Nano Energy 89 (2021) 106394

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Enhanced output performance of ZnO thin film triboelectric

nanogenerators by leveraging surface limited ga doping and insulting bulk
Ping-Che Lee a, Yi-Chen Ou a, Ruey-Chi Wang b, Chuan-Pu Liu a, c, *
a
Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan
b
Department of Chemical and Materials Engineering, National University of Kaohsiung, Kaohsiung 811, Taiwan
c
Hierarchical Green-Energy Materials (Hi-GEM) Research Center, National Cheng Kung University, Tainan 701, Taiwan

A R T I C L E I N F O A B S T R A C T

Keywords: Although triboelectric nanogenerator (TENG) has been developed as a new green energy source, the dominant
Ga doped ZnO charge transfer mechanism regarding surface chemistry has not been fully uncovered yet, especially in semi­
Triboelectric nanogenerator conductor materials. Semiconductor materials are technically important not only capable of tuning total carrier
Work function
concentrations available for charge transfer in TENG, but corresponding optoelectronic properties for applica­
Charge trapping
tions into tribo-tronics. However, doping renders one serious drawback as tribo-charges tend to leak and cannot
Conduction band
be held in place for energy output. In order to prevent carriers from leaking while maintain the characteristics of
tunable carrier concentrations in semiconductors, a two-layer structure of Ga-doped ZnO/undoped-ZnO is pro­
posed by a two-step growth methodology. A ZnO thin film was first grown by magnetron sputter followed by Ga
doping restricted to a shallow surface region by thermal diffusion treatment in the second step. The results
support that surface work function difference between two materials in electrification under the well preser­
vation of tribo-charges retention governs the charge transfer capability responsible for output performance of
TENGs, where the output voltage and current of the ZnO film doped with 0.93 at% Ga can be drastically
enhanced by 16 and 13 times, respectively. However, β-Ga2O3 forms on the surface when Ga concentration is
higher than 0.93 at%. Nevertheless, the even larger work function of β-Ga2O3 than Ga-doped ZnO does not lead
to larger output performance, implying that work function difference is not the prime factor but carrier con­
centration in the conduction band needs to be considered for the performance of TENGs. This work demonstrated
a viable method to modify the work function of ZnO only confined to the surface through doping without dis­
turbing the bulk, optimizing the device structure for TENGs based on semiconductor.

1. Introduction designing high-performance TENGs [12–15].

Triboelectrification has attracted attentions and sparked extensive
research since Wang reported the first triboelectric nanogenerator
(TENG) in 2012 [1,2]. The working efficiency of TENGs relies on the
charge transfer between the two surfaces of the materials in friction [3].
Upon contact-separation, the coupling effect of triboelectrification and
electrostatic induction drive electron drift through the external circuit,
and thus generate open circuit voltage and short circuit current [4,5].
Plenty of merits are unique to TENGs, including abundant material
choice, lightweight, low cost, and high energy conversion efficiency
compared to other nanogenerators [6–8]. TENGs have lent themselves
to a reliable power source for self-powered devices [9–11] and prompted
research to unveil the fundamental physics of triboelectrification for
There have been many attempts to maximize the output power based
on the displacement current model proposed by Wang [16]. The most
imperative way is to enhance tribo-charge generation yield and inducing
more charges at the counter electrode [17]. Therefore, nanostructure
patterns, including pyramids, chessboard lines and nanodots, all extend
the fictional area, resulting in high-output generators [18–21]. Besides,
various surface-modification treatments, such as ionized air injection,
functional group modified polymer, chemical and plasma treatment,
help to maximize surface charge density, also enhance output power
[22–27]. Modulating dielectric constants and electrical properties of the
active materials promise to boast the performance of TEGNs through
charge trapping capability [28–30]. Moreover, the ambient conditions,
such as humidity, temperature and working pressure, have also been

* Corresponding author at: Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan.
E-mail address: cpliu@mail.ncku.edu.tw (C.-P. Liu).

https://doi.org/10.1016/j.nanoen.2021.106394
Received 17 April 2021; Received in revised form 18 July 2021; Accepted 29 July 2021
Available online 2 August 2021
2211-2855/© 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
P.-C. Lee et al.
