Research Article

ISSN 1998-0124 CN 11-5974/O4

2019, 12(9): 2348–2354 https://doi.org/10.1007/s12274-019-2373-0

Controlled growth of uniform two-dimensional ZnO overlayers on

Au(111) and surface hydroxylation
Hao Wu1,2, Qiang Fu1 (), Yifan Li1,2, Yi Cui3, Rui Wang3, Nan Su1,2, Le Lin1, Aiyi Dong1, Yanxiao Ning1, Fan Yang1, and
Xinhe Bao1,2
1
State Key Lab of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
2
Department of Chemical Physics, University of Science and Technology of China, Hefei 2300263, China
3
Vacuum Interconnected Nanotech Workstation, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123,
China

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019
Received: 19 January 2019 / Revised: 26 February 2019 / Accepted: 5 March 2019

ABSTRACT
Ultrathin ZnO nanostructures present interesting two-dimensional (2D) graphene-like structure in contrast to wurtzite structure in bulk ZnO.
Growth on Au(111) has been regarded as a well-established route to the 2D ZnO layers while controlled growth of uniform ZnO
nanostructures remains as a challenge. Here, reactive deposition of Zn in O3 and NO2 was employed, which is investigated by scanning
tunneling microscopy and X-ray photoelectron spectroscopy (XPS). We demonstrate that uniform ZnO monolayer nanoislands and films can
be obtained on Au(111) using O3 and uniform ZnO bilayer nanoislands and films form on Au(111) using NO2, respectively. Formation of
atomic oxygen overlayers on Au(111) via exposure to O3 is critical to the formation of uniform ZnO monolayer nanostructures atop. Near
ambient pressure XPS studies revealed that nearly full hydroxylation occurs on monolayer ZnO structures upon exposure to near ambient
pressure water vapor or atomic hydrogen species, while partial surface hydroxylation happens on bilayer ZnO under the same gaseous
exposure conditions.

KEYWORDS
graphene-like ZnO, two-dimensional materials, hydroxylation, near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS),
scanning tunneling microscopy (STM)

overlayers. Because of the inertness of Au to many reactants,

1 Introduction
Discovery of graphene and its unique properties have stimulated
many explorations of other two-dimensional (2D) layered nano-
structures [1–3]. 2D graphene-like nanomaterials, such as graphitic
carbon nitride (g-C3N4), hexagonal boron nitride (h-BN), transition
metal dichalcogenides (TMDCs), and transition metal oxides, have
found important applications in many fields, e.g. catalysis [4], energy
conversion and storage [4, 5], photodetection [6], and biosensing [7].
Among them, very thin 2D oxide nanostructures serve as versatile
models for studies in surface properties of oxide materials, which
are otherwise inaccessible to most surface science techniques due to
their insulating nature [8–14].
Zinc oxide (ZnO) has found many diverse applications [15, 16]
in semiconductor devices [17] and heterogeneous catalytic processes
such as syngas conversion to olefins [18], methanol synthesis [19],
and water-gas-shift (WGS) reaction [20]. As reported, thin ZnO
films with a few monolayer (ML) thickness show an interesting
planar structure consisting of Zn and O layers merged into the same
plane. Both physical and chemical properties of the graphene-like
ZnO are dependent on the layer number, which are different from
the bulk wurtzite ZnO [3, 21–23]. Preparation of 2D graphene-like ZnO
overlayers supported on solid substrates [24–27] or as being free-
standing [28, 29] has been extensively studied, which show tunable
physical and chemical properties with layer number or thickness [30].
Au(111) can act as an ideal substrate for growth of 2D ZnO
ZnO/Au(111) surfaces present advantages to explore intrinsic chemical
properties of supported ZnO nanostructures [31]. However, controlled
growth of uniform 2D ZnO overlayers on metal surfaces remains a
challenge. Previous works show that monolayer ZnO nanostructures
are easy to form on Pt(111) [25] or Pd(111) [24] surfaces, while
bilayer and beyond are more favored on Au(111) [32–35] and
Ag(111) [36–38] surfaces. It has been demonstrated that the growth
of 2D ZnO overlayers strongly depends on substrate surfaces, growth
atmosphere, growth temperatures, and so on. The common growth
approaches include Zn deposition combined with post-oxidation, Zn
deposition in oxidative atmosphere, and Zn deposition onto oxygen-
adsorbed surface [39]. These routes have been attempted to grow 2D
ZnO on Au(111) [33], while controlled growth of 2D and uniform
ZnO nanostructures has not been achieved.
In this work, we studied the critical factors governing growth of
graphene-like ZnO nanostructures on Au(111) based on scanning
tunneling microscopy (STM) and X-ray photoelectron spectroscopy
(XPS) measurements. Uniform monolayer and bilayer 2D ZnO
nanostructures on Au(111) have been successfully prepared. Oxide
nanostructures under ambient gaseous conditions are often subject
to surface hydroxylation, which strongly influence their catalytic
activities [40, 41]. Using the well-defined ZnO/Au(111) surfaces
we further explore surface hydroxylation of ZnO overlayers in the
presence of H2O, H2, and atomic hydrogen, which show interesting
layer-dependent surface reactivity of the 2D ZnO structures.

