Progress Report

Charge Carrier Engineering www.afm-journal.de

Enhancing the Photoelectric Performance of

Photodetectors Based on Metal Oxide Semiconductors
by Charge-Carrier Engineering
Weixin Ouyang, Feng Teng, Jr-Hau He,* and Xiaosheng Fang*

the ever-changing and developing require-

Semiconductor-based photodetectors (PDs) convert light signals into ments from the fundamental research
electrical signals via the photoelectric effect, which involves the generation, and industrial applications, including
separation, and transportation of the photoinduced charge carriers, as well space communications[2] and flame detec-
as the extraction of these charge carriers to external circuits. Because of their tion,[3] the photoelectric properties of PDs
based on low-dimensional nanostructures
specific electronic and optoelectronic properties, metal oxide semiconduc-
require further improvements, which
tors are widely used building blocks in photoelectric devices. However, the focus on the adoption of appropriate sen-
compromise between enhancing the photoresponse and reducing the rise/ sitive semiconductor materials and the
decay times limits the practical applications of PDs based on metal oxide optimization of device configurations.
semiconductors. As the behaviors of the charge carriers play important roles Metal oxide semiconductors are useful
in the photoelectric conversion process of these PDs, researchers have pro- building blocks in the photoelectric devices
for their specific electronic and optoelec-
posed several strategies, including modification of light absorption, design of tronic properties. Their low-dimensional
novel PD heterostructures, construction of specific geometries, and adoption nanostructures with suitable bandgap,
of specific electrode configurations to modulate the charge-carrier behaviors unique conduction properties, and con-
and improve the photoelectric performance of related PDs. This review aims fined carrier conduction pathways made
to introduce and summarize the latest researches on enhancing the photo­ them suitable candidates for sensitive
materials in photoelectric devices. Besides,
electric performance of PDs based on metal oxide semiconductors via charge-
metal oxide semiconductor nanostruc-
carrier engineering, and proposes possible opportunities and directions for tures are stable and easy to be prepared
the future developments of these PDs in the last section. and processed, which make them prom-
ising for assembling high-performance
PDs in large scale. For photoconductive-
1. Introduction type PDs based on commonly used metal oxide semiconductor
nano­structures such as ZnO and SnO2, they can exhibit high
Semiconductor-based photodetectors (PDs) convert light sig- absorption coefficient and high response resulted from the pro-
nals into electrical signals via the photoelectric effect. Promoted nounced surface effects.[4] However, these surface effects also
by the progressive nanoscience and nanotechnology, PDs have cause the slow response speed of these PDs, which is related to
achieved prolonged developments in last decades.[1] To meet the oxygen absorption/desorption process at the surface of oxide
semiconductors. In the dark, the oxygen molecules absorb on
the oxide surface by capturing the free electrons from the con-
Dr. W. X. Ouyang, Prof. X. S. Fang duction band of these oxide semiconductors, forming a surface
Department of Materials Science
Fudan University depletion layer with low conductivity. Under light illumination,
Shanghai 200433, P. R. China the photogenerated holes migrate to the surface and discharge
E-mail: [email protected] the negatively charged absorbed oxygen ions, causing the
Dr. F. Teng photo­desorption of oxygen molecules from the surface. When
School of Physics the light is off, the oxygen molecules are reabsorbed on the
Northwest University
Xi’an 710127, P. R. China
oxide surface and extract the photogenerated electrons in PDs,
Prof. J.-H. He
leading to the decay of current. Thus, the pronounced surface
Computer effects lead to the slow oxygen absorption/desorption process
Electrical and Mathematical Sciences and Engineering (CEMSE) Division at the surface of oxide semiconductors, causing the long rise/
King Abdullah University of Science and Technology (KAUST) decay times of these related PDs.[5,6] In other cases, the rapid
Thuwal 23955-6900, Kingdom of Saudi Arabia recombination of photogenerated electron–hole pairs (i.e.,
E-mail: [email protected]
short-carrier lifetime) and low-absorption coefficient of semi-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.201807672.
conductor nanomaterials leads to low quantum efficiency and
poor photodetection performance.[7,8] The compromise between
DOI: 10.1002/adfm.201807672 enhancing the responsivity and reducing the rise/decay times

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seriously limits the practical applications of PDs based on metal realize the enhanced specific detectivity. Thus, the controlled
oxide semiconductors.[9] To deal with this problem, it is neces- defect engineering of trap states can endow PDs with both high
sary to track the behaviors of carriers in these PDs and clarify responsivity and fast response.[15]
their influences on the photoelectric properties. This paper aims to provide a brief, systematical, and compre-
In general, the photoelectric conversion processes from hensive introduction of the latest researches on enhancing the
optical signals to electric signals via semiconductor-based PDs photoelectric performance of metal oxide semiconductor–based
mainly involve four steps: PDs via charge-carrier engineering, and possible opportunities
and directions for the future developments of these PDs are
1) Generation of the Charge Carriers: When the incident photo­ns
proposed in the last section.
are absorbed by the semiconductors after the light trapping
process, the photo-excited electrons transit from the valence
band (VB) to the conduction band (CB) of the semiconduc-
tors, while the corresponding holes are left in the VB. The ob- 2. Generation of the Charge Carriers
tained electrons in the CB and holes in the VB are recognized
The generation of photoexcited carriers upon the absorption
as the photoinduced carriers.
of photons is the leading process of photoelectronic detection,
2) Separation of the Charge Carriers: Forced by the applied elec-
and it has primary impacts on the photoelectric conversion pro-
tric field or built-in electric field formed at the interface of
cess. In order to enhance the concentration of photogenerated
heterojunctions, the photoinduced electron–hole pairs are
electrons and holes, increasing the light absorption of active
separated and move toward different electrodes.
semiconductor materials in the PD should be taken into con-
3) Transportation of the Charge Carriers: After being separated,
siderations. The construction of special structures, doping, and
the different charge carriers would travel along the conduc-
taking advantages of the surface plasma resonance effect, the
tion pathways toward alternative electrodes, where the tap-
hot electron injection effect and the multiple excitons effect are
ping and recombination of charges carrier occur and cause
commonly used methods to enhance the light absorption.
decreased photoelectric conversion efficiency.
4) Extraction of the charge Carriers: After the charge carriers
arrived at the electrodes, in accordance with the varied elec-
2.1. Light-Harvesting Structures
trode configurations, they will be extracted and conducted to
the external circuit, which contribute to the photocurrent.
Adjusting the surface roughness for the precise control of light
The photoelectric performance of PDs relates with the behav- scattering, transmission, and reflection is frequently utilized to
iors of these charge carriers. The implement of charge-carrier enhance the light absorption in the optical devices, including
engineering, including the generation of increased amount solar cells and PDs.[16–18] Generally, nanostructures at the
of photoinduced electron–hole pairs resulted from enhanced device surface exhibit excellent photon capturing and confine-
photo absorption, the effective separation of the chare carriers ment abilities to enhance light absorption and improve forward
driven by the applied or inner electric fields at junctions, as well scattering of incident light. Better photon management by
as the efficient transport and extraction of charge carriers pro- employing the nanostructures allows for thinner active layers in
moted by the superior device structures, leads to the modula- the PDs, which not only reduces the cost and amount of mate-
tion of charge-carrier behaviors and promotes the improved rial used, but also decreases the electrical loss during the pho-
photoelectric performance of PDs. tocarrier transport.[19] Recently, a Ω-shaped 1D SnO2@ZnO PD
“5S” is a standard rule for high-performance optoelec- with electrospun SnO2 nanofibers as core and ultrathin ZnO
tronic devices, which stands for high sensitivity, high spectral film as shell has been reported. It exhibits a high photo-to-dark
selectivity, high signal-to-noise ratio, high speed, and high current ratio of up to 104 at around 280 nm.[20] As demonstrated
stability.[1,10] To meet with these requirements and rectify the by both theoretical simulations and experimental comparisons,
low photoresponse and slow response speed of metal oxide the unique compact Ω-shaped nanostructure does contribute
semiconductor–based PDs, researchers have proposed several to photon trapping and gaining process, especially in the back-
strategies, such as modification of light absorption, utilization illumination configuration. Figure 1a,b shows the optical field
of defects engineering, development of novel PD heterostruc- distribution under face and back illumination via finite-differ-
tures, construction of specific geometries, and adoption of spe- ence time domain (FDTD) simulation. The Ω-shaped structure
cific electrode configurations, to achieve enhanced responsivity is proved to be more effective for trapping light illuminated from
and accelerated response speed. Full considerations should be the back side. Once the light is trapped inside the structure, it
taken while applying these strategies so as to meet the different will certainly increase the photon absorption, thus leading to
aspects of the “5S” standards. Taking the defect engineering improved photoelectric properties.
in PDs as an example, similar to its applications in solar cells
and photocatalysts,[11,12] the considerate defect engineering in
PDs can improve the light absorption and prolong the photo- 2.2. Doping
carrier lifetime, leading to good sensitivity, high responsivity,
and even extended photoresponse range.[13,14] The emergence Energy band engineering is also considered as an effective
of defect-induced trap states can shorten the response times method to enhance the light absorption and extend the absorp-
via the promoted recombination of photogenerated charge car- tion spectrum. Due to its simplicity and controllability, doping is
riers. Moreover, the significant reduction of dark current could frequently utilized to modulate the band structure of metal oxide

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Figure 1. a,b) The optical field distribution of Ω-shaped SnO2@ZnO nanostructure under face and back illumination simulated by FDTD. c,d) The
electric-field-intensity distribution of Au/Se hybrid structure under 600 nm light illumination from the top view and side view. e,f) Internal field–assisted
hot electron migration and quantum tunneling at the interface of Au/ZnO hybrid structure with different gate voltage biases. a,b) Reproduced with
permission.[20] Copyright 2017, Wiley-VCH. c,d) Reproduced with permission.[29] Copyright 2016, Wiley-VCH. e,f) Reproduced with permission.[36]
Copyright 2016, American Chemical Society.

