pubs.acs.

org/acssensors Article

All 3D-Printed Flexible ZnO UV Photodetector on an Ultraflat

Substrate
Dongil Lee, Myeong-Lok Seol, Gabrielle Motilal, Beomseok Kim, Dong-Il Moon, Jin-Woo Han,*
and M. Meyyappan
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ABSTRACT: An all three-dimensional (3D)-printed flexible ZnO ultraviolet (UV)

photodetector is demonstrated, where the 3D-printing method is used not only for the
electrode and photosensitive material but also for creating a substrate. An ultraflat and
flexible substrate capable of serving as the backbone layer is developed using a water-
dissolvable polymer layer for surface planarization. A two-layered printing followed by
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surface treatment is demonstrated for the substrate preparation. As mechanical support

but flexible, a thick and sparse thermoplastic polyurethane layer is printed. On its surface,
a thin and dense poly(vinyl alcohol) (PVA) is then printed. A precise control of PVA
reflow using a microwater droplet results in a flexible and extremely uniform substrate. A
Cu−Ag nanowire network is directly 3D printed on the flexible substrate for the
conducting layer, followed by ZnO for the photosensitive material. Unlike the planar two-
dimensional printing that provides thin films, 3D printing allows the electrode to have a
step height, which can be made like a dam to accommodate a thick film of ZnO.
Photosensitivity as a function of various ZnO thickness values was investigated to establish an optimal thickness for UV response.
The device was also tested in natural sunlight along with stability and reliability.
KEYWORDS: additive manufacturing, 3D printing, printed electronics, UV detector, UV sensor, ultraviolet radiation

F lexible and wearable UV photodetectors (PDs) have

attracted considerable interest over the last decade due to
their applications in medical and healthcare, space, military,
and scientific instruments.1−4 A variety of printing techniques
including roll-to-roll gravure, aerosol jet printing, screen
printing, inkjet printing, and three-dimensional (3D) print-
ing5−12 have been used to demonstrate printed and flexible
electronics applications. These demonstrations cover sensors,
energy-storage and -harvesting devices, photodetectors, and
biomedical components among many others, and the range is
expanding from rapid prototyping of a simple component to
complicated on-demand functional devices.13−18 However, all
of these methods have required a mandatory substrate such as
a wafer, glass, or polymer film as the starting material, which
results in issues of inventory management and waste
increase.19,20 A popular 3D-printing method is the fused
deposition modeling (FDM),15,16 which provides direct
writing of the nonconductive thermoplastic material. Complete
3D-printing methods have not yet been accomplished to date
to produce functional devices, largely due to the high surface
roughness of the 3D-printed layer. Thus, commercial off-the-
shelf flat substrates manufactured by other methods have been
used until now. In addition, the lack of conductive filament
sources has necessitated mix-and-match approaches, for
example, 3D printing for the structure and inkjet printing for
the electrodes and/or active layers.14,21,22 This not only
complicates the fabrication process but also increases the
capital expenditure for the equipment infrastructure.
In this work, only a single 3D printer is used for producing
both the flat substrate needed and the conductive electrode. A
double-layered printing method is presented to provide the
ultraflat surface. A thermoplastic polyurethane (TPU) is first
printed for the flexible supporting structure but its surface is
coarse and rough. Then, poly(vinyl alcohol) (PVA) printing is
followed for obtaining a fine and flat surface. The subsequent
surface treatment is applied to further densify and planarize the
surface. High conductivity filaments are not yet common
commercially; however, Cu−Ag nanowire-loaded filaments
showing the highest conductivity have recently become
viable.23,24 Thus, we have attempted to apply a Cu−Ag
nanowire (NW)-based filament for the electrode. With this
substrate−electrode platform, we added ZnO also by the
printing method for the active layer. Photoionization, a process
of electron−hole pair generation due to incident photons, is
the sensing mechanism of the resulting photodetector.25−27
Received: December 23, 2019
Accepted: March 23, 2020
Published: March 23, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acssensors.9b02544

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Unlike other applications, such as gas and biosensors, where
the reaction predominantly occurs at the active material
surface, the photoionization process requires a certain volume
of the active material to sufficiently absorb the photons. In this
regard, thin films often enabled by ordinary inkjet printing may
not be optimal. However, the 3D printing here is able to
fabricate a dam-like electrode to accommodate a thick film
with its height sufficient to fully absorb the light. UV sensors
with various ZnO heights were fabricated, and an optimal film
thickness was identified. The reliability and stability of the
detector over bending cycles were verified. The detector was
also fabricated in a wristband-type form factor and tested
under direct sunlight.
