further split into more and thinner
ZnO nanowires which are organized in a hexagonal cross sec-
tion, as depicted in Figure 2c. As a result, the lateral surfaces
are increasingly dominant, and account for much larger frac-
tion of the total exposed surface than the top surfaces. Appar-
ently, this following growth habit in Figure 2b,c is distinctive
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from the original one and different from the previously
reported ZnO growth model. What is more surprising is that
the splitted adjacent nanowires coalesce together and gradually
develop an integral tube wall when the deposition time is pro-
longed to 9 min as shown in Figure 2d. Altogether, the growth
of these ZnO microtubes can be summarized as a novel nuclea-
tion-growth-split-coalescence process.
Based on the above results, it can be seen that the growth
behavior did not exactly comply with its intrinsic growth mode.
From the structural point of view, it is important to note that
the preferred crystallographic orientation will be changed under
varied growth conditions because they are kinetically driven
during the reaction process. Thus, this unique growth process
is supposed to be driven by some specific growth condition.
In order to understand this fancy growth model and explore
the driving condition, we carry out the following experiments.
Without adding water, the mixture of ZnO powder and graphite
is adopted as the reactant and other experimental conditions
are the same as described earlier. After 10 min, the products
deposited on the substrate are a large area of ZnO microrods
(see Figure S2, Supporting Information). Products with tubular
geometry are not found. This indicates that the presence of
water is highly critical for the microtube growth, and plays
an important role in changing the ZnO crystal growth mode.
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Figure 2. Time-dependent evolution of the ZnO crystal microstructure at different growth stages: a) The hexagonal ZnO microrod nucleates on the
substrate; b) as the amount of H2O/H2 increases, the nanorod grows and begins to split into several irregularly shaped microrods; and c) the trend
continues, and more and more nanowires are formed. At the same time, the area ratio of {01-10} to {0001} increases significantly; d) upon H2O/H2
consumption and flowing out, the disintegration disappears and the adjacent nanowires recoalesce. e) Schematic diagram of the entire growth cycle
of a ZnO microtube.

Considering reactions that water would introduce into the
system as follows
Zn + H2O → ZnO + H2
C + H2O → CO + H2
H2 and water vapor are the additional products comparing with
Equations (1) and (2). Therefore, we propose that the H2/H2O
atmosphere is the crucial factor that markedly affects the ZnO
crystal growth model and drives the formation of ZnO micro/
nanotubes. As the concentration of H2/H2O vapor successively
increases and decreases during the growth procedure, the ZnO
nanorod correspondingly splits and then coalesces. This is cor-
related with a change of the relative surface area between lateral
and top surfaces. According to the Gibbs–Wullf theorem, the
area of each crystal surface depends on its own surface energy.
Specifically, a crystal prefers to expose crystal planes with lower
(3) surface energy.[24] We therefore suggest that the unusual crystal
growth model that is shown in Figure 2e can be mostly ascribed
(4) to the effect of the H2/H2O vapor on the relative surface energy
of the ZnO crystal. Therefore, the relationship between H2/
H2O atmosphere and the relative surface energy of ZnO crystal
is the key to comprehend the growth mechanism of these ZnO
microtubes.
We have studied the surface energy at all possible surfaces of
ZnO, in the absence and presence of H or OH groups coverage
by simulating the possible surface structures under our reaction
conditions. The surface energies are calculated by first-princi-
ples methods based on density functional theory (DFT).[28] All

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the calculations are performed by using Vienna ab initio simu-
lation package (VASP).[29] The Perdew–Burke–Ernzerhof (PBE)
generalized gradient approximation (GGA) is used to cope with
the exchange–correlation functional, and projector augmented
wave (PAW) method is applied to treat the valence electron–ion
interaction.[30,31] An energy cutoff of 400 eV and suitable k-point
Monkhorst–Pack grid are used. The surface energies are given
by the equation as follows
E = [E slab − N Zn (U ZnO
Bulk
− U O ) − N OU O − N HU H ] / 2 A
Bulk
where Eslab is the total energy of the slab per unit cell, U ZnO is
the chemical potential of bulk ZnO, Ui is the chemical potential
of O or H, Ni is the number of them, and A is the total sur-
face area. In this study, we mainly focus on the surface energies
of four low-index facets, namely, (0001), (000-1), (10-10), and
(11-20), and compare their changes in the absence and pres-
ence of H2/H2O.
