Applied Surface Science 536 (2021) 147326

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

High-index crystal plane of ZnO nanopyramidal structures: Stabilization, T

growth, and improved photocatalytic performance
Taehoon Lima, Pegah S. Mirabedinib, Kichang Junga,c, P. Alex Greaneyb,d,
Alfredo A. Martinez-Moralesa,b,c,
⁎

a
College of Engineering - Center for Environmental Research and Technology, University of California - Riverside, Riverside, CA 92507, United States
b
Materials Science and Engineering Program, University of California - Riverside, Riverside, CA 92521, United States
c
Department of Chemical and Environmental Engineering, University of California - Riverside, Riverside, CA 92521, United States
d
Department of Mechanical Engineering, University of California - Riverside, Riverside, CA 92521, United States

ARTICLE INFO ABSTRACT

Keywords: While the low-index planes of Wurtzite ZnO, such as {0001} and {101̄0} are well-understood, the high-index
Zinc oxide crystal surfaces have not yet been thoroughly researched despite possessing structural characteristics that make
Pyramidal structure them suitable for many important surface chemistry processes. The high surface energy of high-index ZnO
High-index facet crystal surfaces makes synthesis challenging to achieve due to their instability during crystal growth. In this
CVD synthesis
work, we present a combined experimental and theoretical analysis of growth and photocatalytic activity of ZnO
Oxygen evolution reaction
high-index crystal facets. Density functional theory calculations are performed to determine the thermodynamic
conditions necessary to stabilize the high-energy semi-polar {112̄2} facets of pyramidal ZnO nanostructures
grown via chemical vapor deposition (CVD). The photocatalytic properties of as-synthesized nanopyramidal
structures for water splitting applications showed a 73% improved photocatalytic performance compared to
CVD-grown hexagonal ZnO nanorods with dominating low-index {101̄0} facets.

1. Introduction Improvements in photocatalytic performance have been achieved via

ZnO is a versatile wide bandgap semiconductor used in a diverse
array of applications due to its piezoelectric [1], photocatalytic [2], and
intrinsic n-type semiconducting [3] properties. The naturally occurring
Wurtzite crystal structure favors a hexagonal prismatic crystal shape
bounded by low-index crystal facets, with non-polar {101̄0} surfaces on
the sides and polar {0001} facets terminating the ends. The intrinsic
properties of low-dimensional crystalline materials can be tuned via
quantum confinement, or by controlling the surface-to-volume ratio.
This makes the ZnO nanostructures suitable for many optical, elec­
tronic, and optoelectronic applications. As a result, ZnO nanostructures
are commonly used in anti-reflective coatings [4], nanowire-based
transistors [5], LEDs [6], lasers [7], and photodetector devices [8].
According to a previous study, quasi-1-dimensional ZnO shows im­
proved photocatalytic activity in comparison to the bulk state due to its
larger surface-to-volume ratio [9]. Morphologies such as nanowire and
nanorod arrays have been extensively researched in photocatalytic
applications including photoelectrochemical water splitting [10], self-
cleaning surface [11], and air/water purification [12,13].
interface engineering [14], surface decoration [15], morphology en­
gineering [16,17], hybridization [18,19], and doping [20]. However,
the hexagonal prismatic structure is not an optimal morphology for
surface catalysis applications involving water. The non-polar {101̄0}
surfaces interact weakly with water molecules, while the polar {0001}
surfaces have difficulty with desorption [21–24] due to the stronger
binding forces on these surfaces.
While the {101̄0} and {0001} crystal planes have been well re­
searched, both theoretically and experimentally [25], the high-index
facets such as {112̄2} have not been fully investigated due to the un­
stable nature of the surface. Diagonal surface facets of ZnO such as
{101̄1} , {101̄2} and {112̄2} planes can form a pyramidal morphology.
These semi-polar surfaces make the pyramidal ZnO nanocrystals a
strong candidate for a photocatalytic material due to their high surface
electrochemical activity and better reversibility of the ad­
sorption–desorption process [26,27].
Synthesis of pyramidal ZnO crystals in colloidal form via hydro­
thermal reaction has been previously reported [28,29]. However, for
many applications, it is desirable to grow crystalline pyramidal ZnO

⁎
Corresponding author at: College of Engineering - Center for Environmental Research and Technology, University of California - Riverside, 1084 Columbia Ave,
Riverside, CA 92507, United States.
E-mail address: alfmart@cert.ucr.edu (A.A. Martinez-Morales).