Address correspondence to qfu@dicp.ac.cn

Nano Res. 2019, 12(9): 2348–2354 2349

2 Experimental
Ultrahigh vacuum (UHV) XPS and STM measurements were
performed in an Omicron multiprobe system, which consists of a
preparation chamber, a spectroscopy chamber, and a microscopy
chamber. The spectroscopy chamber was equipped with XPS,
ultraviolet photoelectron spectroscopy (UPS), and high-resolution
electron energy loss spectroscopy (HREELS, LK-ELS5000). In
addition, a high-pressure cell has been attached to the UHV system,
where gases with pressure up to 1.0 bar can be dosed at room tem-
perature. Samples treated in this cell were transferred back to the
UHV chambers for further surface measurements without exposing
them to air. XPS spectra were acquired using Mg Kα (hν = 1,253.6 eV)
radiation. STM images were processed with SPIP program from
Image Metrology.
Near ambient pressure XPS (NAP-XPS) experiments were performed
by using monochromatized Al Kα (hν = 1,486.6 eV) radiation in
a customized end station from SPECS. This system consists of a
NAP-XPS chamber, a molecular beam epitaxy (MBE) chamber, and
a NAP-STM chamber as described in our previous work [42]. The
background pressure of the three chambers is lower than 3 × 10−10 mbar.
In the NAP-XPS chamber, samples can be investigated in up to 25 mbar
atmospheres and with sample temperatures up to 1,400 K by laser
heating.
Au(111) (MaTeck) was cleaned by cycles of Ar+ sputtering (1.0 kV,
6 × 10−6 mbar Ar, 15 min), annealed at 700 K in 10−6 mbar of O2 to
remove carbon from the surface, and heated in UHV at 750 K. Zn
was deposited by evaporating zinc shots (Alfa Aesar , 99.9999%) in a
low temperature evaporator (Createc). Exposure of O2, NO2, and O3
to sample surfaces was performed by backfilling the chambers. O2
(99.9999%) and NO2 (99.5%) gases were used as-received. O3 dosing
was carried out using a gas mixture of 10% O3 and 90% O2 generated
by a high purity ozone generator system and the gas component was
analyzed using a mass spectrometer (RGA 200) (see the Electronic
Supplementary Material (ESM) for O3 generation). Figure 1 (a) O 1s XPS data of Au(111) surface exposed to O2, NO2, and O3
atmospheres at room temperature: (1) 1 × 10−7 mbar O2; (2) 1 × 10−7 mbar NO2;
(3) 1 × 10−7 mbar O3. (b)–(d) XPS data of Zn/Au(111) surface exposed to O2,
3 Results and discussion NO2, and O3 atmospheres under the same conditions: (b) O 1s region; (c) Zn
L3M45M45 Auger region; and (d) Zn 2p3/2 region.
3.1 Effect of oxidants on oxidation of Au surface and Zn
Reactive deposition of Zn was used to prepare ZnO nanostructures to O2 there was little O 1s signal coming from the surface, and
on Au(111). For growth of metal oxides, both O2 and NO2 have the corresponding Zn L3M45M45 Auger spectrum is the same as the
been extensively used [43, 44], while in this work O3 has been pristine metallic Zn structure on Au(111) (Fig. 1(c)). In case that