Without adding water, the variation of surface energy E
as a function of oxygen chemical potential UO is shown in
Figure 3a. It can be seen that the lateral surface of (11-20)
has the lowest surface energy which remains at a constant
value of 1.13 J m−2. This agrees well with previously reported
value of about 1.00 J m−2.[32] Setting UO to the chemical poten-
tial of oxygen gas, −4.19 eV (as labeled by the dotted line in
Figure 3a), we find that the second most stable surface is the O
terminated (000-1) surface with a surface energy of 1.78 J m−2.
Therefore, under this condition, the most stable and the second
most stable surfaces are (11-20) and (000-1), respectively. Their
structural models are depicted in Figure 3b. The surface energy
ratio between them, E(11-20)/E(000-1), is 0.63. According to
Gibbs–Wulff theorem, the lateral surface should be the facet
mainly exposed face in the nanostructure. These results explain
why the most stable ZnO configuration is a hexagonal column
which is oriented along the c-axis.
We now compare our simulations to the situation that is
(5) relevant for our experiments. To analyze the effects of an air
atmosphere filled with H2/H2O, we now consider surface struc-
tures covered by H or OH. It is found that the stable site for
H is the top of O, and the stable site for OH is the fcc-hollow
site with OH surrounded by three surfaced Zn atoms.[33,34] In
this case, the surface energies depend on chemical potentials
of both H and O, forming a 3D diagram (see Figure S3, Sup-
porting Information). Through our calculation, the most stable
and the second most stable surfaces are, respectively, the H
and OH covered (11-20) surface and H covered O terminated
(0001) surface. The dependence of their surface energy on the
hydrogen and oxygen potentials is shown in Figure 3d,e, and
their structures are shown in Figure 3c. When the values of UH
and UO are taken as the chemical potentials of hydrogen gas
(−3.38 eV) and oxygen gas (−4.19 eV), the corresponding surface
energies of the two surfaces are −1.42 and −0.63 J m−2. Clearly,
in presence of H2/H2O, the lateral surface is still more stable
than the top surface. To clearly reveal the effect of H2/H2O on

Figure 3. a) Surface energy E of various ZnO surfaces in normal air atmosphere as a function of the oxygen chemical potential UO; ball structure models
of the most stable and the second most stable surfaces in air atmosphere b) before adding water in the system and c) after water addition resulting
in surface coverage by H or OH. In presence of water, surface energy E is the function of both oxygen chemical potential UO and hydrogen chemical
potential UH. 3D diagram of the surface energy E of d) (11-20)-H OH and e) (0001)-H surfaces of the oxygen (UO) and hydrogen (UH) chemical
potential after adding H2O to the reaction system.

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Table 1. Calculated surface energies E of the most stable and the second
most stable surfaces, as well as the corresponding energy reduction per-
centage from absence to presence of H2/H2O.
Most stable Second most
Clear surface Surface (11-20)
Surface energy [J m−2] 1.126
H or OH Surface (11-20)-H OH
Covered surface Surface energy [J m−2] −1.42
Comparison Energy decrease percentage [%] 226
the surface energy of ZnO, we compare the change of the rela-
tive surface energy without and with H2/H2O in Table 1. With
H and OH bonding to the surfaces, the surface energy of ZnO
facets obviously lowers, and the lateral surface energy decreases
by 226%, which is 1.67 times of that change on the top surface,
by 135%. Again according to Gibbs–Wulff theorem, in presence
of H2/H2O atmosphere, the lateral surface will take a larger part
than that of without H2O. Thus, driven by the altered surface
energies, the relative side surface coverage first increases upon
the addition of H2/H2O and then decreases along with con-
suming H2/H2O. This is consistent with the experimental obser-
vation of microtube splitting and recoalescing in Figure 2b–d.