https://doi.org/10.1016/j.apsusc.2020.147326
Received 18 February 2020; Received in revised form 20 July 2020; Accepted 20 July 2020
Available online 24 July 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
T. Lim, et al.
(a) γ(1010)-S (b) γ(1010)-Zn
(c)
γ(1010)-S γ(1010)-O
Fig. 1. Profile view of ZnO surface facets after relaxation. (a-c) Slabs of the (101̄0) surfaces viewed along the c-axis, and (d-f) slabs of the (112̄2) surfaces viewed from a
direction perpendicular to the c-axis. (a) Shows the low energy stoichiometric surfaces, (b) and (c) show the same surface depleted of O and Zn, to generate the Zn-
rich and O-rich surfaces, respectively. (d) Shows the Zn and O terminated stoichiometric planes, with (e) showing the O-rich surface, and (f) the Zn-rich surface.
arrays directly on a conductive substrate to minimize interfacial elec­
trical resistance, while making the material more robust and easier to
handle.
In this paper, we report the chemical vapor deposition (CVD)
growth of crystalline ZnO pyramidal arrays with surface {112̄2} facets on
a transparent conductive substrate. Despite the unstable nature of high-
index crystal surfaces, synthesis was achieved by stabilizing the surface
during crystal growth. Experimental conditions were predicted and
guided by density functional theory (DFT) calculations. Crystal growth
conditions were controlled via a modified CVD ZnO synthesis process to
prevent the premature oxidation of Zn precursor in the low-temperature
process [30]. The high-energy surface was stabilized by controlling the
chemical potential of oxygen. As predicted by the DFT calculations and
confirmed by the hydrogen and oxygen evolution reactions from water
splitting experiments, the as-synthesized ZnO nanopyramidal structures
show bi-functionality of p-type and n-type semiconducting character­
istics. To understand the origin of the improved photocatalytic prop­
erties of pyramidal ZnO, the surface geometry, electrochemical prop­
erties, and electrostatic potential of different surfaces were
investigated.
2. Calculation and experimental section
2.1. Surface energy calculations
Electronic structure calculations were performed to compute the
surface energy of the non-polar (101̄0) and semi-polar (112̄2) facets of
ZnO and to determine how the electronic structure of these surfaces
affects the crystal growth process and photocatalytic activity. DFT was
used to compute the total energy of infinite slabs of ZnO with exposed
parallel (101̄0) or (112̄2) facets, as shown in Fig. S1. The slabs for DFT
calculations were cut from bulk ZnO crystal and relaxed. Depending on
where the cut-plane intersects the unit cell, several surface structures
are possible, enabling the formation of stoichiometric surfaces and
surfaces that are O-rich or Zn-rich. In the [101̄0] direction, the packing
of atomic planes follows an AaBbAa sequence. The (101̄0) facet can be
cut between the narrowly spaced Aa planes or the wider aB planes. The
surface energy of both possible cuts was computed. The resulting sur­
faces cut between the wider aB planes were found to be significantly
lower in energy as they are more compact. These lower energy surfaces
are used for the DFT calculation in this work.
The {101̄0} surfaces lie parallel to the polar c-axis of the crystal. Each
layer of atoms in the AaBb packing sequence is stoichiometric, making
the facets nominally non-polar. However, under relaxation, the stoi­
chiometric (101̄0) surface undergoes a small buckling distortion,
2
Applied Surface Science 536 (2021) 147326
(d) γ(1122)-S-Zn (e) γ(1122)-O
(f)
γ(1122)-S-O γ(1122)-Zn
generating a small polarization perpendicular to the surface. Non-stoi­
chiometric {101̄0} surfaces that are deficient in either Zn or O can also
be generated by removal of Zn or O atoms from the surface layer. The
(101̄0) facet, therefore, has three distinct surface energies, (101̄0) S ,
(101̄0) Zn , and (101̄0) O for the stoichiometric, Zn-rich, and O-rich struc­
tures, respectively.
The surface energies of stoichiometric surfaces, (hkwl) S , were cal­
culated by computing the facet energy of relaxed slabs, each containing
a single pair of parallel stoichiometric facets, using the following
equation [31]:
Eslab NO Ebulk
=
(hkwl) S
2A (1)
where Eslab is the total energy of the slab, NO is the number of oxygen
atoms in the slab, Ebulk is the energy of one formula unit of bulk ZnO,
and A is the area of the surface. The factor of 2 in the denominator
indicates the presence of a top and bottom surface in the slab model.
The surface energy of the non-stoichiometric facets depends on the
chemical potential of the reservoir from which the excess surface spe­
cies are drawn. The energies of these surfaces were obtained from
calculations of slabs with one stoichiometric surface and a non-stoi­
chiometric opposing surface. The surface energy of the non-stoichio­
metric facet is given by:
1
= [Eslab Eref (NO , NZn, µO )]
(hkwl) X
A (hkwl) S (2)
with the reference energy
Eref (NO , NZn, µO ) = NZn (Ebulk µO EO2 ) + NO ( µO EO2 ) (3)
where NO and NZn are the number of O and Zn atoms in the system,
respectively. EO2 is the cohesive energy per atom of oxygen in the O2
dimer. The oxygen chemical potential, µO , is defined as the difference
between chemical potential of oxygen in the reactor and half of the O]
O bond energy, and it is plotted over the range for which ZnO is stable.
This gives the low µO limit as the chemical potential at which ZnO is
reduced to Zn metal and O2 gas,
(Ebulk EZn HCP EO2) µO 0 (4)
where EZn HCP is the cohesive energy per atom of HCP Zn metal. The
relaxed low energy geometries of the stoichiometric, Zn-rich, and O-
rich (101̄0) facets are shown in Fig. 1(a)–(c), respectively.
The geometric permutations of the semi-polar {112̄2} surfaces are
more complex with four distinct surface terminations: O- and Zn-ter­
minated stoichiometric surfaces (opposite faces of a stoichiometric slab)
and O-rich and Zn-rich non-stoichiometric surfaces. Although four
different permutations of the top and bottom surface structures can be
T. Lim, et al.
created, from the ZnO crystal structure, it is only possible to determine
three independent surface energy metrics. While the distinct surface