further considered. Oxidation of Au(111) surface and evaporated NO2 is used as the oxidant, two peaks with the binding energies at
Zn in the three oxidant atmospheres were investigated first. A clean 532.2 and 529.5 eV were observed in the O 1s spectrum (Fig. 1(b)),
Au(111) surface was exposed to the three oxidants (O2, NO2, and O3) which are attributed to surface hydroxyl groups (OH) and oxygen
under conditions of 1 × 10−7 mbar for 10 min at room temperature, species bonded to surface Zn atoms (O–Zn), respectively. Meanwhile,
and XPS spectra from the three surfaces were shown in Fig. 1(a). the line shape and peak position of the Zn L3M45M45 Auger spectrum
When exposing to O2 and NO2, no O 1s signals were observed on are close to those of ZnO (Fig. 1(c)) [38], revealing oxidation of
the surface (Fig. 1(a)) and the Au 4f signals (Fig. S1(a) in the ESM) metallic Zn to Zn2+ species.
were the same as the clean Au(111) surface. Thus, no chemisorbed O 1s signal is much stronger upon oxidation in O3, which also
oxygen atoms form on Au(111) under present O2 and NO2 exposure contains two components from O–H (531.1 eV) and O–Zn (529.2 eV)
conditions, which is consistent with the previous reports [45–47]. species, and the Zn L3M45M45 Auger spectrum indicates higher
In contrast, upon exposure to O3 strong O 1s signal at 529.8 eV oxidation degree of Zn than that in NO2 (Figs. 1(b) and 1(c)). It should
originating from atomic oxygen species adsorbed on Au [48] was be noted that the Zn/Au(111) surfaces subjected to the O3 exposure
clearly observed (Fig. 1(a)). Meanwhile, Auδ+ signal was detected have been further exposed to 1 × 10–6 mbar CO to remove any atomic
in Au 4f spectra and the Au–O component becomes stronger with oxygen species adsorbed on bare Au surface (Fig. S2 in the ESM).
smaller take-off angles (Fig. S1(b) in the ESM). The results indicate Therefore, the observed O 1s signals in Fig. 1(b) are all from surface
that O3 can dissociate on Au(111) to produce atomic oxygen species, zinc oxide. Figure 1(d) displays the corresponding Zn 2p3/2 XPS
which bond with surface Au atoms and form one layer of adsorbed spectra. Interestingly, the higher Zn oxidation degree, the lower Zn 2p
oxygen [49]. binding energy position, which is in contrast with the normal positive
Zn was deposited on clean Au(111) surface and oxidation of the binding energy shift with the increasing metal valence state [50].
Zn overlayers was carried out in the three oxidizing atmospheres Another interesting point is that the Au 4f binding energy presents
(1 × 10−7 mbar, 10 min, room temperature) as well, which were then a small shift to a higher position with Zn deposited atop and it
investigated by acquiring XPS core level spectra and X-ray induced shifts back when the zinc was oxidized in NO2 and O3 (Fig. S3 in
Auger peaks (Figs. 1(b) and 1(c)). When the Zn film was exposed the ESM), which indicates alloying reaction between Zn and Au.