Fig. 1. Top-view SEM images of (a) the as-grown and (b-e) various Ga-doped ZnO thin films with diffusion treatment at 550 ◦ C using Gallium(III) acetylacetonate as
the Ga source to reach Ga doping of (b) 0.56 at% (0.035 g), (c) 0.93 at% (0.05 g), (d) 1.31 at% (0.075 g) and (e) 1.75 at% (0.1 g).
reported to affect charge reservation ability at the surface [31–34]. The
aforementioned strategies in the enhancement of output power density
manifest the essence of uncovering the fundamental physical mecha­
nism of contact electrification. Nevertheless, most of them involve either
complicated surface patterning or unstable surface treatments. It is
worth developing a methodology where the relative position of a given
material in the triboelectric series can be systematically tuned to
broaden material selection, at the same time, providing a means to
further justify the underlying working mechanism of TENGs.
It is well accepted that work function implicitly determines the po­
larity of the triboelectric charges and charge transfer ability [35–37].
Therefore, the material with a tunable work function enhances the
output power of TENGs by more options in the selection of triboelectric
materials [38]. Surface work function can be changed by polymers or
organic ligands on surface but not in systematic manner. By contrast, the
electronic structure of a semiconductor can be precisely manipulated
through doping. It was demonstrated that the surface potential of ZnO
nanowires were modified from n-type (Ga-doped) to p-type properties
(Sb-doped) to affect the output performance and polarity of TENGs [39,
40]. Meanwhile, the work function of Al doped ZnO film was shown to
be sensitive to the concentration of substitution Al ions in crystal lattices
[41]. However, those dopants were introduced while growing ZnO by
chemical bath or sol-gel method, suggesting even distribution of dopants
throughout the entire nanowires or films instead of surface modifica­
tion. Conversely, the optimal properties of materials for TENG should be
able to reserve tribo-charges well [29], which contradicts with the
tendency of becoming more conducting with doping. Although doping
through one-step chemical methods is appealing to tune the charge
transfer ability, the resulting homogenous carrier concentrations may be
an adverse side effect.
In the quest of developing high-performance TENGs, we propose to
prepare ZnO thin films with doping confined to shallow surface regions
by post-thermal diffusion to vary surface work function in a control
manner. Comprehensive material characterizations, including kelvin-
probe force microscopy (KPFM), transmission electron microscopy
(TEM), energy dispersive spectroscopy (EDS), x-ray photoelectron
spectroscopy (XPS), are conducted to underline the impact of micro­
structure variation. The limiting doping depth of Ga+3 ions can mitigate
the issue of increasing carrier concentrations in bulk while reserving
excellent charge transfer ability at the surface upon friction with Poly­
dimethylsiloxane (PDMS). Besides, the results imply that work function
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Nano Energy 89 (2021) 106394
in semiconductors is not the sole factor and the relative position of
conduction band minimum and Fermi level that determines the avail­
able carriers also needs to be considered in governing the tribo-charge
transfer during electrification. The work not only justifies the working
mechanism of TENGs further but shed light on large-scale sputtered ZnO
thin film with tunable surface chemistry as an optimized semiconductor
material for the triboelectric application.
2. Materials and methods
The ZnO thin films were first grown on a silicon substrate by
magnetron sputtering. Subsequently, the Ga ions carried by Ar gas were
introduced via thermally evaporated Ga metalorganic precursors (Gal­
lium(III) acetylacetonate) at 550 ◦ C for 2 h in a tube furnace where Ga
ions were diffused into the thin-film and Ga doping concentration was
manipulated by adding different amounts of Ga metalorganic precursors
in the tube furnace. Finally, oxygen plasma treatment was performed to
remove the carbon residue remaining on the surface due to the organic
precursors. All the samples are named undoped ZnO, and 0.93 at%, 1.31
at%, 1.75 at% Ga-doped ZnO thin film according to the atomic ratio of
Ga content measured by EDS. For TENG devices, PDMS was selected as
the reference friction material to rub against various Ga-doped ZnO thin
films. Copper was utilized as the electrode for the Ga-doped ZnO thin
films, whereas PET/ITO substrate was taken as another electrode on
which PDMS was spin-coated. The device size for effective contact area
was fixed at 2 × 2 cm2. The surface morphology and film thickness were
analyzed by scanning electron microscopy (SEM, HITACHI SU8000).
