Showcasing work from Professor Wenping Hu’s laboratory,

School of Science, Tianjin University, Tianjin, China. As featured in:

Organic photodiodes and phototransistors toward infrared Volume 49
Number 3
7 February 2020
Pages 647–1034

detection: materials, devices, and applications

Chem Soc Rev
Chemical Society Reviews

The active layer engineering, device construction and

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integrated applications for infrared organic photodiodes

and phototransistors are discussed in this tutorial review.

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Jiagang Wu et al.
Emerging new phase boundary in potassium
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See Xiaotao Zhang,

Wenping Hu et al.,
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Organic photodiodes and phototransistors toward

infrared detection: materials, devices, and
Cite this: Chem. Soc. Rev., 2020,
49, 653 applications
Cong Wang, Xiaotao Zhang * and Wenping Hu *

Because of their advantages, including easy tunability of optical and electrical properties by tailoring the
molecular structure, flexibility, and compatibility with a low-temperature fabricating process, the use of
organic semiconductors (OSCs) as active layers has shown strong competitiveness as candidates for use
in next-generation high-sensitivity organic photodetectors (OPDs). Infrared (IR) OPDs that are sensitive to
illumination at wavelengths higher than 780 nm have been rapidly developed in recent years driven by
potential applications such as remote control, night vision, and imaging as well as biomedical monitoring. In
this review, after a brief illustration of the mechanisms, we summarize the recent advances in high-
performance IR organic photodiodes (OPDIs) and organic phototransistors (OPTs). We will highlight the state-
of-the-art protocols for constructing qualified IR OPDs, including new OSCs with excellent photoelectric
Received 17th August 2019 properties, optimization of active-layer-fabrication processes, and novel device architectures. Thereafter, we
DOI: 10.1039/c9cs00431a will discuss the IR organic light detector as a platform for integrated applications, such as health monitoring,
spectrometric analysis, and electronic eyes. This review aims to provide readers with a deeper understanding
rsc.li/chem-soc-rev of the design of future IR OPDs and IR-OPD-based integrated practices.

Key learning points

(1) A general introduction to IR OPDIs and OPTs.
(2) Working principles of IR OPDIs and OPTs.
(3) State-of-the-art protocols for high-quality IR OPDIs and OPTs.
(4) Advanced integrated applications based on IR OPDs.
(5) Summary and perspectives on IR OPDs and their applications.

1 Introduction attention due to their promising applications, such as remote

sensing, health monitoring, spectrometric analysis, and night
In the recent years, organic electronic devices, such as field- vision.5–8 According to the application, the key parameters of the
effect transistors (FETs),1 photovoltaic devices (PVs),2 and light- PD, including the range of detectable waveband, photoresponsivity,
emitting diodes (LEDs),3 have seen rapid developments and can and detectivity, need to be adjusted to achieve an optimized
match or even exceed the corresponding performance of amor- performance.7 Indeed, inorganic silicon-based materials as active
phous silicon devices. Photodetectors (PDs) are the key components materials are quite stable. However, based on traditional silicon
in many optoelectronic devices, which convert incident photons semiconductors, the adjustment of device parameters is mainly
with different incident energies into modulable electrical signals.4 realized through doping via a complex process or the introduction
Unlike ultraviolet (UV) and visible (Vis) PDs (response wavelength: of microstructures, such as superlattices. The range of absorp-
o800 nm), infrared (IR) PDs, which are sensitive to illumination tion by photoelectric materials is mainly determined by the
with wavelengths greater than 800 nm, have attracted widespread bandgap of the semiconductor materials. For the IR region, the
performance of most silicon semiconductor materials is still
unsatisfactory.
Tianjin Key Laboratory of Molecular Optoelectronic Science, Department of
Chemistry, School of Science, Tianjin University & Collaborative Innovation Center
p-Conjugated organic semiconductors (OSCs) as active layers
of Chemical Science and Engineering (Tianjin), Tianjin 300072, China. are promising candidates for fabricating high-performance PDs,
E-mail: huwp@tju.edu.cn, zhangxt@tju.edu.cn stemming from their tunable electric energy levels and charge

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transport properties due to the innovative tailoring of organic energy (0.3–1 eV) upon illumination, resulting in the low
molecules in addition to the good compatibility with roll-to-roll, dissociation efficiency of the photogenerated excitons. (iii) The
inkjet printing, and other low-temperature fabrication processes carrier injection phenomenon from the electrode in the dark
over large areas.3–6 By designing a molecular structure with a cannot be ignored because of the reduction in the gap between
narrow bandgap and device optimization, the photoelectric the highest occupied molecular orbital (HOMO) and lowest
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response of the organic light detector, particularly in the IR unoccupied molecular orbital (LUMO) energy levels of the OSCs,
region, is expected to surpass that of a silicon semiconductor- leading to a high dark current.
based device. Moreover, unlike commercial inorganic IR PDs Thus far, tremendous efforts have been made worldwide for
operating at a low temperature, organic photodetectors (OPDs) designing high-sensitivity IR OPDs and their integrated appli-
are generally operable at room temperature, which leads to low cations. Several recent reviews have covered optoelectronic
energy requirements, facilitating real-time portable sensing.8 materials,3,5,6 solution-processed novel-concept PDs,7,9 and IR
However, the performance of currently available IR detectors photodiodes,8 as well as IR OPDs have been frequently dis-
has lagged behind their UV-Vis counterparts because of the cussed as a subsection of certain comprehensive reviews.4,10 In
following inevitable challenges. (i) The material design and general, the most widely studied IR detection devices can be
synthesis for effective light absorption in the IR region with classified into organic photodiodes (OPDIs) and organic photo-
good photogeneration yield and an excellent conducting char- transistors (OPTs) according to different device architectures
acteristic are difficult. (ii) The low dielectric constant of organic and operating mechanisms. Herein, by representing the recent
materials allows them to generate highly localized, tightly development and giving an overall picture of IR detection, we
bound Frenkel excitons (electron–hole pairs) with high binding aim to provide a systematic and accessible review covering
active layer processing, device configuration engineering based
on these two device architectures, and their forefront emerging
functional applications. In Section 2, we begin with the operating
Cong Wang grew up in the mechanism and the key parameters of IR detection devices. In
Tianjin Province, P. R. China. Section 3, we focus on advanced research works on IR-sensitive
She received her PhD from the OPDIs from two representative aspects. One is the active
Department of Chemistry, School layer design, including bulk heterojunctions (BHJs) and charge
of Science, Tianjin University, transfer complexes (CTCs), and the other is device engineering.
and the Collaborative Innovation In Section 4, state-of-the-art strategies for designing high-
Centre of Chemical Science and performance IR OPTs are revealed based on direct- and
Engineering (Tianjin) in 2019 indirect-response devices. Next, we discuss the IR organic light
under the supervision of Professor detector as a platform for integrated applications, such as
Wenping Hu. Then, she joined health monitoring, spectrometric analysis, and electronic eyes.
Nanyang Technological University Finally, after the summary, we suggest future directions and
as a research fellow. Her interest is opportunities in this field. It should be pointed out that this
Cong Wang in the field of organic electronics. review is not intended to provide an exhaustive summary of
Currently, she is working on all the relevant reports of the past decade on IR OPDs, but
infrared field-effect transistors rather highlight important protocols, opportunities, trends, and
fabricated by organic materials. challenges in this field.

Xiaotao Zhang is an Associate Wenping Hu is a Professor at

Professor at Tianjin University. He Tianjin University and a Cheung
was born in 1982 in the Henan Kong Professor of the Ministry of
Province, China. He received his Education, China. He received his
PhD from the Institute of PhD from ICCAS in 1999. Then,
Chemistry, Chinese Academy of he joined Osaka University and
Sciences, in 2012 after he got his Stuttgart University as a Research
MSc at Zhejiang University (2007). Fellow of the Japan Society for the
His research work includes the Promotion of Sciences and an
design and synthesis of novel Alexander von Humboldt fellow,
organic semiconductors, as well as respectively. In 2003, he worked
the fabrication and characterization with Nippon Telephone and
Xiaotao Zhang of organic optoelectronic devices. Wenping Hu Telegraph and then joined
ICCAS as a Full Professor. He
worked for Tianjin University in 2013. His research focuses on
organic optoelectronics.

