Article

www.acsnano.org

All-Printable ZnO Quantum Dots/Graphene

van der Waals Heterostructures for
Ultrasensitive Detection of Ultraviolet Light
Maogang Gong,*,† Qingfeng Liu,*,† Brent Cook,† Bhupal Kattel,† Ti Wang,† Wai-Lun Chan,†
Dan Ewing,‡ Matthew Casper,‡ Alex Stramel,‡ and Judy Z. Wu*,†
†
Department of Physics and Astronomy, University of Kansas, Lawrence, Kansas 66045, United States
‡
Department of Energy’s National Security Campus, Kansas City, Missouri 64147, United States
*
S Supporting Information

ABSTRACT: In ZnO quantum dot/graphene heterojunc-

tion photodetectors, fabricated by printing quantum dots
(QDs) directly on the graphene field-effect transistor
(GFET) channel, the combination of the strong quantum
confinement in ZnO QDs and the high charge mobility in
graphene allows extraordinary quantum efficiency (or
photoconductive gain) in visible-blind ultraviolet (UV)
detection. Key to the high performance is a clean van der
Waals interface to facilitate an efficient charge transfer from
ZnO QDs to graphene upon UV illumination. Here, we
report a robust ZnO QD surface activation process and demonstrate that a transition from zero to extraordinarily high
photoresponsivity of 9.9 × 108 A/W and a photoconductive gain of 3.6 × 109 can be obtained in ZnO QDs/GFET
heterojunction photodetectors, as the ZnO QDs surface is systematically engineered using this process. The high figure-of-
merit UV detectivity D* in exceeding 1 × 1014 Jones represents more than 1 order of magnitude improvement over the best
reported previously on ZnO nanostructure-based UV detectors. This result not only sheds light on the critical role of the
van der Waals interface in affecting the optoelectronic process in ZnO QDs/GFET heterojunction photodetectors but also
demonstrates the viability of printing quantum devices of high performance and low cost.
KEYWORDS: printable ultraviolet photodetectors, interface, van der Waals heterostructures, nanohybrids, zinc oxide quantum dots,
graphene

O ptoelectronic nanohybrids involving graphene and

quantum nanostructures can provide a unique scheme
for high-efficiency exciton dissociation through atom-
istic design and engineering of heterojunctions between the
nanostructures and graphene that are highly efficient in charge
transport.1 These nanohybrids have distinctive advantages over
conventional materials because of: (1) strong quantum effect in
quantum nanostructures such as semiconductor quantum dots
(QDs), which yields superior electronic and optoelectronic
properties including higher light absorption, charge mobility,
and spectra tunability; (2) exciton dissociation and charge
transfer at interface heterojunctions with appropriate interfacial
electronic structures for efficient photocarrier generation; and
(3) high photoconductive gain proportional to the ratio
between the carrier lifetime enhanced by the quantum
confinement in the nanostructures and the extremely short
charge transit time due to the high mobility of graphene.
The ZnO QDs/graphene heterojunction nanohybrids
present an ideal combination of ultraviolet sensitizer and
broad-band transparent conductor for visible-blind ultraviolet
(UV) detection with additional advantages of low cost,
flexibility, and printability. ZnO is a direct bandgap semi-
conductor with bandgap of 3.4 eV. In the form of QDs of high
crystallinity and small dimension typically <10 nm, ZnO QDs
have further enhanced UV absorption and carrier lifetime. In
particular, ZnO QDs are stable in air and can potentially form a
van der Waal interface with graphene without ligands, which is
critical to efficient charge transfer across their interface upon
photocarrier generation. When combined with graphene field-
effect transistors (GFETs), the gate field provides further
tuning to transport properties of the photoelectrons transferred
from the ZnO QDs to the GFET channel, allowing optimal
photoconductive gain as well as high figure-of-merit detectivity
to be achieved in ZnO QDs/GFET heterojunction devices.2
So far, a few reports have demonstrated graphene coupled
with ZnO nanostructures, including QDs, nanoparticles,
Received: February 6, 2017
Accepted: March 22, 2017
Published: March 22, 2017

© 2017 American Chemical Society 4114 DOI: 10.1021/acsnano.7b00805

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Figure 1. Schematic of printable process and materials characterization: (a) printer and a GFET array on silicon dioxide/silicon substrate. (b)
A magnified view of a GFET device with source and drain Au electrodes (top) and an optical micrograph of the fabricated GFET device
(bottom). For this specific GFET, the channel length and width are 7 and 13.2 μm, respectively. (c) Printed ZnO QDs on a GFET channel
(top) and the AFM image of the ZnO QDs on the GFET channel (bottom, the optical micrograph of the ZnO QDs/GFET device are shown
in Figure S1b). (d) Three-dimensional view of the printed ZnO QD/GFET nanohybrid photodetector. (e) Energy level diagram of ZnO QDs/
GFET heterojunctions and charge-transfer process under UV illumination. (f, g) Schematics of ZnO QDs/GFET before (f) and after (g) the
charge-transfer blocking Zn(Ac) shell on a ZnO QD is removed. The effect of Zn(Ac) shell on energy band diagram and charge transfer to
graphene is also illustrated.