semiconductors. The introduction of dopants into semiconduc- metal composition, and environment.[26] By taking advantage
tors causes the formation of impurity energy level and the shift of the light-confinement effect and tunable light absorption,
of absorption edges toward longer wavelength. Therefore, the various plasmonic PDs that combine low-dimensional semi-
photoelectric properties of PDs based on the doped metal oxide conductor nanostructures and these plasmonic metal nanocrys-
semiconductors are largely affected. Dutta et al. prepared sol– tals have demonstrated excellent plasmon-enhanced device
gel ZnO films with p-type conductivity by doping and codoping performance.[27,28] Our group achieved broadband responsivity
with N and Al–N, respectively.[21] Compared with the undoped enhancement of single Se microtube (Se-MT) PDs in the UV–
and codoped films, the N-doped film exhibits better response to vis region by the modification of different metal nanoparticles
UV light. Young and Liu fabricated an indium-doped ZnO nano- (NPs).[29] The pristine Se-MT PD demonstrates broadband
structure UV PD uniformly on a glass substrate, which exhib- photoresponse from 300 to 700 nm with a peak responsivity
ited high sensitivity, fast response speed, and good orientation of about 19 mA W−1 at 610 nm and short rise/decay times of
properties.[22] At 1 V bias, the indium-doped ZnO PD achieves 0.32/23.02 ms. After the deposition of Au NPs with optimal
an on/off ratio of 740 at 365 nm and exhibits the short rise/ sizes and densities on the surface, the Au−NP-decorated Se-MT
decay times of 3.02/1.53 s. When irradiated with 360 nm light, PD achieves broadband responsivity enhancement (≈600–800%)
this PD displays a UV–vis rejection ratio of ≈312. In general, the resulting from both the surface modification and surface
trap states induced by doping could promote the recombina- plasmon coupling. Figure 1c,d shows the electric-field-inten-
tion of charge carriers, which would lead to shortened response sity distribution of Au/Se hybrid structure under 600 nm light
times. Shabannia synthesized vertical Co-doped ZnO nanorod illumination in the top view and the side view, this simulation
arrays on a flexible polyethylene naphthalate (PEN) substrate result further confirms that the LSPR effect can enhance the
and assembled them into a metal–semiconductor–metal light absorption of this hybrid structure.
(MSM)-type UV PD.[23] At 5 V bias, this UV PD exhibits a calcu- Targeting at the defined absorption range and low light
lated responsivity of 8.76 A W−1, a photosensitivity of 250, and absorption of metal oxide semiconductors, the LSPR effect can
very short rise/decay times of 0.229/0.276 s. Though doping can significantly improve the photoelectric performance of PDs
enhance the light absorption of metal oxide nanostructures and based on metal oxide materials. Tian et al. prepared an MSM-
improve their photoelectric properties, and excess amounts of structured UV PD based on a high-quality ZnO thin film grown
dopants could become the trapping and recombination centers on a quartz substrate.[30] The light absorption of ZnO thin film
of photo­generated charge carriers, which would weaken the is enhanced partly in the UV region, and the responsivity of the
photo­response of PDs instead.[24] PD is enhanced from 0.836 to 1.306 A W−1 after the deposition
of Pt NPs on the device surface, revealing the improved pho-
toelectric performance benefiting from the LSPR effect of Pt
2.3. Surface Plasma Resonance Effect NPs. Guo et al. prepared MgZnO MSM UV PDs and conducted
the surface decoration of Pt NPs.[31] Due to the enhanced scat-
Localized surface plasmon resonance (LSPR) is described as the tering of incident light via the surface plasmons of Pt NPs,
photoexcitation-induced collective oscillations of free charges the responsivities of all PDs with different electrode spaces
confined in a highly conductive nanocrystal.[25] In recent years, (3, 5, and 8 µm) were enhanced dramatically.
metal nanocrystals (such as Au, Ag, and Cu) with LSPR effects
have received worldwide attentions for their intriguing optical
properties and versatile technological applications. The absorp- 2.4. Hot Electron Injection Effect
tion and scattering cross-sections of these metal nanostructures
can be tailored over a broad wavelength region from UV and vis- Resonant surface plasmons can decay nonradiatively through
ible to infrared (IR) wavelengths via changing the size, shape, the generation of hot carriers, and the additional scattering

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and relaxation of these high-energy carriers would produce 2.5. Multiple Excitons Effect
photocurrent in PDs.[32,33] The generation of hot carries is
not confined by the bandgap of semiconductor, but rather Generally, one photon excitation can only produce a single elec-
extended to Schottky barrier height or tunnel junction, pro- tron–hole pair, which implies that the conversion efficiency
viding the possibility to detect photons with energies lower from photons to electron–hole pairs can hardly reach a hun-
than the bandgaps of semiconductors. The hybrid metal–semi- dred percent. However, after the absorption of a photon bearing
conductor system would be an excellent unit for manipulating at least twice the bandgap energy, the multiple exciton genera-
the emission of hot carriers and a promising platform for fab- tion effect occurred in semiconductor nanocrystals or quantum
ricating plasmonic PDs with multifunction. These hot-carrier dots induces the generation of two or more electron–hole pairs
processes can be achieved and regulated via the geometric from a single absorbed photon.[37] The trapping of electrons at
design of plasmonic nanostructures, the choice of plasmonic the quantum-dot surfaces leaves behind long-lived holes that
material, and the design of plasmonic material–semicon- are able to circulate through the photoconductor and external
ductor interfaces. The deeper exploration and utilization of circuit multiple times before the recombination with holes. The
the hot electron injection effect would pave ways for improved conversion efficiency from photons to electron–hole pairs in
optoelectronic performance. these devices can exceed 100%.[38] The generation of multiexci-
Ouyang et al. deposited Au NPs on a CdMoO4–ZnO com- tons in these systems happens within 200 fs, which reveals that
posite film by the ion sputtering method.[34] The as-constructed it is an instantaneous event. This multiple exciton generation
PD with an optimized deposition time of Au NPs yields an effect should lead to great improvements in the photoresponse
approximately twofold higher photocurrent and the decay time of PDs.[39]
reduces by half, as compared with the CdMoO4–ZnO PD. The
hot electrons from Au NPs are injected into the CdMoO4–ZnO
composite film, leading to the increased photocurrent. When 3. Separation of the Charge Carriers
the light is off, the Schottky barriers formed between Au NPs
and CdMoO4–ZnO composite film block the carrier transpor- Heterojunctions formed between different semiconductor
tation and accelerate the decay process of current. Thus, the materials have extensive applications in solar cells, photoelec-
hot electron effect and the construction of Schottky junctions trochemical (PEC) cells, PDs, and other photovoltaic devices
from the Au NPs contribute to the improved photoelectric per- due to their profound influences on electronic properties and
formance. Pescaglini et al. built Au nanorod–ZnO nanowire potentials in multifunction and property tuning. Heterojunc-
hybrid systems as a new class of near-IR PDs.[35] The PD shows tions can create built-in electric fields at the interfaces, which
large photoresponse between 650 and 850 nm and an “ultra- efficiently separate photogenerated electron–hole pairs and
fast” transit time within 250 ms. The quantum efficiency was regulate the transportation of carriers in photoelectric devices.
calculated to be ≈3% at 650 nm, more than 30 times larger Referring to the different conduction types of various compo-
than that of the equivalent Au/ZnO planar PDs. The local- nents in heterojunctions based on metal oxide semiconductors,
ized surface plasmons from Au nanorods generate hot elec- we classify the heterojunctions into n–n, p–n, p–i–n, and
trons at the Au−ZnO Schottky barriers. These hot electrons Schottky junctions generally.
are then injected into the ZnO nanowire which functions as a
passive component for charge collection, thus generating the
photo­current. The hot electron generation and injection pro- 3.1. n–n Junction
cess contributes to the improved and extended photodetecting
performance of this hybrid device. If the potential values of the conduction band and valence band
Direct coupling of electronic excitations of optical energy edges of n-type semiconductor A are more negative than those
via plasmon resonances could achieve improved gain and of another n-type semiconductor B, a type-II heterojunction can
selectivity in various optoelectronic applications. Kim and co- be formed between these two n-type semiconductors. Several
workers reported a thin ZnO film transistor incorporated with suitable n-type semiconductors have been utilized to improve
Au nanostructure for plasmon resonance energy detection and the photoelectric properties of ZnO-based PDs.
electric conversion.[36] This plasmonic Au−ZnO field effect tran- Our group prepared a novel CdMoO4–ZnO composite film
sistor (FET)-type PD collects the plasmonic-induced hot elec- by spin-coating CdMoO4 microplates on ZnO film and con-
trons from the physically isolated Au nanostructures, which structed this composite film into a heterojunction PD.[34] The
contributes to the amplification of drain current. Figure 1e,f device structure of this PD is shown in Figure 2a. With an opti-
displays the typical migration process of hot electrons at the mized loading amount of CdMoO4 microplates, this composite
interface of Au/ZnO hybrid structure with different gate voltage film PD achieves an ≈18-fold higher responsivity than the pure
biases. It can be deduced that an electron accumulation layer ZnO film PD at 350 nm with a bias of 5 V bias (Figure 2b), and
is generated under positive gate bias, which can modulate the its decay time shortens to half of the value of the ZnO film PD.
behaviors of charge carriers in the ZnO-based FET. Highly effi- It is demonstrated that the introduced CdMoO4 microplates
cient collection and amplification of hot electrons are achieved form type-II heterojunctions with the ZnO film, which leads to
by the internal electric field and quantum tunneling effect at improved photoelectric performance.
the Au−ZnO junction. In addition, the versatility of plasmonic ZnO nanostructures can also be used to modify the photo­
nanostructures in wavelength tunability endows this device electric properties of other metal oxide semiconductors. Li et al.
architecture an ultrawide spectral response. fabricated UV heterojunction PDs based on ZnO quantum

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Figure 2. a) Schematic diagram of the CMO–ZnO PD. b) Spectral response of the CMO–ZnO PDs and ZnO PD at 5 V bias. c) Spectral responsivity of
the ZTO NW PD and the ZnO QD decorated ZTO NW PD at wavelength range from 250 to 900 nm at a bias voltage of 1 V. The inset is the schematic
illustration of the as-fabricated PD. d) Time-domain photoresponse of two kinds of PDs at 1 V with a light intensity of 0.67 µW cm−2. e) Schematic
diagram of the ZnO−Ga2O3 core−shell microwire APD device. f) Spectral response of the device at −6 V bias. a,b) Reproduced with permission.[34]
Copyright 2017, Wiley-VCH. c,d) Reproduced with permission.[40] Copyright 2017, American Chemical Society. e,f) Reproduced with permission.[43]
Copyright 2015, American Chemical Society.

