Review

www.advmat.de

Biodegradable Materials and Green Processing

for Green Electronics
Wenhui Li, Qian Liu, Yuniu Zhang, Chang’an Li, Zhenfei He, Wallace C. H. Choy,
Paul J. Low, Prashant Sonar,* and Aung Ko Ko Kyaw*

industry. With the adoption of Moore’s

There is little question that the “electronic revolution” of the 20th century Law as a driving force for progress, elec-
has impacted almost every aspect of human life. However, the emergence tronics technology has grown at an
of solid-state electronics as a ubiquitous feature of an advanced modern exponential rate. In turn, the regular
society is posing new challenges such as the management of electronic waste availability of increasingly powerful and/
or cheaper computer chips has seen the
(e-waste) that will remain through the 21st century. In addition to developing
global adoption of electronics technology
strategies to manage such e-waste, further challenges can be identified in ever-increasing complex arrays of con-
concerning the conservation and recycling of scarce elements, reducing the sumer, industrial, medical, space, and
use of toxic materials and solvents in electronics processing, and lowering military applications. The economic and
energy usage during fabrication methods. In response to these issues, the societal benefits of modern electronics
construction of electronic devices from renewable or biodegradable mate- cannot be underestimated, with almost
every aspect of modern human endeavor
rials that decompose to harmless by-products is becoming a topic of great
influenced, on some level, by solid-state
interest. Such “green” electronic devices need to be fabricated on industrial electronic devices. Statistically, the global
scale through low-energy and low-cost methods that involve low/non-toxic consumer electronics market was valued
functional materials or solvents. This review highlights recent advances in at approximately 1172 billion USD in
the development of biodegradable materials and processing strategies for 2017, and it is expected to reach approxi-
mately 1787 billion USD in 2024.[1] When
electronics with an emphasis on areas where green electronic devices show
the sheer volume of electronic equipment
the greatest promise, including solar cells, organic field-effect transistors, and corresponding semiconductor devices
light-emitting diodes, and other electronic devices. such as silicon solar cells is combined
with rapid turnover as older technology is
superseded in a relatively short timeframe,
1. Introduction a significant volume of electronic waste (e-waste) is created. For
example, it has been estimated that 20–50 million ton of con-
The development of the integrated circuit in 1959, largely cred- sumer electronic products are discarded globally every year.[2]
ited to the work of Jack Kilby (Texas Instruments Inc., Texas, This represents approximately 5% of the current municipal
USA) and Robert Noyce (Fairchild Semiconductor Interna- solid waste worldwide. Compounding the escalating volume
tional, Inc., California, USA), has served as a prelude to the of e-waste from consumer electronics, the global distribution
immense global scientific and engineering effort that has of other semiconductor-based devices, such as rooftop photo-
underpinned the growth of the modern solid-state electronic voltaic cells, is rapidly growing. Although the lifetime of such

Dr. W. Li, Y. Zhang, C. Li, Z. He, Prof. A. K. K. Kyaw Y. Zhang, Prof. W. C. H. Choy
Guangdong University Key Laboratory for Advanced Quantum Dot Displays Department of Electrical and Electronic Engineering
Shenzhen Key Laboratory for Advanced Quantum Dot Displays and Lighting, The University of Hong Kong
and Department of Electrical and Electronic Engineering Pokfulam Road, Hong Kong 999077, China
Southern University of Science and Technology Prof. P. J. Low
Shenzhen 518055, China School of Molecular Sciences
E-mail: aung@sustech.edu.cn The University of Western Australia
Q. Liu, Prof. P. Sonar Perth, WA 6009, Australia
School of Chemistry and Physics Prof. P. Sonar
Queensland University of Technology Centre for Materials Science
Brisbane, QLD 4000, Australia Queensland University of Technology
E-mail: sonar.prashant@qut.edu.au Brisbane, QLD 4000, Australia
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.202001591.

