Letter

Cite This: J. Phys. Chem. Lett. 2019, 10, 3557−3562 pubs.acs.org/JPCL

Ultrasensitive Mechano-Stimuli Luminescence Enhancement in ZnO

Nanoparticles
Ya-Chuan Liang, Qi Zhao,* Kai-Kai Liu, Qian Liu, Xian-Li Lu, Xue-Ying Wu, Ying-Jie Lu, Lin Dong,
and Chong-Xin Shan*
Henan Key Laboratory of Diamond Optoelectronic Materials and Devices, Key Laboratory of Material Physics, Ministry of
Education, School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001, China
*
S Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Ultrasensitive mechano-stimuli photoluminescence enhancement was

observed in pyramid-like zinc oxide nanoparticles (ZnO NPs), which are fabricated by
Downloaded via NOTTINGHAM TRENT UNIV on August 27, 2019 at 13:15:31 (UTC).

a facile hydrothermal route. The response of the ZnO NPs to mechanical stimuli is so
sensitive that even an ant walking and acoustic vibration can trigger the luminescence
enhancement. The mechanism for this unusual behavior was attributed to the electron
injection process between crystal boundaries. Thus, this work opens up the possibility of
detecting slight mechanical stimuli wirelessly, rapidly, and sensitively. Importantly, the
sensitive response of the NPs to sound waves can find potential application in devices for
hearing-impaired people.

E arly sensing of danger signals in materials or surroundings

is very important to avoid catastrophic losses. A stimuli-
responsive material is one showing property or signal changes
in response to thermal, molecular, electrical, and mechanical
stimuli, which would be beneficial for the development of
dynamically functional materials and devices.1−3 In particular,
mechano-responsive luminescent (MRL) materials can display
a change in luminescent color/intensity or a switching-on/off
process by responding to a mechanical stimuli such as pressing,
shearing, grinding, rubbing, or stretching.4−7 Considering that
the optical method can offer the unique advantages of wireless
detection and nondestructive analysis, MRL materials have
great potential application in mechano-sensors,8 optical
storage,9 photonic devices,10 etc. Currently, a number of
MRL systems have been developed through various strategies,
mainly including mechanochromism based on polymers,
organic molecules, organometallic complexes, and piezolumi-
nescence (elasticoluminescence) in rare-earth-/transition-
metal-doped inorganic compounds.11,12 The emission color
change in mechanochromic materials triggered by external
mechanical stimuli is associated with their molecular structure
distortion, such as molecular packing, molecular conformation
and intermolecular interactions. By contrast, piezolumines-
cence is generally ascribed to the tilting of the band structure
within an asymmetrical crystal matrix induced by the
piezoelectric potential under straininga phenomenon called
piezophotonic effect.13 In this work, an unexpected and never-
before-reported luminescence enhancement was observed in
zinc oxide (ZnO) nanocrystals under mechanical stimuli.
Interestingly, the luminescent response to external disturbance
was extremely sensitive so that even an ant walking and
acoustic vibration can activate a drastic emission intensity
change. This mechano-stimuli luminescence enhancement can
hardly be elucidated by the reported mechanisms; therefore, a
different explanation, boundary electron injection, is proposed
hereinafter to shed some light on the novel phenomenon.
ZnO, as a well-known wide band gap semiconductor and
environmentally friendly oxide material, has attracted consid-
erable attention in the fields of ultraviolet (UV) photo-
detection,14−16 light-emitting devices,17,18 piezoelectric nano-
generators,19 etc. Generally, two typical photoluminescence
(PL) emission bands can be observed in ZnO nanoparticles
(NPs): UV emission from the near-band edge transition and
visible emission from the crystalline defects.20,21 The wide
band gap (Eg= 3.37 eV) and large exciton-binding energy (60
mV) of ZnO are responsible for its characteristic UV emission.
The defect-related luminescence usually come from the oxygen
vacancies, Zn vacancies, interstitial oxygen, Zn interstitials, or
other impurities in the ZnO matrix.20,22 However, mechano-
stimuli-triggered luminescence change has never been
observed in ZnO NPs.
Herein, ZnO NPs were first synthesized via a facile
hydrothermal route. Scanning electron microscopy (SEM)
images (Figure 1a) show that the as-prepared sample consists
of well-dispersed hexagonal pyramids with an average side
length of 60.19 ± 1.48 nm (Figure 1b). The TEM image
(Figure S1a) further confirms its pyramid-like shape. The
HRTEM image of an individual nanopyramid (Figure S1b)
Received: April 16, 2019
Accepted: June 10, 2019
Published: June 10, 2019

© 2019 American Chemical Society 3557 DOI: 10.1021/acs.jpclett.9b01092

J. Phys. Chem. Lett. 2019, 10, 3557−3562
The Journal of Physical Chemistry Letters Letter

Figure 1. (a) SEM image of the as-prepared ZnO NPs. (b) Statistical size distribution of the ZnO NPs. (c) XPS spectrum of the ZnO NPs. (d)
FTIR spectrum of the ZnO NPs.