dot–decorated Zn2SnO4 nanowires.[40] The optimized hetero- Au/α-Ga2O3/ZnO isotype heterostructure-based Schottky barrier
junction PD displays an ultrahigh on–off ratio of up to 6.8 × 104, avalanche diode.[42] The device exhibits self-powered characteristics
a specific detectivity of up to 9.0 × 1017 Jones, and a photocon- with a dark current lower than 1 pA, a high UV–vis rejection
ductive gain of up to 1.1 × 107. It also presents fast response ratio of 103, and a detectivity of 9.66 × 1012 Jones. It also gener-
speed and excellent stability. Compared with a pristine nano- ates high avalanche gains over 103 and a low ionization coeffi-
wire, this quantum dot–decorated Zn2SnO4 nanowire demon- cient ratio of electrons and holes, leading to a total gain over 105
strates about 10 times higher photocurrent and responsivity and a high responsivity of 1.10 × 104 A W−1, while the layered
(Figure 2c,d). Their high performance originates from the device structure leads to a relatively long decay time of 238 µs.
rational energy band alignment engineering, which allows effi- To accelerate the response speed, Zhao et al. fabricated highly
cient separation of electron–hole pairs at the interfaces. crystallized ZnO–Ga2O3 core–shell microwires into high-per-
The potential differences between the conductive band edges formance solar-blind avalanche PD. The device structure of this
of n-type semiconductors in n–n junctions are usually smaller PD is depicted in Figure 2e.[43] It displays a high responsivity of
than the differences between n-type and p-type semiconductors up to 1.3 × 103 A W−1 at −6 V bias (Figure 2f), a high detectivity
in the p–n junction, thus resulting a weaker driving force for the of 9.91 × 1014 Jones, and ultrashort response times of 20/42 µs.
separation and transport of photogenerated electron and hole Surprisingly, its photoelectric performance in solar-blind wave-
pairs. The avalanche effect can be utilized to remedy these draw- band is comparable to or even higher than that of the commer-
backs of the n–n junction and achieve high-performance PDs.[41] cial Si avalanche PD (APD) (APD120A2 from Thorlabs Inc.),
The avalanche effect occurs when a large external electrical field which makes this core–shell heterostructure highly promising
is applied to a semiconductor system to accelerate the charge for practical solar-blind PDs.
carriers to sufficiently high energy that they can generate addi-
tional electron–hole pairs through collisional ionization, leading
to strongly amplified photoresponse of PDs. Avalanche PDs rely 3.2. p–n Junction
on the avalanche effect of heterojunction at high reverse bias,
and usually exhibit very high photosensitivity and fast response As the most ubiquitous and fundamental building block of
speed, which are able to detect weak or fast changing signals. modern electronics, p–n junctions play a crucial role in modern
Chen et al. grew single crystalline α-Ga2O3 epilayers on nonpolar microelectronics applications, including integrated circuits,
ZnO (1120̄) substrates and demonstrated a high-performance sensors, solar cells, and lasers.[44] Owing to the photovoltaic

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effects resulted from p–n junctions, photoexcited electron–hole nanostructures have been intensively investigated for UV photo­
pairs generated at the p–n junctions are separated by the built- detection. Researchers have prepared p-type ZnO materials via
in electric field. The photoelectrical response speed of the p–n doping and then combined them with n-type ZnO materials
junction is dominated by the drift time of carriers inside the to form p–n homojunctions aiming for superior photoelectric
depletion area of the junction, which differs from the long-time properties. Hsu et al. synthesized vertical p-ZnO:Cu/n-ZnO
photoconductive relaxation of metal oxide semiconductor nano- homojunction nanowires (NWs) and whole ZnO:Cu NWs on a
structures originating from the adsorbates on their surface. ZnO thin film/glass substrate by calcination.[46] The I–V curve
Thus, the adoption of the p–n junction in photoelectric devices of p-ZnO:Cu/n-ZnO NWs displays the rectifying characteristics
can achieve improved photoresponse and fast response speed. and the value of photocurrent is around 6 times larger than that
In recent years, nanostructured p–n and p–i–n junctions of the dark current at −5 V. Li et al. prepared another single-
made from low-dimensional metal oxide nanostructures with crystal p-type ZnO nanowires using P2O5 as the dopant source
various configurations, such as core–shell, axial, crossed, and via a chemical vapor deposition method.[47] An intramolecular
branched structures, have been fabricated to construct high- p–n homojunction is formed in a single ZnO:P NW and displays
performance PDs. p-Type semiconductor materials, as the an on–off ratio as high as 3.2 × 104 at 325 nm. Vabbina et al.
alternative component in p–n junctions, demonstrate promi- grew a p-doped ZnO nanoshell structure around an n-doped
nent and irreplaceable roles in constructing high-performance ZnO nanorod and then a homogeneous radial p–n junction in
photoelectric devices. In order to explore the influences of the ZnO core–shell configuration was built.[48] The fabricated
p–n junctions on the photoelectric properties of metal oxide radial p−n junction PD exhibits a high responsivity of 9.64 A W−1
semiconductor nanostructures, the PDs based on p–n hetero- and a low noise equivalent power of 0.573 pW Hz1/2 under UV
junctions are classified in accordance with the different p-type illumination. Other p-type inorganic semiconductors have also
counterparts (such as inorganic semiconductors and organic been utilized to form p–n junctions with ZnO nano­structures
semiconductors). Considered the specific optical and electric to expect improved photoelectric performance. Flemban et al.
properties of the inorganic–organic hybrids with perovskites fabricated high-quality n-type ZnO nanotubes (NTs) on a p-type
as the representative, the heterojunctions made from the metal Si(100) substrate by pulsed laser deposition (PLD).[49] The fab-
oxide semiconductors and perovskites are also presented at the ricated UV PD demonstrates a superior responsivity of up to
end of this section. ≈101.2 A W−1 and short rise/decay times of 0.44/0.59 s under
365 nm UV illumination (1 mW cm−2) at −5 V. This superior
photoelectric performance is attributed to the p–n junction, the
3.2.1. Metal Oxide + Inorganic Semiconductors high density of photoinduced charge carriers, and the high crys-
tallinity and special geometry of ZnO NTs. In coordination with
Inorganic p-type semiconductors usually possess stable struc- popular 2D materials, Lee et al. developed a mixed-dimensional
tures, controllable band level structure and predictable charac- 1D ZnO NW–2D WSe2 nanosheet van der Waals (vdW) hetero-
teristics, which can be adopted to construct high-performance junction PD.[50] The ZnO–WSe2 heterojunction PD with surface
optoelectronic devices with common metal oxide semiconduc- passivation of amorphous fluoropolymer shows superior perfor-
tors. TiO2 is an intrinsically n-type metal oxide semiconductor mance with a much enhanced on/off ratio of over 106, an ide-
with wide indirect bandgap. It is regarded as one of the prom- ality factor of 3.4–3.6, an extended spectral photoresponses from
ising candidates for UV photodetection, while the rapid recom- 400 to 950 nm, and even self-powering characteristics at 0 V.
bination of photogenerated electron–hole pairs in the TiO2 Carbon nanomaterials have been selected to form p–n het-
nanostructures leads to a low quantum efficiency and poor erojunction with ZnO nanomaterials to achieve favorable UV
photodetection performance. BiOCl nanosheets/TiO2 nano- photodetection. Cuong et al. fabricated a transparent vertical
tube arrays heterojunction UV PD with high performance was ZnO NRs array/thin GO:CNT hybrid film p–n heterojunction
fabricated by a facile anodization process and an impregnation device.[51] This device displays high rectifying characteristics,
method.[45] The device structure of this heterojunction PD is enhanced UV light absorption and high UV light response.
presented in Figure 3a. The pure TiO2 PD exhibits a large dark Its photoelectric performance can be further improved by opti-
current (≈10−5 A), a low on/off ratio (8.5) and slow decay time mizing the GO:CNT ratio and aspect ratio of ZnO NRs. Li et al.
(>60 s), while the optimized BiOCl/TiO2 heterojunction PD combined a semitransparent film of p-type semiconducting
yields a dramatically decreased dark current (≈1 nA) (Figure 3b), single-walled carbon nanotubes (SC-SWNTs) with a molec-
an ultrahigh on/off ratio (up to 2.2 × 105) and fast decay speed ular beam epitaxy-grown n-ZnO layer to build a vertical p-SC-
(0.81 s) under 350 nm at -5 V. Moreover, it exhibits an increased SWNT/n-ZnO heterojunction UV PD. The device structure is
responsivity of 41.94 A W−1 (Figure 3c), a remarkable detectivity shown in Figure 3d.[52] This device exhibits a low dark current,
(D*) of 1.41 × 1014 Jones and a high linear dynamic range of a current rectification ratio of 103, and a photoresponsivity up to
103.59 dB. The greatly improved photoelectric performance is 400 A W−1 in the UV region from 370 to 230 nm. The detector is
mainly attributed to the heterojunctions at the interface, which practically visible–blind with a high UV-to-visible rejection ratio
facilitate the separation of photogenerated charge carriers and of 105 due to extremely short photocarrier lifetimes in the 1D
regulate the transportation of the electrons between electrodes. SWNTs. In Figure 3e, the p-SC-SWNT/n-ZnO heterojunction
ZnO is another well-known n-type metal oxide semiconductor device shows a relatively fast onset of the photo­current followed
with a large bandgap of 3.37 eV and a large exciton binding by a slow approach to saturation. The rise/decay times are cal-
energy of ≈60 meV. Because of its moderate UV absorption, culated to be 14/23 s, respectively. Under the same conditions,
specific electric properties, high stability and low toxicity, ZnO the In−ZnO−In device in Figure 3f shows a significant nonzero

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Figure 3. a) Schematic diagram of the BiOCl–TiO2 UV PD. b) I–V curves for the device in the dark. c) Spectral response of the TiO2 PD and the
optimized BiOCl–TiO2 heterojunction PD at −5 V bias. The inset shows the I–t characteristics of the 6-BiOCl–TiO2 PD at 350 nm under −5 V bias.
d) Schematic of the p-SC-SWNTs/n-ZnO heterojunction under UV irradiation. e,f) Temporal photoresponse of the In−ZnO−In lateral device and the
p-SC-SWNT/n-ZnO heterojunction device under 370 nm light at a bias of −2 V. g) Schematic image of the MoS2/CuO nanosheet-on-1D heterojunc-
tion photodiode. h) Photocurrents curves of the MoS2/CuO photodiode under light illumination of different wavelengths (560, 600, 700, and 760 nm)
at 1 mW power and dark conditions. i) Photoresponsive rise and decay times of the MoS2/CuO photodiode at −2 V under 570 nm light illumination
with Plight = 1.4 mW. a–c) Reproduced with permission.[45] Copyright 2018, Wiley-VCH. d–f) Reproduced with permission.[52] Copyright 2017, American
Chemical Society. g–i) Reproduced with permission.[55] Copyright 2016, American Chemical Society.