energies for the (101̄0) facets can be determined, for the (112̄2) surface,
the energy of the stoichiometric surface, (112̄2) S , is taken as half of the
cleavage energy, (112̄2) S = 2 ( (112̄2) S Zn + (112̄2) S O ) . This is used as
1 powder was loaded in the precursor boat and placed in the middle of the
the reference surface in Eq. (2) to define the energies of the Zn- and O-
rich surfaces, (112̄2) -Zn and (112̄2) -O. These relaxed structures of the
(112̄2) facets are shown in Fig. 1(d)-(f).
The energy calculations were performed using supercells with
(2 × 1) and (2 × 2) periodicity in the plane of the slab for {101̄0} and
{112̄2} structures to allow the system freedom to undergo surface re­
constructions that break the crystal symmetry. To obtain a consistent
set of fully converged surface energies, calculations were performed for
a series of slabs by systematically varying the slab thickness and va­
cuum separation. The computational details are given in the supple­
mentary material along with the detailed geometry of the computed
systems. The surface energy of the (101̄0) terminated slabs was com­
puted to an accuracy of 0.01 J/m2. Convergence was achieved with
slabs having a thickness of 11 or more atomic layers ( 31 Å) and a
vacuum space of 20 Å. In contrast, the convergence of the semi-polar
(112̄2) surface was harder to achieve due to the existence of an internal
field formed in the polar slabs. In this case, surface energies were
computed following the convergence method by Meyer et al. [32],
where the energies of slabs with a series of different thicknesses, t, were
computed and then the 1/ t dependence of the slab energy was extra­
polated to remove the effect of the internal field. This method resulted
in the surface energy of the (112̄2) terminated slabs being computed to
an accuracy of only 0.1 J/m2.
All DFT calculations were performed using the Vienna ab-initio
Simulation Package (VASP) [33–36] within the Perdew-Berke-Ern­
zerhof (PBE) general gradient approximation (GGA) ex­
change–correlation functional [37,38]. The calculations were spin-po­
larized with a plane wave cutoff energy of 400 eV. Core electrons were
modeled implicitly using the projector-augmented wave method (PAW)
pseudopotentials [39,40]. Structures were relaxed using the conjugate
gradient algorithm [41] to minimize the forces for ionic relaxation to
lower than 1 × 10-3 eV/Å. A great deal of care was taken to obtain a
fully converged and relaxed bulk ZnO reference structure, as errors in
the energy prediction of this reference state are the largest source of
uncertainty in the surface energy predictions. The cohesive energy of
the bulk crystal structure was found to be well converged using a
5 × 5 × 5 k-points grid for the Brillouin zone integration. Using this
approach, the modeled bulk ZnO had equilibrium lattice parameters of
a = 3.19 Å and c = 5.30 Å. For the slab calculation, a 5 × 5 × 1 k-
point mesh was used for Brillouin zone sampling with one k-point along
the non-periodic direction perpendicular to the slab.
The surface energies computed using the described procedure above
were used in the Wulff construction to predict the equilibrium mor­
phology of ZnO crystallite growing on a substrate with its c-axis per­
pendicular to the substrate. The energy of the ZnO/substrate interface is
assumed to be zero. The equilibrium morphologies were used for the
theoretical predictions of the height-to-width ratio and the {112̄2} to
{101̄0} surface area ratio of ZnO pyramidal nanocrystals grown under
different oxygen chemical potential conditions. For growth on most
substrates, it is likely that the effective surface energy of the ZnO/
substrate is negative due to the reduction in energy from covering the
exposed substrate and ZnO-(0001) surfaces by bringing ZnO into contact
with the substrate. If the effective ZnO-(0001) /substrate interface en­
ergy is negative, the width-to-height ratio and {112̄2} to {101̄0} surface
area ratio of ZnO pyramidal nanocrystals will be underestimated.
2.2. Experimental procedures
Nanopyramid and nanorod ZnO structures were synthesized based on
our modified CVD method in a three-zone tube furnace (300 mm length/
zone, OTF-1200X-III, MTI Corporation) [42]. Further optimization was
3
Applied Surface Science 536 (2021) 147326
done to control the chamber pressure and distance between precursor
and substrate. In short, to prevent the surface oxidation of Zn powder
(Sigma-Aldrich) precursor, a quartz tube (3 mm inner diameter, 12 cm
length) with one end closed was used as a precursor boat. 0.2 g of Zn
right zone in the tube furnace. The FTO substrate (Sigma-Aldrich) was
placed downstream next to the open end of the precursor boat. During
synthesis, all three zones of the furnace (900 mm total heating zone)
were heated to 450 °C for the nanopyramidal and 500 °C for the nanorods
at a ramping rate of 15 °C/min, under the flow of 100 SCCM nitrogen and
4 SCCM oxygen. The furnace temperature was maintained constant for
30 min to during the crystal growth. The measured pressure during the
synthesis process was 12 torr. The synthesized ZnO was analyzed by
scanning electron microscopy (SEM), x-ray diffraction (XRD) analysis,
and Raman spectroscopy to characterize the morphology, crystal struc­
ture, and crystal defects, respectively. J-V characteristics and electro­
chemical impedance spectroscopy (EIS) under dark and illuminated
conditions were measured to analyze photocatalytic properties and are
discussed later in the manuscript. The photocatalytic performance of
synthesized ZnO nanopyramids and nanorods was tested under 365 nm
UV illumination in an 0.5 M Na2SO4 aqueous solution. Measurements
were performed in a three-electrode photoelectrochemical cell with Ag/
AgCl as the reference electrode and Pt wire as the counter electrode.
3. Results and discussion
3.1. Prediction of crystal growth morphology
A growing crystal arrives at its final morphology either as a result of
anisotropic attachment kinetics producing a shape that becomes kine­
tically frozen in place, or as a result of the growing crystal relaxing
towards its thermodynamically preferred shape. The latter is the shape
that minimizes the total surface energy of the structure and is described
