Ceramics International 49 (2023) 8302–8312

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

High-performance ultraviolet photodetector based on p-PEDOT:PSS film/

p-ZnO:Sb microwire/n-Si double heterojunction
Qingheng Li, Yang Liu, Xinmiao Guan, Tingcha Wei **, Peng Wan, Daning Shi, Caixia Kan,
Mingming Jiang *
College of Physics, MIIT Key Laboratory of Aerospace Information Materials and Physics, Key Laboratory for Intelligent Nano Materials and Devices, Nanjing University
of Aeronautics and Astronautics, No. 29 Jiangjun Road, Nanjing, 211106, PR China

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

Keywords: The development of high-sensitivity ultraviolet photodetectors, which can be compatible with the existing Si-
Double heterojunction based technique, is highly desirable in advanced applications. In this study, a double heterojunction ultravio­
Ultraviolet photodetector let photodetection device consisting of an ITO conductive glass covered by a layer of p-type poly(3,4-
ZnO:Sb microwires
ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) polymer film, a single p-type Sb-doped ZnO
PEDOT:PSS polymer
microwire (ZnO:Sb MW), and an n-type Si substrate was proposed and demonstrated. Using dimethyl sulfoxide
DMSO&CNHs co-treatment
Si film (DMSO) and carbon nanohorn (CNHs) as treated solvent, the electrical properties of PEDOT:PSS polymer film
were positively increased. Correspondingly, the treated photodetector exhibited a strongest photoresponsivity of
approximately 737.8 A/W and largest external quantum efficiency (EQE) of approximately 2.6 × 105%, which
were significantly higher than those of the pristine devices. Besides, the transient response manifests its highly-
stable and faster photoresponse speed of rising/falling times of ~67 μs/2.29 ms. The enhanced photoresponse
properties are attributed to the increased electrical properties of the DMSO&CNHs co-treated PEDOT:PSS film.
Especially, the p-p heterojunction formed at the PEDOT:PSS/ZnO:Sb heterointerface, can effectively accelerate
the transport of photogenerated electron-hole pairs, thus reducing the recombination probability. The proposed
double heterojunction that meeting the criteria of low-cost and eco-friendly would be a competitive option for
the large-scale fabrication of high-performance ultraviolet photodetectors, which are efficient and compatible
with the existing Si-based integrated circuit technology.

1. Introduction for maintaining device performances. Considering that modern elec­

tronics and optoelectronic devices are primarily established on Si, ul­
Ultraviolet photodetectors have been extensively studied for various traviolet photoelectron detection and imaging technology continues to
commercial applications such as biological and biomedical sciences, be an unparalleled exception because the short wavelength of ultraviolet
secure communications, pollution monitoring, water sterilization, flame radiation makes efficient detection with Si difficult and increases the
sensing, and early missile plume detection [1–7]. Currently, most system complexity and cost [17–19]. Therefore, developing ideal ul­
commercially available photodetectors are prepared from traviolet photodetectors with a photoresponse performance that meets
single-crystalline Si-, SiC-, and GaN-based p-n homo- and heterojunction the criteria of low cost, environmental friendliness, and excellent
photodiodes [8–13]. However, the crucial drawback of these inorganic compatibility with the existing Si-based integrated circuit technology is
semiconductor photodetectors is that they are unsuitable for certain confronted with serious challenges [20–22].
applications. Moreover, the device fabrication is high cost in Due to their excellent properties, including high transmittance,
manufacturing and growth, time consuming and requiring expensive electrical characteristics, low-cost preparation, and well-controlled so­
heteroepitaxy growth equipment and complex processing [3,14–16]. lution-processed deposition technique, organic conducting polymer
Research on Si-based electronics and optoelectronics has become one of materials have been extensively used in constructing electronic and
the hottest domains in the world because they hold significant promise optoelectronic devices, such as flexible and wearable electronics,

* Corresponding author.
** Corresponding author.
E-mail addresses: [email protected] (T. Wei), [email protected] (M. Jiang).

https://doi.org/10.1016/j.ceramint.2022.10.362
Received 1 August 2022; Received in revised form 17 October 2022; Accepted 29 October 2022
Available online 2 November 2022
0272-8842/© 2022 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Q. Li et al. Ceramics International 49 (2023) 8302–8312