As presented above, our research provides a new perspec-
tive for the growth of ZnO tubular micro/nanostructures. Our
surface energy calculations suggest that the microtube growth
mechanism reported in Figure 2 can be understood as follows.
After the start of the growth reaction, H2/H2O vapor is gener-
ated and bonded onto the surfaces of the ZnO seeds. This inter-
action leads to the reduction of the surface energy at different
ZnO facets, especially for the lateral {10-10} facets. Specifically,
the surface energy reduction percentage of the lateral surface
is 1.67 times of the top surface, which means that the exposed
area proportion of lateral surfaces is supposed to increase. As
a result, driven by the varying relative surface energy, initially
deposited ZnO microrods appear to split and generate a bundle
of nanowires, exposing more lateral surfaces. As the concentra-
tion of H2/H2O vapor decreases, the splitting tendency disap-
pears and the adjacent nanowires recoalesce into an integrated
ZnO microtube. During this entire process, the crystal cross
section tends to increase, and the diameter of nanowires deter-
mines the tube wall thickness. As a result, high-quality tunable
ZnO microtubes with distinct wall thickness and diameter are
grown on the substrate. Thanks to their particularly smooth
surfaces, regular morphology, hollow construction, and tun-
able scales, these ZnO microtubes are anticipated to show
rather interesting optical properties. Particularly, the tubes may
be anticipated to act as resonators, supporting different types
of modes, bound between the inner and outer surfaces of the
tubes. As such, these wires may serve as interesting optical
microresonators for active optical materials placed in the inside
of the tube. Also, it should be relatively straightforward to
transfer the discovered growth mode to other semiconductor
micro/nanostructures.
We now explore the optical properties of individual ZnO
microtubes distributed in different areas of the substrate
by using a confocal microphotoluminescence spectroscopy.
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Figure 4a–c exhibits the SEM images of representative ZnO
microtubes from the three different sample regions discussed
in Figure 1. The corresponding PL spectra of these typical indi-
vidual tubes at room temperature are shown in Figure 4d–f. It
can be seen that all the ZnO samples exhibit both the char-
stable
acteristic ZnO exciton emission in the UV around 380 nm,
(000-1)
and the broad point defect emission band between 450 and
1.778 600 nm. The reason why no obvious emission mode appears
(0001)-H in the UV emission band might be that the mode spacing is
−0.63 too small to be obviously resolved in the narrow UV band, and
the optical absorption around the band edge region is larger.
135
For the modulation in the defect emission, both the ampli-
tude and period of the modulation vary with the ratio of d/R,
manifesting the effect of the morphology, or rather the ratio
of wall thickness to outer radius, on the spectral modulation.
For the typical small hollow core microtube in Figure 4a, with
an outer radius of about 2 µm, we can clearly observe a set of
resonance peaks in the visible, defect emission region of the
PL spectrum (Figure 4d). Two kinds of resonance modes, WG
mode and FP mode, can possibly be formed. According to the
relationship between mode spacing and cavity size,[20,35,36] the
calculated result is consistent with the effective path length
of WG mode. From the perspective of geometrical optics, the
light wave can circulate inside the tube due to TIRs at only
the outer ZnO/air interface. A ray tracing scheme of this WG
mode is schematically shown in the inset of Figure 4d. On the
basis of the Snell’s law, taking the refractive index of ZnO to
be 2.0, the critical incidence angle of this WG mode is 30°.
According to the plane wave model,[37] the light is confined
inside the tube wall by TIRs at the outer surfaces, forming
the WG mode, if the d/R ratio is larger than 3 / 8. In this
case, the internal surfaces make no contribution to the light
modulation. This phenomenon is essentially the same as the
formation of WG mode in hexagonal ZnO nanorods.[17] For
the large hollow core microtube (Figure 4c), dense and sharp
resonant modes are demonstrated as shown in Figure 4f.