by the Wulff construction. Here we consider only the thermo­
dynamically preferred shape and further restrict consideration to the
Wulff construction of the crystal containing only {101̄0} and {112̄2} facets
to identify conditions under which pyramidal crystals will be thermo­
dynamically preferred over nanorods.
The energy of the different variants of the {101̄0} and {112̄2} facets
are plotted as a function of oxygen chemical potential in Fig. 2. For the
stoichiometric surfaces, the (101̄0) facet is more compact and has a
(a) Oxygen chemical potential ΔμO (eV)
-2 -1 0
6
Surface energy γ (J/m )
{1122}
2
{1010}
4 O-rich
Zn-rich
2
Stoichiometric
(b) 04
Ratio
2 {1122}/{1010}
Height/Width
0
(c)
Fig. 2. (a) Plot of the surface energy of the {112̄2} (black) and {101̄0} (red) facets
as a function of oxygen chemical potential, (b) corresponding surface area
(green) and aspect ratio (blue), and (c) corresponding Wulff construction.
T. Lim, et al.
lower surface energy of 0.9 J/m2, while the surface energy of the
stoichiometric (112̄2) surface is 1.8 J/m2. However, for the non-stoi­
chiometric surfaces, both the O-rich and Zn-rich (112̄2) facets have
lower surface energy than their corresponding (101̄0) facet. The surface
energy versus the chemical potential of oxygen plot in the system
(Fig. 2(a)) shows that there is a small range of O-starved growth con­
ditions under which the Zn-rich {112̄2} facets become lower in energy
than even the stoichiometric{101̄0} surface. However, for the {112̄2}
pyramidal facets, to completely geometrically exclude the {101̄0} facets
from the Wulff construction, (112̄2) must be considerably lower than
(101̄0) , satisfying the inequality,
(101̄0)
(112̄2)
2
3
1+ ()
a 2
c
(≈1.36 for ZnO).
Although this condition is not met in the plot in Fig. 2, it is not ne­
cessary for the {101̄0} facets to be completely excluded for the crystals to
grow in a pyramidal morphology. Fig. 2(b) shows the height/width and
the {112̄2} /{101̄0} area ratio of the Wulff construction (Fig. 2(c)) is
plotted on the same x-axis. Under the oxygen-starved growth condi­
tions, the equilibrium morphology of ZnO crystals transitions from rod-
like to compact pyramidal structures is marked by the drastic increase
in the fraction of semi-polar {112̄2} surfaces.
The DFT calculations anticipate that ZnO with high-index {112̄2}
surface planes can be synthesized when the chemical potential of oxygen
is low. This prediction is consistent with the experimental results. ZnO
pyramidal structures are successfully synthesized when the Zn vapor
partial pressure is significantly higher than that of oxygen near the
substrate. This extremely biased precursor ratio environment is achieved
by modifying the design of the CVD reactor. The prevention of the pre­
mature oxidation of Zn precursor plays an important role in growing the
ZnO crystal with {112̄2} surfaces by creating an environment with highly
concentrated Zn vapor. When the crystals are removed from the reactor
and exposed to air, the surfaces quickly oxidize and become stoichio­
metric, but the crystal morphology remains in the pyramidal shape.
3.2. Morphology and crystal structure analysis
Fig. 3 shows the top-view and cross-sectional SEM images of the
synthesized ZnO nanopyramidal structures (Fig. 3(a) and 3(b),
Fig. 3. (a) Top-view and (b) cross-sectional SEM images of synthesized pyramidal ZnO, (c) schematic drawing of (112̄2) plane for geometric analysis. (d) Top-view
and (e) cross-sectional SEM images of synthesized nanorod ZnO, (f) schematic drawing of (101̄0) plane.
4
Applied Surface Science 536 (2021) 147326
respectively) and the nanorods (Fig. 3(d) and 3(e)). In Fig. 3(c), the φ
(angle of the plane from the c-axis) observed on the {112̄2} crystals
planes is calculated as 32°, which corresponds to the measured angle at
the apex of the pyramidal structure 2φ = 64° when viewed along
101̄0 . The nanopyramids in projection from the side will appear to
have an apex angle range between 64° and 72° (when viewed along
21̄1̄0 ). The pyramidal peak angles measured in Fig. 3(b), provide
compelling evidence that although the {112̄2} crystal facets are not fa­
vored under regular conditions due to their high energy, they have
nonetheless been successfully synthesized through our modified CVD
process. The crystal structure of both ZnO nanostructures are char­
acterized by XRD analysis, as shown in Fig. 4(a). The XRD results in­
clude the peaks from the FTO substrate and the ZnO products. The ZnO
XRD pattern confirms that the product is Wurtzite ZnO. The ZnO peaks
at 34.59°, 36.37°, 47.70°, 63.02°, and 68.04°, refer to the (0002) , (101̄1) ,
(101̄2) , (101̄3) , and (112̄2) crystal planes, respectively. While the peak
ratio of (0002) is higher for the ZnO nanorods, the peak ratio for the
diagonal planes (101̄1), (101̄2) , (101̄3) , and (112̄2) are higher for the ZnO
nanopyramids. The XRD peak ratios for the nanopyramids and na­
norods crystal planes are listed in Table 1. The XRD results confirm that
the nanopyramid and nanorod structures have different crystal or­
ientations. The morphology and crystal structure of pyramidal ZnO
provide important clues to the growth mechanism. In the top-view SEM
imaging, the incomplete ZnO nanopyramids have an irregular surface
pattern. The voids parallel to the c-axis indicate that the pyramids were
formed through side-by-side lateral growth of ZnO rather than layer-by-
layer vertical growth, as it occurs in the growth of ZnO nanorods [43].
The crystal growth mechanism is further supported by Raman
spectroscopy as shown in Fig. 4(b). The two most significant peaks are
observed in both structures at 100 and 440 cm−1, assigned as E2low and
E2high, respectively. The observed differences in the Raman spectra are
attributed to the nanorods with peaks at 121, 382, and 483 cm−1. The
peak at 382 cm−1 is assigned as A1(TO), a phonon vibration mode
parallel to the c-axis, forbidden for the c-plane oriented Wurtzite
structure. The forbidden A1(TO) vibration is observed in the ZnO na­
norods due to its angled crystal orientation. The ZnO nanopyramids
show no A1(TO) vibration because the pyramidal structure is better
T. Lim, et al. Applied Surface Science 536 (2021) 147326