DOI: 10.1002/adma.202001591

Adv. Mater. 2020, 32, 2001591 2001591 (1 of 40) © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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devices is significantly longer than consumer electronics, it has

been estimated that there will be 35 000 ton of photovoltaic Wenhui Li is currently a
waste by 2020, growing to 60 million ton by 2050.[3] postdoctoral fellow with
Unless steps are made to recover, recycle, and reduce Prof. Aung Ko Ko Kyaw’s
our reliance on conventional solid-state electronic devices, group at Southern University
this volume of e-waste will seriously and negatively impact of Science and Technology
the environment.[4] Many semiconductor devices contain (SUSTech), China. He
significant amounts of toxic elements, including mercury, received his B.S. (2010) in
arsenic, chromium, and lead (Pb), which can leach into soils chemical engineering from
and waterways when e-waste is disposed of in landfills; mean- Guangdong University of
while the incineration of plastics leads to the release of vola- Technology (GDUT) and his
tile compounds such as dioxin derivatives, polychlorinated Ph.D. (2018) in materials
dibenzofuran, and polychlorinated biphenyls, which are known science from the Institute
group 1 carcinogens.[5,6] of Process Engineering, Chinese Academy of Sciences.
The desire to reduce the volume and consequent impact of His current research focuses on interfacial engineering
e-waste has brought about a growing interest in “green elec- for highly efficient and stable perovskite solar cells. He
tronics,” whereby some functions and device structures that is also interested in the green processing of electronic
are currently associated with semiconductor electronics are devices.
replaced with devices containing more environmentally friendly
materials. According to European Standard EN13432, at least Prashant Sonar obtained a
90% of all materials used in green electronics must be con- Ph.D. in 2004 from Johannes
verted within 6 months of abandonment into harmless compo- Gutenberg University of
nents, such as water, carbon dioxide, and biomass, through the Mainz (Germany). He moved
action of fungi or microorganisms under certain defined con- to Zurich, Switzerland,
ditions of temperature, humidity, and oxygen concentration.[7,8] to complete postdoctoral
In addition to eliminating (or at least reducing) the use of research at the Swiss Federal
toxic materials in the processing methods and final products of Institute of Technology (ETH
green electronic technologies, the use of degradable materials Zurich) from 2004 to 2006.
offers additional, if perhaps niche, advantages for several dif- From 2006 to 2014, he worked
ferent applications. Insecure disposal of e-waste may permit as a research scientist at
the recovery and exploitation of confidential data by others. The the Institute of Materials
automatic degradation of materials used in green electronics Research and Engineering
ensures that any data previously stored will become perma- of A*STAR, Singapore. He is interested to develop high
nently corrupted, thereby guaranteeing security.[9] The use of performance organic semiconductors and hybrid mate-
biodegradable or biocompatible materials within the context rials for various electronic devices including future green
of green electronics may also be advantageous in the develop- electronics.
ment of medical implants by limiting the need to surgically
remove devices post-diagnosis, monitoring, or therapy, thereby
improving patient outcomes.[10] Furthermore, the advent of Aung Ko Ko Kyaw is an
wearable electronics is also gaining interest in regard to bio- associate professor at the
compatible and biodegradable electronic materials, particularly Department of Electrical
on flexible substrates.[11] This article sets out to review recent and Electronic Engineering
advances in the development of the materials and processing at Southern University of
strategies that underpin the development of green electronics. Science and Technology,
These advances are exemplified through reference to areas China. He received both
where green devices show the greatest potential, and they his B.Eng. and Ph.D. from
include solar cells, organic field-effect transistors, light-emitting Nanyang Technological
devices, and other electronic devices. University, Singapore, in
2007 and 2012, respec-
tively. From 2012 to 2014,
he joined Prof. Alan
2. Biodegradable Materials and Devices Heeger’s lab at the University of California, Santa
2.1. Overview of Biodegradable Materials Barbara (UCSB), USA, as a post-doctoral researcher. He
then worked as a scientist at the Institute of Materials
A working electronic device is considered to consist of several Research and Engineering of A*STAR, Singapore, from
components including substrates, electrodes or interconnect 2014 to 2017. His research focuses on organic mate-
materials, and active layer materials. This section provides rials and devices for energy harvesting and wearable
an overview of the biodegradable materials that have been electronics.
explored for use in these different components and a summary