organic solar cells, light sources, and photodetectors [23–28]. imported into the quartz tube. The growth temperature was set to 1100
Solution-processed optoelectronic devices based on organic materials ◦
C and the growth time was approximately 1 h. The furnace cooled
and/or nanomaterials are one of the most promising approaches for slowly to room temperature when the growth process was completed. A
manufacturing Si-based high-performance ultraviolet photodetectors. sample of ZnO:Sb wires was collected individually at the surface of the Si
Among those organic polymer materials, poly (3,4-ethyl­ substrate and the inner wall of the corundum boat. The sample size can
enedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is a p-type be controlled, for example, the cross-sectional diameter and their
highly conducting conjugated polymer that has been broadly and deeply extraordinarily long length vary from 0.5 to 50 μm, and 0.5–2.0 cm,
investigated because of its high carrier mobility, large and respectively.
well-controlled work function, and high transmittance over a broadband The CNHs sample with a weight of ~20 mg was incorporated into a
spectrum in the range of 250–800 nm [29–34]. Previous investigations DMSO organic solution (volume ~ 2 mL) and then ultrasonically
on the pristine PEDOT:PSS polymer showed that its much lower elec­ dispersed for 10 min. Subsequently, the mixed CNHs&DMSO colloidal
trical conductivity than that of commercially purchased transparent solution (~20 μL) was mixed with the PEDOT:PSS colloidal solution
conducting oxides or metal electrodes has greatly limited its applica­ (conductive grade, 1.3 wt% dispersion in water, ~1 mL). Therefore, the
tions in electronic and optoelectronic devices. Various attempts have PEDOT:PSS polymer was treated with CNHs and DMSO simultaneously
been made to modulate the optical and electrical properties of PEDOT: [41,42].
PSS polymers, including acid treatment or doping with various organic
solvents and non-ionic surfactants [35–40]. Dimethyl sulfoxide (DMSO) 2.2. Device fabrication
is the most commonly used organic solvent to increase the electrical
conductivities of PEDOT:PSS polymers. However, the enhancement of A type of organic-inorganic heterojunction photodetector device
the electrical conductivities of the PEDOT:PSS polymer alone is insuf­ composed of a single ZnO:Sb MW, n-type Si substrate, PEDOT:PSS film,
ficient to effectively improve device performance, especially for the and ITO conducting glass was fabricated. The device was fabricated
achievement of performance-enhanced photodetectors [41–46]. using a facile bottom-up process: (1) An Au layer with a thickness of
This study proposes and designs a vertical-structured photodetecting approximately 50 nm was firstly evaporated on a clean n-type Si sub­
device made of indium tin oxide (ITO) conducting glass covered by a p- strate using electron beam heating evaporation. (2) Using electron-beam
type PEDOT:PSS polymer layer, a single p-type ZnO microwire doped evaporation, two MgO films with a thickness of approximately 5 μm
with Sb (ZnO:Sb MW), and an n-type Si substrate. The fabricated device were deposited on the Si film with a mask template. The width between
exhibited double-heterojunction (p-p-n) behavior and showed ultravi­ the MgO insulating films is approximately 50 μm. (3) A single ZnO:Sb
olet photodetecting characteristics, containing a peak photoresponsivity wire was mechanically placed across the slit of the Si film, with the pre-
of approximately 323.2 A/W, a maximal external quantum efficiency prepared MgO films distributed on both sides of the wire. (4) The pre­
(EQE) of ~1.08 × 105%, and fast response speed of rising/falling times cursor PEDOT:PSS aqueous solution was spin-coated onto the ITO con­
~ 238 μs/4.76 ms under 370 nm light illumination at a reverse bias ducting glasses at 2000 rpm for 1 min, followed by heating at a
voltage of − 10 V. The solvent of DMSO and carbon nanohorns (CNHs) temperature of 100 ◦ C for 8 min (5) Finally, the ITO/PEDOT:PSS
employed as additive were used to modulate the electrical properties of conductive glass was reversely bound to the ZnO:Sb wire of the pre-
the PEDOT:PSS polymer, thus enhancing the photoresponse capabilities fabricated p-ZnO:Sb MW/n-Si heterojunction. A typical device config­
of the fabricated double heterojunction photodetectors accordingly. uration of the designed ITO/p-PEDOT:PSS/p-ZnO:Sb MW/n-Si hetero­
Compared with the pristine double heterojunction photodetector, the junction photodetection device is shown in Fig. 3(a). The fabricated
treated device exhibited the highest photocurrent value, which was ITO/p-PEDOT:PSS/p-ZnO:Sb MW/n-Si heterojunction photodetection
approximately 2.5 times larger than that of the untreated sample; The device that uses untreated PEDOT:PSS conducting polymer is defined as
device also exhibited a superior photoresponsivity of approximately Device-1. After being treated by the CNHs&DMSO colloidal solution, the
737.8 A/W, an enhanced EQE ~2.6 × 105% in the same test conditions. fabricated single ZnO:Sb MW double heterojunction photodetection
Additionally, the rising/decaying times of the treated photodetector device is defined as Device-2.
were sharply lowered to ~67 μs/2.29 ms. The working principle of the
pristine PEDOT:PSS polymer with electrical properties enhanced by 2.3. Characterization of materials and devices
DMSO&CNHs solvent was studied. The influence of DMSO&CNHs on the
photoresponse properties of the fabricated devices was further investi­ The surface morphology and elemental composition of the prepared
gated. The experimental results are expected to facilitate further samples were measured using scanning electron microscopy (SEM) and
research on preparing transparent conductive polymer materials and energy dispersive X-ray (EDS) mapping. Transmission electron micro­
paving the way for developing high-performance organic-inorganic scopy (TEM) images were obtained using an LEO 912AB transmission
hybrid optoelectronic devices. electron microscope. The phases of the as-synthesized ZnO:Sb samples
were characterized by X-ray diffraction (XRD). Optical absorption
2. Experimental Section spectra were recorded using an ultraviolet–Visible spectrophotometer.
Field-effect transistors (FETs) based on a single ZnO:Sb MW were
2.1. Sample Preparation fabricated to study the electrical transport properties of as-synthesized
p-type ZnO:Sb samples. The photoelectrical measurements of the de­
A sample of individual ZnO microwires, which were successfully vice under different light wavelengths and optical power intensities,
doped with Sb (ZnO:Sb MWs), was synthesized using a simple chemical including current-voltage (I–V) characteristics, photocurrent, dark cur­
vapor deposition (CVD) method [45,47,48]. The preparation of the rent, spectral photoresponsivity, and EQE, were tested using a detection
CVD-grown ZnO:Sb MWs was conducted in a tube furnace with bistratal system composed of an EQ-99 light source, a monochromator, and a
quartz tubes. The source materials were highly purified ZnO, Sb2O3, and Keysight semiconductor device analyzer (B1500A). All the measure­
graphite powders (~99.99%). The weights of ZnO, Sb2O3 powder, and ments were conducted at room temperature in ambient air.
graphite powder were set to a 9:1:10 ratio. The well-mixed powder was
contained in a corundum boat, and then placed at the heating zone in the 3. Results and discussions
quartz tube. A clean Si substrate without any metal catalyst or seed layer
was perpendicularly placed on the corundum boat at a distance ~1.55 Using one-step CVD method, individual ZnO:Sb MWs with high
cm away from the top surface of the precursor source. A flow of mixed yields and high crystalline quality have been synthesized [45,47,48]. A
argon (Ar) and oxygen (O2) gases at 125 and 10 sccm, respectively, was typical SEM image in Fig. 1(a) reveals that the CVD-grown single ZnO:Sb

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Fig. 1. Sample characterization of CVD-synthesized

ZnO:Sb wires. (a) SEM image of a single ZnO:Sb
MW. (b) EDS mapping result of a ZnO:Sb MW,
showing the uniform elements of Zn, Sb, and O spe­
cies. (c) XRD result of the CVD-synthesized ZnO:Sb
samples. (d) A schematic illustration of the single
ZnO:Sb MW based FET device. (e) Output character­
istics of a single ZnO:Sb MW based FET by varying the
backgate voltages. Inset: The Ids-Vds plot for the ZnO:
Sb MW based FET at a Vds of 1.0 V. (f) The corre­
sponding Ids-Vg plot at a Vds = 1.0 V.