dark current, an ≈6 times smaller amplitude of the current an excellent rectification ratio, moderate photoresponse and
modulation, and long rise/decay times exceeding 100/600 s, quantum efficiency under UV illumination.[54] As the bandgap
respectively. It is inferred that the introduction of the SWNT/ of Zn1−xMgxO films can be tuned between 3.24 and 3.49 eV by
ZnO heterojunction not only enhances the photoresponse but varying the value of x, at an reverse bias of 1 V, the maximum
also achieves faster response speed in comparison with the lat- responsivity of the devices varies between 0.22 and 0.4 A W−1, and
eral In−ZnO−In device. the detectivity varies between 0.17 × 1012 and 2.2 × 1012 Jones.
p-Type metal oxide semiconductors (such as NiO and CuO) Um et al. built MoS2 nanosheet-on-1D CuO nanowire vdW
have also been utilized to form p–n heterojunctions with n-type heterojunction PDs with an atomically sharp interface and a high-
semiconductors to optimize the photodetecting performance. quality heterojunction. The device structure of these heterojunc-
With the solution-processed p-type NiO and n-type ZnO films tion PD is displayed in Figure 3g.[55] The optimized PD exhibits
as sensitizing materials, Kim et al. fabricated an all-inorganic a low dark current of ≈38 fA at −2 V (Figure 3h), an ultrahigh
p−n NiO/ZnO heterojunction UV PD.[53] Thanks to the inter- responsivity of ≈157.6 A W−1 under 532 nm laser excitation with
facial trap-induced charge injection that occurs at the ITO/NiO intensity of 55 µW, a high rectification ratio of ≈6000 at ± 2 V,
interface by photogenerated holes trapped in the NiO film, the and short rise/decay times of ≈34.6/51.9 ms (Figure 3i).
PD achieves a high gain (EQE) of 25 300%. Moreover, Xie et al. Besides, Hong et al. fabricated a self-powered broadband PD by
fabricated solution-processed p–n heterojunction photodiodes coating an n-silicon nanowire (n-Si NW) array with a layer of
based on NiO/Zn1−xMgxO (x = 0–0.1) hybrid films, which show p-CuO nanoflakes.[56] This p–n heterojunction shows excellent

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rectification characteristics, a low dark current of 0.7 nA at 0 V 3.2.3. Metal Oxide + Perovskites
and distinctive photovoltaic behavior under broadband light
illumination. Under relatively weak visible and near-IR light Perovskites with a typical formula of MAPbX3 (MA = CH3NH3;
illumination (0.48 W cm−2), the CuO/Si NW device displays X = Cl, Br, and I), are the representatives of organic–inorganic
a self-powered high photosensitivity of 1 × 103 and ultrashort hybrids. Endowed with unique electrical and optoelectronic
rise/recovery times of 60/80 µs. In addition, this PD reveals properties, perovskites have drawn worldwide researchers’
a distinctive binary response under a small forward bias. It is attentions and developed broad applications in light emit-
believed that these superior photoelectric properties are attrib- ting diodes, optically pumped lasers, efficient PEC cells and
uted to the specific geometry of the arrayed nanowires, the PDs.[67] The direct bandgap nature, high absorption ability
high surface area, and the built-in field near the CuO/Si NW and complete light absorption of perovskites lead to the high
interface. broadband photoresponse of perovskite-based PDs. The short
conduction pathways for photogenerated charge carriers lead to
fast response speed. Moreover, the very low densities of defects
3.2.2. Metal Oxide + Organic Semiconductors and traps in perovskites ensure the low charge recombination.
These characteristics strongly recommend the organic–inor-
p-Type organic materials usually exhibit the advantages of ease ganic hybrid perovskites as ideal building blocks for high-
of fabricating in large scale, broadband absorption range, and performance PDs. Various perovskites with different structure
the elastic modulating of their semiconductor characteristics, forms (polycrystalline film, single crystal, and low-dimensional
which make them suitable for photodetection.[57] The PDs nanostructure)[68] have been synthesized and combined with
based on the hybridization of p-type organic molecules with metal oxide semiconductors to assemble heterojunction PDs
tunable functionality and n-type inorganic semiconductors with various device configurations, which demonstrate unprec-
with superior intrinsic carrier mobilities, usually present high edented progress in photodetecting performances.
photodetecting performance, due to the efficient photoinduced Yi et al. fabricated a TiO2 nanotube film/CH3NH3PbI3
charge transfer and exciton dissociation resulting from the p–n bilayer device, employing the TiO2 NT film as a photocarriers
heterojunctions. transport layer.[69] The device exhibits satisfactory photoelectric
Polyaniline (PANI) is a well-known p-type conducting performance with a high on/off ratio of 4000, a high detectivity
poly­mer that is suitable for hole collection and transport layer of 1.85 × 1012 Jones, and short rise/decay times of 0.49/0.56 s.
in photoelectronics with p–n junction configuration. Zheng Zheng et al. spin-coated MAPbI3 quantum dots (QDs) onto the
et al. adopted an ordered TiO2 nanowell thin layer and PANI surface of TiO2 NTs to fabricate TiO2 NTs/MAPbI3 QDs heter-
with various morphologies to construct hybrid self-powered ojunction PDs.[70] Compared with pure TiO2 NTs, this hetero-
UV PDs.[58] The hybrid PD with optimized loading amount of structure demonstrates extended response range from UV to
PANI exhibits a high responsivity of 3.6 mA W−1, a large on– visible region, the responsivity in visible range has increased
off ratio of ≈103, excellent wavelength selectivity, short response by three orders of magnitude, while its high UV response per-
times of 3.8/30.7 ms, and good stability under 320 nm light formance is maintained. This PD demonstrates a relative fast
illumination at 0 V. Moreover, Chen et al. fabricated a high- and stable response from 300 to 800 nm and its responsivity
sensitivity self-powered solar-blind DUV PD based on hybrid reaches to 0.2 A W−1 at 700 nm. Apart from the excellent flex-
organic PANI and inorganic MgZnO bilayer.[59] At −1 V bias, ibility and high visible-light transparency, the hybrid PD pre-
the optimized PD shows a low dark current of 0.44 pA, a sents good stability to moist air or repeat bending and heating
sharp cutoff of responsivity at 271 nm and a high detectivity of at low temperature.
1.5 × 1011 Jones. Owing to the hybrid p–n junction, the PD Similarly, Cao et al. designed and fabricated a hybrid PD
exhibits a high on/off ratio of 104 at 0 V, a responsivity of consisting of electrospun ZnO nanofibers and perovskites.[71]
160 µA W−1 at 250 nm, and a high UV–vis (250/400 nm) rejec- Compared to the pristine ZnO or perovskite, the hybrid PD
tion ratio of up to ≈104. exhibits increased on–off ratio, faster response speed, and
Many other organic materials, such as poly(vinyl alcohol) higher responsivity and detectivity. The hybrid PDs based
(PVA),[60] poly(arcylonitrile) (PAN),[61,62] poly(vinyl carbazole) on the disordered ZnO nanofibers possess an on/off ratio
(PVK),[63] polypyrrole (PPy)[64] and even pyrene tricyanofuran of 340 and rise/decay times of 0.2/0.7 s. By optimizing ZnO
derivatives,[65] are also adopted to improve the photoelectric nanofibers to quasialigned arrays, the on/off ratio is further
properties of metal oxide semiconductor–based PDs. Meng enhanced to 2800, and the rise/decay times change to 0.2/0.5 s.
et al. developed a highly ordered 2D TiO2 nanobowl array/ Besides, the responsivity and detectivity reach up to 0.1 A W−1
PVK hybrid heterojunction UV PD.[66] The periodic structure and 1013 Jones in the UV and visible regions in correspond-
of the 2D TiO2 NB array contributes to the spectrum selec- ence to the band gap of perovskite. Compared with the disor-
tivity of the devices and emerges the response peak centered at dered nanofibers, the quasialigned ZnO nanofiber arrays pro-
330 nm. Under 330 nm UV light illumination (144 mW cm−2), vide efficient charge transfer between the perovskite and ZnO,
the device achieves a high responsivity of 8.14 A W−1 at −5 V. shorter transmission paths, and reduced carrier recombination,
The possible transparence, stretchability, flexibility, and ease of which contribute to the significantly improved photodetecting
production of the organic–inorganic hybrid promote their appli- performance.
cations in portable and wearable electronic devices, which are Sun et al. constructed a hybrid PD by combining the n-type
suitable for remote sensing, fiber optic communications and InGaZnO thin film and the all-inorganic CsPbBr3 nanowires
biological imaging. together.[72] This hybrid PD presents excellent photoelectric

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properties such as a low dark current of 10−10 A at −5 V, a high growth process, the integration of ZnO nanorods into a func-
on–off ratio of 1.2 × 104, a short response time of 2 ms, and a tion device can be achieved in the meantime, as presented in
high responsivity of 3.794 A W−1. It is well acknowledged that Figure 4a. The visible–blind devices display great response even
the poor chemical stability of perovskite PD in the presence of in the mid-UV region. It is exhibited in Figure 4b,c that the
oxygen and moisture can easily degrade its optoelectronic prop- PDs with Ni electrodes show better performance both in the
erties, which hinders its practical application.[73] However, in aspects of photocurrent and response time, owing to the larger
this hybrid PD, due to the dual-channel structure of heterojunc- height of Schottky barrier at the Ni/ZnO interface.
tion, perovskite and IGZO would affect the properties of the In general, the surface decoration of metal oxide semicon-
heterojunction simultaneously. As a result, the PD shows good ductors by metals NPs can form localized Schottky junctions,
stability in ambient for 2 months with little reduction in per- which create charge depletion regions at the interface, thereby
formance and even exhibits enhanced photocurrent and on–off reducing the dark currents. Moreover, the plasmonic effects,
ratio in high temperature. the modification of work functions and the induction of charge
transfer caused by the introduction of metals NPs would
lead to improved photoelectric performances. Specially, Chen
3.3. p–i–n Junction et al. demonstrated the decoration of Au NP at the nanowire
surfaces as an effective way to enhance both the photocurrent
In order to further enhance the performance of p–n junction value and photoconductive gain of a single ZnO NW PD.[79] The
PD, insulator layer is introduced between p and n layers to improved photoelectric properties of the Au NP-decorated ZnO
form p–i–n structure, which acts not only as the electroblocking NW PD under UV illumination is attributed to the pronounced
layer, but also the light absorption layer to adjust the spectral electron–hole spatial separation effect via the formation of local-
response range of PD and the spacer layer to prolong the trans- ized Schottky junctions under open-circuit conditions. Besides,
mission path of electrons in the electric field. It is demonstrated the enhanced space charge effect also makes the gain insensi-
that the hybrid PDs with p–i–n junction structures have several tive with the excitation power, which is beneficial for the PD to
figures of merit such as high breakdown voltage, fast response maintain high gain even with the high-power excitation.
and low dark current.[74] Due to the superior electrical, mechanical, and optical prop-
Ling et al. assembled a SnO2 nanoparticle thin film/SiO2/p-Si erties of graphene, graphene-based Schottky photodiodes have
heterojunction PD, which exhibits a stable, repeatable and broad- attracted numerous attentions in recent years. Liang et al. fab-
band photoresponse from 365 to 980 nm.[75] Meanwhile, the ricated a graphene/TiO2 heterojunction PD with high UV light
optimized PD shows high responsivities of 0.285–0.355 A W−1, selectivity by simply transferring single-layer graphene on rutile
an outstanding detectivity of ≈2.66 × 1012 Jones, an excellent TiO2 NRs array.[80] The responsivity and specific detectivity are
sensitivity of ≈1.8 × 106 cm2 W−1, and extremely short response estimated to be 52.1 A W−1 and 4.3 × 1012 Jones, respectively.
times (<0.1 s). It is believed that the large Fermi energy dif- After the wet-chemistry treatment, the UV PD shows an obvi-
ference between the SnO2 nanoparticle thin film and Si lead ously decreased sensitivity, while the rise/fall times are shorted
to a large band offset in the SnO2/Si heterojunction. With the to 80/160 ms and the specific detectivity is increased to 3.2 × 1013
thin SiO2 layer as the electroblocking layer and the oxygen Jones. Similarly, Nie et al. assembled a monolayer graphene
vacancy defects in the SnO2, the carrier transportation in this film/ZnO NR array Schottky junction UV PD by coating ZnO
heterostructure is easily controlled, which facilitates the high- nanorod array with a transparent monolayer graphene film.
response broadband detection. The device structure of this PD is depicted in Figure 4d.[81]
This device reveals effective trapping of the incident UV light
in the top end of ZnO NR array and exhibits highly stable UV
3.4. Schottky Junction response (Figure 4e). A high responsivity of 113 A W−1 and a
high photoconductive gain of 385 at −1 V is achieved. Mean-
Except for the p–n and p–i–n junctions, Schottky junctions while, the formation of Schottky junction, the high crystallinity
formed at the interfaces between conductors (metal or others) of the ZnO NR array and the strong light trapping effect lead to
and semiconductors are also adopted to construct high-perfor- extremely short rise/fall times of 0.7/3.6 ms (Figure 4f).
mance PDs, which can detect radiations with photon energies Insulator layer can also be introduced into the MS struc-
below the bandgap of semiconductors via internal photoemis- ture to form metal–insulator–semiconductor (MIS)-structured
sion. Compared with the photoconductive-type PDs, Schottky PD, which can achieve the modulation of photoelectric perfor-
PDs have numerous advantages, such as fast response speed, mance.[82] Chang et al. fabricated a TiO2 MIS PD by inserting
low dark current, large UV–vis rejection ratio, and possible a polyvinylphenol (PVP) layer in between the metal elec-
self-powering characteristic.[76] Metals and conductors, such as trodes and the TiO2 nanowires.[83] The PD achieves a 29 times
In, Al, Au, Ni,[77] Cu–Al–Mn–Ni shape memory alloy, and ITO larger photocurrent and an effectively suppressed dark cur-
(indium doped tin oxide), are usually utilized to construct high- rent compared with a TiO2 nanowire MSM PD. Apart from
performance Schottky photodiodes. the stable and reproducible dynamic response with an on/off
Liu et al. assembled lateral MSM-type UV detectors based ratio of around 180, this TiO2 MIS PD displays a responsivity
on ZnO nanorod with different metal contacts.[78] With the of 2.46 × 10−3 A W−1 under 390 nm at 5 V, a noise equivalent
combined effect from a ZnO seed layer and an inactive layer power of 7.49 × 10−12 W and a detectivity of 8.86 × 1011 Jones.
for nanorod growth, ZnO nanorods could grow laterally and This MIS PD also tolerates a higher bias and provides a higher
aligned between the interdigitated electrodes. At the end of the gain to amplify the signal.