Adv. Mater. 2020, 32, 2001591 2001591 (2 of 40) © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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of the mechanisms by which these materials can be degraded. method for the preparation of transparent paper substrates
The use of these materials in the design and fabrication of bio- directly from thin (400 µm to 1 mm) wood slices cut perpendic-
degradable devices, including solar cells, organic field-effect ularly to the direction of growth.[25] After removal of the lignin,
transistors (OFETs), light-emitting diodes (LEDs), batteries, and the resulting loose array of lumen (tubular structures com-
biocompatible implantable devices for healthcare is discussed. posed of cellulose microfibers and nanofibers) that was aligned
parallel to the direction of growth was pressed along the lumen
axis, causing the lumen to collapse in random directions. The
2.1.1. Biodegradable Substrates resultant material was composed of an isotropic array of fibers
and had a dense layered structure with a low propensity to dif-
A variety of rigid and flexible substrate materials have been fract light; a transmittance of approximately 90% was observed
developed for use in conventional solid-state and polymer elec- in the resulting “isotropic paper.” A simple device constructed
tronics. The remarkable semiconducting properties of silicon/ by contacting a graphene flake with two gold (Au) electrodes
silicon dioxide (Si/SiO2) substrates used in conventional solid- deposited through a shadow mask exhibited ohmic contact,
state electronics have driven the electronic revolution. The while the introduction of a gate electrode and addition of an
development of advanced nanofabrication techniques, doping electrolyte exhibited a bipolar transistor response. This paper
strategies, and the manipulation of the crystal lattice in these was readily degraded when returned to soil.
Si substrates, coupled with the development of complementary Another transparent substrate based on natural fibers is chitin
solid-state materials, have permitted the relentless evolution (poly-β-(1,4)-N-acetyl-d-glucosamine) nanofiber-based trans-
of solid-state electronics. The development of conducting and parent paper developed by Bae et al. and used as the substrate
semiconducting polymers has generated a considerable interest in an OLED device.[18] Initially, hexafluoroisopropanol was used
in lightweight, flexible, and even stretchable polymer or plastic as the solvent to disrupt the intermolecular hydrogen (H)-bonds
substrates to fully utilize the roll-to-roll manufacturing process in the β-chitin. A 0.4% w/v solution was prepared in this way
to accelerate the commercialization of larger but lighter weight and concentrated to yield a 2.4% alcogel, which was then cen-
electronic products, which holds particular promise for lighting trifugally cast to yield a chitin-based paper with virtually 100%
and display applications. In regard to green electronic tech- transmission in the visible region after processing. Multi-layer
nologies, substrates must display a combination of electrical, OLED devices of the structure ZnS (25 nm)/Ag (7 nm)/MoO3
physical, and mechanical properties appropriate for the desired (5 nm)/NPB (50 nm)/Alq3 (50 nm)/Liq (1 nm)/Al (100 nm)
applications but also be (bio)degradable to innocuous or recov- (ZnS: zinc sulfur; Ag: silver; MoO3: molybdenum trioxide; NPB:
erable constituents. To these ends, substrates based on natural N,N’-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine;
paper fibers and a variety of synthetic polymers such as polydi- Alq3: tris(8-hydroxyquinolinato); Al: aluminum; Liq: 8-hydrox-
methylsiloxane (PDMS), polyvinyl alcohol (PVA), and polylactic yquinolinolato-lithium) were fabricated on these transparent
acid (PLA) have all been identified and explored.[8] chitin papers and they performed similarly to devices fabricated
Natural-Based Substrates: Paper is readily identified as a sub- on polyethylene naphthalate (PEN) plastic substrates, exhibiting
strate for printed electronics given the advanced state of roll- a maximum luminance (Lmax) of 3 890 cd m−2.
to-roll printing methods.[12] The high surface roughness of Silk films and fibers are also suitable natural substances
commercial papers that results from the porous structure of for the engineering of paper-like electronic substrates, as they
the paper fiber network could be advantages for energy storage exhibit biocompatibility and biodegradation rates that can be
devices where large surface area is important for easy absorp- tuned from minutes to days through appropriate modification.
tion of electrolyte and binding with nanomaterials. Moreover, Silks are readily available from a wide range of sources that
the incorporation of conductive materials (i.e., carbon nanotube are low in cost and easy to process. The combination of these
(CNT), silver nanowire (AgNW), metal oxides, graphene, and features is inspiring further exploration of these materials for
conductive polymers) within the paper results in a sufficiently potential applications to electronics in the biomedical industry
high electrical conductivity for the subsequent hybrid materials, (i.e., food sensing applications,[26] improvement of physiolog-
which are then used as substrates in devices such as super- ical recording and targeted drug delivery,[27] and biomedical
capacitors.[13] Indeed, some devices prepared on such modi- implants).[28]
fied conducting paper substrates have performed comparably Fibroin, an insoluble protein present in the silks produced by
with analogous devices deposited on flat conducting polymer a variety of moth genera and insects, offers several features that
substrates.[12,14] However, the porosity and high roughness of can be exploited in the production of paper-like substrates for
the paper could be detrimental to thin film devices, especially green electronics; these features include excellent biocompat-
those utilizing organic materials as semiconducting or dielec- ibility, slow degradation in vivo, ease of chemical modification,
tric layer. This problem is usually remedied by coating or lami- and processability from either aqueous solutions or organic
nating with wax, kaolin, starch, latex, and polymers such as solvents.[29] Recently, Zhao et al. have demonstrated the use of
polyethylene, polypropylene, polyurethane, and PVA. So far, paper-like fibroin films as the substrates for memory devices.[30]
paper substrates have been used in various electronic devices These films can degrade within 24 h in a phosphate-buffered
including solar cells,[15,16] organic LEDs (OLEDs),[17,18] biobat- saline (PBS, pH = 7.4) solution. These fibroin substrate-based
teries,[19] sensors,[20,21] transistors,[22] displays,[23] and radio fre- devices display excellent flexibility and switching performance,
quency identification devices.[24] and the mechanical stresses and bending deformations of the
To expand the range of potential applications for paper-based devices have no obvious influence on the I–V characteristics of
green electronics, Hu et al. have described a relatively simple the high and low resistance states.