(a) (0002)
(b)
Nanopyramids E2low Nanopyramids
Nanorods Nanorods

Intensity (Arb. Unit)

Intensity (Arb. Unit) FTO substrate
E2high

ZB TA(X) A1(TO) ZB TO(X)

(1013)
(1012)

(1011) (1122)
30 40 50 60 70 100 200 300 400 500
-1
600 700
2θ (degrees) Raman shift (cm )
Fig. 4. (a) XRD and (b) Raman spectra results of synthesized nanopyramids and nanorods.

Table 1
XRD peak ratios of ZnO nanopyramids and nanorods from diverse planes. (a) 0.5
Nanopyramid dark
0.4

Current density (mA/cm )

Nanopyramid light

2
Orientation Rectangular Diagonal Nanorod dark
0.3 Nanorod light
Miller index (0002) (101̄1) (101̄2) (101̄3) (112̄2)
Nanopyramid 1 1.77 1.69 1.65 1.35
Nanorod 1.13 1 1 1 1
0.2 OER
0.1

aligned perpendicularly to the substrate. The two peaks at 121 and 0.0
483 cm−1 observed in the nanorods are assigned as TA(X) and TO(X),
-0.1
respectively, which are from the planar crystal defect forming a zinc HER
blende isomorph layer [44]. This planar defect originates from the -0.2
stacking fault in the layer-by-layer crystal growth mechanism in ZnO -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
nanorods. As supported by SEM, these peaks are not observed in the Potential (V vs Ag/AgCl)
nanopyramids due to their side-by-side crystal growth mechanism.
(b) Anodic current (c) Cathodic current
3.3. Photoelectrochemical water splitting
H+ /H2 H+ /H2
Fig. 5(a) shows the J-V characteristics of the water splitting op­
eration of the nanopyramids and nanorods arrays under illumination
and in dark conditions. The figure shows the average plot for 7 samples hν H2O/O2 H2O/O2
of each nanostructure to confirm the reproducibility and reliability.
While the statistical data (Fig. S2) shows that both nanostructures are
reproducible, further controllability is needed to reduce the built-in
experimental variation in the CVD reactor setup, as described in the
supplementary material. When illuminated, both ZnO morphologies
mediate the oxygen evolution reaction (OER), as observed from the FTO ZnO electrolyte FTO ZnO electrolyte
positive current. The onset potential (determined by measuring the x-
intercept of tangent at maximum slope [45]) of ZnO nanopyramids is Fig. 5. Water splitting operation of ZnO nanopyramids and nanorods; (a) J-V
characteristics under dark and 365 nm illumination, (b) energy diagram under
−0.31 V, which is negatively shifted by 45 mV from that of ZnO na­
illumination, and (c) dark condition.
norods. The cathodic onset potential shift in the nanopyramidal ZnO
suggests that the energy barrier for the hole injection to the electrolyte
is reduced [46]. The Tafel slope of the ZnO nanopyramids (43.2 mV/ in the nanopyramid structures. The photoelectrochemical performance
dec) is lower than the nanorods (73.1 mV/dec), indicating a faster of ZnO nanopyramids and nanorods are listed in Table 2 and compared
catalytic reaction and higher OER activity [47]. The nanopyramidal with other results in the literature in Table S1.
ZnO (red line) generates a current density of 0.45 mA/cm2, re­ The increased photocatalytic activity of ZnO nanopyramids is at­
presenting a 73% improvement over the 0.26 mA/cm2 produced by the tributed to the increased surface energy, polarity, enlarged active sur­
ZnO nanorod at 0.6 V vs Ag/AgCl reference electrode. The steeper slope face area, reduced interfacial charge transfer resistance, and increased
in the linear region before the saturation area of the nanopyramidal electron lifetime, as supported by EIS, transient voltage decay analysis,
ZnO indicates that the photogenerated charge carriers are more effec­ and electron lifetime measurement (Fig. 6 and S3 (a) – (b), respec­
tively separated in the nanopyramidal ZnO nanostructures [48]. The tively). The origin of the improved photocatalytic performance is ana­
steady-state illumination induces non-equilibrium electron and hole lyzed by EIS at open circuit potential, as shown in the Nyquist plot
concentrations, resulting in the splitting of the quasi-Fermi level and (Fig. 6(a)) and Bode plot (Fig. 6(b)). The circuit diagram in Fig. 6(c)
band bending, as schematically illustrated in Fig. 5(b) [49]. The pho­ represents the equivalent circuit model used to analyze results from the
tocatalytic operation for OER is due to the innate n-type semi­ Nyquist and Bode plots (listed in Table 3). The EIS results are separated
conducting nature of ZnO and is further improved by the crystal surface into two semi-circles in the Nyquist plot. RS, R1, and CPE1 are internal