The crystal structure was determined by using θ-2θ scan with X-ray
diffraction (XRD, Bruker D8 Discover), while the microstructure was
characterized by TEM (JEOL 2100 F). The surface composition was
analyzed by XPS (PHI 5000 Versa Probe). The surface roughness and
work function were measured by KPFM (Hitachi SPA-400). Hall mea­
surement was employed to measure the electrical properties of the thin
films. The output performance of the TENG devices was carried out
using a linear translation stage and KITHELEY 2400 under the same
fixed contact force of 15 N at the frequency of 1 Hz.
P.-C. Lee et al.
Fig. 2. X-ray diffraction spectra of various Ga-doped ZnO thin films grown on Si(100) substrate: (a) full scan spectra from 20◦ to 60◦ , and (b) fine scan spectra from
34 ◦ to 35◦ .
3. Result and discussion
3.1. Comprehensive microstructure study and physical properties of Ga
doped ZnO
The SEM images shown in Fig. 1 evaluate how Ga metalorganic
precursors affect the surface morphology of all the ZnO thin films under
heat treatment. The pristine ZnO thin film, in Fig. 1(a), consists of the
uniformly and densely packed grains with columnar structure. This film
remains almost intact upon doping treatment in the second step with
different weights of Ga metalorganic precursors (0.035 g, 0.05 g, 0.075
g, and 0.1 g, as shown in Fig. 1(b, c, d, e), respectively, supporting that
thermal doping treatment well preserves the morphology of the pristine
film. Meanwhile, the surface Ga concentrations over a large area
determined by EDX are 0.56 at% (0.035 g), 0.93 at% (0.05 g), 1.31 at%
(0.075 g) and 1.75 at% (0.1 g). The linear increase of Ga concentration
on the surface as increasing the amount of Ga precursor exhibits the
power of this novel process over doping content. By contrast, conven­
tional methods that incorporate dopants during growth such as a
chemical bath or sol-gel method, suffer from drastic morphology vari­
ations. Therefore, through thermal decomposition of metal-organic
precursors, the subsequent thermal diffusion process is an effective
and reliable approach to synthesize doped ZnO thin film while main­
taining the same film morphology, in perfect scenario for the study on
the doping dependence in semiconductor materials of tribo-charge
transfer capability.
Fig. 2 presents the XRD spectra of the various doped ZnO films,
proving that thermal diffusion treatment does not affect the Wurtzite
structure with (0002) preferred orientated columns in the Ga-doped ZnO
films. However, the (0002) peak shifts slightly to a higher angle from
34.536◦ to 34.604◦ with increasing Ga concentration in Fig. 2(b), indi­
cating that smaller Ga ions (0.62 Å) have successfully replaced the larger
Zn ions (0.74 Å) in ZnO crystal. Besides, the full width at half maximum
(FWHM) of the pristine and various Ga doped ZnO films are 0.256◦
(undoped), 0.260◦ (0.56 at%), 0.262◦ (0.93 at%), 0.283◦ (1.31 at%),
0.307◦ (1.75 at%), presenting a broadening trend. Given that the grain
size in the c-axis is identical to the film thickness, the broadening peak
width is related to the nonuniform strain distribution, referring to lattice
distortion caused by the Ga substitution. This further suggests the lattice
distortion is gradient from the surface to the bottom. Finally, the Ga2O3
and GaOOH appears at 1.75 at% Ga in Fig. 2(a) suggests that the
excessive decomposed Ga+3 will react with ambient O2 and H2O at ZnO
surface under heating.
To quantify the tribo-charge yield efficiency of the Ga-doped ZnO
films, KPFM is conducted to evaluate the surface electrical potential
distribution and work function with high surface sensitivity. The surface
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Nano Energy 89 (2021) 106394
Fig. 3. Schematic representation of the KPFM-derived work function series
from the pristine and various Ga-doped ZnO thin films in comparison with that
of PDMS.
images of the Ga-doped ZnO thin film and the standard sample of Au
scanned by KPFM are shown in Fig. S1. Herein, the Au film deposited on
Si substrate with work function of 5.4 eV was employed as the standard
sample due to its conductivity and stability. The mean surface electrical
field of each sample was quantified through averaging all data points
over the scan area of 0.5 µm × 0.5 µm. By comparing the surface elec­
trical potential of the various ZnO thin film and Au standard sample, the
work function is determined as 4.85 eV (undoped ZnO), 4.83 eV (0.56 at
%), 4.80 eV (0.93 at%), 4.79 eV (1.31 at%), and 4.78 eV (1.75 at%).