nanowires, nanorods, and thin films, can be used for high
sensitivity UV detection. Guo et al. reported photoconductors
based on ZnO QDs/graphene structures using mechanically
exfoliated single-layer graphene with responsivity up to 1 × 104
A/W at the UV wavelength of 325 nm.3 A ZnO nanorods/
graphene-based UV photodetectors have shown improved
responsivity of 3 × 105 A/W, which is 1 and 2 orders of
magnitude higher than ZnO nanowire/graphene4 and ZnO
nanoparticles/graphene photodetectors.5 While these results
are promising, the room for improvement is large. In particular,
an ultrahigh photoconductive gain of 1 × 108 charge carriers
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per photon and consequently a high responsivity up to 1 × 107
A/W and detectivity of 7 × 1013 cmHz1/2/W in near-infrared
spectrum were obtained in PbS QDs/GFET heterojunction
devices.1 The key to the high performance is the PbS QDs/
GFET interface through a successful ligand exchange to enable
high-efficiency exciton dissociation and charge transfer across
the PbS QDs/GFET heterojunction interface.1,6,7 This result
illustrates the importance of the interface engineering for higher
performance nanohybrid optoelectronic devices.8−10
Solution processed ZnO QDs are low cost and printable and
therefore are excellent visible-blind UV sensitizers for ZnO
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QDs/GFET heterojunction optoelectronics. The van der Waals
interface between ZnO/graphene critically affects the charge
transfer across the interface and therefore the performance of
the device. This requires an atomic-scale control of the ZnO
QD surface that is typically covered with a layer of reaction
residues after solution synthesis. In this work, we show such a
surface layer could block the charge transfer and diminish the
photoresponse of the ZnO QDs/GFET photodetectors. Using
a robust surface activation process, this surface layer can be
systematically removed. The resulted ZnO QDs/GFET UV
photodetectors with a clean van der Waals interface exhibit
ultrahigh photoresponsivity up to 9.9 × 108 A/W and high
detectivity of 7.5 × 1014 Jones. This result demonstrates the
importance of controlling the heterojunction interface. In
addition, the printing method we have employed for fabrication
of the ZnO QDs/GFET UV detectors is robust and promising
for practical applications of flexible optoelectronics.
RESULTS AND DISCUSSION
The schematic of the nanohybrid photodetector printing
process is illustrated in Figure 1a. The printing of ZnO QDs
in ethanol on GFETs was carried out using a SonoPlot
microplotter through sonication of glass capillary tips. Figure 1b
illustrates a magnified image of a GFET device schematic (top)
in a 36 GFET array shown in Figure 1a and the optical image of
the fabricated GFET device (bottom) on SiO2 (90 nm)/Si
substrates. The Raman spectrum taken on the GFET channel
(black) is depicted in Figure S1 (Supporting Information). The
absence of the D band peak (∼1350 cm−1) confirms the high
quality of the graphene that remains intact after the device
fabrication process.11,12 In addition, the 2D band peak (2686
cm−1) intensity is about twice that of the G band peak’s (1583
cm−1), which confirms the monolayer of graphene as
expected.13 Figure 1c depicts the schematic of the printed
ZnO QDs/GFET nanohybrids device (top) and the atomic
force microscopy (AFM) image taken after the ZnO QDs
printing, indicating a dense ZnO QDs film covering over the
underneath graphene. The thickness of this ZnO QD layer is
around 80 nm. The Raman spectrum of the graphene after the
ZnO QD decoration (red) is also included in Figure S1.
Overall, the Raman spectra before and after ZnO QD
decoration are comparable. Especially, since the D band
remains negligible, the damage of graphene caused by the
ZnO QDs deposition is negligible.
Figure 1d shows the layout of source, drain, and gate
electrodes of the ZnO QDs/GFET photodetectors. The gate
voltage provides tunability of the GFET charge doping state (or
Fermi energy) and therefore the optoelectronic properties of
the ZnO QDs/GFET UV detectors. Since no ligands were
employed, the coupling between ZnO QDs and graphene is
through a van der Waals interface, which is advantageous in
facilitating charge transfer across the interface as we recently
demonstrated in GeSe nanosheet/GFET heterojunction photo-
detectors.10 Figure 1e shows the schematic energy diagram and
the charge transfer mechanism of ZnO QDs/GFET photo-
detector under UV illumination. Upon absorption of the light
over the band gap of 3.59 eV (345 nm), excitons, or electron−
hole pairs, are generated in photoactive ZnO QDs. It should be
mentioned that this band gap is slight larger than the reported
value of ∼3.4 eV for bulk ZnO due to the strong quantum
confinement in ZnO QDs with much reduced dimension of
∼5.6 nm shown in Figure S2. Because the interfacial electric
field created by the Fermi level alignment, the photoexcited
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electrons in the conduction band of ZnO QDs are expected to
transfer to graphene, resulting variation of the GFET channel
conductance as the photoresponse. Considering the strong
quantum confinement provided by highly crystalline ZnO QDs
for prolonged carrier lifetime, in combination with the high
charge mobility of graphene that leads to extremely short
electron transit time, high photoconductive gain, which is
proportional to the ratio of these two times as to be discussed
later, is anticipated for ZnO QDs/GFET nanohybrid photo-
detectors.
A critical process in these ZnO QDs/GFET nanohybrid
photodetectors is the charge transfer from ZnO QDs to
graphene through a van der Waals interface. However, realizing
such an interface remains a grand challenge in achieving high-
performance devices, since an ultrathin charge-transfer blocking
layer can readily form either from contaminated surfaces of the
QDs and graphene, respectively, or during the fabrication of the
heterostructures between them. In the ZnO QD case, an
unreacted zinc acetate dihydrate (Zn(Ac)) shell typically forms
on the surface of the ZnO QDs as an insulating layer that
blocks the electron transfer, as illustrated schematically in
Figure 1f. Considering completely ionized shallow donors of
density No for the insulating layers in semiconducting ZnO, the
maximum band bending U (Vbias = 0) at the interface can be
calculated from Poisson’s equation:14,15
U = Q i 2/8eεoεNo (1)
Where Qi is the voltage-dependent interface charge, e is the
electron elementary charge, εo is permittivity of a vacuum, and
ε is the static dielectric constant. Thus, the width of the
insulating region is
L = Q i /2No ≈ (εU /No)1/2 (2)
Based on these two equations, the corresponding schematic
potential energy band diagrams in the radial direction of single
ZnO QDs are shown in Figure 1f,g. It can be seen that the
conduction channels in ZnO and graphene are separated by the
insulating layer of Zn(Ac), although the distance of conduction
channel of QDs increased under UV light irradiation due to the
excited electrons and releasing of free electrons from oxygen
ions initially absorbed on the ZnO QDs surface (Figure 1f).
The tunnel barrier due to the insulating Zn(Ac) charge
blocking layer should be distinguished from a well-known
interface barrier associated with the electron depletion by the
adsorbed oxygen on the surface of ZnO QDs. The former
remains prominent (Figure 1f), while the latter is dramatically
(Figure 1g) reduced under UV illumination. The electron
depletion effect is caused by oxygen molecules adsorbing onto
the ZnO QDs surfaces and immobilizing the free electrons
present in n-type ZnO QDs semiconductors [O2 (g) + e− →
O2− (ad)], forming a low conductivity depletion layer on the
surface of the ZnO QDs. Under UV illumination, electron−
hole pairs are generated via interband excitation [hυ → e− + h+]
as well as oxygen desorbing from the ZnO surface upon holes
migrating to the surface along the potential slope produced by
band bending [h+ + O2− (ad) → O2 (g)], providing favorable
photocarrier generation of quantum efficiency much beyond
that allowed in conventional semiconductors. Nevertheless,
such a benefit would not be realized in the presence of a charge
blocking interface in ZnO QD/GFET devices. It is particularly
important to mention that such a surface layer is typically thin
and beyond the detection limit of TEM.
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Figure 2. (a−c) XPS spectra of Zn 2p, C 1s, and O 1s signatures on ZnO QDs before and after the charge-transfer blocking Zn(Ac) shell was
removed. (d) Time domain UV (340 nm, 15 μW/cm2, zero gate voltage) photoresponse of the ZnO QD/GFET devices with the three types of
ZnO QDs on GFETs and (e) a magnified view of the dynamic photoresponse of the same two devices in (d) with the Zn(Ac) shell on ZnO
QDs with enhanced photoresponse as the Zn(Ac) shell was systematically removed. The GFET channels in these three samples are the same
(7 μm (length) × 13.2 μm (width)).