5
T. Lim, et al. Applied Surface Science 536 (2021) 147326

Table 2 Table 3
Electrochemical performance of ZnO nanopyramids and nanorods. Equivalent circuit element values.
Property Nanopyramids Nanorods Circuit element RS (Ω) R1 (Ω) CPE1 (μF) RCT (kΩ) CPEDL (μF)

Onset Potential −0.31 V −0.26 V Nanopyramids dark 37.0 1860 7.61 90.1 5.65
Tafel Slope 43.2 mV/dec 73.1 mV/dec Nanopyramids light 33.1 225 32.9 22.5 153
Slope at Linear Region 0.90 mA/Vcm2 0.48 mA/Vcm2 Nanorods dark 49.0 342 22.3 1300 5.30
Current Density at 0.6 V 0.45 mA/cm2 0.26 mA/cm2 Nanorods light 49.2 462 29.4 48.7 13.5
Current Density at −0.6 V −0.19 mA/cm2 −0.05 mA/cm2

nanopyramidal ZnO is derived from the ambipolar nature of the (112̄2)

resistance, bulk resistance, and capacitance, respectively. The lower
frequency semi-circle is assigned to the surface charge transfer, where
RCT is the charge transfer resistance, and CPEDL is the double-layer
capacitance due to the slower charge transfer between the electrode
and ions over the bulk electronic process [50]. ZnO nanopyramids
under illumination show the lowest RCT indicating that the charge
transfer is easier in the pyramidal structure, and the CPEDL is generally
proportional to the active surface area [51]. Therefore, a higher CPEDL
in pyramidal ZnO represents that the active surface area of pyramidal
ZnO is larger than that of the nanorod structure. The lower charge
transfer resistance and larger surface area are the main reasons for the
improved ZnO nanopyramids’ performance. The ZnO nanopyramids are
bounded by semi-polar {112̄2} crystal planes with higher surface energy
and polarity. The high energy surface tends to lower its surface energy
by having adsorbents on the surface [52], and the high electrostatic
potential surface attracts the ionic molecules such as H+ and OH– [53].
Another key difference between the ZnO nanopyramid and nanorod
structures is that the nanopyramids have electrocatalytic properties for
the hydrogen evolution reaction (HER) irrespective of whether they are
illuminated or not. In contrast to OER, HER is generally mediated by p-
type semiconductors and metals with a relatively low Fermi level or
work function. The proposed operation mechanism for electrochemical
HER is driven by the applied bias-induced band bending, as illustrated
in Fig. 5(c) [54]. This bi-functionality in OER and HER catalysis of
crystal facet observed in the DFT study. The electron-withdrawing and
donating operations are both possible on the surface by having both
electro-positive and electro-negative functionalities on the same plane.
The electrostatic potential of the DFT computed stoichiometric
(101̄0) and (112̄2) surfaces was analyzed to determine which structure
has the highest polarity and greater photoelectrochemical activity. Only
stoichiometric planes are considered because although we predict that
the pyramidal morphology is stabilized during growth in oxygen-defi­
cient conditions, these surfaces will quickly become stoichiometric
under ambient conditions. Fig. 7 shows the atomic structure of each
surface with the left-hand side of each plot showing the surfaces’ local
electrostatic potentials plotted on the surface of constant charge den­
sity. The charge density contour value is the same for all plots. The
color scale indicating the local voltage is the same for all surfaces. It is
observed that the two (112̄2) surfaces present a wider variation in the
local electrostatic potential than the (101̄0) surface. The compactly co­
ordinated and charge-balanced structure of the (101̄0) surface offers
smaller variation in the surface potential presented to water molecules
than both the Zn and O terminated stoichiometric (112̄2) facets which
are polarized. The results are supportive of the observations that both
Zn- and O-terminated (112̄2) surfaces are more reactive than the (101̄0)
non-polar facet. Therefore, the (112̄2) facets are more likely to react
with water molecules and are more suitable for water splitting appli­
cations.