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2 Brief illustrations of OPDIs and OPTs A good signal-to-noise performance is the prerequisite of a
high-sensitivity detector. The sensitivity (P), which is calculated
Generally, PDs, which explore the photoelectric properties from P = Iph/Idark, represents the ratio of light current to dark
of OSCs, are divided into several geometries: two-terminal current. Further, for precisely assessing the signal-to-noise
photodiodes and photoconductors, and three-terminal photo- ability, the specific detectivity (D*) or noise equivalent power
transistors.4 The most popular two-terminal OPDI geometry is
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(NEP) should be considered. The NEP is equal to the minimum

typically similar to that of organic photovoltaics (OPVs), as photosensitive power, which can be distinguished from noise;
shown in Fig. 1 (top left), where the organic photosensing it is expressed as NEP = in/R, where in is the root-mean-square
layers (with a heterojunction of different materials) are sand- value of the noise current. The D* value of the device is NEP
wiched between the anode and cathode electrodes (one of which normalized to the active area (A) and modulation frequency of
is semitransparent) with various interfacial layers. Unlike OPVs, the measurement (Df ), which can be calculated as D* = (ADf)1/2/
they are optimized for the applied reverse bias, which improves NEP in cm Hz1/2 W1 (i.e., Jones). Currently, many studies
charge generation and ensures fast charge carrier collection. regarding UV-Vis photodiodes have been used to determine the
Under illumination, the active layer generates electron–hole detectivity using the shot noise assumption (dark current is the
pairs by absorbing photon energy. Thereafter, the photogenerated major contributor to noise), which is expressed as Dh* = RA1/2/
electron–hole pairs are separated and collected by the electrodes. (2qIdark)1/2, as well as IR photodiodes. Actually, noise comes
The drift of the lowest current point is usually due to the photo- from many sources, such as shot noise, thermal noise, flicker
voltaic effect in the asymmetric device structure. noise, and other potential sources.9 However, in the IR range,
To evaluate the performance of OPDs, a series of figures of the dominant component is determined by the working condi-
merits have been used, namely, efficiency, noise, linear range, tion of the device. For example, shot noise only dominates at
and speed. Taking OPDI as the example, typical current–voltage high bias voltages, but thermal noise can overtake at low bias
( J–V) curves are shown in Fig. 1 (bottom left). The photo- voltages. Evidently, an unfaithful assumption often causes the
generated current (Iph), which is defined as the current flowing overestimation of detectivity, perhaps at an order of magnitude.
through the device under illumination as compared to that in the Currently, the direct determination of noise without any
corresponding dark state (Idark), is marked. The responsivity (R), assumption by a power spectral analyzer or lock-in amplifier is
which is expressed as R = Iph/Pin, represents the current flow per the most reliable strategy. In this regard, the key points for achieving
unit of incident light power (Pin). The external quantum efficiency high-sensitivity IR OPDIs are increasing the responsiveness and
(EQE) is an important parameter for evaluating the efficiency, reducing the dark noise.
which is defined as the ratio of the collected carriers (through The linear dynamic range (LDR) has several definitions.
internal electron–hole recombination, etc.) to the number of Commonly, it is the ratio of the maximum photocurrent
incident photons. Here, EQE = Iphhc/Pinlq = Rhc/lq, where h is (Iph,max) to the minimum photocurrent (Iph,min) over which
the Planck constant, c is the velocity of light, q is the charge unit, the current signal exhibits a linear response to the incident
and l is the excitation wavelength. For typical OPDIs, the EQE is power. It can be expressed in dB as LDR = 20 log(Iph,max/Iph,min)
necessarily below 100% because an incident photon produces at or in bits as LDR = log2(Iph,max/Iph,min). Alternatively, it can be
the most one electron–hole pair. expressed as LDR = 10 log(Pin,max/NEP), where Pin,max represents
the saturation signal power. When comparing the parameters
of different devices, it is important to pay attention to their
definitions and logarithmic factors. A wide LDR facilitates
quantitative detection and clear imaging. Due to the fact that
IR light is weak in practical applications, the LDR of detectors is
more related to the weakest light intensity that can be detected.
In addition, the temporal response time (t) can be defined as
the rise time (tr) from 10% to 90% and decay time (td) as that
from 90% to 10%, accompanying light illumination and
removal, respectively. Photodiodes typically permit t values at
the millisecond level due to the effective separation of the
photogenerated electron–hole pairs by the junction of the
active layer.
In photoconductors, which contain single-component materials
and a symmetrical plane or vertical device structure without
junction areas, EQE can exceed 100%, exhibiting a photo-
conductive gain (G) of 41 (G = tr/tt; number of collected
carriers divided by the number of incident photons; tr is the
Fig. 1 A schematic illustration of the typical geometries of OPDIs (left)
electron–hole recombination time, and tt is the carrier transit
and OPTs (right). The J–V curves and typical transfer curves under dark/ time). Alternatively, by introducing injecting layers between
illumination, respectively, are shown below the schematics. the active layer and electrodes, OPDIs can also produce a high

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G value and EQE value exceeding 100% like those of photo- absorption peak can be estimated by DEg = 1240/l (DEg is the
conductors (Section 3.2.2). material bandgap and l is the wavelength of incident light).
A phototransistor is a type of photosensing device consisting Evidently, for near-IR (NIR, l = 800–2500 nm) incident light, the
of a transistor channel in which an additional gate electrode bandgap of the photoactive layer material should be smaller
plays a critical role in effectively amplifying the photocurrent than 1.55 eV. Benefiting from the steady development of efficient
signals and/or suppressing dark currents.11 According to earlier
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photoconverting materials for OPVs, donor (D) and acceptor (A)

reports on organic FETs, the bottom-gate top-contact (BGTC) blends have been widely used due to their highly efficient
structure is the most widely studied among various possible processes of exciton generation, dissociation, and transport.6
configurations, as shown in Fig. 1 (right). The photogenerated Generally, depending on the charge transfer (CT) interaction
electron–hole pairs are dissociated into carriers with the assistance between D and A, organic active layer materials can be sorted
of a vertical electric field, resulting in the modulation of the into two categories: low-bandgap polymer/small-molecule BHJs
electrical properties of the channel. As shown in Fig. 1 (bottom with weak CT interaction and CTCs.
right), two different effects typically occur in the active-channel 3.1.1 BHJ with weak intermolecular CT interactions. In the
layers of OPTs: when the OPTs are operated in the on state case of weak CT interactions, the absorption spectrum of a BHJ
(Vg 4 Vth for an n-type channel, where Vth represents the threshold usually exhibits a simple superposition with that of the D and A.
voltage), Vth shifts due to the photovoltaic effect, whereas in Although several studies have been conducted on non-fullerene
the off state (Vg o Vth), Ioff (the source–drain current of a receptors,2 fullerene receptors, such as C60, [6,6]-phenyl-C61-
transistor in the depletion region) increases due to the photo- butyric acid methyl ester (PC61BM), [6,6]-phenyl-C71-butyric
conductive effect. Obviously, the device is most sensitive when acid methyl ester (PC71BM), etc., still dominate the separation
operating near Vth. As compared to two-terminal devices, the gate and transport of electron–hole pairs in infrared materials due to
field can assist in reducing noise and amplifying light current, the good energy level matching, strong phase separation, and
resulting in improved EQE and D* values of the transistor. It can lower industrial costs. There are four basic synthesis strategies for
be seen that the high field-effect mobility, low dark noise, and low-bandgap polymer/small donor molecules in high-sensitivity
large Vth shifts may be conducive to obtaining highly sensitive IR OPDIs. The molecules with the design strategy mentioned in this
OPTs. Moreover, since the channel of the transistor is directly article are shown in Fig. 2. First, when compared with the bare
exposed to light without shielding from the electrodes, it is aromatic structure (as show in Fig. 2), the quinoid structure is
reasonable to obtain transistors with large LDR that are sensitive deemed to have a smaller bandgap but less stability because of
to extremely weak light by effectively designing the active layers. the reconstruction and therefore it loses stabilization.15 The
Moreover, noise reduction is beneficial for improving the LDR. introduction of fused heterocycle units containing several hetero-
Unfortunately, this increased photoresponse with trapped- aromatic functionalities on the aromatic main core is the most
charges-assisted mechanism in transistors can slow down the basic design tactic for stabilizing the quinoid structure and
temporal response than that of OPDIs due to the time required obtaining a lower bandgap. Secondly, alternately combining the
for the carrier to circulate in the active layer. In this regard, ‘‘push’’ and ‘‘pull’’ units with chemical bonds (D–A concepts) is a
ingenious device design (e.g., the introduction of a junction) popular strategy for modulating the bandgap for both polymers
may be an effective way to resolve this problem. (called D–A polymers) and small molecules (called D–A small
molecules). As a result of the intramolecular CT interaction, a
new energy level structure different from that of the D and A is
3 Advanced strategies for formed. Thirdly, attaching substitution groups is the most direct
high-performance IR-sensitive OPDIs way of tuning the HOMO and LUMO energy levels and can
narrow the bandgap of the conjugated molecules. The electron-
Similar to other photoelectric devices, the quality of IR OPDIs is withdrawing groups can downshift the LUMO energy levels more
closely associated with intricate issues, such as the design of relative to the HOMO level, while electron-donating groups would
molecules as well as the configuration of devices. On one hand, upshift the HOMO energy levels more when compared with the
photoactive layer materials with effective absorption in the IR LUMO energy level. Apart from the strategies described above,
region are a common strategy for achieving detection.5,12 On wherein the energy level is tuned via intramolecular CT, an
the other hand, innovative device engineering can not only alternative method involves enhancing intermolecular inter-
optimize the device performance but also realize IR detection actions (i.e., increasing p–p overlaps between adjacent backbones).
without the necessity of low-bandgap materials.12–14 Therefore, The p–p interaction, which occurs between adjacent conjugated
in the following part, the advanced development of excellent polymer backbones, would enable narrow bandgap polymers
strategies based on active layer design and device engineering with red-shifted absorption spectra, yielding a better charge
for high-performance IR OPDIs will be described. transport characteristic.16 Introducing conjugated side chains
as well as enhancing the planarity of backbones are effective
3.1 Active layer processing methods for strengthening the p–p interaction. In fact, these
The absorption of incident light by the organic photoactive layer strategies are not independent and would be comprehensively
is mainly determined by the energy band structure of OSCs. The considered in molecular design due to their mutual influence
bandgap of OSCs and the wavelength of the corresponding on each other.