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The strong Zn-Au alloying reaction can be further illustrated by
experimental results in Fig. 2. STM images show the formation of
Zn islands after deposition of 0.7 ML of Zn on Au(111) at room
temperature (Fig. 2(a)). Upon heating in UHV at 400 K for 12 h
(Fig. 2(b)), the Zn islands disappeared due to alloying with Au. The
subsequent oxidation in 1  10−7 mbar NO2 at 500 K produced high
density nanoislands on the surface again (Fig. 2(c)). XPS measure-
ments (Figs. 2(d) and 2(e)) reveal a decrease in Zn 2p intensity
induced by the UHV heating and then an intensity increase caused
by the oxidation treatment. These results confirm interdiffusion
of some Zn atoms from top surface to subsurface along with the
formation of ZnAu alloy but from subsurface to the top surface
after the subsequent oxidation yielding surface ZnO species.
Similar alloying reaction has been observed upon growth of ZnO
on Cu(111) [34, 51]. For example, Liu et al. found that Zn wets Cu
surface forming surface alloy layer and then surface oxidation in O2
leads to formation of ZnO layer [51]. Zhao et al. observed that well-
ordered ZnO thin films can be grown on Cu(111) using NO2 [34].
It has been shown that adsorbed atomic oxygen species form on
Au(111) when exposed to 1  10−7 mbar O3 but not in O2 and NO2,
and Zn overlayers deposited on Au(111) can be oxidized in 1  10−7
mbar of NO2 or O3 but not in O2 at room temperature (see Fig. 1). One
can infer decreased oxidation ability in the sequence: O3 > NO2 > O2.
Furthermore, we demonstrate that direct Zn deposition on Au(111)
leads to alloying between them with Zn atoms diffusing to the
subsurface at elevated temperatures and the subsurface Zn atoms
can be pulled out onto the top surface after oxidation forming ZnO
thin films. Overall, these results enlighten us to grow ZnO overlayers
on Au(111) through reactive deposition of Zn in strong oxidant
atmospheres.
3.2 Growth of ZnO nanostructures on Au(111) in NO2
and O3
Based on the above discussions, 10−7 mbar of NO2 or O3 was chosen
to oxidize Zn atoms evaporated onto Au(111) surface. When ZnO
Figure 2 STM images and XPS spectra during the alloying and oxidation of
Zn/Au(111). (a) Zn islands on Au(111); (b) the surface-alloyed Zn/Au(111)
prepared by annealing at 400 K for 12 h in UHV; (c) ZnO/Au(111) prepared by
subsequent oxidation with NO2 (1  10−7 mbar) at 500 K; (d) XPS spectra of Zn
2p3/2 for samples in (a)–(c). (e) Integrated areas of Zn 2p3/2 signals corresponding
to (d).
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Nano Res. 2019, 12(9): 2348–2354
growth was performed at room temperature or below, high-density
nanoislands with disordered surface structure were observed with
heights of ~ 0.2 nm (Figs. 3(a) and 3(b)). Therefore, growth at various
substrate temperatures combined with post-annealing at an elevated
temperature has been attempted in order to obtain ordered ZnO
nanostructures.
Deposition of Zn onto Au(111) has been carried out in 1 × 10−7
mbar NO2 atmosphere at the substrate temperatures of 100, 300,
and 500 K, respectively. The post-annealing in the NO2 atmosphere
at 530 K has been further performed in case of low temperature
growth (e.g. 100 and 300 K). As shown in Fig. 3(c), growth at 100 K
combined with annealing at 530 K in 1 × 10−7 mbar NO2 produced
highly dispersed and well-ordered oxide nanostructures on the Au
substrate. Heights of the surface nanoislands are all 0.33 ± 0.01 nm
(Fig. 3(d)), characteristic of bilayer ZnO structure [33]. In contrast,
much larger islands were formed on the surface at the growth tem-
perature of 300 K and all islands contain bilayer and trilayer domains
(Figs. 3(e) and 3(f)), which are typical in the previous findings
[33, 52]. Besides, the growth at 500 K results in ZnO nanoislands
or nanoparticles at surface steps (Fig. S4 in the ESM). Overall, we
conclude that the optimized growth condition for ordered and
uniform ZnO nanostructures consists of Zn deposition in NO2 at
100 K followed by annealing in NO2 atmosphere at 530 K.
Using the above established growth recipe, we have obtained
well-ordered ZnO bilayer nanostructures with various coverages
(Fig. 4). Line profiles of the formed nanoislands indicate the height
of 0.34 ± 0.01 nm (Fig. 4(e)), and moiré pattern periodicity on the
Figure 3 STM images of Au(111) surfaces subjected to the following ZnO
growth processes: (a) depositing Zn on an O3 pre-adsorbed Au(111) surface