Considering the small value of d/R about 1/40 and wall thick-
ness of less than 1 µm, the formation of WG mode is impos-
sible. And the FP modes are also difficult to identify in such
a microcavity because of its short effective length and low
reflectance of ZnO.[38] The wall thickness of hundreds nano-
meters is similar to the emission wavelength of ZnO. There-
fore, the light wave propagates along closed paths, and is
limited due to TIRs at the outer boundary, simultaneously
at its characteristic inner interface between ZnO tube and
air. This kind of resonant mode derives from circularly mul-
tiple TIRs at interfaces and from reflections between parallel
surfaces, similar to the wave-guided mode in a closed fiber
ring. For the ZnO microtube in Figure 4b, whose scale is
between the two types of nanostructures presented above, no
obvious modulations are observed from the PL spectrum in
Figure 4e. The possible explanations are: (i) the wall thickness
of ZnO microtube is too thin to support the WG mode; (ii)
the relatively smaller ratio of outer radius to light wavelength
(R/λ) leads to larger emission losses than that in the case of
Figure 4c at the corner of the hexagon as depicted in the inset
of Figure 4e; (iii) the cross section of the sample is not per-
fectly hexagonally shaped which may destroy the waveguide
mode shown in Figure 4f.
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Figure 4. a–c) SEM images of representative individual ZnO microtubes with different wall thickness-to-outer-radius ratios, d/R. d) PL spectrum of
a selected ZnO microtube with a d/R ratio larger than 3 / 8. In the spectral region of green ZnO defect emission (500–600 nm), a clear periodic
modulation of the emission spectrum is observed. This suggests that the microtube acts as a whispering gallery (WG) resonator. As illustrated in the
inset, total internal reflection at the outer interfaces confines the emission to the interior of the microtube. e) Correspondingly, PL spectrum for a tube
with a larger radius R × 5 µm and a smaller d/R ratio. Here, the spectral modulation due to WG mode formation is virtually absent. f) PL spectrum of
a tube with R ≈ 10 µm and thin wall thickness showing spectrally narrow fringes due to wave-guided mode, deriving from circularly multiple TIRs at
both outer and inner interfaces. The insets show the diagrams for these three characteristic resonator models.

Taken together, the analysis of our PL spectra suggests that
spectral modulations of defect emission can result in different
forms. When the ratio of wall thickness to outer radius exceeds
3 / 8, light is confined via TIRs at the interface between the
tube outside surface and air, forming the WG mode. As that
ratio decreases to smaller than 3 / 8 , the microtube internal
surfaces contribute to the optical limitation as well. Moreover,
while the value of d/R is small enough, wave-guided mode can
be obviously observed. This means different resonator modes
can be switched by varying the geometric parameter of ZnO
microtubes, which will trigger many interesting optoelectronic
applications.
To confirm the conclusions drawn from the PL measure-
ments, we performed the FEM simulations to investigate
the cavity modes inside the typical microtubes shown in
Figure 4a–c. Here, only TE polarization case is considered for
simplicity. Figure 5 shows the calculated radiation spectra of a
light source put inside the ZnO microtube, with different radii
and wall thicknesses similar to those studied in Figure 4, and
the electric field patterns of some representative resonance
modes based on eigenmode simulations. The radiation peaks
in the spectra correspond to resonant modes excited in the
microtube. In Figure 5a, the electric field patterns clearly dem-
onstrate the excitation of whispering gallery mode. One can
see that the field intensity is high near the outer walls of the
tube, yet small at the inside. This corresponds to the classical
expectation of not having reflections at the inner interfaces.