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Fig. 2 The main synthesis strategies and the maximum absorption region of low-bandgap polymers (left) and small molecules (right) used in IR OPDIs as
mentioned in this review. The ‘‘push’’ units in compounds are marked in yellow, and ‘‘pull’’ units are marked in pink. The spectrum map covers the Vis, NIR,
MIR, and a portion of the FIR ranges; the space between every two grey dotted lines inside the spectrum map is 200 nm.

For conjugated polymers, in 2007, Yan et al. reported the on the various tactics mentioned above.18 Based on the proto-
first polymer-based NIR OPDIs based on the conjugated polymer typical narrow bandgap polymer P4, bridgehead olefin (CQCPh)
P1, a derivative of polythieno[3,4-b]thiophene. For the polythio- substituents increased the planarity of the backbones with
phene backbone, fused thiophene (Th) moieties with the ester negligible rotational disorder, which contributed toward extended
group can stabilize the quinoid structure of the backbone, electron delocalization. In both P5 and P6, the narrowing of
thereby reducing the bandgap of the conjugated system.17 Eopt
g (for P5, it was 0.85 eV; for P6, 0.74 eV) was demonstrated,
Thereafter, Gong et al. reported P2 as the first polymer based illustrating control throughout the NIR and extension into the
on the D–A concept that yielded high responsivity and detectivity shortwave IR region (B1.8 mm).
toward NIR light (from 400 to 1450 nm) when used as the active Generally, there are three kinds of low-bandgap small-molecule
layer.12 The introduction of the electron-withdrawing unit systems for IR-sensitive OPDIs: (i) a squaraine analogue,19 (ii) linear
thieno[3,4-b]diathiazole makes the electron-rich Th chain more small molecules containing electron-donating and electron-
stable and therefore yields a bandgap as low as 0.8 eV. The high withdrawing units,20 and (iii) a metallated large aromatic organic
responsivity of 0.17 A W1 was obtained at 800 nm illumination compound with a ring system.21 For example, Binda et al. reported
at an intensity value of 0.22 mW cm2. In the aggregation state, an NIR-sensitive OPDI based on SQ:PC61BM BHJ active material
the intermolecular interaction can lead to a narrowing of the with high Dh* (3.4  1012 Jones) at 700 nm and an extremely low
bandgap and a red-shift in the main absorption peak. In this dark current value of 2 nA cm2.19 In Wang’s group, the low-
regard, the D–A-conjugated polymer, P3, consisting of benzo[1,2-b: bandgap compound QM-1 with efficient absorption in the broad
3,4-b 0 :6,5-b00 ]trithieno[2,3-d:2,3-d0 ]dithiophene (DTBTT) as a new spectral region of 300–900 nm but weak absorption in the visible
electron-rich building block and (E)-[6,6 0 -bithieno[3,2-b]pyrroly- region was designed and synthesized for use as the active layers for
lidene]-5,5 0 (4H,4 0 H)-dione (TII) as a strong electron-withdrawing small-molecule-based NIR-sensitive OPDIs.20 The OPDIs based on
building block, showed an absorption spectrum extending to QM-1 blended with PC61BM showed a Dh* value exceeding 1011
1600 nm in the presence of a large disk-like DTBTT and linear Jones at 800 nm at a bias voltage of 0.1 V. Forrest et al. demonstrated
polymer chains.16 Furthermore, in Azoulay’s group, promising a series of NIR-sensitive OPDIs based on linked porphyrin-tape
D–A polymers comprising a cyclopenta[2,1-b:3,4-b 0 ]dithiophene dimers, which extended the absorption range from the visible
(CPDT) donor and different acceptors, such as thiophene-flanked region to 1350 nm by spatially extending the conjugation
[1,2,5]thiadiazolo[3,4-g]quinoxaline (TQ, P5) and thiophene-flanked of the p-electron system.21 A peak efficiency of 6.5  0.3% and
thieno[3,4-c][1,2,5]thiadiazole (TT, P6), were synthesized based a response time of t = 2.12  0.02 ns were observed for

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porphyrin-tape/C60 planar heterojunction-based OPDIs. However, exploitation of CTCs blending two large-bandgap materials
the relatively low Dh* value of 2.3  1010 Jones may be attributed that are unresponsive in the IR region can be regarded as an
to the large interface-generated dark current from the reduction alternative approach for obtaining an IR-photoelectric response.
in the interfacial gap (i.e., the energy difference between the For example, Lee et al. reported that an IR OPDI-based mixed
HOMO of the porphyrin tape molecule and the LUMO of film formed by the co-evaporation of 4,4,4-tris(N-3-methylphenyl-
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acceptor C60). N-phenylamino)triphenylamine (m-MTDATA) and copper hexa-

With the development of narrow-bandgap-conjugated mole- decafluorophthalocyanine (F16CuPc) showed a broad optical
cules, better control of the morphology of interpenetrating D–A response from 900 to 1500 nm, but this was not observed for
networks has been the key strategy in the optimization of device the two parent materials, as shown in Fig. 3b and c.24 As a reference,
performance because it can considerably affect not only the a bilayer device based on m-MTDATA/F16CuPc was also fabricated
dissociation and transport of photogenerated electron–hole and showed marginal photoresponse under illumination through
pairs but also the dark current. Typically, a smart design strategy the 1000 nm filter, which indicated that the CT occurred only when
for side-chain engineering was proposed by Liang et al.22 Here, in close contact with D and A. In particular, a special kind of
poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT: CTC called a cocrystal can prove to be a promising strategy for
PSS) is often attached to the anode as a CT-modified layer. The constructing low-bandgap materials at the molecular level by
introduction of 3,4-ethylenedioxythiophene (EDOT) unit similar combining D and A at a special stoichiometric ratio. Because of
to the PEDOT structure on the side chain of the polymer strong CT interactions between D and A, the absorption intensity
increased the vertical phase separation by increasing the inter- in the IR region can be at the same level as that in the visible
action between the polymer and anode, resulting in a significant region, which provides the possibility of broad-spectrum detection
reduction in the dark current at reverse bias. extending into the NIR region.
3.1.2 CTCs via strong intermolecular CT interactions. In In addition, organometallics or metal–organic CTCs are an
the recent years, D–A CTCs have aroused wider interest due to important candidate for potential applications in IR OPDIs. For
their unique optical properties and electrical characteristics. example, IR OPDIs based on bis-(4-dimethylaminodithiobenzil)-
Typically, similar to the D–A strategy used in the molecular Ni(II) (BDN) exhibited strong absorption in the NIR region and
design principle as mentioned above, the generation of a new sub- yielded Dh* values of up to 1.6  1011 Jones at wavelengths
bandgap may lead to a narrowed bandgap of CTCs and the obvious beyond those possible with silicon OPDIs.25 Similarly, MTCNQ
red-shift in the absorption file when compared with the con- (M: metal, such as Cu or Ag; TCNQ: tetracyanoquinodimethane)
stituent components, as shown in Fig. 3a.23 Therefore, the exhibited a fairly low bandgap (o0.33 eV).26 Although a large
number of CTCs show absorption spectra extending to the IR
region, the development of an IR photosensor based on CTCs is
still at an early stage. The cause of device inefficiency may be
attributed to the morphology of the active layer and the molecular
packing not being conducive toward the separation and transport
separation of photoinduced carriers. The mechanism of photo-
electric conversion for CTCs and the fabrication processing of
devices need to be explored further.