MW exhibited straight, sharp edges, smooth side facets, and quadrangle further shown in the inset of Fig. 1(e). In addition, by varying the
morphologies. Fig. 1(b) shows the EDS mapping of a ZnO:Sb MW, dis­ back-gate voltages of Vg, the source-drain current (Ids) was determined,
playing the coexistence of Zn, Sb, and O species. The crystalline struc­ as shown in Fig. 1(f). From the electrical measurements, the monotonic
tures of the as-synthesized ZnO:Sb samples were analyzed. Fig. 1(c) increase in the drain current Ids with increasing negative gate bias in­
shows the XRD patterns of CVD-synthesized ZnO:Sb samples, exhibiting dicates p-type conduction [45,49].
strong diffraction peaks at 31.6◦ , 34.3◦ , and 36.1◦ , which correspond to PEDOT:PSS organic polymers have been widely utilized as alterna­
the (100), (002), and (101) crystal planes, respectively [45]. The XRD tive transparent conducting materials owing to their superior carrier
results confirmed that our samples have a hexagonal wurtzite structure. mobility, large work function, and excellent transparency over a wide
The conductivity of the individual ZnO:Sb samples was determined by spectral range. However, the electrical properties of pristine PEDOT:PSS
the characterization of a single wire based FET devices. In the FET de­ films, especially for the conductivity, is much poorer than that of con­
vice structure, a Si substrate coated with a SiO2 nanofilm (thickness ~ ventional p-type semiconductor materials [23,29,33]. As previously
300 nm) was utilized as the back-gate and dielectric gate oxide. A reported, DMSO has been employed as an organic solvent to enhance the
schematic of a single ZnO:Sb wire-FET device is shown in Fig. 1(d). The electrical properties of PEDOT:PSS polymers [34,41–43]. Nevertheless,
physical channel length measured between the source and drain elec­ the photoresponse performances of photodetectors and solar cells that
trodes (Au) was extracted as approximately 50 μm. Fig. 1(e) depicts the use PEDOT:PSS as a hole-conducting polymer are still significantly
variation in the source-drain current (Ids) as a function of the influenced by the carrier transport properties of the photogenerated
source-drain voltage (Vds) when operated at different back-gate voltages electron-holes. CNHs, which are conical carbon nanostructures, were
(Vg). The enlarged view of the Ids-Vds curves around Vds = 1.0 V is further introduced to treat the PEDOT:PSS polymer. Fig. 2(a) shows the

Fig. 2. The modulation of CNHs&DMSO on the

photon-electrical properties of the pristine PEDOT:
PSS polymer film. (a) TEM observation of the CNHs.
(b) The transmission spectra of the untreated PEDOT:
PSS sample, and the PEDOT:PSS sample treated by
CNHs&DMSO. (c) Schematic illustration of the
PEDOT:PSS microribbon-like structure device, with
Ag pastes working as the symmetrical electrodes. The
corresponding current-voltage relationship of a single
PEDOT:PSS microribbon-like structure device, in
which (d) the PEDOT:PSS sample is untreated and (e)
the PEDOT:PSS samples are treated by DMSO and
CNHs&DMSO, respectively. (f) I–V characteristics of
the untreated PEDOT:PSS film in the dark and under
different-wavelength light illumination, respectively.

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Fig. 3. Device fabrication and characterization of the

as-constructed single ZnO:Sb MW double hetero­
junction photodetectors. (a) Schematic of n-type Si
substrate. (b) Using electron-beam evaporation, Au
electrode was evaporated on the cleaned Si substrate;
then two MgO films were further evaporated on the
both sides of Si substrate. (c) A single ZnO:Sb wire
was mechanically placed on the Si substrate, with the
pre-prepared MgO films distributed along the bilat­
eral sides of the wire. (d) Photodetecting device
structure based on the designed double-
heterojunction, which is composed of a ITO con­
ducting glass covered by a PEDOT:PSS polymer film,
a ZnO:Sb MW, and a Si substrate. In the device, ITO
and Au were employed as electrode materials. (e) I–V
characteristics curves of the fabricated p-ZnO:Sb
MW/n-Si heterostructured device and p-PEDOT:PSS/
p-ZnO:Sb MW heterostructured device, respectively.
(f) The logarithmic I–V characteristics of the fabri­
cated p-PEDOT:PSS/p-ZnO:Sb MW/n-Si double het­
erostructured device (Device-1) in the dark and under
light illumination at 370 nm (the light power in­
tensity ~ 70 mW/cm2). (g) Transient responses of the
fabricated single ZnO:Sb MW double-heterojunction
photodetector (Device-1) at 370 nm illumination at
a reverse bias voltage of − 10 V. (h) The illuminated
light wavelength-dependent photoresponsivity and
EQE at a reverse bias voltage of − 10 V. (i) Schematic
energy band diagram of Device-1 under 370 nm ul­
traviolet illumination at a reverse bias voltage of − 10
V.