Figure 3. (a) Source−drain current of GFET measured under a dark environment in air and in vacuum before and after the ZnO QDs were
added on the GFET channel (14 μm (length) × 13.2 μm (width). (b) Comparison of channel conductance of ZnO QDs/GFET (in air and
vacuum) measured under dark and illumination (340 nm, power density is 15 μW/cm2). (c) UV photoresponsivity versus back gate voltages
calculated from (b) in air (black) and in vacuum (vacuum). Vsd = 10 V for all measurements in this figure.

To shed light on the surface of the ZnO QDs, XPS was
employed to analyze the structural information and surface
composition of the ZnO QDs synthesized by decomposing
Zn(Ac) on the ZnO QD surface. Three samples are included in
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the XPS study: one as-synthesized with surface covered with
the Zn(Ac) (blue), another with Zn (Ac) partially removed
(red), and the third with Zn (Ac) completely removed (black)
(details in Supporting Information). The comparison of the
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high-resolution XPS spectra of Zn 2p, C 1s, and O 1s peaks is
depicted in Figure 2a−c for these three samples. In Figure 2a,
the symmetrical Zn 2p peak is centered at 1021.9 eV for all
three samples of ZnO/Zn(AC), ZnO/Zn(Ac) partial, and
ZnO, corresponding to Zn 2p3/2 binding energy from ZnO.
The O 1s core level peak with a shoulder shape demonstrates
the oxygen species consisting of lattice oxygen and organic
molecules. The three fitted O 1s peaks are located at ∼530.7, ∼
531.8, and ∼532.4 eV (fitted by Gaussians simulation),
respectively. The areas underneath these peaks correspond to,
respectively, the O2− ions within the Zn−O bonding of the
hexagonal wurtzite ZnO QDs, the surface OH species, and O
atoms residue in oxygen-deficient sublattice and the loosely
bound oxygen species like H2O, O2, and oxygenated carbon
impurities on the ZnO QDs surface. Figure 2c shows the
distribution of carbon element, in which the binding energies of
C 1s at 282.6−286.6 eV and 287.2−290.3 eV are the
chemisorbed and unreacted carbon residues in the form of
C−C/C−H, C−O, and CO, respectively. In particular, these
carbon-related residues create a barrier layer to block the charge
transfer from ZnO QDs to graphene.16,17 As the Zn(Ac) was
systematically reduced and removed, the intensity of the carbon
residues peak at 287.2−290.3 eV reduced consistently, as
indicated in Figure 2c. These results demonstrate that the
carbon-based residues went through hydrolysis and were
removed progressively via aging, which is consistent with the
dramatic increase of the photoresponse from zero to
extraordinarily high on the ZnO QDs/GFET heterojunction
photodetectors in response to a 340 nm wavelength UV light
source as shown in Figure 2d. Specifically, it was found that the
photocurrent Iphoto = (Ilight − Idark) can be readily switched
between “on” and “off” states synchronized with the modulated
UV light source. The Iphoto values are 2.1 mA for bare ZnO
QDs, 4.1 × 10−2 mA for ZnO QDs/Zn(Ac) partial cover, and
0.0 mA (beyond the instrument limit) for ZnO QDs/Zn(Ac)
shell with full cover, respectively. The magnified plots of the
dynamic photoresponse for the last two samples are shown in
Figure 2e. Based on the Iphoto values depicted in Figure 2d,e, the
photoresponsivity can be estimated to be 1.5 × 108, 2.9 × 106,
and 0.0 A/W for these three samples. Therefore, this result
reveals the critical importance of a clean van der Waals interface
to high-efficiency charge transfer from ZnO QD to graphene.
The results presented in the rest of this paper were taken on
ZnO QDs/GFET devices using ZnO QDs with Zn(Ac) shell
completely removed.
The source−drain current (Id) versus back gate voltage (Vbg)
characteristics were tested on a representative ZnO QDs/
GFET heterostructure device before and after ZnO QD
decoration, and the result is shown in Figure 3a. The
source−drain voltage Vsd was kept at 10 mV. The GFET is
p-doped with Dirac points at about 25 V in vacuum and beyond
40 V (instrument limitation) in air. This p-type doping was
typical on GFETs on SiO2 gate in this work and may be
attributed to polar molecules adsorbed on the GFET channel
during the GFET fabrication. The observed shift of the Dirac
point (VDirac) toward a smaller value in vacuum indicates some
of these polar molecules may be removed. After the ZnO QDs
decoration, the VDirac was left shifted to about −15 V due to the
slightly higher work function of ZnO as compared to
graphene’s, which is consistent with previous reports.12 Since
the GFET minimum conductance (at VDirac) remained nearly
unchanged after the ZnO QDs application, the additional
charge scattering effect introduced by van der Waals interfacing
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ZnO QDs with graphene is negligibly small. This is important
to maintain the high charge mobility in graphene. As we will
show later, the high mobility of graphene is critical to high
photoconductive gain obtained in these ZnO QD/GFET
heterostructure UV detectors. In contrast to the large shift of
the VDirac on GFETs in air and in vacuum, the VDirac of the ZnO
QDs/GFETs remains almost the same whether the devices
were measured in air or in vacuum, suggesting the effect of
polar molecules such as water, air, and other volatile
contaminants is unlikely significant after the ZnO QD
decoration. This observation may be explained as the
desorption of those loosely attached polar molecules by alcohol
in the ZnO QD suspension during the decoration process,
which is certainly advantageous to form a cleaner interface
between ZnO QDs and GFETs for an efficient charge transfer
in the optoelectronic process.
Figure 3b compares the channel conductance of a ZnO
QDs/GFET in air and vacuum under dark and illumination
with a 340 nm UV light of power density 15 μW/cm2,
respectively. In both cases of in air and in vacuum, the UV
illumination shifted the Id−Vbg curves to left with a comparable
ΔVDirac of 6.8 V for the former and 7.6 V for the latter. At a
given Vbg, the change of the GFET channel conductivity can be
used to estimate the photoresponsivity (Rv) defined as the ratio
of photocurrent to optical power of the ZnO QDs/GFET
heterostructure photodetectors: Rv = Iphoto/Pλ, where Pλ is the
incident UV power density. Figure 3c depicts the calculated Rv
vs Vbg curves in air and in vacuum, and both exhibit complicated
behaviors. First of all, the minimum Rv locates near the Dirac
point VDirac (or the minimum photoresponsivity) in both cases.
With increasing Vbg with respect to the corresponding VDirac for
each case, a monotonic increase of the Rv can be observed
within certain range of the Vbg. On the right-hand side, a broad
peak is present at −3.2 V for the in air and −15.6 V for in
vacuum cases, respectively. The Rv peak values are 9.0 × 106 A/
W in the former and 1.9 × 107 A/W in the latter. At larger Vbg
values on the right side of the peak, the Rv decreases
monotonically saturated at a small value of 5.4 × 106 A/W.
Interestingly, the Rv takes a much steeper increase as the Vbg
(absolute value) is increased on the left side of the minimum
Rv. At Vbg = −40 V, the Rv is 6.5 × 107 A/W for in air and 2.2 ×
107 A/W for in vacuum cases, respectively. Both values are
considerably higher than the photoresponsivity peak values
appearing at lower Vbg. According to this trend, higher Rv is
anticipated if Vbg (absolute value) is further increased beyond
−40 V. The asymmetric Rv−Vbg curve with respect to the VDirac,
specifically the higher Rv on the left side of the Rv minimum
near the Dirac point, is primarily associated with the original
asymmetric Id−Vbg curves and their further deformation upon
UV illumination, as shown in Figure 3b. It should be noted that
the responsivity R is the difference between the Id−Vbg curves
measured in the dark (dashed) and under UV illumination
(solid) in Figure 3b. At the crossing point of the two curves,
which is at Vbg = −20.4 V (in air) and −31.6 V (under
vacuum), respectively, the photoresponsivity falls to zero. This
phenomenon has also been found in PbS QDs/GFET:1 The
photoinduced change in the electric field is equal to the back
gate voltage actuated change in the electric field, where there is
no electric field and field effect to modulate the graphene
conductivity, therefore the photocurrent effect is zero. In
addition, since the variation of the charge mobility in the finite
range of the back gate voltage used in this work is negligible,
the tenability of the gate field is primarily due to the shift of the
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Figure 4. (a) The voltage across the fixed resistor connected in-series with a ZnO QD/GFET photodetector. The total voltage drop across the
photodetector and the resistor is fixed at 100 mV. The photodetector is irradiated by a train of femtosecond laser pulses starting at t = 0 s. The
laser wavelength is 330 nm. Inset: a magnified view near t = 0 s. The red arrows indicate the instances when the photodetector is irradiated by
a femtosecond laser pulse. (b) A schematic showing the intensity of the laser pulse train. The repetition rate of the laser is 25 kHz. (c)
Dynamic photoresponse ID curves of ZnO QD/GFET nanohybrid photodetectors upon UV illumination (340 nm) on/off with channel length
and width of 7 μm × 13.2 μm and UV power density of 15 μW/cm2. (d) Spectral photoresponsivity of the ZnO QDs/GFET photodetectors.