at room temperature; (c) cooling the clean Au(111) to 100 K, pre-adsorbing
10 Langmuir (L) NO2, evaporating submonolayer Zn, and heating in a 530 K,
1 × 10−7 mbar NO2 atmosphere; (e) depositing Zn in 1 × 10−7 mbar NO2 with
Au(111) temperature at 300 K, and then heating at 530 K and in 1 × 10−7 mbar
NO2. (b), (d), and (f) are line profiles corresponding to the red lines in (a), (c),
and (e), respectively.
Figure 4 Bilayer ZnO nanostructures on Au(111) with different coverages
using NO2 as the oxidant: (a) 23%; (b) 45%; (c) 73%; (d) 98%. (e) Scanning line
corresponding to the red line in (a). (f) and (g) are O 1s and Zn 2p3/2 XPS spectra
recorded from surfaces shown in (a) to (d). (h) Integrated areas of O 1s and
Zn 2p3/2 peaks as a function of the apparent coverage.
Nano Res. 2019, 12(9): 2348–2354
island surfaces is about 2.3 nm, which are characteristic for ZnO
bilayer [33]. Figures 4(a)–4(d) suggest that all the prepared ZnO/
Au(111) surfaces contain the same well-defined and uniform ZnO
bilayer nanostructures with various coverages. The corresponding
XPS O 1s and Zn 2p3/2 spectra (Figs. 4(f) and 4(g)) show that the
peak intensities increase with increasing coverage but the peak
positions remain unchanged, i.e. 529.3 eV for O 1s and 1,020.7 eV
for Zn 2p3/2. The integrated peak areas of Zn 2p3/2 and O 1s spectra
(Fig. 4(h)) were correlated with the ZnO bilayer coverage, and linear
relationship has been clearly identified. Accordingly, we conclude
that the well-controlled (from partially to fully covered) layer
growth of uniform ZnO bilayer on Au(111) can be achieved by the
low-temperature Zn deposition in 10−7 mbar NO2 followed by mild
annealing in the NO2 atmosphere.
Although well-defined ZnO bilayer nanostructures have been
grown on Au(111), Ag(111), and Cu(111) surfaces [26, 33, 53],
it remains a challenge to prepare well-defined ZnO monolayer
nanostructures on these coin metal surfaces. Here, an attempt has
been made to prepare ZnO monolayer on Au(111) surface in the
presence of O3. The O-Au(111) surface was obtained by exposing
the pristine Au(111) surface to 1 × 10−7 mbar O3, and then Zn was
deposited onto the surface under UHV at room temperature. With
the following annealing treatment at 520 K in 2 × 10−8 – 4 × 10−8 mbar
O3, ordered nanoislands form on the surface having the same height
of 0.19 ± 0.01 nm, corresponding to the presence of monolayer ZnO
(Fig. 5).
Figures 5(a) and 5(b) show ZnO monolayer islands grown on a
surface terrace and at a surface step, respectively. Monolayer ZnO
islands are distributed evenly on each terrace and at the surface
steps, with different domains marked with I, II, and III in the image
(Fig. 5(b)). The I-type islands have moiré pattern periodicity of
2.3 nm and height of 0.19 ± 0.01 nm, which are typical for the ZnO
monolayer structure. Region-II presents the same moiré pattern but
the height is lower than the Au terrace by 0.05 nm, which is the
difference between monoatomic step height of Au(111) and ZnO.
Thus, the II-type regions can be attributed to ZnO nanoislands
embedded within the Au terraces. The regions marked with III
have the same height of 0.24 nm as Au(111) monolayer step and
show the typical herringbone reconstruction of Au(111) [54] and
they should be Au islands nestled within ZnO monolayer domains.
The embedded ZnO nanoislands and nestled Au nanoislands should
be related to oxidation and annealing effects of the surface Au-Zn
alloy structures. We consider that there is certain atomic position
exchange between Au and Zn, with ZnO occupying Au positions in
the topmost surface and excess Au atoms diffusing onto the terrace
along with high temperature oxidation. Similar structures have been
found in other oxide/metal interfaces such as FeO/Au(111) [10],
NiO/Ag(110) and NiO/Ag(001) [9, 11]. Finally, the deposition of
Figure 5 (a)–(c) Uniform monolayer ZnO nanostructures on Au(111) with
different coverages using O3 as the oxidant: (a) and (b) monolayer ZnO nano-
islands; (c) a full monolayer ZnO film. (d) Line profiles from the red and blue
lines in (a) and (b).
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2351
Zn for prolonged time leads to the formation of a well-ordered, full
ZnO monolayer film as shown in Fig. 5(c).
It has been reported that bilayer ZnO nanostructures tend to
form on the coin metal surfaces in O2 or NO2, while monolayer ZnO
nanostructures grow on Pt(111), Pd(111), and Rh(100) surfaces
in O2 [24–26, 33, 53]. Exposure of noble metal surfaces to O2 leads