TEM image of the as-synthesized CNHs samples. The optical properties

Table 1
of the PEDOT:PSS samples, untreated and treated with CNHs via DMSO,
The electrical conductivities of the fabricated microribbon-like PEDOT:PSS de­
were measured, respectively. The transmittance spectra are shown in
vices, in which the PEDOT:PSS polymer films were untreated, treated by DMSO
Fig. 2(b). It is clearly illustrated that the transmittances are measured to
additive, and treated by DMSO&CNHs co-additive, respectively.
be approximately 80% in the ultraviolet–visible wavelengths. In
Sample x (mm) y (mm) z (μm) G (S) σ (S/
particular, the negligible influence of CNHs&DMSO on the trans­
m)
mittance of PEDOT:PSS samples indicates that the introduced
CNHs&DMSO exhibit nearly negligible absorbability at optical pristine PEDOT:PSS 0.770 2.42 1.26 2.09 × 60
10− 3
wavelengths. DMSO-PEDOT:PSS 0.582 2.46 1.50 2.01 × 5666
The influence of DMSO and CNHs&DMSO on the electrical conduc­ 10− 3
tivities of the PEDOT:PSS samples were studied severally. The precursor CNHs&DMSO-PEDOT: 0.686 2.32 1.37 2.40 × 5933
PEDOT:PSS aqueous solution was spin-coated onto a quartz substrate at PSS 10− 3
2000 rpm for 1 min. A metal-semiconductor-metal device based on the
untreated and treated PEDOT:PSS solution was constructed, respec­
conductivity in the prepared PEDOT:PSS polymer film was ascribed to
tively. A schematic of the fabricated single-microribbon-like device is
the intermolecular interactions between DMSO and the sulfonic acid
shown in Fig. 2(c), where x and y are measured under an optical mi­
groups of PSS. The introduction of DMSO can remove and dissolve the
croscope, and z is obtained from the AFM results. In the fabricated single
PSS molecules, weakening the Coulombic attraction between the PEDOT
microribbon-like PEDOT:PSS devices, Ag paste was employed as sym­
and PSS chains. Therefore, the incorporated DMSO can rearrange the
metrical electrodes. The electrical properties of the pristine PEDOT:PSS
PEDOT polymer chains and optimize the inter-chain interactions, thus
polymer, the PEDOT:PSS polymers treated by DMSO solvent and
enhancing the conductivity [34,41–43]. On this basis, the solution of
CNHs&DMSO co-solvent, were tested at room temperature, respectively.
CNHs was added to the PEDOT:PSS polymer, which has been treated
The corresponding I–V curves are shown in Fig. 2(d) and (e), respec­
with DMSO. The conductivity of the PEDOT:PSS polymer films
tively. By a comparison, the conductivities of the three PEDOT:PSS
co-treated with CNHs and DMSO was calculated to be approximately
samples were evaluated according to the following formula [34,50]:
5933 S/m. There is an insignificant modulation of the electrical con­
y y dI ductivity of the PEDOT:PSS polymer film. Compared to the pristine
σ=G • = • (1)
xz xz dV PEDOT:PSS, the conductivity of the PEDOT:PSS polymer materials can
be significantly increased by DMSO treatment [35,51,52]. In addition,
where σ and G are the conductivity and conductance, respectively. x, y, the photoelectrical properties of the pristine PEDOT:PSS film, the
and z are the three-dimensional sizes of the fabricated single- PEDOT:PSS film treated with DMSO solvent, and the CNHs&DMSO
microribbon-like devices. Additionally, the dI/dV values can be co-additive, were studied. The PEDOT:PSS film-based device was char­
derived from the plotted I–V curves. The conductivities of the prepared acterized under monochromatic light irradiation at wavelengths ranging
PEDOT:PSS polymer films can be obtained according to Eqn. (1). from 350 to 550 nm. The I–V curves in Fig. 2(f) reveals that the PEDOT:
As shown in Table-1, the conductivity of the untreated PEDOT:PSS PSS film has little photoresponse to ultraviolet and visible light signals,
polymer film was approximately 60 S/m. After the handling by the so the PEDOT:PSS films are also treated by the DMSO solvent and
DMSO additive, the conductivity was increased up to approximately CNHs&DMSO co-additive.
5666 S/m. As previously reported, the mechanism of DMSO-enhanced As we described in the Experimental Section, a photodetecting