Concurrently, the work function of PDMS as the counter materials is
measured to be 6.81 eV. The work functions of all the materials are
compared in Fig. 3. In the context of the electron-cloud-potential-well
model, the electron transfer capability upon friction between the
tribo-pair is directly related to the work function difference between
them, which converts to 1.96 eV (undoped), 1.98 eV (0.56 at%),
2.01 eV (0.93 at%), 2.03 eV (1.31 at%), and 2.04 eV (1.75 at%), about
4% change, between the ZnO thin film and PDMS in this case. The
ascending work function difference with Ga doping reinforces the po­
tential of boosting tribo-charge transfer efficiency by doping at the
surface when rubbing with PDMS or other materials at a similar position
in the triboelectric series.
To further clarify the role of Ga doping, electrical properties are
analyzed and discussed next. Ga-doped ZnO is a well-known conductive
transparent oxide electrode [42,43], where free electrons are released
by substituting Ga+3 for Zn+2 ions. The Hall measurement results are
obtained from all the samples with Ti/Au electrodes as ohmic contacts
on the surface in Fig. S2. Apparently, as Ga doping increases to 0.93 at%,
carrier concentration increases whereas mobility decreases due to
scattering with dopants. Nevertheless, the sudden drop of carrier
P.-C. Lee et al.
concentration at the even higher Ga doping concentration of 1.31 at%
against the upward trend is intriguing, likely corelated to the Ga2O3
formation.
TEM analysis is carried out to further explore the microstructure of
all the samples, Fig. 4 examines the 0.93% Ga-doped ZnO thin film
representing a typical example. This film is comprised of columnar
Fig. 5. Schematic of Ga+3 diffusion process into ZnO and Ga2O3 formation mechanism at ZnO surface in excess of Ga+3 ions.
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Nano Energy 89 (2021) 106394
Fig. 4. Cross-sectional TEM analysis of the 0.93 at
% Ga-doped ZnO thin film. (a) Bright-field image
with four Ga compositions measured by EDX at the
place of 20, 30, 40 and 80 nm away from the sur­
face marked by white circles and the area marked
by the red circle denotes where the corresponding
(b) HR-TEM image and (c) nano-beam diffraction
pattern are taken. (d) Bright-field image of the
1.31 at% Ga-doped ZnO thin film covered with a
thin Ga2O3 surface layer confirmed by (e) nano-
beam diffraction pattern taken from the area indi­
cated by the red circle in (d).
grains in Fig. 4(a) with high crystal quality in the hexagonal closed
packed structure as demonstrated by high resolution TEM image and
diffraction pattern in Fig. 4(b) and 4(c), respectively. However, the
(0002) interplanar spacing distance is 0.259 nm, shorter than 0.261 nm
of standard ZnO, testifying the substitution of smaller Ga+3 ions of
62 pm for the larger Zn+2 ions. It is more fascinating to find out the
P.-C. Lee et al.
Fig. 6. Output performance of TENG: (a) open circuit voltage, (b) short circuit current of undoped and Ga-doped ZnO thin films with various doping levels and (c)
summary of doping-dependent maximum voltage output with the corresponding schematic thin film structure representing the Ga doping status.