Table 1. Performance Comparison of ZnO Nanostructure/Graphene UV Photodetectors

structurea rise time (s) fall time (s) bias voltage (V) photoresponsivity (A/W) gain ref
ZnO QDs/G 5.0 85.1 10.0 9.9 × 108 3.6 × 109 this work
ZnO QDs/G N/A N/A 5.6 1 × 107 1 × 108 12
ZnO QDs/G N/A N/A 1.0 × 10−3 1 × 104 1 × 104 3
ZnO NWs/G 0.3 2.5 8.5 13.8 N/A 29
ZnO NWs/G 9.5 38 5.0 ∼6.0 N/A 30
ZnO NRs/G 3.2 66.3 1.0 3.0 × 105 1 × 106 8
ZnO NRs/G 0.7 × 10−3 3.6 × 10−3 1.0 113.0 385 31
ZnO NRs/G >500.0 >1000.0 20.0 22.7 N/A 32
ZnO NPs/G 9.0 × 10−3 1.1 × 10−2 20.0 640.0 N/A 5
a
Note: QDs, quantum dots; NWs, nanowires; NRs, nanorods; NPs, nanoparticles; G, graphene.

Fermi energy at the applied gate voltage. This result, therefore,
provides a quantitative evaluation of the tunability of the
photoresponsivity of ZnO QDs/GFET hybrid photodetectors
using a gate voltage.
The shift of the Dirac point observed in Figure 3b upon light
illumination implies that electrons are transferred to graphene.
To further understand this charge-transfer process, a femto-
second pulse laser source is used to determine the temporal
response of the ZnO QDs/GFET. The sample is illuminated by
a train of laser pulses with a repetition rate of 25 kHz. The
wavelength is centered at 330 nm. The energy density per laser
pulse is ∼5 μJ/cm2. During the measurement, the sample is
connected in series with a fixed resistor. The total voltage
across the sample and the resistor is fixed at 0.1 V. The
photoinduced conductivity change in the sample will result in a
change in the voltage across the resistor, which is measured by a
200 MHz oscilloscope. The measured voltage is shown in
Figure 4a. The laser pulse-train begins to illuminate the sample
at t = 0 s, and the intensity of the pulse train is illustrated in
Figure 4b. After the light illumination is turned on, the voltage
across the resistor drops gradually as a function of time, and the
change is saturated within 1 ms. The effect originated from
individual pulses can be seen in a magnified view of the curve
near t = 0, which is shown as the inset in Figure 4a. The voltage
change is most rapid right after the pulses strike the sample,
which is presumably induced by the charge transfer from the
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QDs to graphene. The charge-transfer process is not fully
complete before the next pulse arrives at the sample, which
indicates that the overall charge-transfer time is comparable to
the separation between two laser pulses (40 μs). Moreover, the
effects from each pulse accumulate until the saturation occurs.
This indicates that (1) the free carriers generated by the charge
transfer have a rather long recombination time (as shown
below, the recombination time is on the order of 10 s); and (2)
the charge transfer ceases after some net charges are built up in
the QDs. The overall rising time of the signal is ∼0.3 ms.
Therefore, the total energy density (power × rising time)
needed to saturate the detector is around 40 μJ/cm2. As we will
show, very similar saturation energy density is found when the
detector was illuminated by an orders of magnitude less intense
continuous-wave light source.
Figure 4c shows two on/off cycles of the dynamic
photoresponse to UV light pulses. The ratio of the photo-to-
dark current Iphoto/Id is about 1.7. The asymmetric pattern can
be clearly seen with a shorter rising time of ∼5.0 s in response
to the UV light on, which is considerably shorter than the
falling time of ∼85 s in response to the UV light off. The rising
time measures approximately the electron−hole recombination
time (or carrier lifetime to be discussed later), and the observed
rising time of 5.0 s is anticipated from the strong quantum
confinement in ZnO QDs. The longer falling time suggests the
presence of moderate charge trapping mechanisms. Consider-
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Figure 5. (a) Photoresponsivity (solid with left scale) and gain (dashed with right scale) as a function of the UV (340 nm) light intensity at
different Vsd of 1, 5, and 10 V, respectively. (b) Photoresponsivity (solid with left scale) and gain (dashed with right scale) as a function of the
Vsd under different UV (340 nm) light intensities of 2.5, 9.0, and 15 μW/cm2, respectively. The y-axis is the logarithmic scale. (c) Gain of
experimental measurement (black dots) and theoretical fitting (red curves) versus illuminating power. The inset of (c) shows the spectra of
current noise density of pure GFET (black) and ZnO QDs/GFET (red) device in the logarithmic coordinates. (d) Detectivity D* as a
function of the UV (340 nm) light intensity (black axis and solid curves) and Vsd (red axis and dashed curves).

