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
acoustic vibration can activate a drastic emission intensity
change. This mechano-stimuli luminescence enhancement can
hardly be elucidated by the reported mechanisms; therefore, a
in response to thermal, molecular, electrical, and mechanical different explanation, boundary electron injection, is proposed
stimuli, which would be beneficial for the development of hereinafter to shed some light on the novel phenomenon.
dynamically functional materials and devices.1−3 In particular, ZnO, as a well-known wide band gap semiconductor and
mechano-responsive luminescent (MRL) materials can display environmentally friendly oxide material, has attracted consid-
a change in luminescent color/intensity or a switching-on/off erable attention in the fields of ultraviolet (UV) photo-
process by responding to a mechanical stimuli such as pressing, detection,14−16 light-emitting devices,17,18 piezoelectric nano-
shearing, grinding, rubbing, or stretching.4−7 Considering that generators,19 etc. Generally, two typical photoluminescence
the optical method can offer the unique advantages of wireless (PL) emission bands can be observed in ZnO nanoparticles
detection and nondestructive analysis, MRL materials have (NPs): UV emission from the near-band edge transition and
great potential application in mechano-sensors,8 optical visible emission from the crystalline defects.20,21 The wide
storage,9 photonic devices,10 etc. Currently, a number of band gap (Eg= 3.37 eV) and large exciton-binding energy (60
MRL systems have been developed through various strategies, mV) of ZnO are responsible for its characteristic UV emission.
mainly including mechanochromism based on polymers, The defect-related luminescence usually come from the oxygen
organic molecules, organometallic complexes, and piezolumi- vacancies, Zn vacancies, interstitial oxygen, Zn interstitials, or
nescence (elasticoluminescence) in rare-earth-/transition- other impurities in the ZnO matrix.20,22 However, mechano-
metal-doped inorganic compounds.11,12 The emission color stimuli-triggered luminescence change has never been
change in mechanochromic materials triggered by external observed in ZnO NPs.
mechanical stimuli is associated with their molecular structure Herein, ZnO NPs were first synthesized via a facile
distortion, such as molecular packing, molecular conformation hydrothermal route. Scanning electron microscopy (SEM)
and intermolecular interactions. By contrast, piezolumines- images (Figure 1a) show that the as-prepared sample consists
cence is generally ascribed to the tilting of the band structure of well-dispersed hexagonal pyramids with an average side
within an asymmetrical crystal matrix induced by the length of 60.19 ± 1.48 nm (Figure 1b). The TEM image
piezoelectric potential under straininga phenomenon called (Figure S1a) further confirms its pyramid-like shape. The
piezophotonic effect.13 In this work, an unexpected and never- HRTEM image of an individual nanopyramid (Figure S1b)
before-reported luminescence enhancement was observed in
zinc oxide (ZnO) nanocrystals under mechanical stimuli. Received: April 16, 2019
Interestingly, the luminescent response to external disturbance Accepted: June 10, 2019
was extremely sensitive so that even an ant walking and 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 peaks of Zn 2p, O 1s, and C 1s can be observed from the
that corresponds to the (0001) plane of wurtzite ZnO,23 which pattern, and no other elements can be found from the spectra.