gradient spatial distribution of Ga within 80 nm into the bulk in Fig. 4
(a). The Ga concentration at the top surface is 0.95 at%, then drops to
0.42 at%, 0.16 at%, and finally nearly 0 at% (0.08 at%) at 20, 40, 80 nm
away from the surface, respectively. Identical results are obtained from
additional 10 line-profiles taken from different regions only to ensure
data consistency. Please note that the 0.95 at% Ga concentration at the
top surface is consistent with the value of 0.93 at% determined in Fig. 1
within the discrepancy between TEM and SEM. The concentration
gradient evidently manifests surface diffusion not only as the universal
effective doping methodology without modifying film morphology, but
allowing a thin film composed of a single material with two distinct
electrical properties. Intriguingly, on the other hand, when the Ga
concentration reaches 1.31 at%, a continuous polycrystalline layer with
random orientation starts to form on the top of the columnar ZnO
crystals, as shown in the TEM image in Fig. 4(d) and diffraction pattern
in Fig. 4(e), which is identified as the monoclinic Ga2O3. The presence of
Ga2O3 is also detected in the 1.93 at% Ga-doped ZnO sample as in Fig. 2
(a), implying that Ga doping can be exercised only to a limit until the
formation of Ga2O3 by the diffusion treatment.
Based on microstructure and chemical composition study, the
possible Ga+3 diffusion pathways and scenario of Ga2O3 formation are
proposed in Fig. 5. On heating, the Gallium acetylacetonate precursors
decompose and release Ga+3 into carrier gas flow. Then, Ga+3 was
driven in and absorbed at the surface defect sites through the boundary
layer by concentration gradient, accelerated by thermal decomposition
of ZnO at the elevated annealing temperature of 550 ◦ C [44]. Subse­
quently, surface absorbed Ga+3 diffuse into ZnO bulk through lattices
and grain boundaries, forming the concentration gradient profile with
the depth determined by the diffusion length. The presence of the Ga-O
bonding in the XPS analysis (Fig. S3 in supplementary material)
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Nano Energy 89 (2021) 106394
confirms Ga+3 diffusion in and substitution for Zn+2 in ZnO lattices.
However, as the concentration of Ga+3 ions increases beyond the solid
solubility level in ZnO, the surplus Ga+3 ions residing at the ZnO surface
would proceed oxidation with residual or decomposed oxygen to form a
uniform β-Ga2O3 film on the surface, blocking Ga+3 ions from further
diffusion in. The proposed diffusion mechanism provides a design rule
for further optimizing the doping concentration at the surface, such as
heating at even higher temperatures to induced faster diffusion with
higher solubility level.
Doping in ZnO should be accompanied by variations of electrical
properties, as analyzed in Fig. S2. Indeed, by Hall measurements, carrier
concentration increases linearly up to 0.93 at% Ga to reach 5.87 × 1018
cm− 3, then decreases to 2.42 × 1018 cm− 3 at 1.31 at% Ga and finally
quickly drops to 3.78 × 1016 cm− 3 at 1.75 at% Ga, whereas carrier
mobility decreases monotonically. The highest carrier concentration
range is about 2 orders of magnitude lower than that reported previously
in the case of Ga doping concentration of around 0.25–5 at% [45],
which should be related to the Ga concentration gradient and the
overestimation of the film thickness responsible for conductivity in this
study. The drop of carrier concentration at 1.31 at% Ga may be caused
by the formation of β-Ga2O3 on surface leading to Schottky contact
rather than ohmic contact because the electron affinity of β-Ga2O3 is
4 eV, which is 0.6 eV higher than ZnO. Evidently, the deviation of the
electrical properties of ZnO thin films upon thermal diffusion treatment
with Ga from bulk properties reflects the effective control over surface
properties that will play a predominant role in our research.
3.2. Contact electrification of Ga-doped ZnO thin film against PDMS
First, by rubbing the Ga-doped ZnO thin film with PDMS for the
P.-C. Lee et al.
Fig. 7. Schematics showing the superior application into triboelectric nanogenerators by (a) the new design of the Ga-doped thin film through surface diffusion
treatment in comparison with (b) self-assembled Ga-doped ZnO nanowire array by coprecipitation [40].