ing the high-quality crystallinity of and lack of band gap states ZnO QDs/graphene heterojunction. If this layer is removed, an
in the ZnO QDs in this work, confirmed in Figure S2e, the extraordinary Rv, anticipated from the high photoconductive
charge traps are most probably caused by defects on the surface gain, can be achieved in the ZnO QDs/GFET heterostructure
of ZnO QDs, such as oxygen vacancies.18,19 It should be photodetectors.
pointed out that the response times in our ZnO QDs/GFET The photoconductive gain is typically determined by the
heterojunction devices are consistent to the slightly shorter ratio of the carrier lifetime in QDs (Tlife) and the carrier transit
ones reported on single crystalline ZnO nanowire UV detectors time in the graphene channel (Ttransit). At a low intensity of
(rising time of ∼1 s and falling time of ∼3 s) due to weaker illumination, all of the holes generated from photoinduced
quantum confinement effect in the nanowires with considerably electron−hole pairs will occupy the surface states of ZnO QDs.
larger dimension.20,21 The similar asymmetric photoresponse in These holes are trapped at the surface and complete the
the nanowire case indicates that the surface defects on ZnO recombination with the negative charged oxygen ions. The
nanostructures indeed play the dominant role of charge photoconductive gain can be expressed as12
trapping. Iphhv T
hv 1
The spectral responsivity shows a consistent trend with the G= = (a0qNVW ) = a0ϕ life n
qiWL qiWL Ttransit 1 + i
absorption spectrum of the ZnO QDs casted on a glass
substrate in Figure 4d with a UV band edge at about 345 nm. In
i () 0

particular, despite the high responsivity of 1.8 × 108 A/W at (3)