reveals the highly crystalline nature of the ZnO nanoparticles The Zn 2p and O 1s peaks can be attributed to ZnO, while the
(NPs). The XRD pattern of the samples is shown in Figure S2, peaks of C 1s possibly stem from the functional groups
and the diffraction peaks correspond well to hexagonal wurtzite adsorbed on the crystal surface. In addition, the FTIR
ZnO (JCPDS 89-1397).24 spectrum was employed to investigate the functional groups
XPS spectra are collected to determine the chemical on the surface of the ZnO NPs, as shown in Figure 1d. The
compositions of the ZnO NPs. As shown in Figure 1c, the absorption peaks located at 1550 and 1420 cm−1 can be
3558 DOI: 10.1021/acs.jpclett.9b01092
J. Phys. Chem. Lett. 2019, 10, 3557−3562
The Journal of Physical Chemistry Letters Letter

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 broad and ranges from 250 to 380 nm. Under excitation at 365
vibration of the carboxylic group (−COO−), confirming the nm, the ZnO sample exhibits a strong and broad emission
adsorption of acetate on the ZnO crystals.25 The absorption band from 430 to 700 nm peaking at 560 nm. The strong
bands at 3600−3700 cm−1 can be assigned to the stretching visible emission is believed to be derived from the transitions
vibration mode of −OH groups from the adsorbed water. The from trap levels,30 although the exact type of the defects
broad absorption band observed at around 500 cm−1 belongs (interstitial, vacancy, impurity, etc.) in the ZnO matrix is still
to the stretching vibration mode of Zn−O. The XPS and FTIR under debate. To shed more light on the carrier recombination
observations further confirm the composition of the as- process in the ZnO NPs, the transient fluorescence spectra was
synthesized ZnO NPs. measured. Figure S3 shows the excited-state lifetimes of the
As is known, the −COOH groups can adsorb certain facets fluorescent defects excited by a 350 nm laser. The decay curve
of crystal nuclei and inhibit the growth of these crystal can be fit to a two-order exponential function as following:
planes.26,27 Empirically, the surfactant molecules prefer to
y = y0 + C1 exp( −t /τ1) + C2 exp(−t /τ2) (1)
adsorb on the lattice plane where the atomic planar density
(APD) is higher. In this case, the ZnO nanocrystals adopt a
where y is the emission intensity; y0, C1, and C2 are constants; t
hexagonal-close-packed (hcp) structure, where the atomic
is time; τ1 and τ2 are decay lifetimes of the emission. τ1 and τ2
planar density28 of (0001) and (1000) is determined to be 1.1 are calculated to be 374.27 and 28.97 ns, respectively. Herein,
× 1019 and 5.9 × 1018 atoms/m2, respectively. Consequently, τ1 may come from the defect-level recombination inside the
the −COOH groups would adsorb on the (0001) planes ZnO NPs, whereas τ2 is probably ascribed to the surface
preferentially because of the higher APD, resulting in the faster defects’ recombination.31,32
growth of (1000) planes than that of the (0001) planes. Thus, Interestingly, an unexpected luminescence enhancement was
the fast growing (1000) facets shrink and the ZnO crystals are observed when an external mechanical stimuli was exerted on
bound by (0001) planes which exhibit the hexagonal pyramid the as-prepared ZnO NPs. As shown in the inset of Figure 2b,
shape eventually. The base of the pyramid-like ZnO nano- the ZnO NPs show an orange-yellow fluorescence under UV
crystals is the (0001) plane, while the lateral faces were lamp. The enhanced luminescence was clearly observed when
surrounded by (011̅0), (1̅100), (1̅010), (01̅10), (11̅00), and the ZnO powder was lightly scratched in a circle shape as a
(101̅0) planes.29 This is confirmed by the HETEM image proof-of-concept of mechanical stimuli. It can be seen that the
(Figure S1b), which clearly shows the (0001) plane of the luminescence intensity of the circular region is significantly
pyramid surface. higher than the surrounding, and the luminescence will recover
The luminescent properties of the ZnO NPs have been to the original situation when the external stimulus is removed.