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device composed of an ITO conducting glass covered by a layer of p-type were firstly determined when operated at a reverse bias voltage of − 10
PEDOT:PSS polymer, a single p-ZnO:Sb MW, and an n-type Si substrate V. Shown in Fig. 3(h), the responsivity and EQE were maximal at a light
was fabricated. The device that used an untreated PEDOT:PSS layer was wavelength of 370 nm with an optical power intensity of 70 mW/cm2.
defined as Device-1. Fig. 3(a)–(d)illustrate the process for the fabrication The maximum responsivity was calculated as approximately 177.5 A/W.
of ITO/p-PEDOT:PSS/p-ZnO:Sb MW/n-Si double heterojunction photo­ The maximum EQE was derived as approximately 5.9 × 104% (Fig. 3(h),
detector, and the specific steps have been expressed in detail in the the green solid line). Consequently, the as-designed ITO/p-PEDOT:PSS/
experimental part. A schematic illustration of the as-designed p-PEDOT: p-ZnO:Sb MW/n-Si double heterojunction can be used to construct ul­
PSS/p-ZnO:Sb MW/n-Si heterostructure photodetector is expressly traviolet photodetectors.
shown in Fig. 3(d). First, uniform coverage of the PEDOT:PSS film with a To exploit the working mechanism, the ultraviolet photoresponse
thickness of 80 nm over the ITO glass can be realized. During the performance in such devices can be expressed by the feature of their
preparation, the PEDOT:PSS solution, spin speed, and annealing tem­ energy-band alignment. A schematic illustration of the carrier transport
perature and time could be modulated to obtain highly smooth PEDOT: mechanism of the fabricated ITO/p-PEDOT:PSS/p-ZnO:Sb MW/n-Si
PSS films with uniform thickness, thus achieving the reduction of heterojunction photodetector is presented in Fig. 3(i). When the PEDOT:
interface traps and optimizing junction properties [44,53]. Electrical PSS, ZnO:Sb MW, and n-Si substrate are in contact in the dark, electron
properties of as-constructed p-PEDOT:PSS/p-ZnO:Sb MW and p-ZnO:Sb transfer occurs across the interface from Si to ZnO:Sb, and the holes
MW/n-Si heterostructure devices should be examined, respectively. As travel in the opposite direction until their Fermi levels become aligned,
previously reported, a single wire-type organic-inorganic hybrid device yielding the generation of a built-in potential ΔE1. The band would bend
composed of a ZnO:Sb MW with one segment covered by a PEDOT:PSS at the ZnO:Sb/Si heterointerface [20,21]. As we previously described
polymer film was fabricated [45,54]. The I–V curve of the fabricated above, a p-p heterojunction can be generated at the ZnO:Sb/PEDOT:PSS
p-PEDOT:PSS/p-ZnO:Sb MW heterostructured device is shown in Fig. 3 interface because of the diffusion movement of holes. Thereby, a space
(e) (red-point plot), illustrating the diode-like property. This diode-like charge region is created at the heterointerface between ZnO:Sb MW and
property could be assigned to the p-p heterojunction, which is formed PEDOT:PSS film, resulting in a built-in electric field ΔE2, which main­
between the p-ZnO:Sb MW and p-PEDOT:PSS films [41,55]. The elec­ tains the balance between the drift movement and diffusion movement
trical transport characterization of the p-ZnO:Sb MW/n-Si hetero­ of holes under the zero-bias condition (See Fig. 3(i)) [41,58]. Illustration
structured device was also performed, and the I–V curve is also plotted in energy band diagram, the direction of the built-in electric field ΔE1 at
in Fig. 3(e) (navy blue-point plot). It is demonstrated that the observed the p-ZnO:Sb/n-Si heterointerface is in accordance with ΔE2. The pho­
rectifying behavior can be attributed to the p-n heterojunction formed togenerated electron-holes can occur when the device is illuminated by
between the ZnO:Sb MW and Si substrate [20,56]. ultraviolet light (~370 nm). Under the driven of built-in electric field
The electrical characterization of as-constructed p-PEDOT:PSS/p- force ΔE1 and the applied reverse bias voltage, the photogenerated
ZnO:Sb MW/n-Si heterostructure device was measured, and the typical electron-hole pairs will be separated in opposite directions, which re­
I–V characteristics in darkness on the logarithmic ordinate scale is sults in photocurrent generation in the external circuit. At the interface
depicted in Fig. 3(f) (the blue point-line plot). The rectification ratio is between ZnO:Sb MW and PEDOT:PSS layer, the built-in electric field
evaluated to about 4.25 at ± 10 V, thus resulting in a double hetero­ ΔE2 can significantly facilitate the transport of photogenerated holes,
junction. Upon illumination at 370 nm with an optical power intensity of resulting in a significant enhancement of the external current.
70 mW/cm2, the photoelectrical results in Fig. 3(f) (violet point-line As we mentioned above, electrical properties of the pristine PEDOT:
plot) show a noticeable increase in the photocurrent compared to that PSS polymer can be observably increased using a treatment of
in the dark. Fig. 3(g) illustrates the photoswitching characteristics of the DMSO&CNHs solvent. The photodetector using the DMSO&CNHs-
fabricated double heterojunction device when operated at a reverse bias treated PEDOT:PSS polymer layer as the hole conducting polymer was
of − 10 V. It is evident that the fabricated device rapidly responds to the defined as Device-2 for a comparison. To investigate the influence of the
switching of the illumination light between the ON and OFF states. The DMSO&CNHs additive on the photoresponse performance of the con­
ON/OFF current ratio reached ~15-fold. Therefore, the p-PEDOT:PSS/ structed photodetectors, light-detecting measurements of the I–V char­
p-ZnO:Sb MW/n-Si double heterojunction can monitor ultraviolet light acteristic curves, photoresponsivity spectra, and EQE were performed.
signals. Fig. 4(a) shows the I–V characteristics of Device-1 and Device-2, which
The photoresponsivity (R) and EQE were calculated to evaluate the were operated under dark and 370 nm light illumination with a light
photoresponse performance of the fabricated p-PEDOT:PSS/p-ZnO:Sb power intensity of 70 mW/cm2. As shown in the image, the dark current
MW/n-Si heterostructured devices [45,56,57]. R is typically defined as of the fabricated devices increased from 1.8 × 10− 4 A to 5.0 × 10− 4 A at
the photocurrent, which could be generated in the effective area of the a reverse bias voltage of − 10 V by introducing the DMSO&CNHs addi­
photodetectors per unit of excited light power. Thus, R is derived using tive into the pristine PEDOT:PSS polymer. This phenomenon can be
the following formula: attributed to the enhanced conductivity of PEDOT:PSS film. Both de­
vices demonstrated an apparent photoresponse when exposed to 370 nm
Iph − Id
R= (2) ultraviolet irradiation. Device-2 exhibited a noticeable increase in the
PA
photocurrent, which was larger than that of Device-1 at − 10 V. The
While an important figure of merit for the photodetectors, EQE, reverse bias-dependent photocurrent-enhanced ratio of Iph(Device-2)/Iph
describing the photoelectric transition efficiency of the photodetectors, (Device-1) is shown in Fig. 4(b), revealing that the largest ratio was
was also employed to depict the photoresponse characteristics. The EQE extracted to about 3-fold. The switchable photoresponse properties of
is defined by the following formula: the devices were measured. Fig. 4(c) shows the time-dependent photo­
Rλ hc currents of different photodetectors under 370 nm light illumination
EQE = (3) with an optical power intensity of 70 mW/cm2 at a reverse bias voltage
eλ
of − 10 V. It can be observed that the output currents of Device-2 are
In the formula, Iph, Id, P, and A are the photocurrent, dark current, significantly increased for the dark and light-on conditions, as compared
the optical power of incident light, and the effective irradiation area, to that of Device-1.
respectively. In addition, λ, h, and c are the wavelength of the incident The spectral photoresponse of the devices was measured as described
light, Planck’s constant, and velocity of light, respectively. To precisely in the Experimental Section. Fig. 4(d) illustrates the wavelength-
demonstrate the sensitivity of the fabricated p-PEDOT:PSS/p-ZnO:Sb dependent photoresponse spectra of Device-1 and Device-2 at − 10 V,
MW/n-Si heterostructure photodetector (In the fabricated photode­ respectively. In the photoresponse measurements, the light power in­
tector, the PEDOT:PSS sample was untreated.), the responsivity and EQE tensity was fixed at 70 mW/cm2. The maximum photoresponsivity of the