340 nm, it decreases by about 2 orders of magnitude or more at
400 nm or longer wavelengths. This confirms the absence of
the band gap states in the highly crystalline ZnO QDs obtained
for this work, and the ZnO QDs are responsible for the UV
absorption in these ZnO QDs/GFET heterojunction devices
with extraordinary spectral selectivity. The Rv value is 2.6 × 108
and 1.8 × 108 A/W under 310 and 340 nm UV illuminations,
respectively, at Vsd = 10 V. As shown in Table 1 that compares
the Rv values and other relevant parameters of ZnO
nanostructure/graphene UV photodetectors, the Rv values of
the ZnO QDs/GFET devices in this work are about 2 orders of
magnitude greater than the best reported on the ZnO
nanostructure/graphene devices. This difference illustrates the
importance of controlling the surface of ZnO nanostructures, as
we discussed in Figures 1 and 2, since the photoresponse could
be sensitively affected by orders of magnitude if the charge
transfer is blocked by an undesired interface layer across the
4120
where Iph is the photocurrent, q is the elementary charge, W is
the graphene channel width, a0 is the photogenerated carrier-
transfer efficiency from QDs to the graphene channel, ϕ is the
quantum efficiency of ZnO QDs, i0 is the saturation light
intensity on the QDs when all of the surface states are filled, i is
the illuminating light intensity, n is a phenomenological fitting
parameter, and V = μVsdL−1 is the carrier drift velocity in
graphene with the channel length L, the carrier mobility μ, and
−1
source−drain voltage Vsd. The Ttransit = L2μ−1Vsd is the carrier
transit time in the graphene channel. For the ZnO QDs/GFET
heterostructure photodetectors, with W = 13.2 μm, L = 7.0 μm,
Vsd = 10.0 V, and μ ∼ 53.6 cm2 V−1 s−1, the Ttransit is estimated
to be ∼0.9 ns. The lifetime of photogenerated holes can be
extracted from an approximation fitted by a biexponential
function in Figure 4c, which yields Tlife ∼ 10.2 s.1,22,23 This
indicates the lifetime of the holes (10.2 s) in the ZnO QDs is
over 1 × 1010 orders of magnitude greater than the electron
DOI: 10.1021/acsnano.7b00805
ACS Nano 2017, 11, 4114−4123
ACS Nano
transit time in the graphene channel (0.9 ns). This means that a
very short transit time of the electrons in the GFET channel
compared with the longer lifetime of the holes (Ttransit ≪ Tlife)
will lead to a higher gain for the photodetector device. At the
low power density limit, the a0ϕ ∼ 1,12 therefore eq 3 yields a
gain ∼1 × 1010. To our knowledge, it is the highest gain that
has been reported in the literature for UV detection. It
represents more than an order of magnitude enhancement over
the highest value recently reported on UV photodetectors using
an optimized self-assembled monolayer between ZnO QDs and
GFET for improvement of the interface.12 The higher gain
obtained in the ZnO QDs/GFET heterostructure photo-
detectors suggests that the van der Waals interface can be
more efficient for charge transfer. It should be noted that the
photoconductive gain has contributions from both the ZnO
QD surface electron depletion effect and the high mobility of
graphene. In a recent work, we made a comparative study on
the optoelectronic properties of ZnO nanoparticles fused
through nanojunctions and the similar ZnO nanoparticles on
graphene channels of dimension of 1−2 mm (width) × 0.3−0.4
mm (length).24 In both cases, the dimension of the ZnO
nanoparticles is comparable to the Debye length for optimal
surface electron depletion effect. Interestingly, the photo-
conductive gain in the former (contribution of the surface
electron depletion effect) was found to be on the order of 1500,
which means a higher gain exceeding 1 × 107 is attributed to
the high charge mobility of the graphene in the ZnO QDs/
GFET devices.
Figure 5a depicts the photoresponsivity (solid) and gain
(dashed) versus light intensity curves measured on the ZnO
QDs/GFET heterojunction devices at different Vsd of 1, 5, and
10 V, respectively. Figure 5b shows the photoresponsivity and
gain dependent on the Vsd under different light intensities of
2.5, 9.0, and 15 μW/cm2, respectively. It should be noted that
the photoresponsivity increases monotonically with the bias
voltage (Vsd) of a photoconductor (Figure S3), while higher
signal-to-noise ratio is observed typically at a larger bias. Figure
5c demonstrates the gain of our experimental measurements
and theoretical fitting as a function of the illuminating power. A
monotonic decrease of gain with increasing UV illumination
power is attributed to the saturation of the surface states in
QDs and reduced average lifetime of holes, and the maximum
gain of 3.6 × 109 was obtained experimentally for an
illuminating power of 2.3 pW at 10 V bias voltage. The red
curve is the best fit for experimental gain with fitting
parameters: a0ϕ =0.82, i0 = 1.5 pW, and n = 1.15. The
theoretical calculation predicts the gain can be reached as high
as ∼9.2 × 109 with an illuminating power of <1 fW. The high
performance in photoresponsivity and gain indicates this
nanohybrid device can be used as high-sensitivity UV sensors.