3.2 Engineering of device configuration

3.2.1 Electrodes. Generally, asymmetrical metal electrodes
with different work functions are deposited on the bottom and
top of the semiconductor by vacuum deposition in sandwich-
like IR OPDIs. Metals with lower work functions matching the
LUMO of the acceptor (Al, Ag, etc.) are usually used as cathodes,
and metals with higher work functions matching the HOMO of the
donor (ITO, Au, etc.) are usually used as anodes. Simultaneously,
the electrode needs air stability and at least one electrode needs to
be transparent to ensure the entrance of incident light. Beyond
traditional electrode fabrication, novel electrode preparation
processes may also bring some unexpected performance out-
comes to IR-sensitive OPDIs.
The traditional electrode fabrication process (vacuum deposition)
inevitably causes infiltration into the organic active layer and
Fig. 3 (a) Energy band structure of the CTCs. (b) Molecular structures of
therefore yields a higher dark current, which is critical for
m-MTDATA and F16CuPc. (c) Absorption files and log J–V characteristics
of a m-MTDATA:F16CuPc device comparing each component irradiated
fabricating high-performance IR-sensitive OPDIs. To address
with 1000 or 1300 nm illuminations. Reproduced with permission from this issue and suppress the dark current, Xiong et al. fabricated
ref. 24. Copyright r 2013 Elsevier B.V. a PEDOT conducting electrode on a flexible substrate by the

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Fig. 4 (a) Device structure and performance of IR OPDIs with transfer-printed contacts. Reproduced with permission from ref. 27. Copyright r 2016,
Royal Society of Chemistry. (b) Schematic illustration, absorbing file, and device performance of plasmon-enhanced organic Schottky photodetector.
Reproduced with permission from ref. 14. Copyright r 2016, John Wiley and Sons.

printing method and then transferred it onto the active layer 3.2.2 Blocking and extracting interfacial layers. To ensure
instead of a vacuum-deposited metal electrode (Fig. 4a).27 The efficient charge carrier collection, appropriate electrodes possessing
as-prepared OPDIs with such a transferred electrode exhibited electronic energy levels matching those of the OSC layer are
nearly two orders of magnitude higher detectivity and lower necessary for the reduction of contact resistance and efficient
dark current. Impressively, the LDR reached 120 dB, benefiting carrier collection. Furthermore, the interfacial layer, which is
from the low dark current by transferring electrodes, which introduced between the electrode and active layer, plays a
matches that of Si-based photodetectors (120 dB). critical role in optimizing the performance.
Moreover, through the innovative design of the electrode Since sandwich-like IR OPDIs are generally operated with an
(work function, morphology, thickness, etc.), a particularly inter- applied bias voltage, the dark current contribution induced by
esting alternative can be introduced to obtain IR-sensitive PDs, charge injection from the device contact into the active layer is
breaking through the limitation of the low-bandgap organic a serious problem to a high-sensitivity device. As an alternative,
active layer, called an organic Schottky barrier photodetector charge injection can be expected to be notably inhibited if the
(SBPD). The thermal carriers of the metal electrode generated Schottky barrier between the electrode contact and active layer
by light excitation can move across the Schottky barrier for is sufficiently high by introducing an electron-blocking layer
values between the work function of the electrodes and energy (EBL) at the anode side and hole-blocking layer (HBL) at the
levels of the active layers, which is lower than the bandgap cathode to prevent the injection of electrons and holes into
of the semiconductors. However, these sub-gap photons are the semiconductors, respectively, as shown in Fig. 5a and b.
usually too weak to detect. Accompanied by the localized surface The energy levels and molecular structures of commonly used
plasmon resonances (LSPRs) and an out-of-plane Fabry–Pérot interfacial layers, as well as the work function of electrodes, are
cavity within the metal/organic/metal device configuration, summarized in Fig. 5d. A representative example was first reported
plasmonic nanohole electrodes fabricated by Hou et al. could by Gong et al. in 2009.12 By modifying the interfacial layers of
successfully enhance the IR response selectively by taking poly(9-vinylcarbazole) (PVK) between the active layer and electro-
advantage of the sub-gap absorption, as shown in Fig. 4b.14 des, the detectivity of OPDIs was dramatically improved and LDR
The high on/off ratio of 41000 and the responsivity of in excess of 100 dB could be achieved. Ma et al. reported polymer
0.1 mA W1 at a wavelength of 830 nm proved that this new OPDI sensing from 300 to 1000 nm with a peak Dh* value greater
concept works well for IR OPDIs. In the future, many device than 1013 Jones and a respectable LDR value of 148 dB at a
engineering efforts need to be developed, and the device can be wavelength of 850 nm under 0.5 V bias by introducing a thin
further optimized for use in narrowband, high-responsivity crosslinkable EBL poly[N,N 0 -bis(4-butylphenyl)-N,N 0 -bis(phenyl)-
IR OPDs. benzidine] (poly-TPD), which considerably reduced the dark

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Fig. 5 Sketch of (a) blocked charge injection from the metal contacts into the active material at reverse bias in the dark and (b) under illumination.
(c) Sketch of a photomultiplier in OPDIs. (d) Comparison of work functions of metals, energy levels of interfacial layers, and usual range of electronic
energy of the active layers (the dotted line on the blue rectangle represents the LUMO and the red one represents the HOMO range of low-bandgap
active semiconductor layers). Insets show the chemical structures of the interfacial layers used in this section. (e) Schematic diagram of a resonant-
cavity-enhanced organic BHJ photodetector and performance of cavity-enhanced photodetectors based on DBRs. Reproduced with permission from
ref. 13. Copyright r 2017, John Wiley and Sons.

current density and simultaneously preserved the photoresponse.28 at the ITO/ZnO and ZnO/active layer interfaces under reverse
On the other hand, the larger Schottky barrier increased the bias. However, the dark current of the device was 46 mA cm2,
difficulty of carrier extraction, resulting in longer response times. leading to a lower calculated D* value than that without inter-
Moreover, interfacial layers have been employed at the facial layers due to the unblocked charge injection. Nevertheless,
electrode interface to achieve high photocurrent gain, which is a better interfacial layer should be designed to retain a reason-
unsatisfactory in traditional organic IR-sensitive OPDIs (Fig. 5c). able photocurrent gain and suppress the dark current in a future
Hammond et al. reported high photocurrent gain of up to 500 by device configuration.
introducing tailored naphthalenetetracarboxylic dianhydride 3.2.3 Optical cavity architecture. Unlike CTCs, in many
(NTCDA) to the anode interface as an HBL and bathocuproine BHJ systems without low-bandgap polymers/small molecules,
(BCP) as a tunneling layer (TL).29 The underlying mechanism the CT states are typically two orders of magnitude weaker than
could be attributed to the accumulation of photogenerated the absorption of neat compounds. Exploiting the CT absorption
holes, thereby causing secondary charge injection from the band provides an elegant strategy for achieving an IR response
anode. Recently, IR-sensitive OPDIs with ZnO as an interfacial without utilizing any low-bandgap materials. Currently, a represen-
layer on an ITO anode achieved an ultrahigh EQE value of tative method for enhancing the IR response of CT excitations in
140 000% with 30 s UV-light irradiation.30 The long response OPDIs involves the introduction of a resonant optical cavity device
time is consistent with the photoconductive gain mechanism. architecture with smartly designed optical manipulation.
The phenomenon was attributed to UV-light-illumination- Previously, Yang et al. realized the enhancement of sub-gap
induced oxygen desorption, which reduced the injection barriers optical absorption in the IR region and charge extraction using