investigated by PL spectroscopy and CCD spectrometry. The luminescence enhancement induced by mechanical
Figure 2a exhibits the fluorescence spectrum of the ZnO NPs stimuli is also demonstrated by the emission spectra, which
powder excited by a xenon lamp. The PL excitation spectrum, obviously shows that the luminescence intensity is increased
which was obtained by monitoring the emissions of 560 nm, is dramatically after stimuli (Figure 2b). In order to evaluate if
3559 DOI: 10.1021/acs.jpclett.9b01092
J. Phys. Chem. Lett. 2019, 10, 3557−3562
The Journal of Physical Chemistry Letters Letter

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, As expected and interestingly, the luminescence enhancement
also have this phenomenon, ZnO QDs and nanowires have was clearly observed (as shown in Figure 3), and the
been synthesized. The typical morphological and luminescent luminescence intensity will increase as a function of the
characterizations of the as-prepared samples have been sound volume in the decibel range of 40−60 dB (Figures 3 and
analyzed by scanning electron microscopy (SEM), trans- S5). To demonstrate the difference more clearly, the photos of
mission electron microscopy (TEM), and CCD spectrometry. luminescent ZnO NPs were transferred into a pseudocolor
As shown in Figure S4, mechano-stimuli luminescence map by MATLAB software to visualize the intensity
enhancement of ZnO QDs and nanowires cannot be detected. distribution. Thus, the audio signal can be converted into an
Interestingly, the response of the ZnO NPs to mechanical optical signal directly and the sound volume can even affect the
stimuli is so sensitive that even an ant walking can trigger the luminescent intensity. It is worth noting that the sound stimuli
luminescence enhancement (the average weight of an ant is that can trigger the ZnO NPs is exactly in the frequency and
only 50 mg). The ultrasensitive stimuli-responsive lumines- volume range audible to the human ear. Therefore, the as-
cence can be clearly observed by the naked eye, as shown in prepared NPs may find potential application in security alerts
Figure 2c. The corresponding video is shown in Supple- or communication assistance for hearing-impaired people.
mentary Movie 1. The corresponding footprint distributions of On the basis of the experimental results mentioned above, it
the ant are derived by extracting the gray scale of the real-time is speculated that the luminescence enhancement of the ZnO
captured image as presented in Figure 2d. The clear footprints NPs is ascribed to an electron injection process initiated by
suggest the possibility of recording detailed information mechanical stimuli. During the hydrothermal synthesis process,
through the change of gray value in sensing applications. the zinc acetate decomposed to produce ZnO crystal nucleus:
In view of the ultrasensitive response to mechanical stimuli, Zn(CH3COO)2 + H 2O → ZnO + 2CH3COOH
we considered if the luminescence enhancement of as-prepared
ZnO NPs can be triggered by another weak mechanical As discussed above, the CH3COO− groups adsorbed on the
stimuliacoustic vibration. To test this hypothesis, the NPs crystal face to induce the formation of the pyramid-like
were exposed to several audio sources including the sounds of nanostructure. It is worth noting that the number of adsorbed
air-raid warning, thunder, and whistle at different decibel levels. acetate groups varies with the APD of crystal planes, thereby
3560 DOI: 10.1021/acs.jpclett.9b01092
J. Phys. Chem. Lett. 2019, 10, 3557−3562
The Journal of Physical Chemistry Letters Letter

leading to the diversity in charge density of different surfaces. realize stimuli-responsive behavior and can find application in
Under UV irradiation, the electrons are excited into the sensing for stress, friction, and even sound.
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
■
*
ASSOCIATED CONTENT
S Supporting Information
with the charge density of different planes. Therefore, an The Supporting Information is available free of charge on the
electron injection process will occur if different faces of the ACS Publications website at DOI: 10.1021/acs.jp-
ZnO crystal contact with each other when the ZnO powders clett.9b01092.
are exposed to mechanical stimuli (such as stirring, scratching,
etc.), which results in the carrier recombination between Synthesis and characterization; TEM (Figure S1a) and
crystal boundaries. Thus, the enhanced luminescence will be HRTEM (Figure S1b) images, XRD pattern (Figure
S2), and fluorescence decay curve (Figure S3) of as-
observed. The corresponding mechanisms of the external
prepared ZnO NPs; TEM images and luminescent
force-enhanced photoluminescence processes are shown in
response to stimuli of other ZnO nanostructures (QDs
Figure 4.
and nanowires) (Figure S4); additional sound-stimu-
According to the above analysis, three factors are mainly
lated luminescent enhancement results (Figure S5); PL
responsible for the luminescence enhancement: (a) the
and PLE spectra of ZnO NPs after annealing and SiO2
aggregation of carrier on the surface, (b) anisotropic electron
coating (Figure S6) (PDF)
distribution on crystal faces, and (c) direct contact of the ZnO
grains. To verify the hypothesis, a series of experiments were Movie of ant triggering luminescence enhancement of
conducted. The aggregation of carrier on the crystal surface is the sample as in Figure 2c,d (MP4)
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
■ AUTHOR INFORMATION
Corresponding Authors
a current as high as 0.24 μA was obtained. One can imagine *E-mail:[email protected].