This excitation of WG mode is seen for tubes with small outer
diameter (R = 2 µm) and comparatively large wall thickness
(d = 1.1 µm). It is in accordance with the former corresponding
analyses as illustrated in the inset of Figure 4a. The resonance
wavelengths of the calculated mode perfectly match those of
the corresponding radiation peaks marked as arrows in the
spectra. In addition, FEM simulations also demonstrate a more
complex mode (the second pattern of Figure 5a at 607 nm)
inside such a microcavity. For these modes, TIRs occur at
both inner and outer boundaries. The relatively larger leakage
of light for such a mode reduces its quality factor and hence
these modes contribute less to the intensity modulation of the
calculated or measured spectra. Figure 5c shows the spectra
and the electric field distributions of the resonance modes
inside the microtube with a large hollow core (R = 20 µm,
d = 0.4 µm). Obviously, the light is confined via multiple
continuous TIRs at the inner and outer boundaries, forming
waveguide modes as predicted above. As for the ZnO micro-
tube with a moderate d/R as shown in Figures 4b and 4b,
quite obvious wave-guided modes are well confined inside
the microtube except for some leakage of light at the cor-
ners of the hexagonal tube. Because d/R of Figure 5b is still
above the critical value of 3 / 8 , WG modes can be formed
which is also demonstrated by our simulations. Based on both
our experimental analysis and the numerical simulations,
it can be preliminarily concluded that the optical modula-
tion inside different physical mechanisms contribute to the
coherent modulation of the emission spectra and that a vari-
ation of tube geometry may be used to select the dominant

132 wileyonlinelibrary.com © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Optical Mater. 2016, 4, 126–134

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Figure 5. a–c) The calculated radiation spectra of the typical ZnO microtubes similar to Figure 4a–c with a light source putting inside, and the cor-
responding electric field distributions (eigen-wavelengths shown as insets) of the representative WG mode (red arrows), complex WG mode (gray
arrows), and wave-guided mode (green arrows).
mechanism. To further confirm this conclusion, we have also
simulated another three tubular ZnO microcavities with fixed
outer radius R (2 µm) and decreasing ratio of d/R (= 0.55,
0.30, 0.10) (Figure S4, Supporting Information). The simula-
tions are in perfect accordance with the results stated above,
and indeed confirm that the spectral fringes in the emission
spectra of tubular ZnO microcavities are determined by the
ratio of wall thickness to outer radius.
3. Conclusion
In summary, we have developed a surface-energy-driven
approach to control the growth of ZnO tubular microcavi-
ties. Microtubes with different wall thickness-to-outer radius
ratios can be achieved through a new nucleation-growth-split-
coalescence growth process. As demonstrated by a detailed
growth study of ZnO crystals and by first-principles calcula-
tions, the formation of H2/H2O vapor is largely responsible for
the change of ZnO surface energy, and drives the morphology
change of microtubes. The proposed crystal growth model pro-
vides a new method to control the formation of ZnO micro-
structures. Furthermore, we demonstrated that the fabricated
microtubes could be employed as tunable optical resonators.
In the typical individual ZnO microtubes deposited in separate
zones, the formation of distinctly different whispering gallery
modes and wave-guided modes gives rise to pronounced inten-
sity modulations of the emission spectra of these tubes. The
effect of the unique tubular structure on the intensity modu-
lations is discussed theoretically based on a plane wave model
and FEM simulations, which agrees well with the experimental
results. We believe that our work would not only provide a pro-
found understanding of the growth mechanism of ZnO micro-
tube but also promote the development of tubular cavity–based
optical devices.
Adv. Optical Mater. 2016, 4, 126–134 © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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FULL PAPER
4. Experimental Section
The reaction was performed in an open quartz tube without any catalysts,
templates, or carrier gases. In a typical experimental procedure, zinc
oxide powder (0.06 g), graphite powders (0.06 g), and 0.01 mL water
were well mixed and loaded into a small quartz boat. A cleaned Si wafer
was covered over the top of the boat. At the same time, the furnace was
heated to 1050 °C at a rate of 25 °C min−1. After the furnace reached
the desired temperature, the quartz tube containing the blended raw
material was quickly inserted. The reaction requires only 10 min.
Then the quartz boat was removed out of the furnace and cooled to
room temperature. As a result, a large amount of crystal-like product
was found to be deposited on the Si substrate. The morphology and
crystal structure of the products were characterized by field emission
scanning electron microscopy (FE-SEM, Zeiss Auriga S40) and XRD
(PANalytical Empyrean) with Cu Kα radiation (λ = 1.54 Å). EDS was
used to evaluate the composition of the microstructures. The optical
properties of the ZnO microtubes were measured using a confocal
microphotoluminescence system (JY LabRAM HR800 UV) using an
He Cd laser of 325 nm as the excitation source.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was financially supported by NSFC (61475173, 61378074) and
sponsored by Shanghai Rising-Star Program (A type 14QA1404000).
Received: August 7, 2015
Revised: September 2, 2015
Published online: September 24, 2015
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