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Fig. 4. Comparison of the photoresponse properties

for the fabricated photodetectors, in which the
PEDOT:PSS samples are untreated and treated by
CNHs&DMSO solvent. (a) The logarithmic I–V char­
acteristics of the fabricated Device-1 and Device-2 in
dark and under light illumination at 370 nm (The
light power intensity ~ 70 mW/cm2). (b) The
photocurrent ratio of IDevice-2/IDevice-1 as a function of
the reverse bias voltage. (c) Comparative photo­
response behaviors of the different photodetecting
devices under alternating on and off cycles at 370 nm
light illumination with a light intensity of 70 mW/
cm2. The devices were operated at a reverse bias
voltage of − 10 V. (d) Wavelength-dependent photo­
responsivity of the fabricated Device-1 and Device-2
operated at a reverse bias voltage of − 10 V is given
for comparison. (e) Wavelength-dependent photo­
responsivity-enhanced ratio of the devices. (f)
Wavelength-dependent EQE of the fabricated Device-
1 and Device-2 operated at a reverse bias voltage of
− 10 V is given for a comparison.

devices peaks at approximately 370 nm, which is in good accordance of the photoresponse peak increases from 177.5 A/W to 450.0 A/W. In
with the resulting ultraviolet–Visible transmission and absorption addition, the responsivity at visible wavelengths exhibits an observable
spectra of ZnO:Sb samples [45,56]. The sharp photoresponse peak at a increase in the photoresponse intensity. The enhanced photo­
wavelength of ~370 nm suggests that the electron-hole pairs generated responsivity at visible wavelengths could be attributed to the excellent
in the ZnO:Sb MW active region contribute to the photocurrent through transport capacity of electron-holes generated in the Si substrate [51,
the separation of the photogenerated carriers. By introducing the 52]. The dependence of RDevice-2/RDevice-1 enhancement ratio on the
DMSO&CNHs solvents into the PEDOT:PSS polymer layer, the intensity illuminated light wavelengths is shown in Fig. 4(e). Accordingly, the

Fig. 5. Light-power-intensity-dependent I–V charac­

teristics of the fabricated Device-1 (a) and Device-2
(b) under 370 nm light illumination. (c) Light
power density dependent photocurrents of the fabri­
cated Device-1 and Device-2 when operated at a
reverse bias voltage of − 10 V. (d) Light power density
dependent responsivities of the fabricated Device-1
and Device-2 when operated at a reverse bias
voltage of − 10 V. (e) Light power density dependent
RDevice-2/RDevice-1 ratio of the fabricated devices at a
reverse bias voltage of − 10 V. (f) Light power density
dependent EQE of the fabricated Device-1 and
Device-2 at a reverse bias voltage of − 10 V. Time-
transient photoresponses under an inverse bias of
− 10 V at 370 nm light illumination with different
power densities (g) for the Device-1 and (h) for the
Device-2.

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wavelength-dependent EQE of Device-1 and Device-2 working at − 10 V particular, the photocurrents obtained for Device-2 at any fixed light
bias is depicted in Fig. 4(f). Clearly, the intensity of the maximum EQE power intensity were observably larger than those of Device-1. Due to
increased from 6.0 × 104% to 1.5 × 105%. The enhancement of the the modulation of the electrical properties of the PEDOT:PSS polymer
spectral photoresponse in the as-constructed single ZnO:Sb MW films using the CNHs&DMSO solvent, the comprehensive photo­
organic-inorganic double heterojunction photodetectors can be attrib­ detection capabilities of the fabricated p-PEDOT:PSS/p-ZnO:Sb
uted to the improved electrical properties of the PEDOT:PSS polymer, MW/n-Si double heterojunction devices can be greatly improved.
which was treated using the DMSO&CNHs solvents. In addition to the above-mentioned figures of merit, the response
When operated under 370 nm light illumination with different op­ speed and stability are also considered as important indices to assess the
tical power intensities in the range of 0–70 mW/cm2, the photoelectric optoelectronic capability of the fabricated photodetectors, revealing
performances of the fabricated single ZnO:Sb MW double- their great potential for monitoring ultrafast optical signals. To evaluate
heterojunction photodetectors were further investigated. Fig. 5(a) and the response of the photodetector to an ultrafast pulse signal, the
(b) show the I–V curves of Device-1 and Device-2, respectively. As ex­ response characteristics of the devices to a pulsed laser (370 nm, 10 Hz)
pected, the photocurrent increased significantly with an increase in the and an oscilloscope were measured. As illustrated in Fig. 6(a), there is no
light intensity at a reverse bias of − 10 V. That is, the number of free noticeable change in the output bias during each cycle, indicating the
carriers exhibits a linear enhancement with the increase of incident outstanding reproducibility and stability of the fabricated single ZnO:Sb
photons, which have been absorbed by the devices. When working at a MW double-heterojunction photodetector. In addition, the output bias
reverse bias voltage of − 10 V, the relationship of the corresponding of Device-1 increased rapidly and reached a steady state when the laser
photocurrents as a function of the light power intensity can be well light was turned on and decreased quickly after the laser was turned off,
fitted, as illustrated in Fig. 5(c). The results showed a promising linear indicating the high response speed of the photodetector. And the pho­
inclination in the photocurrent values with increasing incident optical toresponse speed was above the detection limit of Keysight B1500A. As
power. In addition, the photocurrents of Device-2 were much larger than illustrated in Fig. 6(b), the response time is accurately characterized by
those of Device-1. the time taken from 10% to 90% of the maximum photocurrent;
The light-power-intensity-dependent responsivity and EQE of the whereas, to better assess the decay process, a second-order exponential
devices were analyzed, and are shown in Fig. 5(d)–(f). In the measure­ fit was applied (shown in the inset of Fig. 6(b)) [14,25,42]. The pho­
ment, the devices were operated at − 10 V under 370 nm light illumi­ toresponse switching curve shows that the photodetector could accu­
nation. The calculated responsivities and EQE decreased monotonously rately distinguish and respond to each pulsed signal, giving rise to an
by varying the light intensity owing to hole-trapping saturation [42,45, ultrafast rising/falling times of 238 μs/4.76 ms, respectively. The fast
54]. From these figures, the calculated R and EQE of Device-2 are as high response/recovery speeds of the device are believed to be related to the
as 737.8 A/W and 2.60 × 105%, respectively. These values are almost rapid separation and transportation of photogenerated electron-hole
2.5-fold larger than those of Device-1. Fig. 5(g) and (h) show the tran­ pairs by the built-in electric field in combination with the applied
sient response of the photodetectors at a reverse bias voltage of − 10 V at reverse bias voltage at the junction interface.
370 nm light illumination with optical power intensities ranging from 1 The photoresponse time of Device-2 was further tested at − 10 V bias
to 70 mW/cm2, respectively. As illustrated in the figures, the fabricated voltage upon 370 nm laser excitation. The transient response results are
photodetectors instantaneously reacted with the light-switching trans­ shown in Fig. 6(c), which exhibits a steady, rapid, and repeatable pho­
formation and generated a corresponding current, demonstrating the toresponse with a sharp pulse signal. Accordingly, the time-resolved
excellent sensitivity and repeatability of our devices. In addition, a photoresponse of a single periodic pulse is shown in Fig. 6(d). The fast
complete evolution process of the overshooting feature can be observed response time, with a rise time of 67 μs and a decay time of 2.29 ms,
from the shapes of the photoresponse curves with rounded heads. In respectively, can be derived. By a comparison, the faster photoresponse