that if there were no external circuit (the situation in *E-mail: [email protected].
measuring equipment), generated carriers will saturate and a
ORCID
part of photogenerated carriers would be accumulated on the
surface of ZnO NPs. The surface acetate groups play a key role Qi Zhao: 0000-0002-1369-6823
in the anisotropic electron distribution. In order to validate it, Lin Dong: 0000-0002-4126-6812
the as-prepared ZnO NPs were annealed in air at 300 °C to Notes
remove the surface groups. As the FTIR spectra illustrate in The authors declare no competing financial interest.
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
■ ACKNOWLEDGMENTS
This work was financially supported by the Natural Science
also emit visible luminescence, but the mechano-stimuli Foundation of China (21601159 and 61604132), the Key
luminescent enhancement cannot be observed. Another Project of Henan Province (171100210600), and the National
precondition for electron injection is the direct contact of Science Foundation for Distinguished Young Scholars of China
the ZnO crystals. To prove that, the ZnO nanocrystals were (61425021).
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
■ REFERENCES
(1) Sagara, Y.; Yamane, S.; Mitani, M.; Weder, C.; Kato, T.
emission spectrum of the ZnO@SiO2 shows a broad band Mechanoresponsive Luminescent Molecular Assemblies: An Emerg-
centered at 560 nm, which is almost the same as that of the ing Class of Materials. Adv. Mater. 2016, 28, 1073−1095.
bare ZnO, confirming that the coating of the SiO2 did not (2) Sagara, Y.; Kato, T. Mechanically Induced Luminescence
change the energy level of the ZnO nanocrystals. However, as Changes in Molecular Assemblies. Nat. Chem. 2009, 1, 605−610.
expected, the mechano-stimuli enhancement of photolumi- (3) Yang, Z.; Chi, Z.; Mao, Z.; Zhang, Y.; Liu, S.; Zhao, J.; Aldred,
nescence was not observed after the ZnO nanoparticles were M. P.; Chi, Z. Recent Advances in Mechano-Responsive Lumines-
embedded in the SiO2 matrix. cence of Tetraphenylethylene Derivatives with Aggregation-Induced
Emission Properties. Materials Chemistry Frontiers 2018, 2, 861−890.
These experimental results have proved the hypothesis that (4) Ma, Z.; Wang, Z.; Meng, X.; Ma, Z.; Xu, Z.; Ma, Y.; Jia, X. A
the electron injection process mainly contributes to the Mechanochromic Single Crystal: Turning Two Color Changes into a
mechano-stimuli luminescent enhancement of the as-prepared Tricolored Switch. Angew. Chem., Int. Ed. 2016, 55, 519−522.
ZnO NPs. Considering that very slight force is needed to move (5) Wang, Y.; Zhang, I.; Yu, B.; Fang, X.; Su, X.; Zhang, Y.; Zhang,
the ZnO nanocrystals, this mechanism also explains why the T.; Yang, B.; Li, M.; Zhang, S. X. Full-Color Tunable Mechano-
response to stimuli is so sensitive. fluorochromism and Excitation-Dependent Emissions of Single-Arm
In summary, pyramid-like ZnO nanocrystals, which exhibit a Extended Tetraphenylethylenes. J. Mater. Chem. C 2015, 3, 12328−
distinct mechano-stimuli luminescent enhancement, were 12334.
fabricated with a hydrothermal method. The emission intensity (6) Xu, B.; He, J.; Mu, Y.; Zhu, Q.; Wu, S.; Wang, Y.; Zhang, Y.; Jin,
C.; Lo, C.; Chi, Z.; Lien, A.; Liu, S.; Xu, J. Very Bright
change has ultrahigh sensitivity to external mechano-stimuli so
Mechanoluminescence and Remarkable Mechanochromism Using a
that it can be triggered by relatively weak force, such as ant Tetraphenylethene Derivative with Aggregation-Induced Emission.
walking and acoustic vibration. On the basis of a series of Chem. Sci. 2015, 6, 3236−3241.
experiments, the electron injection process in crystal (7) Zhang, Q.; Su, J.; Feng, D.; Wei, Z.; Zou, X.; Zhou, H.
boundaries is proposed to be responsible for the luminescent Piezofluorochromic Metal-Organic Framework: A Microscissor Lift. J.
enhancement. Therefore, this work provides a new route to Am. Chem. Soc. 2015, 137, 10064−10067.