■
EXPERIMENTAL SECTION
Figure 1a presents a schematic illustration of the device structure and
the process. All layers were fully printed using the 3D printer shown
Figure 1. (a) Schematic diagram of the 3D-printed UV photo-
detector, (b) top view image of the fabricated device, (c) image of the
device under bending status, (d) cross-sectional scanning electron
microscopy (SEM) image of the sensing region of the device, and (e)
magnified view of the printed ZnO film.
in Figure S1. An illustration of the detailed fabrication steps can be
found in Figure S2. To achieve the flat printed substrate, the TPU
layer was printed through a nozzle heated at 220 °C and the water-
soluble PVA layer was then overlaid on the TPU surface through the
nozzle heated at 235 °C. The size of the substrate was fixed at 2 cm in
width and 8 cm in length. To planarize the PVA surface, the sample
was placed under a humidity bath. The relative humidity of the bath
Figure 2. (a) Cross-sectional SEM and optical surface profiler images of the printed flexible substrate before and after the moisture soaking process,
(b) measured surface roughness, and (c) soaking time for the PVS surface to reach total flatness for various as-printed PVA thickness values.
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was close to 95%, and the moisture soaking process was carried out
under room temperature. The purpose of the moisture soaking into
the PVA is 2-fold: densification of the PVA film and planarization of
its surfaces. By increasing the soaking time, PVA reflow occurs and
partially permeates into the interface region with the TPU. As a result,
the PVA is thinned down and its surface becomes flat, as shown in
Figure S3. After the substrate planarization, the Cu−Ag-based
conductive filament (purchased from Multi 3D LLC) was printed
at 185 °C for electrodes. To confirm the conductivity of the printed
pattern, various values for the width, length, and height of the 3D-
printed Cu−Ag electrodes were evaluated, as shown in Figure S4. The
wire was bonded using a silver paste to assure contact with the
multimeter. The end-to-end resistance for the case with a height of 0.8
mm, width of 1.2 mm, and length of 6 cm was about 55−62 Ω, which
assures its metallic property. A pair of circular electrodes was cross-
coupled, but not in short-circuit, to accommodate the subsequent
sensing material, as shown in Figure 1a. Afterward, the isopropyl
alcohol (IPA)-based ZnO nanoparticle solution was printed through a
0.26 mm syringe needle as the active layer in the same 3D printer (see
Figure S1), followed by natural drying at room temperature for 24 h.
The surface morphology was characterized by scanning electron
microscopy (SEM) using a Hitachi S-4800 scanning electron
microscope. The flatness of the substrates was characterized using
an optical surface profiler (Sensofar, model S-neox) before and after
the planarization process. Electrical and optoelectronic measurements
of the fabricated PDs were carried out on a semiconductor
characterization system (Agilent 4156C) under UV LED (10 W@
365 nm). All measurements were performed in air and at room
temperature.
■ RESULTS AND DISCUSSION
Figure 1b shows the image of the final device. The ZnO
channel length between the Cu−Ag electrodes is 600 μm.
Figure 1c presents the flexibility of the fabricated device. The
tilted cross-sectional SEM image of the device is shown in
Figure 1d. The magnified view of the ZnO layer is shown in
Figure 1e. The size of the nanoparticles ranges from 50 to 200
nm. The final device is then packaged or encapsulated to
protect from any environmental contamination such as
particles and gas molecules.
Figure 2a presents the flatness of the printed substrate
before and after the moisture soaking. The PVA is known to be
water soluble due to the hydroxyl group.21,28 By exposing it to
an aerosol of micron-sized water droplets generated by
nebulizing the water, its surface dissolves and gently melts.