output cycles of TENGs under the constant contact force of 15 N at the
fixed frequency of 1 Hz, the polarity is confirmed in Fig. 6(a) that
electron charges would transfer from ZnO to PDMS since the ZnO side
always generates positive voltages over the separation stage. This also
coincides with our KPFM results on the relative magnitude of work
function in that ZnO favors donating electrons to PDMS. More specif­
ically, Fig. 6(a) and 6(b) show the output voltage, current density and
output power (Voc*Isc) of the TENG made of the undoped as well as
0.56 at%, 0.93 at%, 1.31 at%, and 1.75 at% Ga-doped ZnO thin film are
(4 V, 16.5 nA/cm2, 66 nW), (25 V, 112.5 nA/cm2, 2.81 μW), (65 V,
225 nA/cm2, 14.6 μW), (45 V, 200 nA/cm2, 9 μW) and (20 V, 100 nA/
cm2, 2μW), respectively. Apparently, the output voltage and current
monotonically increase with Ga doping concentration and reach the
maximum value at 0.93 at%, which are 16 times and 13 times higher
than those of the undoped ZnO film. The same trend in the output
performance with various Ga doping concentrations was also justified by
another hard tribo-material of PI/Cu to contrast with the soft material of
PDMS as shown in Fig. S4, fully supporting the proposed mechanism to
be universal. Besides, it is notable that the voltage waveform of each
TENG is not identical and has been studied in detail [5].
Combining the above mentioned two systems, the enhanced perfor­
mance of TENGs is ascribed to the synergistic effects of increased free
carriers at the surface due to Ga doping and enlargement of work
function difference by upward shifting of Fermi level of ZnO, as shown
in Fig. 6(c). Since the work function of ZnO is lower than that of PDMS,
PDMS is in favor of receiving electrons from ZnO during electrification,
rendering PDMS negatively charged and ZnO positively charged. When
Ga doping concentration is smaller than 0.93 at%, Ga-doped ZnO films
with higher Ga content tend to make work function smaller and release
more electrons into PDMS during mechanical contact and separation. If
the Fermi level shifts toward the conduction band, more electrons are
thermally activated and jump into the conduction band. Hence, the
narrowing work function as increasing Ga content suggests that more
electrons are available at the Ga-doped ZnO surface, promoting the yield
of charge transfer.
The performance of ZnO-based TENGs is enhanced rather signifi­
cantly by Ga doping to reach 65 V and 225 nA/cm2 and even out­
performs the previously reported TENG with similar structure composed
of PDMS against Ga-doped ZnO nanowires with 250 nm thickness pre­
pared by hydrothermal method, reaching the best output performance
around 20 V and 60 nA/cm2 [40] by more than 3 and 4 times. Although
the thickness differs by two times, the comparison still works since they
are all thicker than the critical thickness of around 150 nm [15], beyond
which the thickness will be insignificant. This comparison clearly
manifests the adopted doping strategy particularly is advantageous not
only in offering the option to tune work function and hence free carrier
concentration but also optimizing carrier concentration gradient profile
inside the semiconductor materials. Contrary to the common doped-ZnO
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Nano Energy 89 (2021) 106394
nanowires or thin films where dopants are bound to distribute uniformly
throughout, the current approach is intended for setting up non-uniform
distribution of Ga in depth where Ga dopants only reside in a shallow
region from the surface leaving behind the rest of the film unaltered. The
bulk ZnO remains insulting for charge trapping, preventing
tribo-charges from recombination with induction charges, evidenced by
gradual increase in output voltage increase over the first 100 cycles as
shown in Fig. S5. Therefore, the pristine film is modified as comprised of
a conductive top part with doping and an insulating bottom part without
doping, well suited for the operation of TENGs. The presence of the
intermediate insulting layer has been shown experimentally and theo­
retically to be vital for high output performance by hindering the
recombination of generated tribo-charges and induction charges [29]. In
this case, the unaffected bottom ZnO layer acts as a charge trapping
layer in the 0.56 at% and 0.93 at% Ga-doped thin films, as shown in
Fig. 7(a), promoting charge retention at the surface to be responsible for
the enhanced output performance. Comparatively, the even Ga distri­
bution throughout the ZnO thin film, as shown in Fig. 7(b), accelerates
the conduction of induction electrons through the bulk in recombination
with the positive tribo-charges at the surface, leading to a drastic decay
of surface tribo-charge density causing less output performance as in
[40]. This comparison undoubtedly confirms the significance of syner­
gistic effects of the charge trapping layer and Ga doping of the proposed
method. The performance of the TENGs in this study could be further
enhanced by replacing the Si substrate with other conductive materials
to facilitate the charge induction process.