The specific detectivity (D*), another key figure of merits for
a photodetector, was characterized, and the results are shown in
Figures 5d. The D* can be calculated using the following
equation:
A × Δf
D* = (Jones)
NEP (4)
where A is the active area of the device in cm , Δf is bandwidth
2
in hertz, NEP is the noise equivalent power with the unit of A/
Hz1/2, which represents the incident light power required for
the device output signal to be equal to the noise current. NEP is
1/2
expressed as NEP = in2 /R i , where the in2 is the mean square
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Article
noise current and can be calculated from the spectra density of
the noise power. The in2 of the hybrid ZnO QDs/GFET devices
monotonically decreases with increasing frequency, which can
be fitted by in2 ∝ 1/f in the low frequency range up to kHz,
demonstrating that the 1/f noise determines the current noise
behavior at low frequencies (the inset of Figure 5c). From the
noise power density curves, the NEP can be calculated as ∼1.3
× 10−18 W/Hz1/2, and Figure 5d illustrates the calculated
detectivity D* at different light intensities and Vsd values. At Vsd
= 10.0 V, the obtained D* exceeds 1 × 1014 Jones at 340 nm at
room temperature. The best D* value of 7.5 × 1014 Jones is 1
order of magnitude higher than the previously reported highest
value on the ZnO/self-assembled monolayer/graphene UV
photodetector12 as well as that for the PbS QD/GFET infrared
detectors.1
CONCLUSIONS
In conclusion, ZnO QD/GFET heterojunction UV detectors
have been obtained by printing highly crystalline ZnO QDs
onto the GFET channel. A clean van der Waals interface
formed between the ZnO QDs and graphene after the surface
Zn (Ac) layer on ZnO QDs was thoroughly removed, enabling
high-efficiency exciton dissociation and charge transfer across
the ZnO QD/GFET heterojunction upon UV illumination.
This ZnO QD/GFET heterojunction device inherits the
advantages of the strong light−solid interaction and quantum
confinement of the QDs and the high charge mobility of
graphene, both are essential to achieving high performance in
optoelectronic devices. The extraordinary photoconductive gain
up to 3.6 × 109 in addition to the UV detectivity of 7.5 × 1014
Jones illustrate the importance of this multiscale design and
engineering of photon absorption, exciton dissociation, and
charge transport in nanostructured optoelectronics that are
promising for practical applications.
METHODS
Chemical and Materials. Zinc acetate dehydrate (Zn(Ac),
99.999% trace metals basis), potassium hydroxide (KOH, reagent
grade, 90%), ethanol, and acetone were purchased from Sigma-Aldrich
and used without further purification. The resistivity of the deionized
water is 18.25 (MΩ·cm).
ZnO QDs Synthesis. In one beaker, 1 mM (mmol) of Zn(Ac) was
added into 10 mL of ethanol and stirred at 70 °C for 1 h. After the
Zn(Ac) was fully dissolved, the solution was cooled to room
temperature. In another beaker, 1.7 mmolof KOH was added into
10 mL of ethanol and dissolved via sonication for 1 h. The two
solutions were cooled to 0 °C in ice water. The KOH solution was
then injected slowly as one drop at a time into the Zn(Ac) solution.
The resultant solution was stored in a refrigerator at 4 °C for 4 weeks
to reach full precipitation. Thirty mL of hexane was then added to the
solution before the ZnO QDs were extracted via centrifugation at 4000
rpm at room temperature. After washing three times using an ethanol/
hexane (2:3 volume ratio) mixture solution, ZnO QDs were dried in
air for 10 h and then stored in ethanol for future use. The main
reaction process involved in the ZnO QDs growth is described in
Supporting Information. The diameter and diameter distribution of
ZnO QDs can be controlled through the reaction conditions including
reactant concentration, reaction temperature, and time.25 However,
the surface of the as-synthesized ZnO QDs may be terminated with an
amorphous layer of reaction residues such as reactants Zn(Ac) and
intermediate [Znx(OH)y](2x−y)+. Complete elimination of this surface
insulating layer is therefore critical for efficient charge transfer across
the ZnO QD/graphene interface and was carried out by controlling
the hydrolysis process. It has been found that the insulating layer is
difficult to remove by simply washing with solvents in addition to risks
DOI: 10.1021/acsnano.7b00805
ACS Nano 2017, 11, 4114−4123
ACS Nano
of further surface contamination by the solvent employed. In order to
address this critical issue, we have developed a robust aging process by
keeping the ZnO QDs in the storage solution of ethanol for different
periods of times to exhaust the residues. Figure S2a−c demonstrates
the TEM images of three representative stages of ZnO QDs with
respect to the aging times. At 14 days, the ZnO QDs were still capped
by an amorphous layer, as shown in Figure S2a. This amorphous layer
comprised reactants Zn(Ac) and intermediate [Znx(OH)y](2x−y)+,
which forms the insulating layer coated on the ZnO QDs surface.
When extending the aging time to 21 days, as shown in Figure S2b,