(a) -2500 (b)

0 Nanopyramids dark
θ (degree)

Nanopyramids light
-20 Nanorods dark
Nanorods light
-2000 -40
-60
-80
-1500
105 104 103 102 101 100 10-1
Zim (Ω)

Frequency (Hz)
-1000
105 Nanopyramids dark
Nanopyramids light
|Z| (Ω)

4 Nanorods dark
Nanopyramids dark 10 Nanorods light
-500 Nanopyramids light 103
Nanorods dark
102
Nanorods light
0
0 500 1000 1500 2000 2500 105 104 103 102 101 100 10-1
Zre (Ω) Frequency (Hz)
(c) RS R1 RCT

CPE1 CPEDL

Fig. 6. (a) Nyquist plot of ZnO nanopyramids and nanorods under dark and illumination; (b) Bode phase (top) and amplitude (bottom) plots; and (c) equivalent
circuit model.

6
T. Lim, et al.
4. Conclusion
Although the pyramidal structures with {112̄2} facets are generally
not stable due to their relatively high surface energy, our DFT calcu­
lations show that these morphologies are stabilized under a Zn-rich
growth condition. The Wulff crystal structures show a transition to
eliminate {101̄0} nonpolar facets and form pure pyramidal structures
with {112̄2} semi-polar surfaces as the environment becomes oxygen-
deficient. This suggests a correlation between the growth condition and
the final morphology of materials. Using this correlation, we tailored
our CVD process to obtain materials that are normally unstable and
difficult to grow. The nanopyramidal ZnO structures with semi-polar
{112̄2} facets were synthesized for improved photocatalytic perfor­
mance. The synthesis process for the pyramidal ZnO was accomplished
via the prevention of the premature oxidation of Zn vapor to create an
oxygen-deficient condition, allowing for the crystal growth environ­
ment necessary to achieve the ZnO nanopyramidal morphology. The
pyramidal ZnO shows higher photocurrent density under the UV illu­
mination in comparison to the ZnO nanorod structure. The improved
photocatalytic performance of the pyramidal ZnO is a result of the
lower interfacial resistance at the surface of ZnO due to its higher
surface energy, electrostatic potential, and polarity. The technique for
the controlled crystal growth of high-index facets demonstrated in this
work opens up opportunities for the application of ZnO pyramidal na­
nostructures to a wide range of applications in surface physics and
chemistry.
CRediT authorship contribution statement
Taehoon Lim: Conceptualization, Methodology, Investigation,
Validation, Formal analysis, Writing - original draft. Pegah S.
Mirabedini: Formal analysis, Methodology, Software, Investigation,
Visualization, Data curation, Writing - original draft. Kichang Jung:
Investigation, Validation. P. Alex Greaney: Formal analysis,
Methodology, Software, Resources, Writing - review & editing. Alfredo
A. Martinez-Morales: Resources, Supervision, Funding acquisition,
Project administration, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ­
ence the work reported in this paper.
Acknowledgements
Electron microscopy was performed using the Nova Nano-SEM 450
in CFAMM at UC Riverside. This research was partially supported by a
grant from UC Solar MR-15-328386.
Appendix A. Supplementary data
Supplementary data (computational details, photocatalytic statis­
tical data and electron lifetime measurement) to this article can be
found online at https://doi.org/10.1016/j.apsusc.2020.147326.
7
Applied Surface Science 536 (2021) 147326
Fig. 7. Electrostatic potential on the stoichiometric
ZnO facets (left side of the surface) and atomic lo­
cations with red atoms indicating O and silver for Zn
(right side) on the surface of (a) (101̄0) , (b) Zn-ter­
minated (112̄2) , and (c) O-terminated (112̄2) .
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 Supplementary Material
High-Index Crystal Plane of ZnO Nanopyramidal Structures: Stabilization,
Growth and Improved Photocatalytic Performance
Taehoon Lima, Pegah S. Mirabedinib, Kichang Junga,c, P. Alex Greaneyb,d, Alfredo A. Martinez-Moralesa,b,c,*
a
College of Engineering - Center for Environmental Research and Technology, University of California - Riverside, Riverside, CA 92507, United States
b
Materials Science and Engineering Program, University of California - Riverside, Riverside, California 92521, United States
c
Department of Chemical and Environmental Engineering, University of California - Riverside, Riverside, California 92521, United States
d
Department of Mechanical Engineering, University of California - Riverside, Riverside, California 92521, United States