As shown in the cross-sectional SEM and optical profiler
images, the thickness of the PVA layer is reduced due to its
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ACS Sensors pubs.acs.org/acssensors
permeation into the TPU interface and self-densification. In
addition, whereas a few irregular empty spaces are found in as-
printed PVA, no voids are found after the soaking step. This
implies that the moisture soaking process involves a reflow of
PVA. More importantly, the result of the PVA reflow makes
the film surface flat and smooth. As shown in the optical
profiler images, the as-printed PVA pattern shows linear line
and space. The peak-to-peak height difference of the as-printed
pattern is approximately 70 μm. However, after the
planarization, the peak-to-peak height becomes smaller than
the resolution of the optical profiler. This means the surface
roughness becomes less than 100 nm. Figure 2b shows the
peak-to-peak height as a representation of the surface
roughness for various PVA film thickness values. For a PVA
thickness of 100 μm, the peak-to-peak height is saturated at 20
μm even after sufficient soaking time. In this case, the PVA is
fully consumed into TPU. The surface becomes flat for PVA
thickness greater than 200 μm, indicating the existence of a
minimum coating thickness. Figure 2c shows the soaking time
to reach the saturation point of smoothing. The soaking time
linearly increases as the coating gets thicker. Therefore, the
optimum thickness for the coating was set at 200 μm. The two-
step printing followed by moisture-induced reflow demon-
strated here could be a backbone process for future flexible
printed electronics.
To assure the wavelength selective absorbance of the printed
ZnO film, the test material on transparent glass was printed
and scanned with a UV−vis spectrophotometer (Shimadzu
UV-3600 Plus). It is seen that the printed ZnO has nearly 95%
absorbance for 300−380 nm but nearly negligible absorption
in the visible wavelength range, as shown in Figure S5. The
current−voltage sweep was performed under dark and during
illumination at 8 μW/cm2 and a peak wavelength of 365 nm.
As shown in Figure S6, the current increases with the applied
voltage and no saturation is observed up to 10 V. The
photoresponse was characterized using 365 nm UV light at
various intensities. As shown in Figure 3a, the photocurrent
spontaneously increases upon UV irradiation. To verify the
impact of substrate flatness, two other control samples were
co-tested. The first control sample was made directly on TPU
Figure 3. (a) Photoresponse of the sensor under various UV
intensities, (b) photoresponse calibration curve for various intensities,
(c) photoresponse characteristics for various operation voltages, (d)
the responsivity replotted using the data from (c), and (e) measured
peak photocurrent for various electrode heights at 5 V under 8 mW/
cm2.
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and the second control device was made on PVA before the
soaking planarization process. As shown in Figure S7, the
proposed device on the PVA-flattened surface showed the
largest photocurrent. The improved sensor performance is
attributed to the better interface quality and good contact
property between the Ag electrode and the ZnO film.
The response and recovery times at 8 mW/cm2 are 0.46 and
0.64 s, respectively, which are comparable to or better than the
values listed in the review in ref 1. The UV intensity
dependence in Figure 3b shows linearity over the power
density from 0.25 to 8 mW/cm2, and the sensitivity is
measured as 0.16 μA per mW/cm2. The operation voltage
dependence was also tested; even with the voltage down to 0.1
V, a stable baseline (i.e., dark current) is seen with a response
shown as a log-scale current plot in Figure 3c. When the
operation voltage is reduced from 5 to 0.1 V, the total current
is reduced 2 orders of magnitude. By combining the reduced
drive voltage and associated current, the total power
consumption, i.e., the product of current and voltage, is
reduced greater than 3 orders of magnitude. This low power
operation can be advantageous for mobile low power
applications. However, the trade-off for the low voltage
operation is the sensor response. As shown in Figure 3d, the
low voltage operation reduces the sensor response by
approximately half. The loss of sensor response is associated
with the greater charge recombination in the ZnO film at low
voltages. To leverage the 3D electrode or the electrode with a
height, Figure 3e shows that the photocurrents measured from
various devices with different electrode heights (Hel). The
photoresponse increases linearly up to Hel = 600 μm. Then, the
performance improvement levels off by Hel = 1 mm. When Hel
is further increased, the performance gets degraded, indicating
the existence of an optimal sensor volume. The thick ZnO
device (Hel = 600 μm) exhibits six times greater response than
the thinnest device (Hel = 200 μm) fabricated here. The
behavior in Figure 3e for the small film thickness is linear,
indicating that the response current would be far smaller for
typical thickness values (20−50 μm) achieved in inkjet
printing. As the volume of the sensitive material increases,
the absorbance of UV increases due to larger photon capture
efficiency.27,29,30 However, when the electrode is too tall,
photon scattering and shadowing effects adversely impact the
performance.