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an ultrathick poly(3-hexylthiophene) (P3HT):PC61BM blend will focus on the strategies for achieving high-performance IR
(thickness: 14 mm) as the photoactive layer and high reverse OPTs based on these two detection mechanisms.
voltage of 200 V.31 However, the low on/off ratios and high
operating voltages of the devices deterred their practical appli- 4.1 Direct-response IR-sensitive OPTs
cations. Tang et al. introduced a resonant optical cavity device Increasing the orientation of the thin film is considered to be a
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that exploited the weak sub-gap absorption of the intermolecular very efficacious strategy for obtaining a significant enhancement
CT states of the BHJ blend to achieve IR detection and a tunable in carrier mobilities; therefore, the photoresponsive properties
response wavelength (Fig. 5e).13 The mirrors on both the sides of are dramatically improved. For example, in Chen’s work, along
the BHJ active layer simultaneously acted as electrodes modified the crystalline texture orientation after annealing treatment under
by ultrathin interlayers to achieve the desired work function. In 80 1C, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY-BF2) film-
this case, the detection wavelengths were determined by the based NIR OPTs exhibited one order of magnitude higher mobility
cavity thickness. Therefore, utilizing a simple metal–metal reso- (0.11 cm2 V1 s1) than that of the as-grown amorphous film
nant optical cavity architecture (glass/Au (30 nm)/PEIE (1 nm)/ (Fig. 6a).33 As a result, a remarkable photoresponsivity value of
poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] 1.14  104 A W1 and sensitivity as high as 104 under an 850 nm
(PBTTT):PC61BM/MoO3 (10 nm)/Ag(100 nm)), the authors broadened laser could be achieved, which were two orders of magnitude higher
the absorption wavelength of the PBTTT:PC61BM blend from the than those of non-annealed films. Similarly, in Kim’s work, the
visible to the NIR regions by enhancing sub-gap absorption. By performance of low-bandgap polymer-based OPTs also showed a
adjusting the thickness of the active layer from 115 to 190 nm, strong dependence on the film-annealing treatment.34 OPTs based
wavelength-tunable IR OPDIs could be achieved in a range between on as-spun poly(3-(5-(benzo[c][1,2,5]thiadiazol-4-yl))thieno[3,2-b]-
700 and 1000 nm with an EQE value of 410%. Considering the thiophen-2-yl)-2,5-bis(2-octyldodecyl)-6-(thieno[3,2-b]thiophen-2-
introduction of a significant amount of parasitic absorption from yl)pyrrolo-[3,4-c]pyrrole-1,4(2H,5H)-dione (pTTDPP-BT) exhibited
noble metal electrodes, the high conductivity of PEDOT:PSS-coated ambipolar charge transport with hole mobility of 0.007 cm2 V1 s1
distributed Bragg reflectors (DBRs) was employed for the back- and electron mobility of 0.005 cm2 V1 s1, as well as a negligible
reflecting electrode to replace Au. The DBR cavity devices photocurrent. However, thermal annealing at 200 1C considerably
showed superior Dh* performance (close to 1013 Jones), which increased the carrier mobilities; therefore, the drain current
suggested that the performance of cavity PDs approached that of dramatically increased under NIR illumination and the response
commercial broadband Si detectors. The development of the time reduced below 100 ms.
resonant cavity device, which makes low-bandgap materials Further, high-sensitivity IR-sensitive OPTs could be realized
unnecessary for fabricating IR detectors, broadens the selection using crystalline one-dimensional (1D) nanowire (NW) photo-
of material choices. However, it also brings batch challenges for active channels. The outstanding responsivity of crystalline 1D
industrial manufacturing due to the response wavelength, NW-based IR-sensitive OPTs could be attributed to the following
which heavily depends on the thickness of the active layer. two points. The first is the lower density of structural defects
and faster charge transport of such 1D NWs. The other is the
larger trap density originating from the semiconductor/insulator
4 State-of-the-art strategies for interface and the semiconductor/air interface due to the large
high-performance IR OPTs surface-to-volume ratio of the nanostructures, leading to a shift in
the threshold voltage and secondary injection of induction carriers
Based on the detection mechanism, IR-sensitive OPTs can be from the electrodes because of doping effects. For example, due
divided into two categories. One is the direct-response mode to the enhancement in the doping effects because of the 1D
simultaneously using the IR active layer as the charge transport nanostructure (as shown in Fig. 6b), IR-sensitive OPTs based on
channel. Based on the mentioned design concepts for active (3E,7E)-3,7-bis(2-oxoindolin-3-ylidene)benzo-[1,2-b:4,5-b 0 ]-difuran-
materials, the typical semiconductors applied to IR-sensitive 2,6(3H,7H)-dione (PBIBDF-TT) NWs were reported by Zhu et al.35
OPTs include phthalocyanine or porphyrin analogues,32 boron- Under NIR illumination (intensity: 47.1 mW cm2), the highest
dipyrromethene (BODIPY) dye,33 DPP-based polymer or small photocurrent/dark current ratios and photoresponsivity values as
molecules,34 and other low-bandgap polymers.35 However, high as 1.3  104 and 440 mA W1 for the p-type channel and
for IR OPTs, designing and synthesizing OSCs with both 3.3  104 and 70 mA W1 for the n-type channel could be
efficient IR absorption and better charge transport properties achieved, respectively. The photoresponsivity was 7 times
(41 cm2 V1 s1) is still a challenge. Therefore, the performance higher and the photoswitching ratio was 20 times higher than
of a direct-response device can be efficaciously improved by their thin-film counterparts.
optimizing the preparation process of the active layer. The other Similar to OPDIs, the BHJ could be employed for IR OPTs in
category is the indirect-response mode, which separates the the form of active layers prepared using low-bandgap polymers or
photosensitive layer from the transport layer. Electron–hole small molecules as electron donors and the fullerene derivative
pairs are generated and separated in the photosensitive layer as the electron acceptor. This favors photon absorption and
under IR light, one of which is injected into the conductive charge separation at the interfaces of junctions. Furthermore, a
channel to change the electrical signals, thereby separating the BHJ formed by two materials would enable the effective trapping
light absorption and charge transport duties. In this section, we of one type of carrier in one component with fast transport of the

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Fig. 6 (a) SEM and AFM images (left) of the oriented film and the performance of IR OPTs based on the oriented films (middle) in the dark and under
IR illumination at different intensities (right). Reproduced with permission from ref. 33. Copyright r 2017, John Wiley and Sons. (b) Schematic diagram
(left, i), doping mechanism (left, ii), and performance of IR OPTs based on 1D nanowires under negative gate (middle) and positive gate (right) voltages.
Reproduced with permission from ref. 35. Copyright r 2016, The Royal Society of Chemistry. (c) The optical image (left) of 2D crystals of organic
semiconductors and photoelectrical properties under IR illumination with different intensities (middle, right). Reproduced with permission from ref. 38.
Copyright r 2018, John Wiley and Sons.

oppositely charged carriers in another component, thereby yield- of the device was optimized by using the Al2O3/SiO2 hybrid
ing high photoconductive gain. For example, in Zhao’s work, a dielectric layer.37 Therefore, the device could be switched on
small-bandgap polymer, i.e., DPP–DTT, was chosen for the NIR only with a gate voltage of 3 V. However, for the BHJ system, the
light-absorbing and hole-transporting materials, and DPP–DTT: sensitivity could be limited by its relatively high dark current,
PC61BM BHJ was used as the active layer for IR OPTs.36 When which could be optimized by the device architecture strategy in
compared with transistors based on a pure DPP–DTT film, with the future.
extracted hole (mp) and electron (mn) saturation mobilities of On the other hand, the suppression of dark current is also
0.14 cm2 V1 s1 and 0.06 cm2 V1 s1, respectively, mp and mn the main task in enhancing the performance of PDs, particularly
values in DPP–DTT:PC61BM-based transistors were 0.3 and 8  in IR-sensitive PDs. In the off state, a very low dark current
106 cm2 V1 s1, respectively, suggesting the predominant (o1 pA) is easy to realize in OPTs operating in the UV-Vis region
hole-transporting/electron-trapping characteristic of the BHJ due to the vertical electric field of the gate; even the thickness
after the introduction of PC61BM. Therefore, the device exhibited of the active layers is approximately 20–100 nm. However, for
ultrahigh responsivity (5  105 A W1) as well as excellent low-bandgap OSC-based single-component OPTs, significant
photoconductive gain (41  104) at Vg = 30 V under an leakage resulting from the bulk thermal generation of carriers
808 nm laser at 67 nW cm2. Furthermore, the operating voltage may escape from the upper region of the thick channel beyond