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Other natural materials that are widely available and offer if the resultant devices are used in the medical field. However,
potential applications as biocompatible and biodegradable in electronics, the metal electrodes are ultra-thin films with
substrates include shellac, hard gelatine, collagen, chitosan, limited capacity for harm. However, metals such as Au, Ag,
alginate, and dextran, among many others. For example, shellac platinum (Pt) and copper (Cu) may not be suitable for green
is secreted by female lac beetles to form tunnel-like tubes as electronics because of their non-biodegradable nature even in
the beetles traverse tree branches, from where the shellac can the state of an ultra-thin film. The commonly used metals as
then be harvested.[31] After processing, shellac forms a film that electrodes and contacts in green electronics are iron (Fe), mag-
is generally quite smooth, which is extremely helpful in elec- nesium (Mg), zinc (Zn), and their alloys and oxides.[42] Such
tronic applications. Hard gelatine contains properties similar metal thin films are biocompatible with the human body and
to shellac and can also form biocompatible films with smooth easy to dispose.[10] Rogers et al. measured the dissolution rates
surfaces. Although the use of shellac and hard gelatine as of several metallic nanomembranes and found that although
substrates is still in its initial stages, Irimia-Vladu et al. have the dissolution rates are different, some metal thin films can
reported transistor devices with good electrical characteristics be dissolved in deionized (DI) water and simulated body fluids
that have been fabricated from several different organic semi- (Hanks’ balanced salt solution, HBSS). These metal thin films
conducting materials supported by shellac and hard gelatine have also been used to construct short-life time devices, thereby
substrates.[32] Although these natural-based substrate materials demonstrating their feasibility as biodegradable electrodes for
have the advantages of resource abundance, low cost, biodeg- green electronics.[43] Figure 1-i shows the dissolution behav-
radability, and negligible immunoreaction to human body, iors of several metal or alloy contacts and associated changes
there are some limitations for their wide applications and per- in electrical resistance. Although the dissolution rates vary, the
formance improvement of fabricated devices. For example, thin film contacts are all biodegradable in DI water or HBSS
good biodegradability indicates relatively low environmental (with pH values of 5–8). Most metals can be dissolved in acidic
stability. Consequently, certain conditions and processes used solution (pH < 7), as in the digestive system, illustrating why
during device fabrication, such as high temperatures and harsh these metal films are considered biocompatible.
solvents, may not be compatible with the properties of natural In regard to biodegradable electrodes or contacts, the main
product-based substrates. In addition, the variable degradation issue of concern is whether the metals are toxic or radioactive,
rates of different substrates would not match the requirements thereby resulting in damage to the human body. Bao et al. fab-
of certain long-life devices. All these drawbacks significantly ricated biodegradable transistors using Fe, rather than Au, for
influence the wide applications and limit the device perfor- electrodes to make the resultant devices completely degradable.[9]
mance improvement. Therefore, environmentally compat- Devices based on Fe electrodes demonstrate a greater negative
ible synthetic substrates, the properties of which can be tuned threshold voltage compared with that of devices based on Au.
through judicious choice of reactants, attract attention. This is because of the mismatch of the work function of Fe with
Synthetic-Based Substrates: A variety of synthetic polymers, the highest occupied molecular orbital energy level of the semi-
known for their use in biomedical implants, have also been conductor, and an excellent hole mobility value of 0.12 cm2 V−1 s−1
identified as potential materials to construct film-like sub- can be achieved. Au is an edible substance and will not damage
strates for green electronics.[33] For example, PDMS has been the human body; however, it is not biodegradable owing to its
approved for use by the National Heart, Lung, and Blood Insti- insolubility in common acid or base solutions. Thus, whilst Au
tute of the United States, has proven to be an excellent sub- electrodes can be used to create biocompatible electronics, they
strate in flexible and stretchable electronics.[34–36] The readily are not biodegradable. In the biodegradable electronic devices
modified chemical structure of the polymer has allowed for a fabricated by Bao et al., the Fe electrodes can rapidly degrade
good degree of engineering of the resulting polymer proper- within 1 h in an acidic solution with a pH of 4.6.[32]
ties,[37] and various synthetic polymer-based devices have been Other metals have also been reported as biodegradable elec-
fabricated and implanted into living tissues to study functions trodes for electronic devices with traceless dissolution in cer-
in both medical diagnosis and therapy.[38] Other biodegradable tain solutions. Mg is the most used metal electrode because
and biocompatible synthetic polymers, including polycaprolac- it can dissolve in DI water, as well as acid and base solutions.
tone (PCL), poly(3-hydroxybutyrate) (PHB), poly(4-hydroxybu- Rogers et al. reported transient electronics where Mg/MgO is
tyrate), poly 3-hydroxyoctanoate, poly(glycolic acid), poly(l-lac- used as the electrode, along with other biodegradable mate-
tide), poly(glycolide-co-caprolactone), poly(lactide-co-e-caprolac- rials such as Si/SiO2.[44] The device degrades in approximately
tone), poly(glycerol sebacate) (PGS), and poly(1,8-octanediol-co- 10 min after being dipped into DI water. They proposed the
citrate), have been explored in similar applications. Specific following mechanism (Figure 1-ii). When Si or Mg reacts with
details regarding electronic devices based on these biodegrad- water, soluble Si(OH)4 or Mg(OH)2 is directly formed through
able substrates will be discussed in Section 2.3. hydrolysis. Sometimes SiO2 or MgO can be formed as an
intermediate that reacts again with water to form Si(OH)4 or
Mg(OH)2. Besides dissolution in DI water and a well-known
2.1.2. Biodegradable Electrodes or Contact Materials reaction with an acid to form soluble metal salt substances,
Rogers et al. and Zhao et al. also studied the degradation of
Metals or alloys are the first choice for electrodes or con- Mg in a base solution. Rogers et al. simulated body fluid using
tact materials because of their high conductivity in electronic a PBS solution (pH = 7.4) at 37 °C, and the Mg electrode dis-
devices.[39–41] There is a general notion that these types of mate- solved within 2 min.[44] Zhao et al. used the same solution but
rials are difficult to degrade and may injure the human body increased the pH value to 10; it took the Mg electrode 12 h to