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Figure 4. a) Schematic diagram for the UV PD based on laterally aligned ZnO nanorods. b) I–V characteristics of the ZnO nanorod PDs with different
metal electrodes measured at 365 nm and in dark. c) UV response–time curves of the ZnO nanorods with Sn and Ni electrodes. d) Schematic illus-
tration of the MLG film/ZnO NR array Schottky junction UV PD. e) I–t curves of the MLG film/ZnO NR UV PD at 365 nm. f) A single normalized I–t
cycle at 50 Hz. g,h) Ids versus Vds of the 2D Au−TiO2 and Au−WO3−TiO2 plasmonic devices at 785 nm (power density of 20 mV cm−2) with VG = 0 V
and Vds = 1 V. i) Schematic diagram of the MIS structure with insulator intermediate for the control of the height of Schottky barrier. a–c) Reproduced
with permission.[78] Copyright 2010, American Chemical Society. d–f) Reproduced with permission.[81] Copyright 2013, Wiley-VCH. g,i) Reproduced with
permission.[84] Copyright 2018, American Chemical Society.

Due to the efficient carrier transport between adjacent layers, heterojunctions. The impedancometry measurements in
2D heterojunctions are frequently adopted in high-performance Figure 4i confirms the modulation of charge transfer at the
PDs. Zhuiykov’s group developed 2D Au−TiO2-based plasmonic 2D MS interface using MIS architectonics. Besides, broad-
devices with 2D MS heterojunctions, which exhibited substan- band photoresponsivities in the UV and visible region are also
tially enhanced photoresponsivity and demonstrated improved observed for the Au−WO3−TiO2 heterostructures.
response speed under visible light illumination.[84] To circum-
vent the undesired dark current in the plasmonic devices, a 2D
WO3 nanofilm (≈0.7 nm) was employed as the intermediate 3.5. External Applied Field
layer on the MS interface to develop the MIS 2D heterostruc-
ture. As illustrated in Figure 4g,h, the presence of 2D WO3 External applied field such as magnetic field can have great
between Au and TiO2 nanofilms results in a slight enhancement influences on the photoelectric performance of heterojunction
of the photocurrent density compared with that of the Au−TiO2 PDs.[85] Deka Boruah and Misra fabricated cobalt-integrated
film. It is also displayed in the insets that the dark current den- zinc oxide nanorod (Co–ZnO NR) array as a novel heterostruc-
sity decreases considerably from 110 µA of the Au−TiO2 device ture for UV PD.[86] This PD exhibits highly tunable photoelastic
to the value of 14 µA of the Au−WO3−TiO2 device at Vds = 1 V. response, which shows 2.15 times enhancement in response
As a result, a 13.4% improvement of the external quantum current as compared to the pristine ZnO NRs PD. The applied
efficiency is obtained for the fabricated 2D Au−WO3−TiO2 external magnetic field can enhance the response current

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value of this Co–ZnO NRs PD by 186%. It is concluded that region down to 224 nm. It also exhibits fast response, high pho-
the opposite polarizations of electron and holes in the presence toresponsivity and stability. The 0D characteristic of the ZnO
of external magnetic field contribute to effective separation of QDs enable the possibility for highly stable flexible devices.
electron−hole pairs that have drifted upon UV illumination. Their photoelectric performance could be further improved by
Moreover, the Co–ZnO NRs PD shows much shorter rise/ exploiting the above-mentioned multiple exciton effect.[37]
decay times of 1.2/7.4 s, as compared to the 38/195 s of the
pristine ZnO NRs. The deeper understanding of the influences
of external applied fields on the behaviors of charge carriers 4.1.2. 1D Structures
in related PDs could provide new pathways to modulate their
photo­electric properties. 1D inorganic semiconductor nanostructures, such as nano-
wires, nanobelts (NBs), nanorods (NRs) and nanotubes, have
attracted tremendous research interests as fundamental
4. Transportation of the Charge Carriers building blocks for nanoscale electronics and optoelectronics
for their unique electrical and optical properties.[91] 1D nano-
4.1. Adjusting Transport Channels structures possess several features that make them candidates
for high-performance PDs.[70] On the one hand, their large sur-
Due to the different nanostructures of metal oxide semicon- face area to volume ratios cause the existence of numerous trap
ductors adopted in the PDs, the photogenerated charge carries states at the surface, leading to significantly prolonged lifetime
can transport towards different dimensions, and the transport of photo­generated carriers. On the other hand, 1D nanostruc-
channels for the separated charge carriers to go through before tures can provide long path length for photon absorption while
they arrive at the electrodes are quite different, thus making a short channels for carrier transport, leading to increased light
great difference to the photoelectric properties of these PDs. absorption and fast carrier transit. Besides, due to their huge
aspect ratios, 1D nanostructure is mechanically flexible along
their longitudinal direction, which makes it suitable for flexible
4.1.1. 0D Structures PDs. The rational design of the morphology and composition
of 1D metal oxide nanostructures will enable their utiliza-
0D structures such as nanoparticles and quantum dots have tions as functional building blocks to build PDs with unique
been utilized in metal oxide–based PDs. Jin et al. fabricated a spectral selectivity and sensitivity. Various 1D metal oxide
visible–blind solution-processed UV PD based on colloidal ZnO nanostructures including binary oxides (such as ZnO, SnO2,
nanoparticles.[87] The devices exhibit low dark currents with Ga2O3, Nb2O5, and WO3) and ternary oxides (such as Zn2SnO4,
a resistance >1 TΩ, high UV photocurrent efficiencies with a ZnGa2O4, Zn2GeO4, and In2Ge2O7) have been successfully syn-
responsivity of 61 A W−1 at 370 nm (1.06 mW cm−2) and short thesized and constructed into PDs.[92]
rise/decay times of <0.1/≈1 s. Because of the very large surface- Molina-Mendoza et al. deposited individual TiO2 fibers onto
to-volume ratio of ZnO NP films, the light-induced desorption the prepatterned Ti/Au electrodes on SiO2/Si substrates and
of oxygen from the NP surfaces could significantly remove elec- characterized their optoelectronic properties.[93] Figure 5a shows
tron traps and increase the free carrier density, which effectively a typical I–V curve of the PD based on TiO2 nanofiber in dark
reduces the height of Au/ZnO Schottky barrier for electron and under 455 nm light illumination. The as-fabricated PD pre-
injection and contributes to the satisfactory UV photodetection. sents a high UV responsivity of 90 A W−1 at 375 nm and a short
Graphdiyne (GD) possesses both sp and sp2 carbons with two response time of ≈5 s. The PDs are sensitive to light polariza-
diacetylenic linkages between the adjacent carbon hexagonal struc- tion, with an anisotropy ratio of 12%. It is believed that the com-
tures and exhibits an electronic conductivity of 2.56 × 10−1 S m−1. bination of large surface area and low 1D transport resistance in
It is promising for the optoelectronic and photocatalytic appli- the electrospun TiO2 fibers contribute to the fast response and
cations for its semiconducting behavior with a theoretical- high responsivity. Moreover, Hsu et al. demonstrated a novel
calculated band gap of 0.47 and 1.12 eV.[88] Li and co-workers strategy to integrate a carbon nanotube and TiO2 in a core–shell
prepared graphdiyne:ZnO nanocomposites by the self-assembly fashion as 1D PD.[9] Radial Schottky barriers between carbon
of GD nano­ particles onto the surface of PrA-modified ZnO nanotube cores and TiO2 shells and surface states at TiO2 shell
NPs, and then assembled the nanocomposites into UV PDs.[89] surface, facilitate the separation of photogenerated electrons and
The junction formed between the GD NP and ZnO NP greatly holes and regulate electron transport, leading to an ultrahigh
improves the carrier separation and transport, leading to sig- gain of 1.4 × 104 and ultrashort rise/decay times of 4.3/10.2 ms.
nificantly enhanced photoresponse. The device exhibits a high Moreover, radial Schottky junction and defect band absorption
responsivity of 1260 A W−1 and short rise/decay times of 6.1/2.1 s, extend the detection range to visible zone.
compared with a much lower responsivity of 174 A W−1 and much Due to the specific 1D nanostructures, the PDs constructed
longer rise/decay times of 32.1/28.7 s from the pure ZnO device. from ZnO single nanowire or nanobelt are expected to exhibit high
Mitra et al. demonstrated high-performance flexible DUV on/off current ratios and fast response speed. However, the meas-
PDs based on ZnO QDs synthesized by femtosecond-laser urement of the very low photocurrent of ZnO single nanowire
ablation in liquid (FLAL) technique.[90] This method produces UV PDs requires high-precision measurement systems, which
highly stable and reproducible ZnO QDs and allows the opera- hinders their further application. Ren et al. prepared ZnO nano-
tion of as-fabricated PDs at ambient conditions. Carbon-doped wires with unique nanostructure characterized by long chains of
ZnO QD-based PD can detect efficiently in the DUV spectral closely attached ZnO nanocrystals with ZnO/ZnO nanocrystal