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gate control. Therefore, one rational strategy is downscaling the as either an excellent conducting layer combined with an organic
active layer to a few nanometers, corresponding to a fully absorber or absorption layer to sensitize the wide-bandgap
depleted region in the off state. Hu et al. recently demonstrated organic conducting channels. In Yang’s group, boosted photo-
that high-sensitivity NIR OPTs could be realized by using ultra- sensitivity was reported when using a bilayer of organic BHJ
thin two-dimensional (2D) crystals of a low-bandgap OSC as the materials (PBDTT-DPP:PC71BM, PBDTT-DPP:poly[2,6 0 -4,8-di(5-
active layer (Fig. 6c).38 Through the facile dropcasting method
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ethylhexylth-ienyl)benzo[1,2-b;3,4-b]dithiophene-alt-5-dibutyl-
on the surface of water, high-quality air-stable 2D crystals of n- octyl-3,6-bis-(5-bromothiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4-dione])
type OSCs (a furan-thiophene quinoidal compound, TFT-CN) as the IR sensitizer and a zinc oxide (ZnO)/zinc oxynitride (ZnON)
with strong absorbance of around 830 nm were prepared, and semiconductor as the conduction channel (Fig. 7a).39 The
their thickness was only 4.8 nm. Due to the single-crystal nature, spontaneous formation of ultrathin ZnO on the surface of
2D crystals offered efficient carrier injection and intrinsic defect- ZnON films could form an effective band alignment for electron
free carrier transport, thereby allowing excellent responsivity transfer from the dissociation of excitons in the BHJ while
(9  104 A W1) and EQE (106%). Furthermore, in ultrathin facilitating the electron transfer and hole blocking of ZnO. As a
structures, the channel can be fully depleted and operated at an result, the D* value over the IR regions of hybrid structures
extremely low Ioff in the dark, leading to an extremely low dark significantly increased to over 1012 Jones. The LDR also benefits
current of 0.3 pA and very high Dh* value of 6  1014 Jones under from good noise control, soaring to 122.3 dB. Oh et al. demon-
an 808 nm laser. strated high-performance PDs extending to the IR region using
gold nanorods (Au NRs)-decorated n-type OSCs and N,N 0 -bis(2-
4.2 Indirect-response IR-sensitive OPTs phenylethyl)-perylene-3,4:9,10-tetracarboxylic diimide (BPE-PTCDI)
Until now, most OSCs with considerable field-effect mobility NWs.40 When combined with the excellent charge transport
have usually had wider bandgaps, hindering the development characteristics of single-crystalline BEP-PTCDI NWs and the light
of direct-response IR-sensitive OPTs. To broaden the selection scattering and LSPR effects of Au NRs, the hybrid system provided
of materials and realize optimally performing devices, the novel photoresponse in the NIR spectral region with an R value
introduction of an organic IR-photosensitive implanted layer of 10.7 A W1 and EQE value of 1.35  103% under 980 nm
into the transistor serves as an efficacious strategy for the illumination.
target. The selection of a photosensitive layer needs to consider In the other case, Kim et al. revealed a creative method for
both the light absorption and exciton separation efficiencies. realizing novel NIR-sensing OPTs by inserting an IR light-absorbing
The conducting channel should consider the carrier mobility conjugated polymer layer between the dielectric layer and the gate,
and on/off ratio. In addition, the energy level of the two layers as shown in Fig. 7b.41 When compared with basic transistors
needs to match in order to guarantee the carriers crossing the without any inserted layer, which exhibited a p-type characteristic
junction. Here, we focus on two placement methods: one involves in the dark and were unresponsive to IR light, OPTs with the
implanting a layer onto the conducting layer, and the other designed low-bandgap poly[{2,5-bis-(2-ethylhexyl)-3,6-bis-(thien-2-yl)-
involves placing a gate-sensing layer between the dielectric layer pyrrolo[3,4-c]pyrrole-1,4-diyl}-co-{2,20 -(2,1,3-benzothiadiazole)]-5,50 -
and the gate. diyl} (PEHTPPD-BT) gate-sensing layer could detect NIR light up to
In the first case, for example, Peng et al. realized detection in 1000 nm. By optimizing the thickness of the gate-sensing layer, the
the IR region and optimized the device performance by placing the individual device without adjacent device interference achieved a
sensitizer on top of the CuPc conducting channel.32 Benefiting from maximum responsivity value of 0.25 A W1 under 1000 nm
the planar heterojunction (PHJ) of the CuPc/PbPc configuration, illumination at a density of 0.79 mW cm2. Through the sequential
high R and EQE values could be achieved, namely, 77.4 mA W1 charge induction process, the PEHTPPD-BT layers absorbed the
and 11.9%, respectively, which were 76% higher than those of OPTs NIR photons, leading to the indirect generation of charge carriers
based on a single component (i.e., CuPc). The improved perfor- and electrical enhancement in the P3HT channels. Moreover, the
mance of the PHJ device could be mainly attributed to the high devices showed excellent long-term stability without such a
absorption of PbPc in the NIR region, high hole mobility of the charging phenomenon and the flexible arrays (10  10) based
CuPc layer, and excellent matching of the HOMO levels between on a gate-sensing layer could exclusively sense NIR light with a
PbPc and CuPc. Furthermore, to enhance the exciton dissociation visible-light-cut (VLC) film (P3HT) on the substrate. Although
efficiency, hybrid–planar BHJ with a PbPc:PTCDA (PTCDA: 3,4,9,10- this responsivity may not be ideal for IR OPTs due to the lack of
perylenete-acarboxylic dianhydride) mixture as the sensitizer was a photogating effect, it presents a new perspective in the design
introduced into the IR detection mechanism; higher responsivity of reliable flexible IR OPTs and a smart system for exploring the
and EQE values of 322.4 mA W1 and 49.5%, respectively, could be photoinduced charge transport mechanism.
achieved. Moreover, the charge separation at the junction could
significantly improve the temporal response speed (tr: 0.5 ms; td:
0.67 ms). A similar approach was implemented in another 5 Emerging functional applications
chloroaluminum phthalocyanine (AlClPc)/C60 heterojunction.
Alternatively, an inorganic substance can also be introduced When compared with a green or red light, as the wavelength
as a charge transport/sensitizing layer to further expand material becomes longer, NIR light has a stronger penetrating capability
systems and achieve high-performance IR OPTs. It can serve and exhibits longer propagation paths. On the basis of current

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Fig. 7 (a) Schematic diagram and energy band alignment, absorbing file, transfer curves, and device performance of PBDTT-DPP:PC71BM/ZnON/ZnO
planar hybrid devices. Reproduced with permission from ref. 39. Copyright r 2016, American Chemical Society. (b) Schematic, absorbing file, and
responsivity of the device with gate-sensing and VLC layer. Reproduced with permission from ref. 41. Copyright r 2018, John Wiley and Sons.

reports, the application of NIR OPDs based on an all-organic has been regarded as a powerful tool for emergency diagnosis
active layer mainly focuses on the following three aspects: real- and health care, which allows the accurate monitoring of health
time health monitoring, spectrometric analysis, and electronic indicators associated with pulsatile changes in tissue blood
eyes for sensing under NIR light. Both OPDIs and OPTs have volumes (calculation formulas and details are not emphasized
made an important contribution in different application scenarios in the current review; more details can be seen in the references),
on the basis of their own characteristics. Benefiting from the fast such as heart rate (HR), heart rate variability (HRV), and pulse
dynamic response, OPDIs are preferred for instantaneous imaging. pressure (PP), through a cuff-less approach.
Moreover, the simple vertical device structure is conducive toward The key components of the PPG sensor include a PD, an
the fabrication of a large-area panel array for imaging. For OPTs, LED, and a signal collector (e.g., oscilloscope). During systolic
the detection of extremely weak signals is uniquely advantageous and diastolic processes, both the optical density and path length
because the signal can be effectively regulated under additional of the illuminated tissue change on account of the variation in
vertical electric field regulation and it easy to integrate with other erythrocytes in the vasculature and light-absorbing hemoglobin
components in plane to realize different functions. that are carried by them. As a result, a regular pulse of blood
induces a periodic change in the light intensity illuminated on
5.1 Wearable devices for real-time health monitoring the PD. Generally, the operation of PPG sensors involves two
Most basic human characteristics can be evaluated by the flow mechanisms accompanied by the generation of two different
of blood in the subcutaneous tissue. As a consequence, NIR integrated configurations. The first is the reflection mode; a
light is highly favored for skin-interfaced health-monitoring light detector is placed next to an LED component on the same
devices. Among various health-monitoring devices, photo- side of the human subject. The light emitted from the LED
plethysmography (PPG), which is noninvasively conducted, is reflected by the skin tissue and then measured by the PD.