3561 DOI: 10.1021/acs.jpclett.9b01092

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

(8) Jin, X.; Götz, M.; Wille, S.; Mishra, Y. K.; Adelung, R.; Zollfrank, nism, and Luminescence Properties. Cryst. Growth Des. 2014, 14,
C. A Novel Concept for Self-Reporting Materials: Stress Sensitive 1819−1826.
Photoluminescence in ZnO Tetrapod Filled Elastomers. Adv. Mater. (28) Pung, S.; Lee, W.; Aziz, A. Kinetic Study of Organic Dye
2013, 25, 1342−1347. Degradation Using ZnO Particles with Different Morphologies as a
(9) Schäfer, C. G.; Gallei, M.; Zahn, J. T.; Engelhardt, J.; Hellmann, Photocatalyst. Int. J. Inorg. Chem. 2012, 2012, 1−9.
G. P.; Rehahn, M. Reversible Light-, Thermo-, and Mechano- (29) Joo, J.; Kwon, S. G.; Yu, J. H.; Hyeon, T. Synthesis of ZnO
Responsive Elastomeric Polymer Opal Films. Chem. Mater. 2013, 25, Nanocrystals with Cone, Hexagonal Cone, and Rod Shapes via Non-
2309−2318. Hydrolytic Ester Elimination Sol−Gel Reactions. Adv. Mater. 2005,
(10) Yang, Q.; Wang, W.; Xu, S.; Wang, Z. L. Enhancing Light 17, 1873−1877.
Emission of ZnO Microwire-Based Diodes by Piezo-Phototronic (30) Dutta, M.; Jana, S.; Basak, D. Quenching of Photoluminescence
Effect. Nano Lett. 2011, 11, 4012−4017. in ZnO QDs Decorating Multiwalled Carbon Nanotubes. Chem-
(11) Tu, D.; Xu, C.; Yoshida, A.; Fujihala, M.; Hirotsu, J.; Zheng, X. PhysChem 2010, 11, 1774−1779.
LiNbO3:Pr3+: A Multipiezo Material with Simultaneous Piezo- (31) Choi, S.; Phillips, M. R.; Aharonovich, I.; Pornsuwan, S.;
electricity and Sensitive Piezoluminescence. Adv. Mater. 2017, 29, Cowie, B. C. C.; Ton-That, C. Photophysics of Point Defects in ZnO
1606914. Nanoparticles. Adv. Opt. Mater. 2015, 3, 821−827.
(12) Larson, C.; Peele, B.; Li, S.; Robinson, S.; Totaro, M.; Beccai, (32) Shi, H.; Li, W.; Sun, L.; Liu, Y.; Xiao, H.; Fu, S. Synthesis of
L.; Mazzolai, B.; Shepherd, R. Highly Stretchable Electroluminescent Silane Surface Modified ZnO Quantum Dots with Ultrastable, Strong
Skin for Optical Signaling and Tactile Sensing. Science 2016, 351, and Tunable Luminescence. Chem. Commun. 2011, 47, 11921.
1071−1074.
(13) Wang, Z. L. Piezopotential Gated Nanowire Devices:
Piezotronics and Piezo-Phototronics. Nano Today 2010, 5, 540−552.
(14) Gedamu, D.; Paulowicz, I.; Kaps, S.; Lupan, O.; Wille, S.;
Haidarschin, G.; Mishra, Y. K.; Adelung, R. Rapid Fabrication
Technique for Interpenetrated ZnO Nanotetrapod Networks for Fast
UV Sensors. Adv. Mater. 2014, 26, 1541−1550.