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Figure 5. a) Current–voltage characteristics of the TiO2 nanofiber PD in dark and under 455 nm light illumination. Upper inset: SEM image of a TiO2
fiber PD. Lower inset: Photocurrent as a function of the light power. b) I–V curves of a Bi2OxSe device under different incident light powers. c) I–V curves
of a Bi2O2Se device under different incident light powers. Inset of (b) and (c): Optical images of the devices, the scale bar is 10 µm. a) Reproduced with
permission.[93] Copyright 2016, The Royal Society of Chemistry. b,c) Reproduced with permission.[99] Copyright 2018, Wiley-VCH.

junctions.[94] The unique ZnO nanowire-based UV PD exhibits 5 V. As a result, this WO3 NB PD exhibits a high UV sensitivity
much higher photoresponse currents (at the mA level) and on/ with an on–off ratio of up to 1000, a spectral responsivity of
off current ratios (≈1000) than those of the ZnO nanocrystal- 2.6 × 105 A W−1 and an ultrahigh EQE of up to 8.1 × 107%.
based UV PD. Under the UV irradiance of 120 mW cm−2
and a low bias of 0.5 V, the peak photocurrent and on/off current
ratio of the ZnO nanowire PD are 56 and 36 times higher than 4.1.3. 2D Structure
those of the ZnO nanocrystal UV PD, respectively.
Wu et al. grew VO2 microwires on a SiO2/p-Si(100) substrate 2D materials possess a layered structure weakly bonded by
and bonded an individual VO2 microwire onto the ends using van der Waals forces in atomic or molecular thickness and
silver paste to fabricate a PD.[95] This VO2 PD exhibits a linear I–V infinite planar dimensions, which are easy to prepare and
curve with a low dark current, while a nonlinear curve is observed transfer. Varying from zero-gap and semimetallic graphene
by varying the light intensities. The PD achieves an extremely to broad bandgap semiconductors and large bandgap insula-
high responsivity of 7069 A W−1, an EQE of 2.4 × 1010% and a tors, 2D materials offer a broad variety of building blocks with
detectivity of 1.5 × 1014 Jones at a bias of 4 V under UV illumina- remarkable electronic, photonic and mechanical properties and
tion (1 µW cm−2). The highly efficient hole-trapping effect resulted become the research focus in the next few decades.
from the unequal barrier heights at the two contacts, contribute to 2D layered semiconductors interact with incident light
the high responsivity and EQE in this VO2 PD. The responsivity strongly, presenting satisfactory photon absorption and electron–
of VO2 PD is 6 and 4 orders higher than that of the PDs based hole generation. The electronic and optoelectronic properties of
on graphene (or MoS2) and GaS, respectively, depicting the great 2D layered materials can be easily tuned via adjusting the dimen-
potential of PDs based on metal oxide nanostructures. sion, conducting intercalation, forming heterostructures, etc.,
Because of their complex functionalities and tunable prop- which could lead to improved performance of related devices.[98]
erties achieved via adjusting the components ratio, 1D ternary The atomic-thick 2D layered semiconductors with high trans-
oxides show potential applications in photocatalysts, elec- parency and good mechanical flexibility provide the possibilities
troluminescence devices, UV PDs, and so forth. Zhou et al. for flexible, wearable, or portable electronics. As an emerging
developed high-performance solar-blind DUV PDs based on 2D layered material with high carrier mobility, near-ideal sub-
individual single-crystalline Zn2GeO4 nanowires.[96] The opti- threshold swing and high air stability, Bi2O2Se has shown great
mized device demonstrates outstanding solar-blind photo­ potential for infrared detection. Li et al. prepared high-quality
detecting performances with a responsivity of 5.11 × 103 A W−1, ultrathin Bi2O2Se sheets and coexisted Bi2OxSe nanosheets via a
an EQE of 2.45 × 106%, a detectivity of ≈2.91 × 1011 Jones, and low-pressure chemical vapor deposition method, and character-
short rise/decay times of ≈10/13 ms, which shows great advan- ized their near-IR photodetection performance.[99] Figure 5b pre-
tages over other reported Zn2GeO4-based devices. sents the I–V curves of the PD based on triangle shaped Bi2OxSe
With respect to the single-crystalline nature of 1D nanostruc- nanosheet with different light powers. Compared with the tri-
tures adopted in reported PDs, it allows only the band-edge angle shaped Bi2OxSe nanosheet, the PD based on high-quality
modulation along the radial direction. However, the energy ultrathin Bi2O2Se sheets exhibits more excellent IR detection
bands are still flat along the axial direction, which inevitably performance, as shown in Figure 5c. The response time, respon-
leads to a large dark current due to the intrinsic carrier con- sivity and detectivity of the Bi2O2Se nanosheets near-IR PD can
centration. He et al. achieved the controlled growth of poly­ reach to 2.8 ms, 6.5 A W−1 and 8.3 × 1011 Jones, respectively,
crystalline WO3 nanobelts via varying the applied voltages showing potentials for ultrafast and flexible PDs.
in the electrospinning process.[97] As compared to the single- 2D nonlayered materials with both the novel properties
crystalline counterparts, the polycrystalline NBs present much of their bulks and the 2D characteristics can be necessary
more crystalline grains and boundaries in the WO3 NB PD, complement to 2D layered materials. For instance, the surfaces
leading to an effectively suppressed dark currents of 12 pA at of 2D nonlayered materials are filled with the surface dangling

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bonds, enabling their surfaces with high chemical activity and by using the glancing angle deposition (GLAD) technique.[106]
enhancing their capability of catalysis, sensing and carriers The 1D In2−xO3−y based PD exhibits a maximum responsivity of
transfer. 2D nonlayered materials have been developed for opto- ≈15 A W−1 and an internal gain of ≈47 at ≈380 nm, which cor-
electronic devices, including PDs and solar cells.[100] Sun et al. responds to the near band gap transition of the In2O3 columnar
achieved the molecular self-assembly synthesis of ultrathin array. Compared to the In2O3 NP and In2O3 nanorod based PDs,
2D nanosheets of transition metal oxides (TiO2, ZnO, Co3O4, the vertical transportation of the photoinduced carriers in the
and WO3) by the rational employment of lamellar reverse nanostructure arrays through the short distance towards elec-
micelles.[101] The synthesized ultrathin transition metal oxide trodes facilitates the shortening of rise/decay times to 1.9/2.3 s.
nanosheets possess confined thickness, high specific surface
area and chemically reactive facets. They were deposited on a
single-layer graphene back electrode to build transparent and 4.1.5. Composite Films
flexible UV PDs. These PDs exhibit ohmic behaviors, large
photocurrent densities up to the order of mA cm−2 and highly The weak photon absorption and high recombination rate of
stable and reproducible time response. Hai et al. achieved a electron–hole pairs in individual metal oxide nanostructures
WO3 monolayer with an uniformed thickness of ≈0.74 nm over limit their applications in photodetection. Composite films con-
the large-area Si wafer by atomic layer deposition (ALD).[102] structed by mix-dimensional nanostructures can take advantages
Under 785 nm light illumination with a power intensity of of the specific properties of different components, so as to achieve
2.0 × 103 mW cm−2, the as-fabricated monolayer WO3 PD the synergic improvements of photoelectric properties.[107]
exhibits a high responsivity of 71.6 A W−1, a high EQE of Carbon materials such as graphene, graphdiyne, activated
1.13 × 104, short response time of ≈2.5–2.7 ms, and superior carbon and carbon nanotubes, are suitable candidates for com-
long-term stability. Their group also grew monolayer WO3 on posite film PDs owing to their superior optical and electric
large-area SiO2/Si wafer by ALD.[103] The deposited WO3 mon- properties.[108,109] Chen et al. proposed the UV-assisted photo-
olayer exhibits a wider bandgap of 3.53 eV. Under 320 nm chemical reduction of GO in zinc oxide nanowires (ZNWs) sus-
UV-A light illumination with a power of 0.25 mW, the mon- pension to achieve the formation of graphene sheets attached
olayer WO3-based phototransistor-type PDs have demonstrated in ZNWs network and the enhancement of UV absorption.[110]
a photoresponsivity up to ≈0.329 A W−1 at Vds = −5 V, extremely Compared with the PDs based on pure ZNWs, the optimized
fast response time of less than 40 us and long-term stability. PD based on RGO/ZNWs composite exhibits an enhanced
Considered the inevitable disadvantages of commonly used photoresponse with a photocurrent density of 5.87 mA cm−2,
wet-chemical methods, it is very important to develop novel and an on/off current ratio of 3.01 × 104, and a responsivity of
facile methods for the fabrication of high quality 2D nonlay- 1.83 A W−1 under a UV irradiation (3.26 mW·cm−2) at 1.0 V. It
ered materials. Feng et al. fabricated 2D polycrystalline Ga2O3 is deduced that the extremely large interface area of graphene/
nanosheets with a thickness of less than 10 nm from the direct ZNWs suppresses the carrier recombination and improves the
oxidation of GaSe nanosheets.[104] A solar-blind phototransistor- carrier transport, thus leading to the photoresponse enhance-
type PD based on 2D Ga2O3 is assembled. Under 254 nm UV light ment. Saravanan et al. prepared granular activated carbon
(0.5 mW cm−2), the responsivity, detectivity and external quantum (GAC) materials via the simple gas activation of silkworm
efficiency of the PD at Vds = 10 V are 3.3 A W−1, 4.0 1012 Jones and cocoons and coated them on the ZnO nanorods (ZNRs) to
1600%, respectively. The PD also exhibits fast rise/decay times of form a core−shell structure.[111] Compared to the low photo-
30/60 ms and good stability. As the development of micro/nanofab- current (≈1 µA) of the PD based on ZnO NPs in Figure 6a,b,
rication technologies, more metal oxide semiconductor–based 2D the as-assembled GAC/ZNR core–shell UV PD exhibits a supe-
nanostructures would be produced and their fascinating properties rior photocurrent of 16 mA in Figure 6c,d. As the well-aligned
could facilitate the performance enhancement of related PDs. GAC/ZNR core−shell structure exhibits strong light absorption
and increased generation of charge carriers, the GAC/ZNR
PD exhibits a high on–off ratio of 1585, compared to the low
4.1.4. Arrays on–off ratio of 40 from the as-grown ZNR PD. Apart from the
fast adsorption ability of GAC, the finest distribution of GAC
The application of periodic micro/nanoarrays assembled from on ZNRs results in rapid electron transportation between the
1D and 2D nanostructures, have been extended from highly conduction bands of GAC and ZNRs, leading to shortened rise/
integrated devices such as FETs and PDs, to flexible PDs, active decay times. Furthermore, this core−shell structure-based UV
matrix displays, and PD arrays, which mostly present excel- PD also exhibits good repeatability and long-term stability.
lent mechanical, electronic, and optoelectronic properties.[98] Plasmonic metal NPs and dyes are also utilized to modify the
Wu et al. adopted a facile wet-chemical etching approach for light absorption of composite film, so as to achieved enhanced
controlled patterning of CVD-grown 2D Bi2O2Se film and performance. Wang et al. demonstrated Ag NP-decorated ZnO
obtained centimeter-scale well-ordered 2D Bi2O2Se arrays with PDs for UV light sensing.[112] Due to the localized Schottky junc-
tailorable configuration.[105] The optimized PD assembled tion between ZnO film and Ag NPs, the dark current density
from 2D Bi2O2Se arrays displays a negligible dark current of of ZnO UV PDs decreases obviously from 60 to 38 mA cm−2.
≈3 nA at Vds = 0.1 V, a high photoresponsivity of ≈2000 A W−1 In particular, the device exhibits obviously increased peak
at 532 nm with the incident power of ≈0.1 nW and excellent responsivity at around 380 nm, which can be attributed to the
air stability. Goswami et al. synthesized 1D perpendicular strong incident light scattering derived from the narrow-band
In2−xO3−y nanostructure arrays with highly porous structure quadrupole plasmon resonance of Ag NPs in the UV range.