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Fig. 8 (a) Illustrations of the process flow for the assembly of (i) reflection- and (ii) transmission-mode PPG. (b) Photograph of the measurement layout
(up); typical output signals measured by ECG, cPPG, and hPPG sensors, and illustration of the pulse transit time (PTT) (middle); variation in the PP at
different postures (bottom). (a and b) Reprinted with permission from ref. 37. Copyright r 2017, John Wiley and Sons. (c) (i) Photograph, (ii and iii)
microscopic images of the top silver electrode and skin surface, (bottom) 3D microscopic image of the skin conformal near-IR PPG, and beats per minute
(BPM) analyzed from the measured output signals using fast Fourier transform (FFT) signal processing. Reprinted with permission from ref. 42. Copyright
r 2018, John Wiley and Sons.

As shown in Fig. 8a(i), a transfer-printing process developed by flexible PPG sensor (hPPG) was proven to be capable of con-
Zhao and collaborators is displayed to fabricate a reflection- tinuously monitoring HRV. Moreover, when compared with a
mode PPG sensor on the fingertip or wrist.37 A thin stretchable commercial reflection-mode PPG sensor (cPPG), it showed more
acrylic adhesive is attached to the skin beforehand to implement accurate tracking of the changes in the PP for different human
the transfer process. The other mechanism is the type of trans- body postures with less power consumption.
mission. As shown in Fig. 8a(ii), LED and NIR-light probes are In addition, rapid responsivity and skin conformability are
integrated onto a flexible substrate and then wrapped around a the general features of skin-conformal PPG sensors, which should
fingertip like a bandage. In this type, the tissue is irradiated by an be optimized. Recently, photodiodes have become popular because
LED and the light intensity is measured by a PD on the other side. of their rapid response behavior due to their vertical sandwich
It is obvious that, in this mode, the detection position is limited construction. Impressively, by carefully optimizing the thickness
to the extremities, where light can penetrate the skin tissue. of the active layer, Someya et al. developed ultrathin NIR OPDIs
However, such a change in light density could be very marginal. (o3 mm) with an outstanding on/off switching frequency of over
To address this issue, a high-sensitivity NIR OPD with a low 1 kHz using a 200 nm-thick active layer.42 When the PPG sensor
operation voltage for use as the PPG sensor has become was attached to the human fingertip, the skin texture was clearly
imperative because not only can it perceive extremely weak light visible even when the sensor fully covered the fingertip (Fig. 8c).
signals but also eliminate the LED power requirement, reducing Consequently, continuous stable cardiovascular signals can be
power consumption and low charging frequency of wearables. read out, and the conformal OPDIs exhibited more sensitivity
Interestingly, a flexible PPG sensor integrating a low-voltage than devices on a rigid substrate.
(o3 V), high-sensitivity NIR OPT (D* = 5.7  1013 Jones) with The NIR organic PPG sensors discussed above are an important
a commercial inorganic LED was developed by Zhao and basis for fabricating flexible monitoring devices for arterial vessels
collaborators.37 Together with the electrocardiogram (ECG) signal under the dermis. However, they only achieved limited index
of a human subject as a reference (Fig. 8b), the high-quality detection. Therefore, for further analyzing additional health

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features (such as pulse oxygenation), an advisable approach is an array of selective-wavelength OPDIs with a resonant cavity
the ratiometric analysis of signals generated by different wave- structure.13 In accordance with different thicknesses of the
lengths of incident light, which have differences in the molar PBTTT:PC61BM active layer, each pixel position exhibited a different
extinction coefficient of oxygenated and deoxygenated hemoglobin, resonance wavelength linearly in the range of 700–1100 nm.
such as red light and NIR.43 The development of broadband OPDs The water transmittance spectrum measured by the miniature
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covering visible and NIR ranges provides an opportunity for organic spectrometer is basically consistent with that of a commercial
IR pulse oximetry, although they pose a series of challenges such as Fourier-transform IR spectrometer, implying a neoteric idea for
the stability of the IR LED in air, power consumption, signal the development of a portable miniaturized spectrometer without
reproducibility, and matched degree of signal magnitudes under the need for monochromators. Furthermore, OPDs sensitive to
both red and NIR radiations. shortwave IR could be used to analyze organic molecules. For
example, the vibration absorption of water and ethanol is distin-
5.2 Portable spectrum analyzer for industry and medicine guishable in absorption for l 4 1200 nm. Ng et al. creatively
The spectrophotometric methodology enables the qualitative and identified the percentage of ethanol in a water–ethanol mixture
quantitative analyses of a substance by measuring the absorbance and the quality of a beer sample using P5:PC71BM BHJ-based IR
of light within a certain wavelength range. In a spectrometer, as OPDIs, which could provide a broad-spectrum response of up to
light at different wavelengths is continuously irradiated onto the 1550 nm.44 As shown in Fig. 9a, as the percentage of ethanol in the
sample, the absorption intensity corresponding to different wave- mixed sample increased, the light transmission linearly increased at
lengths can be obtained. Recently, the proof of concept of an 1270 nm and decreased at 970 nm. Based on the characteristic
organic miniature spectrometer at IR wavelengths demonstrated response of ethanol in water between 1200 and 1400 nm, the
emerging achievements in many applications, such as the measured spectral data corresponded to a standard curve of a 5%
quantitative analysis of water or other organic content in water–ethanol mixture, which is the same as the factory value,
industrial or agriculture processes, medical imaging for biological implying the accuracy and effectiveness of the IR OPD spectrometer.
tissue analyses, and so forth. Another application involves the spectroscopic imaging of
Because the O–H bond vibration absorption of water molecules biological tissues. As mentioned in Section 5.1, IR light with an
is confirmed at 970 nm, a spectrometer can be used to monitor enhanced penetration path can sense deep tissue information
moisture. Tang et al. fabricated a miniature spectrometer based on in living organisms. Since certain tissues, such as hemoglobin

Fig. 9 (a) Transmission spectra of the water–ethanol mixture (ethanol percentage increases from 0% to 100% in steps of 10%) using an organic BHJ
OPDI and the spectroscopic analysis of the beer sample. Reproduced with permission from ref. 44. Copyright r 2018, John Wiley and Sons.
(b) Schematic diagram and fat content simulation of the tissue samples using the organic array for IR spectral imaging. Reproduced with permission from
ref. 45. Copyright r 2018, John Wiley and Sons.