Next, the stability and reliability under mechanical
deformation are examined. Any cross response due to ambient
gas molecules and particle contamination can be effectively
avoided by proper encapsulation. However, heat is more
difficult to avoid due to its nature. Therefore, it is important to
verify the impact of temperature. Figure 4a shows that the
baseline current shift due to environmental temperature
change is negligible. Bending cyclic endurance test was also
carried out by measuring the baseline resistance shift for
repeated bending up to 500 cycles at a bending radius of 7.5
mm. Figure 4b shows that the degradation due to mechanical
fatigue is about 8%. The source of fatigue is speculated to be
the depercolation of ZnO nanoparticles and the contact
property, which requires further work to enhance the adhesion
property of nanoparticles and the interface between the active
film and electrode. In addition to the laboratory test, a real
environmental outdoor test was conducted during a full day
from 9:00 AM to 6:00 PM in Mountain View, California. The
test sample was wrapped on a mannequin hand-exposed to
natural sunlight. As shown in Figure 4c, the UV power density
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ACS Sens. 2020, 5, 1028−1032
ACS Sensors pubs.acs.org/acssensors
Figure 4. (a) Impact of temperature on the baseline current of the
device; (b) repeatability and cyclic endurance of bending cyclic stress;
and (c) UV power density and resistance change from natural
sunlight.
grows up to 3.3 mW/cm2 from 9:00 to 13:00 and then
continues to drop after the peak until sunset. The results were
found to be consistent with a commercial UV sensor,
confirming the capability of the 3D-printed UV sensor to
function as an ambient UV dosimeter.
■ CONCLUSIONS
A fully 3D-printed flexible and ultraflat surface substrate is
presented with a two-step printing followed by a moisture
soaking process to densify and planarize the top surface. The
first sparse and thick TPU layer provides the mechanical
support and flexibility. The second fine and thin PVA layer
along with moisture-induced reflow provides the dense and flat
surface. Owing to the nature of the 3D electrode, a thick
volume of the photosensitive ZnO material can be printed.
Compared to two-dimensional (2D) thin-film (Hel = 200 μm)
ZnO sensors, the thick film (Hel = 600 μm) structure shows 6-
fold greater UV response. A negligible cross response to
temperature and superior bending cyclic endurance are also
obtained. The proposed substrate printing process can be a
platform for all 3D-printed electronics in the future, and the
demonstrated 3D-printed UV sensor can be a foundation for
wearable and flexible electronics.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssensors.9b02544.
Main components of the 3D printer, process flow of the
3D-printed ZnO UV photodetectors, planarization of
the 3D-printed flexible substrate, size dependence of the
electrode and impact of the substrate flatness on
performance (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Jin-Woo Han − Center for Nanotechnology and Universities
Space Research Association, NASA Ames Research Center,
Moffett Field, California 94035, United States; orcid.org/
0000-0002-5118-1310; Phone: +1 650 604 3985;
Email: jin-woo.han@nasa.gov
1031
Article
Authors
Dongil Lee − Center for Nanotechnology and Universities Space
Research Association, NASA Ames Research Center, Moffett
Field, California 94035, United States; orcid.org/0000-
0001-6678-5451
Myeong-Lok Seol − Center for Nanotechnology and Universities
Space Research Association, NASA Ames Research Center,
Moffett Field, California 94035, United States
Gabrielle Motilal − Center for Nanotechnology, NASA Ames
Research Center, Moffett Field, California 94035, United States
Beomseok Kim − Center for Nanotechnology and Universities
Space Research Association, NASA Ames Research Center,
Moffett Field, California 94035, United States; orcid.org/
0000-0002-3718-3029
Dong-Il Moon − Center for Nanotechnology and Universities
Space Research Association, NASA Ames Research Center,
Moffett Field, California 94035, United States; orcid.org/
0000-0001-8292-1978
M. Meyyappan − Center for Nanotechnology, NASA Ames
Research Center, Moffett Field, California 94035, United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssensors.9b02544
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the In-Space Manufacturing
Program of the Space Technology Mission Directorate
(STMD) and Advanced Exploration Systems (AES) Office
of the NASA HEOMD. The authors are grateful to Curtis Hill
for his support. G.M. was an intern at NASA Ames from the
University of the West Indies, St. Augustine, Trinidad and
Tobago under the International Internship Program.
■ REFERENCES
(1) Zou, Y.; Zhang, Y.; Hu, Y.; Gu, H. Ultraviolet Detectors Based
on Wide Bandgap Semiconductor Nanowire: A Review. Sensors 2018,
18, No. 2072.
(2) Soci, C.; Zhang, A.; Xiang, B.; Dayeh, S. A.; Aplin, D. P. R.; Park,
J.; Bao, X. Y.; Lo, Y. H.; Wang, D. ZnO Nanowire UV Photodetectors
with High Internal Gain. Nano Lett. 2007, 7, 1003−1009.