Fig. 6. Photoresponse characteristics of the fabricated Device-1 under 370 nm pulse laser irradiation with a modulation frequency of 10 Hz at − 10 V bias: (a)
multiple cycles and (b) one cycle with the calculated rising/falling times. Photoresponse feature of the fabricated Device-2 under 370 nm pulse laser irradiation with
a modulation frequency of 10 Hz at a reverse bias voltage of − 10 V: (c) multiple cycles and (d) one cycle with the calculated rising/falling times.

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speed achieved in Device-2 can be attributed to the PEDOT: PSS polymer DMSO&CNHs co-treated PEDOT:PSS film can be responsible for the
materials, which have been treated by the CNHs&DMSO solvent. observably enhanced photocurrents in the as-designed p-PEDOT:
To understand the influence of CNHs&DMSO on the photoresponse PSS/p-ZnO:Sb MW/n-Si double heterojunction photodetectors.
performance, three devices based on carefully designed ITO/p-PEDOT: The stability of the fabricated ITO/p-PEDOT:PSS/p-ZnO:Sb MW/n-Si
PSS/p-ZnO:Sb MW/n-Si double heterojunction structures were further double heterojunction photodetector is critical to meet real-world ap­
fabricated. In the devices, the used PEDOT:PSS films were untreated, plications. In photodetectors, the used PEDOT:PSS materials have been
treated with DMSO solvent and CNHs&DMSO solvent, respectively. The treated using CNHs&DMSO solvent. In general, the stability of photo­
photoelectric properties of the fabricated double heterojunction photo­ detectors can be divided into their photostability and long-term stabil­
detectors were studied. The logarithmic I–V curves of these photode­ ity. First, photostability is evident from the transient switching response
tectors in the dark and under 370 nm light illumination at an optical of the as-constructed double-heterojunction photodetector. The photo­
power intensity of 70 mW/cm2 are shown in Fig. 7(a)-(c) sequentially. switching responses were recorded for a constant operation at − 10 V
Furthermore, the transient photoresponses of the three fabricated de­ under 370 nm light illumination with an optical power intensity of 70
vices under ultraviolet light illumination at 370 nm were tested, and are mW/cm2. As illustrated in Fig. 8(a), Device-2 exhibits stable and
shown in Fig. 7(d). All photoresponse measurements were performed at reproducible ON/OFF behavior over 190 consecutive cycles, especially
a reverse bias voltage of − 10 V, and the incident light power intensity for electrically stable features. Subsequently, the as-prepared ITO/p-
was fixed at 70 mW/cm2. The measured photocurrent under ON/OFF PEDOT:PSS/p-ZnO:Sb MW/n-Si double heterojunction devices are kept
ultraviolet light was calculated and found to be − 1.2, − 1.78, and − 3.66 in an air environment with 50% humidity for about eight weeks, while
mA, respectively. Interestingly, the photocurrent of the detector using without any encapsulation and protection. During the stored procedure,
the CNHs&DMSO-treated PEDOT:PSS polymer film was 2-fold larger we conducted a stability measurement of the fabricated photodetector,
than that of the device in which the p-PEDOT:PSS polymer film was observing its photoswitching responses when measured at − 10 V under
treated with DMSO solvent; while the photocurrent was 3-fold larger 370 nm illumination via light power intensity ~70 mW/cm2. The
than that of the device in which the p-PEDOT:PSS film was untreated. measured time-domain response of the device over a series of ON/OFF
Besides, the ON/OFF ratios of the fabricated devices were evaluated to switching cycle. It suggests that the photodetector maintained a good
approximately 6.5 (for the pristine PEDOT:PSS), 3.9 (for the DMSO electrical stability without degrading the photoactive PEDOT:PSS
treated PEDOT:PSS), and 10.1 (for the DMSO&CNHs cotreated PEDOT: polymer. The experimental results suggest that the proposed photode­
PSS), respectively. tector is suitable for long-term, highly reliable ultraviolet photo­
The origin of DMSO and CNHs on the photoresponse-enhanced detection. By comparing with previously reported literature on the
characteristics of the fabricated photodetection devices were studied. demonstration of Si-based heterojunction ultraviolet photodetectors, the
In the PEDOT:PSS polymer, the modulation of DMSO solvent can be photoresponse performances of our fabricated ITO/p-PEDOT:PSS/p-
employed to eliminate PSS and enrich the corresponding PEDOT grains, ZnO:Sb MW/n-Si double heterojunction photodetectors that operate at
thus producing more hopping positions for charge carriers and charge reverse bias voltage is preeminent (see Table 2). The double hetero­
conduction [34,41,43]. The incorporation of CNHs can boost the acti­ junction photodetectors proposed and demonstrated in this study can
vation energy and mobility of the charge carriers in the DMSO-treated achieve ultrahigh photoresponsivity and EQE, thus exhibiting consid­
PEDOT:PSS polymer. The DMSO&CNHs co-treated composite polymer erably good comprehensive performances.
film can supply a rapid transfer pathway of the charge carriers and
abundant ion diffusion channels [37,51,52]. Under ultraviolet light 4. Conclusion
illumination, electrons located in the valence band of the ZnO:Sb wires
can be easily excited up to the conduction band, generating electro­ In summary, a new generation of high-performance ultraviolet
n–hole pairs inside the ZnO:Sb samples. Driven by the applied reverse photodetectors based on ITO/p-PEDOT:PSS/p-ZnO:Sb MW/n-Si double
bias voltage and built-in potential, an optical current in the external heterojunctions was successfully proposed and demonstrated. The
circuit is formed. The enhanced electrical properties of the as-prepared photoresponse characteristics of the proposed photodetector were