We have compared the results on the output voltage of ZnO-based
TENGs from the literature with ours in Table. S1. Apparently, the best
performance of the TENG based on Ga-doped ZnO film in the current
work outperforms all the other ZnO-based TENGs reported except the
one based on MgZnO/PDMS [15], which should be considered as
another material system due to its wider bandgap than ZnO. Intrigu­
ingly, ZnO can be made into a wide variety of morphologies, which
make fair comparison difficult due to different contact area. However,
whereas the research on TENG based on semiconductor multilayer thin
film is rare, our ZnO-film-based TENG devices represent the smallest
contact area due to flat surface compared with all the other nano­
structured ZnO-based TENGs. Therefore, we demonstrate a facile
method to synthesize a two-layered ZnO structure, restricting the Ga
dopants from driving-in and confined at the shallow surface through
thermal diffusion, which provide advantages over tunable work function
and carrier concentration for effective charge transfer, optimally
reaching the best output that outperforms all the reported results. This
comparison undoubtedly confirms the significance of synergistic effects
of the charge trapping layer and Ga doping of the proposed method. The
performance of the TENGs in this study could be further enhanced by
replacing the Si substrate with other conductive materials to facilitate
the charge induction process.
P.-C. Lee et al.
Fig. 8. Schematic illustration of the relative band structure with the potential charge transfer routes of (a) undoped ZnO vs. PDMS, (b) Ga-doped ZnO vs. PDMS and
(c) Ga2O3 vs. PDMS during friction.
Intriguingly, when Ga concentration is higher than 0.93 at%, the
TENG’s performance reverses and becomes deteriorated even through
the work function difference keeps on increasing in the same trend. This
observation conflicts with the common electrification mechanism,
where the higher work function difference do lead to the larger output
power, implying some other decisive factors need to be considered. The
free carrier density in semiconductors might be the key governing the
tribo-charge transfer behavior and could be varied by orders of magni­
tudes, determined more precisely by the difference between the con­
duction band minimum and the Fermi energy level rather than the work
function. When Ga concentration is excessive, β-Ga2O3 forms on the
surface, which is an intrinsic n-type semiconductor. Comparing with
ZnO, the dielectric constant is similar, being 8–9 ε0 for ZnO and 10 ε0 for
Ga2O3 [46,47], and the surface roughness of all the samples are nearly
identical, as shown in Fig. S6 and Table. S2. While both are direct
bandgap materials, the major differences resort to the bandgap and the
conduction band minimum. The bandgap is 3.2 eV for ZnO and 4.5 eV
for β-Ga2O3, whereas the conduction band minimum, same as electron
affinity, is 4.5 eV for ZnO [48] and 4 eV for β-Ga2O3 [49]. Therefore, the
energy level between Fermi-level and conduction band minimum is
estimated to be 0.45 eV, 0.4 eV, and 0.78 eV for undoped ZnO,
Ga-doped ZnO, and β-Ga2O3, respectively, as shown in Fig. 8. Evidently,
while Ga doping makes the Fermi level closer to the conduction band
and therefore contributes more free electrons, β-Ga2O3 possesses the
least electron density available for charge transfer over to PDMS among
all the five samples, which should be responsible for the decline in
output decay. The decreasing trend of carrier concentration as Ga con­
centration reaches 1.31 at% and 1.75 at% are also evidenced in Fig. S2.
This work shed light on the underlying working mechanism of TENG,
where the work function difference between the tribo-pairs should be
accompanied by the available carrier density to fully determine the
generated tribo-charge density during contact electrification. Here, we
demonstrate the difference between Fermi-energy level and conduction
band minimum is one important key factor in TENG when comparing
different semiconductor materials with similar dielectric properties and
electronic structures.
4. Conclusion
ZnO thin films doped with various Ga doping concentrations are
achieved without varying film morphology by the proposed two-step
growth method, where Ga+3 is doped into ZnO crystals in the second
step by thermal decomposition and diffusion. When Ga doping con­
centration is less than 0.93 at%, Ga+3 proves to be the substitution for
Zn+2, occupying Zn+2 site in the ZnO lattices, through XPS analysis and
7
Nano Energy 89 (2021) 106394
exhibits a concentration gradient profile to a certain depth. KPFM results
confirm that the surface work function of the ZnO film can be system­
atically tuned in a decreasing manner by Ga doping, and the triboelectric
output is increased when rubbing against PDMS. Compared with the
undoped ZnO, the output voltage and current of the 0.93 at% Ga-doped
ZnO film are dramatically enhanced by 16 and 13 times, respectively.