to formation of chemisorbed atomic oxygen species, which help
to disperse and oxidize evaporated Zn atoms on the surfaces. The
present results reveal that using O3 as the oxidant, atomic oxygen
overlayers form on the coin metal surfaces as well, which should
account for the formation of monolayer ZnO nanostructures on
Au(111). It is expected that the controlled growth of uniform ZnO
monolayer islands or film may also happen on both Ag(111) and
Cu(111) surfaces in O3 atmosphere.
3.3 Hydroxylation of monolayer and bilayer ZnO surfaces
As discussed above, uniform monolayer or bilayer ZnO nanostructures
including nanoislands and films can be prepared on Au(111) by
controlling substrate temperatures and oxidants. The ZnO/Au(111)
surfaces can be used as well-defined model systems to study surface
chemistry. Among all, hydroxylation of oxide surfaces plays an
important role in surface physical and chemical properties. Hy-
droxylation of ZnO single crystal surface has been reported [55, 56],
as well as the hydroxylation of ZnO overlayers supported on Pt(111)
and Pd(111) surfaces, in which the metal substrate may contribute
to activation of H2O and H2 [24, 25, 57]. On ZnO/Au(111) surfaces
Au is inert to activate H2 and H2O, and hydroxylation of ZnO is
mainly determined by the chemical reactivity of ZnO overlayers.
Here, both monolayer and bilayer ZnO overlayers supported on
Au(111) were exposed to water vapor and hydrogen sources.
Figure 6 shows acquired NAP-XPS spectra after exposing monolayer
ZnO nanoislands (0.4 ML) supported on Au(111) to water vapor at
different partial pressures. The hydroxyl-related O 1s component
appeared at 531.8 eV when water pressure increased to 10−5 mbar
(Fig. 6(a)), revealing that hydroxylation of ZnO occurs under this
condition. Upon further increasing the water pressure, the original
O 1s peak (O–Zn) at 529.1 eV shifted to 530.2 eV and the component
at 531.8 eV (–OH) became dominant (Figs. 6(a) and 6(c)), indicating
that the ZnO surface has been largely hydroxylated. Meanwhile, the
corresponding Zn 2p3/2 peak shifted from 1,020.7 to 1,021.6 eV
after the surface hydroxylation (Fig. 6(b)). Both ZnO-related O 1s
and Zn 2p3/2 binding energies present similar positive shifts, i.e. +1.1 eV
for O 1s and +0.9 eV for Zn 2p3/2. These results indicate that the
surface hydroxylation leads to rigid band shift of the monolayer
ZnO structure, which may be attributed to different doping states
of ZnO layer or altered ZnO–substrate interaction induced by the
surface functionalization.
Figure 6(c) shows a quantitative analysis of the O 1s components
at different water vapor pressures revealing the increasing
hydroxylation of ZnO. Based on the surface oxygen amounts we
Figure 6 NAP-XPS studies of monolayer ZnO island on Au(111) exposed to
different pressures of water vapor. (a) O 1s; (b) Zn 2p3/2; (c) integrated areas of
different oxygen species shown in (a).
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propose that the surface hydroxylation takes place following the
equation of 2ZnO + H2O → ZnO·Zn(OH)2. The results indicate
that monolayer ZnO has a strong ability to activate H2O under near
ambient conditions and can be largely functionalized by surface
hydroxyl groups. Interestingly, although monolayer ZnO presents
the similar graphene-like atomic structure, its surface reactivity
is much higher than graphene and other graphene-like two-
dimensional layers.
Similar NAP-XPS measurements were performed on bilayer ZnO
nanostructures supported on Au(111) under various water vapor
atmospheres (Fig. S5 in the ESM), which again demonstrated the
facile hydroxylation of bilayer ZnO and the rigid band shifts of O1s
and Zn 2p spectra along with the surface hydroxylation. Since only
the top ZnO layer of the bilayer ZnO structure can be hydroxylated,
the relative concentration of OH component is much lower than
that on the monolayer ZnO structure (Fig. S5 in the ESM).
Exposure of the ZnO/Au(111) surfaces to hydrogen molecules
and atomic hydrogen species has been further explored. When
the ZnO/Au(111) surface was exposed to 0.1 mbar D2, no any OD
groups were detected by HREELS (Fig. S6(a) in the ESM), which
is different with H2 dissociation on the ZnO(0001) surface [58].
However, after exposure to 0.01 mbar atomic D species a peak at
327 meV has been clearly recorded (Fig. S6(b) in the ESM), which
is characteristic for O–D stretching vibration. Thus, the supported
ZnO overlayers are easily hydroxylated by atomic hydrogen atoms