Figure 2. (a) Photoluminescence excitation (PLE) spectrum monitored at 560 nm and the photoluminescence (PL) spectrum excited by 365 nm
of the ZnO NPs. (b) Fluorescence spectra of the as-prepared ZnO NPs before and after stimuli. The inset shows the corresponding photographs.
(c) Photograph of an ant walking on as-prepared sample. (d) The corresponding footprint distributions derived by extracting the gray scale of the
real-time captured image.

shows clear lattice fringe with interplanar spacing of 0.26 nm
that corresponds to the (0001) plane of wurtzite ZnO,23 which
reveals the highly crystalline nature of the ZnO nanoparticles
(NPs). The XRD pattern of the samples is shown in Figure S2,
and the diffraction peaks correspond well to hexagonal wurtzite
ZnO (JCPDS 89-1397).24
XPS spectra are collected to determine the chemical
compositions of the ZnO NPs. As shown in Figure 1c, the
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peaks of Zn 2p, O 1s, and C 1s can be observed from the
pattern, and no other elements can be found from the spectra.
The Zn 2p and O 1s peaks can be attributed to ZnO, while the
peaks of C 1s possibly stem from the functional groups
adsorbed on the crystal surface. In addition, the FTIR
spectrum was employed to investigate the functional groups
on the surface of the ZnO NPs, as shown in Figure 1d. The
absorption peaks located at 1550 and 1420 cm−1 can be
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Figure 3. Photographs and intensity distribution maps of the ZnO NPs upon exposure to various sounds at different decibel levels: (a) air-raid
warning, (b) thunder, and (c) whistle (scale bar: 1 cm).
attributed to the asymmetric and symmetric stretching
vibration of the carboxylic group (−COO−), confirming the
adsorption of acetate on the ZnO crystals.25 The absorption
bands at 3600−3700 cm−1 can be assigned to the stretching
vibration mode of −OH groups from the adsorbed water. The
broad absorption band observed at around 500 cm−1 belongs
to the stretching vibration mode of Zn−O. The XPS and FTIR
observations further confirm the composition of the as-
synthesized ZnO NPs.
As is known, the −COOH groups can adsorb certain facets
of crystal nuclei and inhibit the growth of these crystal
planes.26,27 Empirically, the surfactant molecules prefer to
adsorb on the lattice plane where the atomic planar density
(APD) is higher. In this case, the ZnO nanocrystals adopt a
hexagonal-close-packed (hcp) structure, where the atomic
planar density28 of (0001) and (1000) is determined to be 1.1
× 1019 and 5.9 × 1018 atoms/m2, respectively. Consequently,
the −COOH groups would adsorb on the (0001) planes
preferentially because of the higher APD, resulting in the faster
growth of (1000) planes than that of the (0001) planes. Thus,
the fast growing (1000) facets shrink and the ZnO crystals are
bound by (0001) planes which exhibit the hexagonal pyramid
shape eventually. The base of the pyramid-like ZnO nano-
crystals is the (0001) plane, while the lateral faces were
surrounded by (011̅0), (1̅100), (1̅010), (01̅10), (11̅00), and
(101̅0) planes.29 This is confirmed by the HETEM image
(Figure S1b), which clearly shows the (0001) plane of the
pyramid surface.
The luminescent properties of the ZnO NPs have been
investigated by PL spectroscopy and CCD spectrometry.
Figure 2a exhibits the fluorescence spectrum of the ZnO NPs
powder excited by a xenon lamp. The PL excitation spectrum,
which was obtained by monitoring the emissions of 560 nm, is
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broad and ranges from 250 to 380 nm. Under excitation at 365
nm, the ZnO sample exhibits a strong and broad emission
band from 430 to 700 nm peaking at 560 nm. The strong
visible emission is believed to be derived from the transitions
from trap levels,30 although the exact type of the defects
(interstitial, vacancy, impurity, etc.) in the ZnO matrix is still
under debate. To shed more light on the carrier recombination
process in the ZnO NPs, the transient fluorescence spectra was
measured. Figure S3 shows the excited-state lifetimes of the
fluorescent defects excited by a 350 nm laser. The decay curve
can be fit to a two-order exponential function as following:
y = y0 + C1 exp( −t /τ1) + C2 exp(−t /τ2) (1)
where y is the emission intensity; y0, C1, and C2 are constants; t
is time; τ1 and τ2 are decay lifetimes of the emission. τ1 and τ2
are calculated to be 374.27 and 28.97 ns, respectively. Herein,
τ1 may come from the defect-level recombination inside the
ZnO NPs, whereas τ2 is probably ascribed to the surface
defects’ recombination.31,32