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preparation process and post-treatments. The

excess defects and grain boundaries of the
building blocks in the semiconductor crystals
would increase the trapping and recombina-
tion possibilities of photogenerated charge
carries on their way towards electrodes, thus
leading to weakened photoresponse. To mini-
mize this deficiency, it is necessary to adopt
exquisite and precise preparation processes
as well as appropriate post-treatments to
fabricate semiconductor crystals with high
crystallinity and moderate defects, so as to
increase the efficiency of charge-carrier trans-
port and improve the photoelectric perfor-
mance of related PDs.

4.2.2. Applied Bias Voltage

The applied bias can accelerate the diffusion

of charge carriers toward electrodes along
the direction of electric field. Forced by the
applied bias, the depletion of the charge car-
Figure 6. a) Schematic illustration of the fabricated PDs based on the ZnO film. b) On–off
switching properties of the corresponding ZnO PD. c) Schematic illustration of the ZNR@ riers out of the junctions is reduced, which
GAC core−shell structure. d) On–off switching properties of the corresponding ZNR@GAC leads to increased photocurrent and short-
PD. a,b) Reproduced with permission.[89] Copyright 2016, Wiley-VCH. c,d) Reproduced with ened response times. However, the further
permission.[111] Copyright 2017, American Chemical Society. increase of applied voltage will increase the
short noise and lead to increased dark current
Besides, the shading effect and surface defect passivation of and power consumption.[114] Thus, it is necessary to choose an
Ag NPs cause the dramatic decreases of responsivities at the appropriate operation voltage to make a balance between high
other wavelengths. As a result, the response peak at around performance and facile power supply in practical application.
380 nm becomes more significant and the response of device
presents excellent wavelength selectivity. Mottram et al. devel-
oped dye-sensitized thin-film phototransistors consisting of 4.2.3. Surface/Interface Carrier-Transport Modulation
ultrathin In2O3 layers (<10 nm) and self-assembled monolayers
of light absorbing organic dye D102.[113] In accompany with the As for the optoelectronic devices constructed from nanostruc-
extremely high internal signal gain resulted from the improved tures, the dramatically increased surface-to-volume ratios,
electronic coupling in this unique heterostructure, the opti- interfacial areas and surface–environment interactions have
mized transistor exhibits a preferential photo­response centered great influences on the device performance. The modula-
at ≈500 nm with a maximum photosensitivity of ≈106 and a tion of surface/interface charge-carrier generation, diffusion,
responsivity of up to 2 × 103 A W−1. Moreover, the hybrid In2O3/ and recombination/transport processes should be taken into
D102 bilayer channel appears transparent with an average considerations in constructing high-performance PDs. For
optical transmission of >92% in the wavelength range of metal oxide nanomaterials, the presence of abundant deep-
400−700 nm, depicting its great potentials for transparent PDs. level states at the surfaces of metal oxides combining with a
gas desorption/reabsorption process could contribute to high
photosensitivities.[115] The surface effects resulted from engi-
4.2. Other Factors Influencing the Carrier Transport neering the size of nanomaterials and several surface treat-
ments, such as heat treatments and Au−NP decoration, have
Except for the heterojunctions, there are some other factors such demonstrated impacts on the surface band bending, which
as crystallinity of semiconductors, applied bias voltage and sur- dominates the photon–electron conversion behaviors. By mod-
face/interface problems, having influences on the behavior of car- ifying the specific thin depletion region near the surface, the
riers in the transport process. Corresponding measures have been optoelectronic properties of PDs based on metal oxides nano-
taken to deal with these factors. structures are tunable.[116,117] However, due to the slow photo-
carrier relaxation behaviors caused by the surface adsorption/
desorption processes, a long recovery time has been observed
4.2.1. Improved Crystallinity in PDs based on single metal oxide nanostructure. To achieve
both increased photosensitivities and shortened recovery time,
The photoelectric properties of semiconductors are strongly several strategies including the introduction of heterojunctions
affected by their crystallinities, which are dominated by the and the construction of core–shell and network geometries to

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achieve the modulation of interface carrier transport have been functions would form Schottky junctions with p-type semi-
proposed.[9,19,118] Chen et al. grew ZnO nanobelt networks conductors. Excluding the influences from the surface states
on the prefabricated Ti/Au electrodes by a vapor-liquid-solid of semiconductors, the adoption of two metal electrodes with
method and fabricated the ZnO NB-network PD.[119] Com- large difference in work functions causes asymmetric metal
pared with a long recovery time of 32.95 s in the single ZnO contacts and a built-in potential, endowing Schottky diodes
NB-based PD, a fast recovery time of 0.53 s is observed in the with rectifying and self-powering characteristics. Ouyang et al.
ZnO NB-network PDs. The significantly shortened recovery grew bismuth oxychloride (BiOCl) nanosheet arrays on a piece
time resulted from the dominated electron transport, which is of Cu foil (denoted as BiOCl–Cu) and fabricated the BiOCl–Cu
achieved by a number of NW–NW junction barriers formed in samples into BiOCl–Cu-1 and BiOCl–Cu-2 PDs by adopting dif-
the network. ferent electrode configurations.[114] Under 350 nm light illumi-
To go a step further, by taking advantages of photon-trapping, nation at 5 V, the BiOCl–Cu-1 PD with both Ag electrodes on
surface plasmonic resonance (SPR), piezophototronic effects, the BiOCl film yields a relatively high photocurrent of 353 pA,
and interface carrier-trapping/transport control, Guo et al. the rise/decay times are calculated to be 0.56/0.59 s. Moreover,
designed a photon-alternative UV PD based on self-bending- a higher photocurrent of 1040 pA is achieved by the BiOCl–
assembled ZnO nanowires.[120] The carriers could be efficiently Cu-2 PD with one Ag electrode on the BiOCl film and the Cu
controlled by the surface/interface states of these ZnO nano- foil substrate as the other electrode, while the response speed
wires. Through effective surface/interface carrier-transport mod- remains nearly the same. Due to the different work functions of
ulation, detectivities as high as 1.69 × 1016/1.71 × 1016 Jones at the Cu foil and the Ag electrodes, a self-powering characteristic
380 nm with 0.2 V bias are realized by alternating nanoparticle/ is also presented in this PD. At 0 V bias, the BiOCl–Cu-2 PD
nanowire active layers, respectively. Meanwhile, the optimized achieves a photocurrent of 11.81 pA at 350 nm with an on–off
UV PD shows short rise/decay times of 0.023/4.79 ms, which ratio of 125.3.
could satisfy the practical needs. The detailed explorations of The design of the Schottky barriers with asymmetric elec-
carrier generation, diffusion, and recombination/transport pro- trode shapes on the PDs can achieve photodetection with a low
cesses are beneficial to figure out the charge-carrier dynamics or even zero power supply. Chen et al. demonstrated a novel
contributing to the photoresponse behavior and to come up ZnO PD based on the asymmetric MSM structure consisting of
with corresponding measures to improve the photoelectric per- one Au interdigitated electrode with wide fingers and the other
formance of metal oxide semiconductor–based PDs. one with narrow fingers.[122] These ZnO PDs exhibit attractive
self-powered characteristics, the increase of asymmetric ratio
between the width of wide fingers and narrow fingers in the
5. Collection of the Charge Carriers interdigitated electrodes leads to the enhanced responsivity of
this ZnO self-powered UV PD, which reaches up to 20 mA W−1
5.1. Contact Type for an asymmetric ratio of 20:1. A physical model based on
band energy theory has been developed to illustrate the origin
Most of the key performance parameters of electronic and optoe- of the photoresponse at 0 V in this device, which demonstrates
lectronic devices, such as photocurrent, on/off ratio and response a new route to assembling self-powered PDs. By using a 2D
speed, are significantly affected by the electrical contacts con- physical model based on the drift-diffusion theory, Song et al.
necting the channel with external circuits.[121] The macroscopic investigated the influences of asymmetric semicircular and
contact resistance is determined by the Schottky barrier height asymmetric triangular Schottky barriers on the photoelectric
defined by the band alignment between the semiconductor chan- performance of MgZnO MSM PD[123] At 5 V, compared to the
nels and metal electrodes, the doping degree of the semicon- MgZnO MSM PD with symmetric rectangular Schottky barrier,
ductor, and the quality of interface. The device configuration of the dark currents of the MgZnO MSM PDs with asymmetric
PDs has great effects on the contact resistance, which is crucial semicircular and triangular Schottky barrier are reduced by a
for their performance parameters. With low contact resistances, factor of 15 for each electrode structure, while the photocur-
the PDs with Ohmic contact normally possess excellent proper- rents are enhanced by factors of 1.2 and 2, respectively. The
ties including large photoconductive gain and high responsivity. highest on/off ratio of 7294 is achieved in the MgZnO MSM
The ohmic contact can be realized through combining a contact PD with asymmetric triangular Schottky barrier at a bias of 5 V
metal with a matched work function with the band structure of under 260 nm light illumination with a power of 0.4 µW. By
the channel material. After the exclusion of the Fermi level–pin- incorporating different metals to provide a higher asymmetry,
ning effect which results in almost unchanged Schottky barrier the on/off ratio of these PDs can be further increased.
height, various strategies including changing the contact metal If the time for the charge carrier to travel between two elec-
(such as Au, Cr, Ti, Pd, Ni, and even graphene), heavily doping trodes is shorter than the life time of charge carriers, the charge
by ion implantation and edge contacts, have been proposed to carrier could transfer through the channel for several times
achieve ohmic contact and improved device performance. before their combination, leading to enhanced responsivity and
gain while prolonged response time.[124] Miao et al. fabricated
black phosphorus (BP) Schottky diodes with asymmetric metal
5.2. Electrode Configuration contacts between gold and aluminum electrodes.[125] The work
function difference between the two metal electrodes results in
Metals with large work functions would form Ohmic con- a built-in potential, endowing BP Schottky diodes with rectifying
tacts with p-type semiconductors, while metals with low work characteristics. With a relatively long channel length of ≈1 µm,