(15) Liu, J.; Lu, R.; Xu, G.; Wu, J.; Thapa, P.; Moore, D.
Development of a Seedless Floating Growth Process in Solution for
Synthesis of Crystalline ZnO Micro/Nanowire Arrays on Graphene:
Towards High-Performance Nanohybrid Ultraviolet Photodetectors.
Adv. Funct. Mater. 2013, 23, 4941−4948.
(16) Park, J.; Lee, J.; Noh, Y.; Shin, K.; Lee, D. Flexible Ultraviolet
Photodetectors with ZnO Nanowire Networks Fabricated by Large
Area Controlled Roll-To-Roll Processing. J. Mater. Chem. C 2016, 4,
7948−7958.
(17) Liang, Y. C.; Liu, K. K.; Lu, Y. J.; Zhao, Q.; Shan, C. X. Silica
encapsulated ZnO quantum dot phosphor nanocomposites: Sol-gel
preparation and white-emitting device application. Chin. Phys. B 2018,
27, 078102.
(18) Lu, Y. J.; Shi, Z. F.; Shan, C. X.; Shen, D. Z. ZnO-based deep-
ultraviolet light-emitting devices. Chin. Phys. B 2017, 26, 047703.
(19) Yang, D.; Qiu, Y.; Jiang, Q.; Guo, Z.; Song, W.; Xu, J.; Zong, Y.;
Feng, Q.; Sun, X. Patterned Growth of ZnO Nanowires On Flexible
Substrates for Enhanced Performance of Flexible Piezoelectric
Nanogenerators. Appl. Phys. Lett. 2017, 110, 063901.
(20) Ischenko, V.; Polarz, S.; Grote, D.; Stavarache, V.; Fink, K.;
Driess, M. Zinc Oxide Nanoparticles with Defects. Adv. Funct. Mater.
2005, 15, 1945−1954.
(21) Zeng, H.; Duan, G.; Li, Y.; Yang, S.; Xu, X.; Cai, W. Blue
Luminescence of ZnO Nanoparticles Based on Non-Equilibrium
Processes: Defect Origins and Emission Controls. Adv. Funct. Mater.
2010, 20, 561−572.
(22) Liu, K.; Shan, C.; Zhou, R.; Zhao, Q.; Shen, D. Large-Scale
Synthesis of ZnO Nanoparticles and their Application as Phosphors in
Light-Emitting Devices. Opt. Mater. Express 2017, 7, 2682.
(23) Zhou, X.; Xie, Z.; Jiang, Z.; Kuang, Q.; Zhang, S.; Xu, T.;
Huang, R.; Zheng, L. Formation of ZnO Hexagonal Micro-Pyramids:
A Successful Control of the Exposed Polar Surfaces with the
Assistance of an Ionic Liquid. Chem. Commun. 2005, 5572.
(24) Pandey, P.; Kurchania, R.; Haque, F. Z. Controlled Hydro-
thermal Synthesis, Structural and Optical Analysis of Nanometer-
Sized ZnO Spheres. Optik 2015, 126, 301−303.
(25) Hong, R.; Pan, T.; Qian, J.; Li, H. Synthesis and Surface
Modification of ZnO Nanoparticles. Chem. Eng. J. 2006, 119, 71−81.
(26) Ma, D.; Yang, D.; Jiang, J.; Cai, P.; Huang, S. One-Dimensional
Hexagonal-Phase NaYF4: Controlled Synthesis, Self-Assembly, and
Morphology-Dependent Up-Conversion Luminescence Properties.
CrystEngComm 2010, 12, 1650.
(27) Zhao, Q.; Shao, B.; Lü, W.; Jia, Y.; Lv, W.; Jiao, M.; You, H.
Ba2GdF7 Nanocrystals: Solution-Based Synthesis, Growth Mecha-

3562 DOI: 10.1021/acs.jpclett.9b01092

J. Phys. Chem. Lett. 2019, 10, 3557−3562