Interestingly, an unexpected luminescence enhancement was
observed when an external mechanical stimuli was exerted on
the as-prepared ZnO NPs. As shown in the inset of Figure 2b,
the ZnO NPs show an orange-yellow fluorescence under UV
lamp. The enhanced luminescence was clearly observed when
the ZnO powder was lightly scratched in a circle shape as a
proof-of-concept of mechanical stimuli. It can be seen that the
luminescence intensity of the circular region is significantly
higher than the surrounding, and the luminescence will recover
to the original situation when the external stimulus is removed.
The luminescence enhancement induced by mechanical
stimuli is also demonstrated by the emission spectra, which
obviously shows that the luminescence intensity is increased
dramatically after stimuli (Figure 2b). In order to evaluate if
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Figure 4. Mechanisms of the mechanical stimuli-enhanced photoluminescence processes.
Figure 5. (a) Photocurrent dynamics under UV light illumination with the center wavelength at 365 nm. The inset is the illustration of the test
process. (b) Fourier transform infrared (FTIR) spectroscopy pattern of the zinc oxide nanoparticles before and after annealing. (c) TEM image of
ZnO@SiO2 core−shell nanostructures.
other ZnO nanostructures, such as ZnO QDs and nanowires,
also have this phenomenon, ZnO QDs and nanowires have
been synthesized. The typical morphological and luminescent
characterizations of the as-prepared samples have been
analyzed by scanning electron microscopy (SEM), trans-
mission electron microscopy (TEM), and CCD spectrometry.
As shown in Figure S4, mechano-stimuli luminescence
enhancement of ZnO QDs and nanowires cannot be detected.
Interestingly, the response of the ZnO NPs to mechanical
stimuli is so sensitive that even an ant walking can trigger the
luminescence enhancement (the average weight of an ant is
only 50 mg). The ultrasensitive stimuli-responsive lumines-
cence can be clearly observed by the naked eye, as shown in
Figure 2c. The corresponding video is shown in Supple-
mentary Movie 1. The corresponding footprint distributions of
the ant are derived by extracting the gray scale of the real-time
captured image as presented in Figure 2d. The clear footprints
suggest the possibility of recording detailed information
through the change of gray value in sensing applications.
In view of the ultrasensitive response to mechanical stimuli,
we considered if the luminescence enhancement of as-prepared
ZnO NPs can be triggered by another weak mechanical
stimuliacoustic vibration. To test this hypothesis, the NPs
were exposed to several audio sources including the sounds of
air-raid warning, thunder, and whistle at different decibel levels.
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As expected and interestingly, the luminescence enhancement
was clearly observed (as shown in Figure 3), and the
luminescence intensity will increase as a function of the
sound volume in the decibel range of 40−60 dB (Figures 3 and
S5). To demonstrate the difference more clearly, the photos of
luminescent ZnO NPs were transferred into a pseudocolor
map by MATLAB software to visualize the intensity
distribution. Thus, the audio signal can be converted into an
optical signal directly and the sound volume can even affect the
luminescent intensity. It is worth noting that the sound stimuli
that can trigger the ZnO NPs is exactly in the frequency and
volume range audible to the human ear. Therefore, the as-
prepared NPs may find potential application in security alerts
or communication assistance for hearing-impaired people.
On the basis of the experimental results mentioned above, it
is speculated that the luminescence enhancement of the ZnO
NPs is ascribed to an electron injection process initiated by
mechanical stimuli. During the hydrothermal synthesis process,
the zinc acetate decomposed to produce ZnO crystal nucleus:
Zn(CH3COO)2 + H 2O → ZnO + 2CH3COOH
As discussed above, the CH3COO− groups adsorbed on the
crystal face to induce the formation of the pyramid-like
nanostructure. It is worth noting that the number of adsorbed
acetate groups varies with the APD of crystal planes, thereby
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leading to the diversity in charge density of different surfaces.
Under UV irradiation, the electrons are excited into the
conduction band and then trapped by the defect level to
exhibit a yellow emission. Meanwhile, the number of
photogenerated carriers gathered at the crystal surfaces varies
with the charge density of different planes. Therefore, an