(3) Bai, S.; Wu, W.; Qin, Y.; Cui, N.; Bayerl, D. J.; Wang, X. High-
Performance Integrated ZnO Nanowire UV Sensors on Rigid and
Flexible Substrates. Adv. Funct. Mater. 2011, 21, 4464−4469.
(4) Chang, H.; Sun, Z.; Ho, K. Y. F.; Tao, X.; Yan, F.; Kwok, W. M.;
Zheng, Z. A Highly Sensitive Ultraviolet Sensor Based on a Facile in
Situ Solution-Grown ZnO Nanorod/Graphene Heterostructure.
Nanoscale 2011, 3, 258−264.
(5) Park, S. H.; Su, R.; Jeong, J.; Guo, S. Z.; Qiu, K.; Joung, D.;
Meng, F.; McAlpine, M. C. 3D Printed Polymer Photodetectors. Adv.
Mater. 2018, 30, No. 1803980.
(6) Yang, H.; Leow, W. R.; Chen, X. 3D Printing of Flexible
Electronic Devices. Small Methods 2018, 2, No. 1700259.
(7) Ul Hasan, K.; Nur, O.; Willander, M. Screen Printed ZnO
Ultraviolet Photoconductive Sensor on Pencil Drawn Circuitry over
Paper. Appl. Phys. Lett. 2012, 100, No. 211104.
(8) Tran, V. T.; Wei, Y.; Yang, H.; Zhan, Z.; Du, H. All-Inkjet-
Printed Flexible ZnO Micro Photodetector for a Wearable UV
Monitoring Device. Nanotechnology 2017, 28, No. 095204.
(9) Gupta, A. A.; Arunachalam, S.; Cloutier, S. G.; Izquierdo, R.
Fully Aerosol-Jet Printed, High-Performance Nanoporous ZnO
Ultraviolet Photodetectors. ACS Photonics 2018, 5, 3923−3929.
(10) Tong, S.; Yuan, J.; Zhang, C.; Wang, C.; Liu, B.; Shen, J.; Xia,
H.; Zou, Y.; Xie, H.; Sun, J.; et al. Large-Scale Roll-to-Roll Printed,
https://dx.doi.org/10.1021/acssensors.9b02544
ACS Sens. 2020, 5, 1028−1032
ACS Sensors pubs.acs.org/acssensors Article

Flexible and Stable Organic Bulk Heterojunction Photodetector. npj (29) Ocola, L. E.; Wang, Y.; Divan, R.; Chen, J. Multifunctional UV
Flexible Electron. 2018, 2, No. 7. and Gas Sensors Based on Vertically Nanostructured Zinc Oxide:
(11) Dong, Y.; Zou, Y.; Song, J.; Li, J.; Han, B.; Shan, Q.; Xu, L.; Volume versus Surface Effect. Sensors 2019, 19, No. 2061.
Xue, J.; Zeng, H. An All-Inkjet-Printed Flexible UV Photodetector. (30) Liu, K.; Dai, B.; Ralchenko, V.; Xia, Y.; Quan, B.; Zhao, J.; Shu,
Nanoscale 2017, 9, 8580−8585. G.; Sun, M.; Gao, G.; Yang, L.; et al. Single Crystal Diamond UV
(12) Gong, M.; Liu, Q.; Cook, B.; Kattel, B.; Wang, T.; Chan, W.-L.; Detector with a Groove-Shaped Electrode Structure and Enhanced
Ewing, D.; Casper, M.; Stramel, A.; Wu, J. Z. All-Printable ZnO Sensitivity. Sens. Actuators, A 2017, 259, 121−126.
Quantum Dots/Graphene van Der Waals Heterostructures for
Ultrasensitive Detection of Ultraviolet Light. ACS Nano 2017, 11,
4114−4123.
(13) Seol, M. L.; Ivaškevičiu̅tė, R.; Ciappesoni, M. A.; Thompson, F.
V.; Moon, D. Il.; Kim, S. J.; Kim, S. J.; Han, J. W.; Meyyappan, M. All
3D Printed Energy Harvester for Autonomous and Sustainable
Resource Utilization. Nano Energy 2018, 52, 271−278.
(14) Kim, K.; Kim, B.; Lee, C. H. Printing Flexible and Hybrid
Electronics for Human Skin and Eye-Interfaced Health Monitoring
Systems. Adv. Mater. 2019, No. 1902051.