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the BP Schottky diode exhibits rectifying behavior with a rectifi- of SnS quantum dots and Zn2SnO4 nanowires as light sen-
cation ratio of 1.05 × 102 at a gate voltage of 0 V. Under 650 nm sors.[127] Compared with the pristine Zn2SnO4 nanowire PD,
light illumination with an intensity of 38 W cm−2, the respon- the hybrid PD exhibits high photoconductive gain of up to
sivity and EQE measured at Vds = −1 V and VGS = 10 V are cal- 1.6 × 106 and specific detectivity of up to 3.8 × 1016 Jones in
culated to be ≈3.5 mA W−1 and 0.65%, respectively. Besides, the the UV region. Meanwhile, the photoresponse range extends
BP Schottky diode exhibits fast response, the rise time and fall from the UV to the NIR region. This PD still displays a re-
time are both less than 2 ms. At an ultrashort channel length sponsivity up to 19 A W−1 at 950 nm, which corresponds to
of ≈30 nm, the device exhibits a current rectification ratio the bandgap of SnS (≈1.3 eV). Besides, taking advantages of
(Iforward/Ireverse) of up to 1.5 × 103 at the gate voltage of −20 V. some specific effect can also endow semiconductor systems
However, the electric field–induced barrier thinning causes with the ability of broadband photodetection. It is interest-
significantly increased tunneling current under reverse bias, ing to consider the coupling between new structural concepts
leading to nonrectifying output characteristics. In view of these and optoelectronic applications based on up (down) convert-
related references, it is necessary to adopt suitable channel ers,[128,129] which can achieve light harvesting in the long
length to balance the photoresponse and response speed. (short) spectral range and the extended photon up(down)-
conversion range using sunlight irradiation and optimized
device configuration for maximum energy conversion.
2) 2D van der Waals Heterostructures: The high mobility, 2D, and
6. Conclusion and Prospective
thickness-dependent bandgap and light absorption endow
Varied strategies that researchers have utilized to improve the 2D materials with favorable optical properties and electronic
photoelectric performance of metal oxide semiconductor–based performances, which have attracted tremendous interests
PDs have been reviewed and summarized, in accordance with in many fields including FETs, solar cells, PDs, and flexible
the different steps those photoinduced charge carriers have electronics.[130] 2D vdW heterostructures with smooth het-
involved in the photoelectric conversion process. The charge- erointerface, tunable bandgap, and ultrafast carrier transport
carrier engineering has proved its effectiveness on achieving are advantageous for applications in high-performance PDs.
enhanced photoresponse and improved response speed of these Their atomically thin thickness results in ultrafast charge
PDs. An ideal PD should meet different requirements in terms transfer confined in 2D, and the strong light–matter inter-
of excellent spectral selectivity, high responsivity, large detec- actions lead to enhanced light absorption, contributing to
tivity, fast speed, and excellent stability. Until now, there are the fast response speed, large responsivity, and high sensi-
substantial technological issues remaining in improving the tivity of PDs. By choosing appropriate materials and stacking
photoelectric properties of PDs based on metal oxide semicon- sequences with careful band alignment engineering, high-
ductors. Since most of the as-developed strategies only achieve performance optoelectronic devices based on 2D vdW hetero­
performance enhancement from one single aspect without sys- structures such as SnO/MoS2[131] and MoS2/VO2[132] have
tematic consideration, it is urgent to conduct the exploration been fabricated.[133] Chen et al. built hybrid n-type 2D-layered
of novel sensitive semiconductor nanostructures and the effi- MoSe2/p-type MoOx vdW heterojunction PDs on SiO2/Si
cient engineering of device architecture simultaneously. More substrates.[134] These vertical MoSe2–MoOx p–n heterojunc-
efforts should be devoted to deepening the understanding of tion PDs display obvious rectifying characteristics. The opti-
how the behaviors of charge carrier influence the photoelectric mized device exhibits a responsivity of 3.4 A W−1, a detectivity
performance of the related PDs and exploring more systematic of 8.5 × 107 Jones, and an EQE of 1665.6% at Vds of 5 V under
strategies to improve the efficiency of photoelectric conversion 254 nm light illumination (0.29 mW cm−2). Besides, the flex-
process. ibility and transparence of the vdW structure endow this PD
In recent years, numerous new trends and requirements, great potentials for wearable optoelectronics.
such as broadband photodetection, self-powering character- 3) Self-Powered Photodetectors: The self-powered PDs, which can
istic, adoption of 2D vdW heterostructures, and performance operate with low power consumption or without any external
enhancement achieved by specific effects in developing high- power supply, have attracted considerable attention for the
performance PDs based on metal oxide semiconductors, have next-generation optoelectronic devices.[135] By exploiting the
been revealed. photovoltaic effect or utilizing the built-in energy harvesting
unit to convert the incident light into an electrical signal, self-
1) Broadband Photodetector: PDs with a broad spectral response powered PDs can achieve the independent, sustainable, and
from the ultraviolet, visible to the near infrared region have maintenance-free monitoring of ambient light, which are
attracted fast-growing interests in a variety of applications, in- promising for portable/wearable electronics and working in
cluding image sensing, chemical/biological sensing, optical harsh conditions. Self-powered PDs can be generally classi-
communication, daylong surveillance, etc. Unfortunately, the fied into two different types. One contains photoconductive
wide bandgap nature of most metal oxide semiconductors de- devices integrated with energy harvesting units such as na-
termines that they are only suitable for UV–vis PD because nogenerators, solar cells, and supercapacitors, which can col-
of the light absorption limited in the UV–vis region. Thus, lect energy from the external environment and drive the light
combining oxide semiconductors with narrow bandgap sem- sensor to achieve detection.[136] The other one is photovoltaic
iconductors such as metal sulfides to extend their absorp- PD based on the photovoltaic effect. According to the charge
tion range into NIR region is crucial for the construction of separation features of different interfaces, they can be divided
broadband PDs.[126] Li et al. developed hybrid nanostructures into three types: Schottky junction, p–n/n–n junction, and

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PEC cell.[137,138] Zhao et al. constructed a self-powered solar- superior deformability.[118] This device presents an on–off
blind PD based on a highly crystallized ZnO–Ga2O3 core– ratio of 13.4 and a detectivity value of 8.14 × 108
shell heterostructure microwire.[139] At zero bias, the PD Jones under UV illumination (3.8 mW cm−2) at 10 V bias.
displays an ultrahigh responsivity of 9.7 mA W−1 at 251 nm It also demonstrates reliable detection of UV light at a wide
and a fast response speed (rise/decay times of <100/900 µs), range of intensities. With a folded Miura structure, the paper
which make it highly suitable for self-powered photodetec- PD array can be oriented in four different directions via tes-
tion in practice. The deeper insight into the relationship of sellated parallelograms to endow the device with excellent
photoresponse properties with material structure and device omnidirectional light-harvesting capabilities. Moreover,
configuration is required to construct high-performance self- benefi­ting from this paper folding technique, the device can
powered PD.[44] Moreover, the piezophototronic effect,[140] be repeatedly stretched (up to 1000% strain), bent (bending
thermophototronic effect,[141] photogating effect,[142] as well angle ±30°), and twisted (up to 360°) without noticeable
as the coupling between ferromagnetic electrodes and nano­ performance degradation. This highly deformable electron-
structured materials[143] are novel routes to improving the ics design featuring the Miura origami structure provides
self-powering performance of PDs. guidances for the future developments of flexible and
4) New Concept Photodetectors: Remarkable features such as deformable PDs. Specially, our group developed a fiber-shaped
transparence,[144] flexibility,[145] stretchability,[146] printabil- p-CuZnS/n-TiO2 UV PD, as presented in Figure 7a. Benefi­
ity,[147] and multifunctionality[148] are in great need for the ting from the unique nanotube array structure and p–n junc-
construction of novel wearable,[149] visualized,[150] wire- tion, this PD exhibits an outstanding responsivity of 640
less, and real-time[151] PDs. These emerging new-concept A W−1, a high EQE of 2.3 × 105%, and a large photocurrent
PDs would benefit daily life and industrial production value of ≈4 mA at 3 V under 350 nm UV illumination
greatly.[152] By using printable ZnO nanowires and carbon (1.26 mW cm−2), as shown in Figure 7b,c.[153] Meanwhile,
electrodes with origami-based techniques, Lin et al. fabri- it shows a self-powered property with a high responsivity
cated a simple and low-cost paper-based PD array featuring of 2.5 mA W−1 and a short response time of less than

Figure 7. a) Device structure of the fiber-shaped p-CuZnS/n-TiO2 NTAs PD. b) Responsivity and EQE of the fiber-shaped UV PD as a function of wave-
length at 3 V. c) The on–off switching tests of the fiber-shaped PD at the straight state and bent state (≈50°). d) Schematic illustration of the wearable
PD as a real-time UV monitor. Reproduced with permission.[153] Copyright 2018, WILEY-VCH.

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0.2 s at 0 V under 300 nm UV illumination (0.48 mW cm−2). [7] X. S. Fang, L. F. Hu, K. F. Huo, B. Gao, L. J. Zhao, M. Y. Liao,
The ultrahigh photocurrent enables it to be easily integrated P. K. Chu, Y. Bando, D. Golberg, Adv. Funct. Mater. 2011, 21, 3907.
with commercial electronics to function as a real-time monitor [8] M. Li, J. Zhang, H. Gao, F. Li, S. E. Lindquist, N. Wu, R. Wang,
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