but rather difficult to react with H2 in sub-millibar range.
Previous works have reported that ultrathin ZnO overlayers
grown on Pt(111) and Pd(111) can be hydroxylated even under UHV
conditions on the basis of infrared (IR) and STM characterizations
[24, 25, 57]. It has been shown ZnO bilayers on Ag(111) and Au(111)
are inert to exposure of H2 or D2O at 300 K under UHV conditions
[57, 59], while we demonstrate that both ZnO monolayers and
bilayers on Au(111) can be hydroxylated when exposing to high
pressure water. Therefore, the hydroxylation of ultrathin ZnO
overlayers helps to stabilize the graphitic ZnO nanostructures while
metals such as Pt and Pd mediate the surface hydroxylation process.
To further investigate the effect of the ZnO layer number on the
surface hydroxylation, XPS measurements were conducted over
different ZnO nanostructures (Fig. 7). Monolayer ZnO nanostructures
with coverages of 0.5 and 0.8 ML were hydroxylated when exposed
to atomic hydrogen, with the ratio of O–H species (531.8 eV) to
O–Zn (530.2 eV) around 2:1 (Fig. 7(a)), which means that 67% of
oxygen atoms in monolayer ZnO combine with atomic hydrogen to
form hydroxyl groups. In comparison, the bilayer ZnO was partially
hydroxylated by atomic hydrogen with the ratio of O–H species
(532.0 eV) to O–Zn (529.6 eV) at 1:3 (Fig. 7(b)). Assuming that the
detected photoelectrons are similar from the top layer and the
bottom layer in the bilayer ZnO structure, we calculated that 50%
Figure 7 XPS O 1s spectra of (a) monolayer ZnO with different coverages (0.5
and 0.8 ML) and (b) ZnO bilayers on Au(111) when exposed to atomic
hydrogen until the saturated hydroxylation. (c) Total oxygen amounts of ZnO
with different coverages on Au(111) before and after hydrogenation.
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Nano Res. 2019, 12(9): 2348–2354
of the top layer oxygen atoms are hydroxylated, which is smaller
than that on the monolayer ZnO structure. The quantitative
analysis of the surface concentration of hydroxyl species formed on
ZnO overlayers further confirms that monolayer ZnO exhibits higher
hydrogenation activity than bilayer ZnO, revealing the layer-
dependent surface reactivity of the 2D ZnO supported on Au.
Whereas the surface hydroxylation with H2O leads to an increased
O/Zn ratio (see Fig. 6(c)), it is expected that the total oxygen
amounts in the ZnO monolayer and bilayer nanostructures should
be unchanged after the hydrogenation by atomic hydrogen. Indeed,
a quantitative analysis reveals that the O 1s peak areas remain nearly
constant before and after the hydroxylation (Fig. 7(c)).
4 Conclusion
O2, NO2, and O3 have been used to oxidize Au(111) surface and Zn
overlayers. We found that chemisorbed oxygen layers form on
Au(111) when exposed to O3, and Zn deposited on Au(111) can be
oxidized by either O3 or NO2 at room temperature. Accordingly,
well-controlled growth recipes have been established to achieve
layer growth of 2D ZnO on Au(111). Deposition of Zn at 100 K
in 1 × 10−7 mbar NO2 combined with annealing at 530 K in the
same NO2 atmosphere produces uniform ZnO bilayer nanoislands or
full film. Room temperature growth of Zn on O-Au(111) surface
via pre-exposure to 1 × 10−7 mbar O3 and then annealing at 520 K
in 2 ~ 4 × 10−8 mbar O3 results in the formation of uniform ZnO
monolayer nanoislands or full film. Both ZnO monolayer and bilayer
surfaces can dissociate water vapor under near ambient pressure
conditions forming surface hydroxyl groups. Meanwhile, surface
hydroxylation occurs via the direct hydrogenation with atomic H
species. Overall, monolayer ZnO shows higher reactivity for surface
hydroxylation than bilayer ZnO.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (Nos. 21825203, 91545204, 21688102,
and 21621063), the National Key Research and Development
Program of China (Nos. 2016YFA0200200 and 2017YFB0602205),
and Strategic Priority Research Program of the Chinese Academy
of Sciences (No. XDB17020000). The authors thank the support
for Nano-X from Suzhou Institute of Nano-Tech and Nano-Bionics
(SINANO). The fruitful discussion with Yuemin Wang in Karlsruhe
Institute of Technology (KIT) is highly appreciated.
Electronic Supplementary Material: Supplementary material
(further details of O3 generation, atomic hydrogen generation, and
other XPS/STM/EELS measurements) is available in the online
version of this article at https://doi.org/10.1007/s12274-019-2373-0.
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