(15) Xu, Y.; Wu, X.; Guo, X.; Kong, B.; Zhang, M.; Qian, X.; Mi, S.;
Sun, W. The Boom in 3D-Printed Sensor Technology. Sensors 2017,
17, No. 1166.
(16) Espera, A. H.; Dizon, J. R. C.; Chen, Q.; Advincula, R. C. 3D-
Printing and Advanced Manufacturing for Electronics. Prog. Addit.
Manuf. 2019, 4, 245−267.
(17) Kim, S. J.; Han, J.-W.; Kim, B.; Meyyappan, M. Single Walled
Carbon Nanotube Based Air Pocket Encapsulated Ultraviolet Sensor.
ACS Sensors 2017, 2, 1679−1683.
(18) Kim, S. J.; Moon, D.-Il.; Seol, M.-L.; Kim, B.; Han, J.-W.;
Meyyappan, M. Wearable UV Sensor Based on Carbon Nanotube-
Coated Cotton Thread. ACS Appl. Mater. Interfaces 2018, 10, 40198−
40202.
(19) Xi, M.; Wang, X.; Zhao, Y.; Zhu, Z.; Fong, H. Electrospun
ZnO/SiO2 Hybrid Nanofibrous Mat for Flexible Ultraviolet Sensor.
Appl. Phys. Lett. 2014, 104, No. 133102.
(20) Yang, D.; Lee, J.; Kim, D.; Cho, I.; Ok, J. G.; Park, I. Flexible
Ultraviolet and Ambient Light Sensor Based on a Nanomaterial
Network Fabricated Using Selective and Localized Wet Chemical
Reactions. Langmuir 2018, 34, 4132−4141.
(21) Lee, Y.; Han, J.; Choi, B.; Yoon, J.; Park, J.; Kim, Y.; Lee, J.;
Kim, D. H.; Kim, D. M.; Lim, M.; et al. Three-Dimensionally Printed
Micro-Electromechanical Switches. ACS Appl. Mater. Interfaces 2018,
10, 15841−15846.
(22) Foo, C. Y.; Lim, H. N.; Mahdi, M. A.; Wahid, M. H.; Huang, N.
M. Three-Dimensional Printed Electrode and Its Novel Applications
in Electronic Devices. Sci. Rep. 2018, 8, No. 7399.
(23) Kim, M. J.; Cruz, M. A.; Ye, S.; Gray, A. L.; Smith, G. L.;
Lazarus, N.; Walker, C. J.; Sigmarsson, H. H.; Wiley, B. J. One-Step
Electrodeposition of Copper on Conductive 3D Printed Objects.
Addit. Manuf. 2019, 27, 318−326.
(24) Cruz, M. A.; Ye, S.; Kim, M. J.; Reyes, C.; Yang, F.; Flowers, P.
F.; Wiley, B. J. Multigram Synthesis of Cu−Ag Core−Shell Nanowires
Enables the Production of a Highly Conductive Polymer Filament for
3D Printing Electronics. Part. Part. Syst. Charact. 2018, 35,
No. 1700385.
(25) Duan, Y.; Cong, M.; Jiang, D.; Zhang, W.; Yang, X.; Shan, C.;
Zhou, X.; li, M.; Li, Q. ZnO Thin Film Flexible UV Photodetectors:
Regulation on the ZnO/Au Interface by Piezo-Phototronic Effect and
Performance Outcomes. Adv. Mater. Interfaces 2019, 6, No. 1900470.
(26) Kwon, D.-K.; Porte, Y.; Ko, K. Y.; Kim, H.; Myoung, J.-M.
High-Performance Flexible ZnO Nanorod UV/Gas Dual Sensors
Using Ag Nanoparticle Templates. ACS Appl. Mater. Interfaces 2018,
10, 31505−31514.
(27) Fan, H.; Sun, M.; Ma, P.; Yin, M.; Lu, L.; Xue, X.; Zhu, X.; Li,
D.; Ma, J. UV Photodetectors Based on 3D Periodic Au-Decorated
Nanocone ZnO Films. Nanotechnology 2016, 27, No. 365303.
(28) Yoon, J.; Han, J.; Choi, B.; Lee, Y.; Kim, Y.; Park, J.; Lim, M.;
Kang, M. H.; Kim, D. H.; Kim, D. M.; et al. Three-Dimensional
Printed Poly(Vinyl Alcohol) Substrate with Controlled On-Demand
Degradation for Transient Electronics. ACS Nano 2018, 12, 6006−
6012.

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