electron injection process will occur if different faces of the
ZnO crystal contact with each other when the ZnO powders
are exposed to mechanical stimuli (such as stirring, scratching,
etc.), which results in the carrier recombination between
crystal boundaries. Thus, the enhanced luminescence will be
observed. The corresponding mechanisms of the external
force-enhanced photoluminescence processes are shown in
Figure 4.
According to the above analysis, three factors are mainly
responsible for the luminescence enhancement: (a) the
aggregation of carrier on the surface, (b) anisotropic electron
distribution on crystal faces, and (c) direct contact of the ZnO
grains. To verify the hypothesis, a series of experiments were
conducted. The aggregation of carrier on the crystal surface is
the presupposition of an electron injection process. To verify
this, the photocurrent dynamics of the as-prepared ZnO NPs
under UV-light irradiation was measured. Figure 5a shows that
a current as high as 0.24 μA was obtained. One can imagine
that if there were no external circuit (the situation in
measuring equipment), generated carriers will saturate and a
part of photogenerated carriers would be accumulated on the
surface of ZnO NPs. The surface acetate groups play a key role
in the anisotropic electron distribution. In order to validate it,
the as-prepared ZnO NPs were annealed in air at 300 °C to
remove the surface groups. As the FTIR spectra illustrate in
Figure 5b, the bands at 1550 and 1420 cm−1 coming from the
stretching vibration of the carboxylic group disappear in the
annealed sample. Figure S6a shows that the annealed ZnO NPs
also emit visible luminescence, but the mechano-stimuli
luminescent enhancement cannot be observed. Another
precondition for electron injection is the direct contact of
the ZnO crystals. To prove that, the ZnO nanocrystals were
coated with SiO2 to inhibit the contact between grains. The
TEM image in Figure 5c shows that the ZnO@SiO2 core/shell
nanostructures was fabricated. As presented in Figure S6b, the
emission spectrum of the ZnO@SiO2 shows a broad band
centered at 560 nm, which is almost the same as that of the
bare ZnO, confirming that the coating of the SiO2 did not
change the energy level of the ZnO nanocrystals. However, as
expected, the mechano-stimuli enhancement of photolumi-
nescence was not observed after the ZnO nanoparticles were
embedded in the SiO2 matrix.
These experimental results have proved the hypothesis that
the electron injection process mainly contributes to the
mechano-stimuli luminescent enhancement of the as-prepared
ZnO NPs. Considering that very slight force is needed to move
the ZnO nanocrystals, this mechanism also explains why the
response to stimuli is so sensitive.
In summary, pyramid-like ZnO nanocrystals, which exhibit a
distinct mechano-stimuli luminescent enhancement, were
fabricated with a hydrothermal method. The emission intensity
change has ultrahigh sensitivity to external mechano-stimuli so
that it can be triggered by relatively weak force, such as ant
walking and acoustic vibration. On the basis of a series of
experiments, the electron injection process in crystal
boundaries is proposed to be responsible for the luminescent
enhancement. Therefore, this work provides a new route to
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realize stimuli-responsive behavior and can find application in
sensing for stress, friction, and even sound.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jp-
clett.9b01092.
Synthesis and characterization; TEM (Figure S1a) and
HRTEM (Figure S1b) images, XRD pattern (Figure
S2), and fluorescence decay curve (Figure S3) of as-
prepared ZnO NPs; TEM images and luminescent
response to stimuli of other ZnO nanostructures (QDs
and nanowires) (Figure S4); additional sound-stimu-
lated luminescent enhancement results (Figure S5); PL
and PLE spectra of ZnO NPs after annealing and SiO2
coating (Figure S6) (PDF)
Movie of ant triggering luminescence enhancement of
the sample as in Figure 2c,d (MP4)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail:zhaoqiv@126.com.
*E-mail: cxshan@zzu.edu.cn.
ORCID
Qi Zhao: 0000-0002-1369-6823
Lin Dong: 0000-0002-4126-6812
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was financially supported by the Natural Science
Foundation of China (21601159 and 61604132), the Key
Project of Henan Province (171100210600), and the National
Science Foundation for Distinguished Young Scholars of China
(61425021).
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J. Phys. Chem. Lett. 2019, 10, 3557−3562