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Figure 1. i) Dissolution behavior of metal or alloy thin film contacts in DI water and HBSS (pH = 5–8). Reproduced with permission.[43] Copyright 2014,
Wiley-VCH. ii) Proposed mechanism of Mg/MgO and Si/SiO2 chemical reaction in DI water. Reproduced with permission.[44] Copyright 2012, American
Association for the Advancement of Science.

dissolve at room temperature (25 °C), which was significantly used as the electrode material in organic electronics because
longer than it took at 37 °C, indicating that dissolution kinetics of its ultrahigh conductivity. For example, Bao et al. reported a
are highly dependent upon pH value and temperature.[30] Many large-scale PEDOT:PSS film formed via solution shearing with
similar metal electrodes have been used in green electronics, a conductivity of 4600 S cm−1. The organic photovoltaic (OPV)
such as Zn, tungsten (W), Fe, molybdenum (Mo), and their devices fabricated with this film as the electrode exhibited a
respective oxides, and they can be found within the published comparable efficiency with that fabricated with indium tin oxide
review papers cited in refs. [10,40,41]. (ITO) electrode.[46] Hori et al. reported the fabrication of an
Researchers have made significant attempts to develop organic electronic device to deliver neurotransmitters in vitro
certain organic materials into interconnects or electrodes. and in vivo.[47] In such a device, Hori et al. used PEDOT:PSS
Several common high-conducting polymers including polypyr- as both the anode and cathode electrodes because of its bio-
role (PPy), polyaniline (PANI), polythiophene (PT), and PT compatible property. When the device was connected to a cir-
derivatives, such as poly(3,4-ethylenedioxythiophene) (PEDOT), cuit with an applied voltage, oxidation and reduction occurred
have been utilized successfully as electrode materials.[10] These repeatedly on the anode and cathode electrodes, respectively,
polymers have typically needed to be doped to achieve higher and conductivity was achieved.[47] With regard to the degrada-
conductivity exhibited by similar metals (with conductivity of tion of such conducting polymers, one strategy is to develop
101–105 S cm−1); then, their conducting state could be used for composite containing conducting polymers and biodegradable
the purpose of interconnectors or electrodes. As reviewed by insulating matrix. In this case, the biodegradation is classified
Prof. Alan G. MacDiarmid,[45] the conductivity of conducting as type I (see Section 2.2) in which the matrix is degraded in
polymers can reach a similar value as those metallic conductors suitable conditions and the non-degradable components are
such as Ag and Cu. That is the reason why these conducting biocompatible. PEDOT:PSS, because of its biocompatibility, is
polymers are termed “synthetic metals.” As a representative thus used to develop conducting composite, belonging to this
sample, PEDOT:polystyrene sulfonate (PSS) has been widely type. Another strategy to develop biodegradable conducting