this insulating layer thickness reduced as the residue partly converted
to ZnO, making the QDs size slightly increased. Complete removal of
the amorphous surface layer was achieved at the aging time of ∼28
days, as shown in Figure S2c. These three types of ZnO QD samples
were used to make the ZnO QD/GFET heterostructure UV detectors,
and the measured optoelectronic properties clearly illustrate the
importance of removing the charge-transfer blocking amorphous
surface layer. Other sample characterization was carried out using
UV−vis-absorption spectrum, TEM, and XPS.
ZnO QD/GFET Device Fabrication. Monolayer graphene
fabricated using chemical vapor deposition (CVD) was transferred
onto heavily doped Si (100) substrates with 90 nm of SiO2 and
annealed in Ar:H2 (500 sccm:500 sccm) at 400 °C for 15 min to clean
up the residues of graphene-transfer process.26,27 The GFET channels
of 20 μm wide and 10 μm long were patterned using multiple steps of
photolithography, and the details of the process have been reported
earlier.28 Patterned Au (80 nm)/Ti (2 nm) source and drain contact
electrodes were deposited in an electron-beam evaporator, followed by
lift-off. ZnO QDs in ethanol were suspended via ultrasound agitation
before printing. They were printed on the GFET channel by a
microplotter (SonoPlot, Inc.) through sonication of glass capillary tips.
The plotter has a built-in calibration for the dispenser tips to measure
the resonant frequency of glass capillary tips and can adjust the
sonication frequency from 200−600 kHz for a given dispensing ink.
The tips can also be used to measure the surface inclination and
declination for smooth substrates so that smooth automated printing
can be done. Printing schematics can be drawn through software
provided for lines, dots, squares, circles, and arch designs.
Time-Resolved Photoresponse Measurements. The sample
(ZnO/GFET photodetector) was excited by 330 nm pump laser
pulses. The pulses had a duration of ∼40 fs and were produced from
the frequency doubling of the output of a noncollinear optical
parametric amplifier NOPA (Orpheus-N-2H, Light Conversion). The
NOPA was pumped by a Yb:KGW regenerative amplifier running at a
rate of 25 kHz (Pharos, Light Conversion). During the measurement,
the photodetector was connected in series with a resistor that had a
fixed resistance (∼5 kΩ). A power supply was used to provide a
constant voltage (100 mV) to the sample and the resistor. The real
time change of the potential drop across the resistor was determined
using a 200 MHz oscilloscope. The on/off of the pulses were triggered
by a built-in pulse picker inside the Pharos, which has a ns rise time.
The temporal resolution of the setup was ∼10 ns, which was primarily
limited by the speed of the oscilloscope.
Optical and Optoelectronic Characterization. UV−vis absorp-
tion spectra of ZnO QDs were measured at room temperature using a
UV-3600 Shimadzu UV−vis-NIR spectrophotometer. High-resolution
transmission electron microscope (HRTEM) images were taken on
ZnO QDs using a field emission FEI Tecnai F20XT with an
accelerating voltage of 200 kV. The optical images of GFET devices
were taken on a Nikon Eclipse LV 150 optical microscope with a CCD
camera. The I−V characteristics of the back-gated GFETs and their
dynamic photoresponse were measured using a xenon lamp as the light
source and an Agilent B1505A semiconductor device analyzer in a
probe station. The UV light was produced by a xenon lamp through a
monochromator (Oriel Apex, Newport), and the output optical power
at the sample was calibrated using an optical power meter connected
to a Si photodiode (Oriel Apex, Newport). The reference diode was
traceable to NREL certification. The noise spectra were measured via a
Stanford Research SR760 spectrum analyzer and an Agilent E3631 A
voltage source.
4122
Article
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsnano.7b00805.
Figure S1: Raman spectrum of the pristine monolayer
graphene (black) and after ZnO QDs deposition. Figure
S2a−c: The TEM images of ZnO QDs reaction at 4 °C
for 14, 21, and 28 days of reaction or aging, respectively.
Figure S3: I−V curves for ZnO QDs/GFET device under
dark and illumination, and photoresponsivity as a
function of bias voltage (PDF)
AUTHOR INFORMATION
Corresponding Authors
*E-mail: gmg@ku.edu.
*E-mail: qfliu@ku.edu.
*E-mail: jwu@ku.edu.
ORCID
Maogang Gong: 0000-0002-2031-781X
Wai-Lun Chan: 0000-0001-8697-9894
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The authors acknowledge support in part by ARO contract no.
ARO-W911NF-16-1-0029 and NSF contract nos. NSF-DMR-
133773 and NSF-DMR-1508494. This research was also
supported by Plant Directed Research and Development
funds from the Department of Energy’s National Security
Campus, operated and managed by Honeywell Federal
Manufacturing and Technologies, LLC under contract no.
DE-NA0002839. The ultrafast measurement is supported by
the U.S. National Science Foundation, grant DMR-1351716.
W.-L.C. also acknowledges the support provided by the New
Faculty General Research Fund (NFGRF) at the University of
Kansas.
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