Fig. 7. Investigation of the photoresponse-enhanced

mechanism for the fabricated single ZnO:Sb MW
double-heterojunction photodetectors. The logarith­
mic I–V characteristics of the devices in the dark and
under the 370 nm illumination with the optical power
intensity of 70 mW/cm2, in which the PEDOT:PSS
film is untreated (a), treated by DMSO (b), and
treated by CNHs&DMSO (c). (d) Comparison of the
time-resolved photoresponses of the fabricated
different photodetectors under 370 nm light irradia­
tion at a power density of 70 mW/cm2 at a reverse
bias voltage of − 10 V.

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Fig. 8. Photostability and long-term stability mea­

surement of the fabricated single ZnO:Sb MW double
heterojunction photodetector. (a) 190 cycles of tran­
sient photoresponse curve of the fabricated PEDOT:
PSS/ZnO:Sb/Si double heterojunction photodetector
under 370 nm light illumination of 70 mW/cm2 at a
reverse bias of − 10 V. In the device, the used PEDOT:
PSS films is treated by CNHs&DMSO. Inset: Enlarged
5 cycles photoresponse curves. (b) Long-term test of
the photoswitching features of the fabricated device
(~8 weeks). (c) Photocurrent of the device under 370
nm light illumination at a reverse bias voltage of − 10
V.

Table 2
A comparison between the fabricated p-PEDOT:PSS/p-ZnO:Sb MW/n-Si double heterojunction photodetector in this work and other previously reported works on the
Si-based ultraviolet photodetectors.
Photodetector Bias Wavelength (nm) Responsivity (A/W) EQE Response time Ref.

black phosphorus/Si − 5V 300–1600 3.2 1217% 22/50 ms [59]

Zn:NiO/p-Si − 4V 350–650 0.945 184% <0.15/0.1 s [60]
Te/p-Si − 2V 370–2240 249 76,350% 3.7/4.4 ms [61]
ZnO/NiO/Si − 8V 26–600 ~100 – 14.8/9.7 s [62]
TiO2/Si − 4V 365 6.74 – 127.6/120.3 μs [63]
ZnO/Si − 4V 300 ~100 – 16.6/12.8s [64]
Si/NiO − 2V 350–600 0.43 89.5% <30/30 ms [65]
PEDOT:PSS/ZnO:Sb MW/Si (untreated) − 10 V 370 323.2 1.08 × 105% 238 μs/4.76 ms This work
PEDOT:PSS/ZnO:Sb MW/Si (DMSO&CNHs co-treatment) − 10 V 370 737.8 2.6 × 105% 67 μs/2.29 ms This work

significantly increased by modulating the electrical properties of the analysis, Device Characterizations. Daning Shi: Supervision, Funding
PEDOT:PSS polymer through treatment with the DMSO&CNHs solvent. acquisition. Caixia Kan: Conceptualization, Funding acquisition,
Upon ultraviolet irradiation of 370 nm incident light at an external bias Formal analysis, Supervision. Mingming Jiang: Conceptualization,
voltage of − 10 V, the treated photodetector revealed a strong respon­ Resources, Methodology, Data Curation, Funding acquisition, Writing-
sivity of approximately 737.8 A/W and a high EQE of approximately 2.6 review & editing, Supervision. All authors read and approved the final
× 105%, which are much larger than that of the untreated devices. manuscript.
Further, the transient response manifests their high repeatability and
fast photoresponse speed of rising/falling times ~67 μs/2.29 ms. The Declaration of competing interest
photoresponse-enhanced mechanism of the carefully designed single
ZnO:Sb MW double heterojunction photodetectors was studied and can The authors declare that they have no known competing financial
be assigned to follows (i) the improved electrical properties of p-PEDOT: interests or personal relationships that could have appeared to influence
PSS transparent conductive materials via DMSO&CNHs treatment; (ii) the work reported in this paper.
the created p-p heterojunction at PEDOT:PSS/ZnO:Sb interface can
facilitate a faster hole transport, thus lowering the recombination rate of Acknowledgements
photogenerated carriers and increase the photoresponse behavior. This
work can open a new avenue approach for developing high-performance This study was supported by the National Natural Science Founda­
low-dimensional ultraviolet photodetector for future photoelectronic tion of China (Grant Nos. 11974182, 11874220 and 52202099), the
applications, even on Si-chip optoelectronic integrated systems. Fundamental Research Funds for the Central Universities (NO.
NC2022008), and Funding for Outstanding Doctoral Dissertation in
CRediT authorship contribution statement NUAA (BCXJ22-14).

Qingheng Li: Conceptualization, Methodology, Sample Preparation References

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