1. Computational details

The {101̅0} and {112̅2} slabs are cut out of the bulk crystal as shown in Fig. S1. Surface structures with (2×1) and
(2×2) periodicity for {101̅0} and {112̅2} are generated, resulting in a surface area of 34.87 and 71.05 Å for the
{101̅0} and {112̅2} slabs, respectively. A surface area larger than the smallest possible unit is chosen to allow for
symmetry breaking reconstruction.
A consistent set of fully converged surface energies is obtained by performing a series of energy calculations for slabs
with systematically varying slab thickness and vacuum separation. To converge the surface energy of the (101̅0) facet
with respect to slab thickness, t, slabs with 5 to 16 atomic layers (thickness of 14 to 45 Å ) are generated and fully
relaxed following the computational method described in the main article. For the (112̅2) surface energy slabs are
generated with 5 to 10 double layers (thickness of 15 to 30 Å ). To find the optimum vacuum distance and avoid
interaction between layers, slabs with a vacuum space, d, of 15 to 35 Å are tested. All atoms are allowed to fully relax
in the x- y- and z- directions. For the (101̅0) surface, the surface energy is converged for slabs with 11 or more layers
(𝑡 ≥ 31 Å ) and computed to an accuracy of 0.01 Jm-2. Convergence of the semi-polar (112̅2) surface is harder to
achieve due to the existence of an internal field set up in the polar slabs. The converged surface energy is obtained
through extrapolating the 1/𝑡 dependence of the slab energy on thickness to remove the effect of the internal field,
following the convergence method by Meyer et al [1]. As a result of this more complex procedure, the surface energy
of the (112̅2) facets is computed to a lower accuracy of 0.1 Jm-2. A vacuum spacing of 20 Å is found to be sufficient
to avoid interactions between layers. The surface energies of stoichiometric surfaces were calculated by computing
the facet energy of relaxed slabs, each containing a single pair of parallel facets by using equation 1 in the main
document [2].
To study the change in surface energy with respect to the chemical potential of oxygen, nonstoichiometric slabs, with
an excess or deficiency of oxygen, are generated by cutting the top or bottom surface from a different position in the
c-axis direction. The energy of these surfaces were computed using the energy of the stoichiometric slab using
equation 2 in the main document.
The oxygen chemical potential, 𝛥𝜇𝑂 , defines the potential of oxygen relative to half of the cohesive energy of the
1
oxygen dimer, 𝐸𝑂𝑡𝑜𝑡
2
, and is plotted over the range for which ZnO is stable. This gives the low 𝛥𝜇𝑂 limit as the
2

chemical potential at which ZnO is reduced to Zn metal and O2 gas (equation 4 in the main document.)

1
Fig. S1. Computational cell geometries of the generated {101̅0} and {112̅2} slabs, demonstrating surface areas, slabs
thickness (t), vacuum space (d), and the cell vectors in terms of unit cell lattice parameters a, b, and c (where x is an
integer number in range 5-11 for the {101̅0} surface and 5-8 for the {112̅2} slabs).

2
2. Photocatalytic statistical data

Fig. S2 shows the statistical data of the onset potential, slope and current density at 0.6 V for the
photoelectrochemical performance measurements of synthesized ZnO nanopyramids (NPy) versus nanorods (NR).
Although the results show some deviation within the same structure type, there is a noticeable difference between the
performance of the NPy and NR nanostructures. The electrochemical performance results are related to the density
and morphology of nanostructures, effective surface area and surface state [3–5]. These properties are derived from
the experimental conditions and parameters during crystal growth and are inherently affected by built-in experimental
variation in the CVD equipment setup and reaction process. Experimentally, factors such as the distance between the
source and substrate, temperature profile along the CVD reactor, mass of Zn power precursor, and O and Zn vapor
partial pressures affect the density and surface state of as-synthesized nanostructures [6–9]. The measured performance
is compared with other works reported in the literature focused on the morphology engineering of ZnO nanostructures,
as listed in Table S1.

Fig. S2. Statistical data of photoelectrochemical performance of ZnO nanopyramid (black) and nanorod (red)
structures; (a) Onset potential, (b) Slope, (c) Current density at 0.6 V, and (d) Box chart legend.

3
 Table S1. Comparison of photoelectrochemical performance results in this work versus results in the literature.

Onset Slope Current at 0.6

Morphology Electrolyte Light power Reference
Potential (V) (S) V (mA/cm2)
Our nanopyramid 0.5 M Na2SO4 1.0 mW/cm2 -0.40 0.97 0.47 -
2
Our nanorod 0.5 M Na2SO4 1.0 mW/cm -0.33 0.44 0.28 -
2
Nanowire 0.01 M Na2SO4 0.4 mW/cm -0.24 0.68 0.32 [10]
Urchin-like 0.01 M Na2SO4 0.3 mW/cm2 -0.22 0.79 0.42 [11]
2
Nanoparticle 0.5 M NaClO4 100 mW/cm 0.37 0.23 0.06 [12]
2
Nanoforest 0.5 M Na2SO4 100 mW/cm -0.19 1.06 0.68 [13]
2
Tetrapod 0.5 M Na2SO4 100 mW/cm -0.22 0.53 0.34 [14]
Nanorod-nanosheet 0.5 M Na2SO4 100 mW/cm2 -0.27 1.15 0.65 [15]
2
Patterned nanorod 1.0 M Na2SO4 100 mW/cm -0.09 1.14 0.61 [16]
2
Thinfilm (002) 0.5 M Na2SO4 72 mW/cm -0.2 0.55 0.36 [17]
2
Nanotree 0.5 M Na2SO4 100 mW/cm 0 0.88 0.47 [18]
Nanotube 1.0 M KOH 100 mW/cm2 -0.36 1.48 0.91 [19]

3. Electron lifetime measurement

The transient photovoltage decay (Fig. S3(a)) is measured to calculate the electron lifetime (Fig. S3(b)) of the photo-
excited electron in the ZnO nanopyramids and nanorods using the following equation:

𝑘𝐵 𝑇 𝑑𝑉𝑂𝐶 −1
τ= ( )
𝑒 𝑑𝑡

The pyramidal ZnO shows higher stability of photo-generated carriers, resulting in a prolonged electron lifetime as
calculated from the voltage drop result. The photocatalytic performance of pyramidal ZnO is enhanced by the longer
photo-excited carrier lifetime and lower interfacial resistance (Fig. 6 in the main manuscript).

Fig. S3. (a) Open circuit voltage drop measurement, and (b) calculated electron lifetime.

4
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