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polymers is to incorporate flexible and nonconjugated seg- operational characteristics and developed machining process.
ments into the backbone structure. After degradation, the Conditions including pH values, temperatures, doping levels,
resultant small conjugated segments are not toxic and can be and concentrations of certain elements, such as chlorides, phos-
further degraded or removed by the environment or the body’s phates, and calcium, have been studied.[10] Some studies have
immune system. This degradation is classified as type II (see shown that the nanomembranes could be fully decomposed
Section 2.2). Some conducting polymers containing biodegrad- within 10 days without generating toxic by-products.
able segments in the backbone belong to this type, for example, Other than the aforementioned Si materials, there are
polyurethane (DCPU). other conductors that may serve as active layer materials,
Another representative organic electrode is the carbon including metal oxides (e.g., gallium oxide, tin oxide [SnO2],
nanotube (CNT) because of its metallic, semiconducting, and and indium oxide) and ternary oxides (e.g., ITO and fluorine-
superconducting electron transport.[48] CNT electrodes are doped tin oxides [FTO]); these conductors, especially ITO,
widely applied in electrochemical devices[49] because of their are widely used in solar cell applications without sacrificing
distinct properties that include nano-sized diameters, excel- the transparency of the resulting devices.[57] Another repre-
lent electrochemical activities, electrical conductivity, and bio- sentative material is zinc oxide (ZnO) because of its facile
compatibility. Individual CNT electrodes offer remarkably high synthesis, high thermal stability, solution processability, and
mass transfer coefficients because of the radial diffusion pro- decent charge transport properties.[58] Furthermore, the by-
cesses.[50] These features greatly promote application in the product of zinc hydroxide is a metabolite that can be processed
electrochemical area.[51,52] In addition, some modifications can by the human body. The degradation mechanisms of these
be done with CNT[53,54] that is incorporated with metal oxide, materials can be confirmed through knowledge of dissolution
DNA, or graphene for a unique application in the subsequent chemistry, density functional theory, and molecular dynamics
devices. Despite these promising properties, it is still difficult simulation tools. These efforts are helpful in designing mate-
to widely use organic materials as electrodes. For example, the rials to reduce the large quantities of future e-waste through
use of orthogonal solvents for polymer electrodes (to ensure no detailed understanding of the break-down mechanisms.
damage occurs to the active layer materials) is a challenge in While traditional semiconductors have their own advantages,
and of itself and complicates the fabrication of devices even the emergence of conductive polymers is allowing researchers
more. The nano-sized CNT is often toxic; thus, the physiolog- to focus on organic electronic devices and their intrinsic
ical efficacy cannot be confirmed. Additionally, individual CNT properties, which include the ease of structural modification,
electrodes show vanishingly small response currents. There- versatility for various electronic devices, solution processability,
fore, metals remain the preference for acting as electrode mate- and the potential for large-scale production and low-cost prod-
rials in green electronics. ucts through the utilization of roll-to-roll technology.[59]
The key for conductive polymers has been their conjugated
structure that contains, in a broad sense, alternating single
2.1.3. Active Layer Materials and double bonds along the polymer mainchain. In the begin-
ning, the conductive synthetic polymers primarily included
The development of green active layer materials poses the main PPy, poly-phenylene vinylene (PPV), PANI, PEDOT, and PT