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and fat, are particularly sensitive to IR light, many diseases, In the case of NIR to visible-light organic upconversion
such as arteriosclerosis and ischemia, can be diagnosed by IR devices, a visible image system could be directly rendered without
spectroscopy. For instance, Wu et al. realized the spectral imaging any readout electronics and external visualization incorporated
of resected fat under a muscle layer of 3 mm-thick beef slices using within a digital camera. This can be realized by integrating an
IR OPDIs integrated with silicon-switching diodes in a 4  4 pixel NIR OPD and an organic LED in series into one device. In the
array, as shown in Fig. 9b.45 The absorption intensity of fat at
Published on 12 December 2019. Downloaded by Indian Institute of Technology Chennai on 9/14/2024 5:44:28 AM.

absence of NIR illumination, the poor carrier transport behavior

1200 nm was significantly higher than that of the muscle, and of the photoactive layer and the introduction of holes or EBLs
both the types of tissues showed similar absorption at 1152 nm; maintain the organic LEDs in the off state. Under NIR impinge-
therefore, the detected results were normalized by calculating the ment, the upconverter can be seen in visible light due to photo-
transmittance ratio TR = %T1200nm/%T1152nm. Spectral imaging can generated carriers induced by NIR stimulation injected into the
clearly show the fat on both the sides under the muscles, providing emitting layer and recombined with the opposite carriers from the
a promising candidate for a next-generation economical, scalable electrode. Among the various figures of merit, photon-to-photon
bioimager. (p-to-p) efficiency is the main consideration, which depends on the
Although some inspiring results have been recently reported, characteristics of both photodetection (p-to-e) and light emission
certain technical and analytical challenges persist. (i) Qualitative (e-to-p) of the device. At the same time, the brightness intensity
and quantitative analyses of spectra based on organic photo- also needs to be considered. Recently, Li et al. proposed a novel
detectors in the mid-IR region have not been formulated, which all-organic upconversion device architecture that can be considered
will become imperative for the further study of the vibrational as an IR-photosensitive active layer inserted between the organic FET
rotation of molecules and the characterization of functional and emission layer.47 Benefiting from the gain mechanism of carrier
groups. (ii) Currently available infrared organic spectrum analyzers accumulation induced by the gate electric field, the as-prepared
are still connected to complex readout devices, and they cannot devices produced typical p-to-p upconversion efficiency (maximum:
independently collect and analyze data to automatically yield perfect 28.7%) under the illumination of 10.4 mW cm2; nevertheless, the
results. (iii) The preparation of biocompatible and implantable brightness was less than 20 cd m2. Under the best working
infrared detectors is still an ongoing task, which is essential conditions of the device, where brightness and efficiency balance
for real-time nondestructive monitoring and imaging of the each other, the effective efficiency was evaluated to be as high as
human body. 7% under the illumination of 3.26 mW cm2, which is among
the highest upconversion efficiencies in all-organic upconversion
5.3 Electronic eyes beyond the human body devices. Inevitably, it also marginally enhanced the dark current.
In the recent years, the ‘‘electronic eye’’ has become a popular In the above cases, the discussed upconverters were fabricated
topic in high-tech fields, such as traffic control, night vision, in the bottom-absorbing and bottom-emitting configurations.
and clinical applications. One of its functions is transforming Actually, the transparent upconversion device imaging at the
light signals beyond the range of human perception in order to opposite side of the light source is necessary for practical applica-
detect signals. According to whether the terminal collection is tions such as night vision or see-through functions in cell phones,
an electrical or visible-light signal, current research on organic glasses, cameras, or car windshields. Fabricating a transparent
electronic eyes for NIR detection can be distinguished into upconversion device requires the absorption wavelength of the
matrix devices and optical upconversion devices. active materials to be only in the visible-blind IR region and the
For a matrix device, the electrical signals generated by the electrodes to be as transparent as possible. Strassel et al. prepared
NIR OPDs after illumination are sent to the external readout transparent upconversion devices based on selective-NIR-response
integrated circuit (ROIC), yielding a current intensity distribution OPD material (squaraine dye) in combination with semitransparent
diagram. The better linear dynamics of the NIR OPD and better electrodes such as Ag (12 nm) or Au (8 nm) and an external
matched image are simulated on a computer. Wang et al. aluminum tris(8-hydroxyquinolinate) (Alq3) layer.48 As shown in
simulated the memory function of the human retina with a Fig. 10b, the device showed good transparency and transmittance
three-component integrated pixel, including a voltage divider as of up to 80%. In Liu’s work, a blend of chloroaluminum
the photosensing element and a floating-gate organic field- phthalocyanine (ClAlPc) and C70 was used as an NIR response
effect transistor (FGOFET) as the readout element (Fig. 10a).46 layer and a phosphorescent organic LED based on 4,4 0 -bis-
The voltage divider was constructed by concatenating two detectors: (N-carbazolyl)-1,1 0 -biphenyl (CBP) doped with 2-phenylpyridine
an IR PD based on low-bandgap vanadylphthalocyanine (VOPc): ( fac-tris) iridium(III) [Ir(ppy)3] was selected for outputting green
N,N 0 -bis(2,6-diisopropylphenyl)-tetraphenoxy-3,4,9,10-perylenedi- light. Impressively, they succeeded in demonstrating a real three-
carboxi-mide (ROT300) BHJ and a light detector with no response dimensional (3D) image by illuminating an object with NIR
in the IR region based on N,N 0 -1H,1H-perfluorobutyldicyano- irradiation (Fig. 10c).49 Furthermore, objects covered by remora
3,4,9,10-perylenedicarboximide (N1100). NIR light can trigger can be detected by the human eye by presenting a visible image
memory events by permanently altering the FGOFET’s conductance, using the upconversion device, which demonstrated the concept
while green light insufficiently transformed into a photoswitching of see-through glasses. However, it is still difficult to balance
component rather than memory. Therefore, a flexible, filter-free but efficiency and transparency. In the pursuit of transparency, some
color-distinguishing photosensor array successfully converted NIR parameters are often sacrificed, such as the conductivity of
illumination into electronic signals for imaging. electrodes and thicknesses of the active and interfacial layers.

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Fig. 10 (a) A 3D schematic of a retina pixel and the measured current intensity distribution diagram in 30 pixels over the pupil of a toy dog under NIR
illumination at different intensities. Reproduced with permission from ref. 46. Copyright r 2017, John Wiley and Sons. (b) Transparent NIR-to-green
upconversion device operation in the presence of NIR. Reproduced with permission from ref. 48. Copyright r 2018, American Chemical Society.
(c) Digital photograph of the line-shaped shadow mask and LED under NIR illumination (left); digital photograph of the line-shaped shadow mask when a
sewage box was placed between the mask and the camera (middle) and green organic LED emission when the NIR penetrates the sewage box and
irradiates the upconversion device (right). Reproduced with permission from ref. 49. Copyright r 2015, John Wiley and Sons.

The goal of the electronic eye is to simulate the imaging active layer and contact, the dark current could be dramatically
system of the naked eye and realize the imaging function of IR night decreased and the photogain could be enhanced such as that
vision. At present, the number of imaging pixels of an organic possible with a photomultiplier.30 In addition, through inno-
electronic eye is still relatively low. Miniaturizing the pixels and vative device configuration engineering, such as introducing a
improving the resolution will be a future trend. For upconversion nanohole electrode14 or optical cavity architecture,13 an IR
devices, to realize the high-resolution sensing of an object, linear response could be achieved even with wavelength selectivity
dynamic characteristics need to be further improved. that does not utilize any low-bandgap material. For IR OPTs,
the strategies for improving device performance mainly focus on
the morphology of the active layer for direct-response transistors,
6 Conclusions and perspectives and the introduction of photosensitive layers broadens the
selection of materials and improves the performance based on
Over the last few years, significant progress has been made with the indirect-response mode. The tremendous advancements
regard to IR OPDs and their applications. In the case of OPDIs, achieved have successfully resulted in the use of IR OPDs in
through careful active layer design, state-of-the-art IR OPDIs integrated applications, including health monitoring,37 analog
can detect light extending to 1600 nm with Dh* values of nearly electronic eyes,46 and miniature spectrometers.13 However,
1013 Jones and that to 1800 nm with Dh* of approximately unceasing efforts are still strongly desired to improve the overall
1012 Jones.16,18 By introducing interfacial layers between the quality of IR OPDs further and meet more requirements of

668 | Chem. Soc. Rev., 2020, 49, 653--670 This journal is © The Royal Society of Chemistry 2020
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diverse practical applications. In our view, the following three polishing the manuscript. This work was supported financially by
aspects will continue to be the main topics in this area. the National Key R&D Program (2016YFB0401100, 2017YFA0204503),
Firstly, the launch of emerging materials with efficient IR the National Natural Science Foundation of China (51633006,
wavelength absorption and excellent exciton separation/transport 51703159, 51733004, 21875158, 91833306, 51725304, 91433115,
properties in terms of molecular engineering and its combination 21661132006, 21473222).
Published on 12 December 2019. Downloaded by Indian Institute of Technology Chennai on 9/14/2024 5:44:28 AM.

with other protocols are still the main challenges, resulting in

present IR PDs being unable to catch up to those involving visible References
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670 | Chem. Soc. Rev., 2020, 49, 653--670 This journal is © The Royal Society of Chemistry 2020