Except the increased work function difference through Ga doping into
ZnO, the limited Ga diffusion to a certain depth helps to reserve the rest
of the bulk ZnO as insulting, which serves as a charge trapping layer to
suppress recombination of tribo-charges with induction charges, further
facilitating the TENG’s performance. On the other hand, when Ga be­
comes excessive to more than 0.93 at%, TEM and XRD microstructure
characterizations suggest formation of a continuous Ga2O3 layer at the
surface. The β-Ga2O3 is characterized by a larger bandgap and reduces
the charge transfer ability for poorer output performance of TENGs,
although the work function difference between β-Ga2O3 and PDMS is
even larger. In this work, a two-step approach is proposed only to modify
the ZnO thin film surface by surface diffusion with Ga as a conducting
layer while preserving bulk ZnO as a charge trapping layer. Moreover,
the underlying working mechanism of TENGs also depends on carrier
density in the conduction band of semiconductor materials in addition to
work function difference.
CRediT authorship contribution statement
Ping-Che Lee: Conceptualization, Data curation, Formal analysis,
Writing – original draft. Yi-Chen Ou: Formal analysis, Data curation.
Ruey-Chi Wang: Supervision. Chuan-Pu Liu: Funding acquisition,
Project administration, Supervision, Validation, 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 influence
the work reported in this paper.
Acknowledgements
The research was supported by Hierarchical Green-Energy Materials
(Hi-GEM) Research Center, NCKU, R.O.C. technically as well as Ministry
of Education and Ministry of Science and Technology, R.O.C. financially,
(Grant NO. MOST 107-2221-E-006–021-MY3, MOST 107-2221-E-006-
020-MY3, MOST 109-2622-8-006-005, MOST109-2623-8-006-005,
MOST 110-2634-F-006-017). The authors also gratefully acknowledge
P.-C. Lee et al.
the use of HR-SEM (Hitachi SU8000 by Ms H.L. Sze) and Ultrahigh
resolution TEM (JEOL JEM-2100 F CS STEM by Ms S.W. Tseng) in the
Instrument Center of National Cheng Kung University in Taiwan.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.nanoen.2021.106394.
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Ping-Che Lee received his B.S. (2018) and M.S. (2020) degree
in material science and engineering form National Chung Kung
University, Taiwan. He is currently working as a research as­
sistant under the supervision of Prof. Chuan Pu Liu at National
Cheng Kung University. His research interests include piezo­
electric nanogenerator based on micro-structure modified ZnO
and masters in transmission electron microscope.
Yi-Chen Ou received her M.S. (2020) degree in material sci­
ence and engineering form National Chung Kung University,
Taiwan. She is currently working as a process intergration
engineer in micron. Her previous research interests include
tribo electric nanogenerator based on micro-structure modified
ZnO.
Nano Energy 89 (2021) 106394
Ruey-Chi Wang is a distinguished professor in the Department
of Chemical and Materials Engineering at National University
of Kaohsiung, Taiwan, R. O. C. She received her Ph.D. degree in
materials science and engineering from National Cheng Kung
University, Tainan, Taiwan, in 2006. She received the Young
Investigator Award (Ta-You Wu Memorial Award) from the
National Science Council (NSC), Taiwan, in 2010. Her current
research interests are focused on nanomaterials and
nanodevices.
Dr. Chuan-Pu Liu received his PhD degree from Department of
Material Science and Metallurgy in the University of Cam­
bridge in 1998, followed by a post-doc researcher at Materials
Research Lab in the University of Illinois at Urbana-
Champaign. He then Joined Department of Materials Science
and Engineering in National Cheng Kung University, Taiwan in
2000. He serves as a distinguished professor at the same
department now. He has published about 250 journal paper
and 10 patents. His current research interests include semi­
conductor nano-materials, TEM atomic scale imaging, nano-
devices, piezotronic and triboelectric nanogenerators, lithium
ion battery, gas and chemical sensor.