issue that must be overcome for future commercialization of (see their chemical structures in Figure 2). Now, the organic
green electronic devices. The discovery of conducting organic semiconductors have extended to a series of other materials
polymers is particularly relevant to both the active layer in elec- which have excellent π-conjugation structure. The previous dec-
tronics and allied fields such as organic solar cells.[55] Although ades witnessed the tremendous advancement of organic semi-
some studies have classified dielectric materials (mainly avail- conductors in organic, flexible, and printed electronics. Some
able for OFETs and circuit design) to the active layer,[8] in this of the π-conjugated motifs used as building blocks in organic
review, we focused primarily on the conductors and/or semi- semiconductors have developed into their own subjects of
conductors that are crucial for all types of electronic devices. investigation; these included diketopyrrolopyrrole (DPP),[60,61]
Because of their excellent conducting properties, traditional isoindigo,[62] naphthalenediimide (NDI),[63] perylene diimide
semiconductors are mainly based on metal oxides and Si deriva- (PDI),[64] benzothiadiazole (BT),[65] benzodithiophene,[66] car-
tives (e.g., different forms of Si and Si germanium (Ge) alloys). bazole,[67] and triphenylamine (TPA).[68] However, not all
A traditional device has typically been fabricated on a thick these materials have been proven suitable in green electronics
wafer. Because the resulting integrated circuit would not decom- because their C-C bonds usually resist to biodegradation. To
pose for several hundred years, they are considered non-bio- overcome this issue, one effective strategy developed involved
degradable. To facilitate the dissolution process for these types mixing non-biodegradable polymers with biodegradable, yet
of materials, nanomembranes or nanowires were developed insulating, polymers. The resulting composites undergo type I
to improve their biodegradability. For example, Rogers et al. degradation (vide infra), whereby the organic polymers were
studied the transient form of Si by using a Si nanomembrane not disintegrated, but the biodegradable materials could be
as the semiconductor to fabricate a series of workable devices, fully degraded.[69] However, this strategy has not yet matured
including resistors, photodetectors, field-effect transistors, and to the point of being ready for applications in green electronics.
diodes.[56] Great efforts have been devoted to investigating the Researchers have also tried to find naturally existing con-
dissolution mechanism of these types of materials in various jugated materials to construct semiconductors for electronic
biofluids and aqueous solutions. Most work has been focused devices. Furan has shown the promise as a building block, as
on studying Si-based materials because of their excellent its derivatives are affordable from natural sources,[70] and the

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Figure 2. Chemical structures of various active layer materials (PPy: polypyrrole; PPV: poly-phenylene vinylene; PT: polythiophene; PEDOT: poly­
(3,4-ethylenedioxythiophene); PANI: polyaniline; PDPP-PD: polymer diketopyrrolopyrrole-phenylenediamine; PDI: perylene diimide; NDI: naphthalenediimide).

study of furan-based semiconducting materials could be con- allowed for the resulting degradability of the polymer. Not only
sidered one step closer to achieving green electronics. Oligo- were the DPP materials biodegradable, but so were other com-
furans (with a mobility of 10−2 cm2 V−1 s−1) have been widely ponents in the device. Subsequently, this device showed both
studied as an active semiconductor material in OFET devices, high hole mobility (0.12 cm2 V−1 s−1) and excellent biodeg-
and furan-substructures have been extensively used as building radability. In DI water (pH = 7), the device was quite stable;
blocks within the backbone of conjugated materials. Sonar however, it was totally disintegrated within 30 days in a buffer
et al. combined furan and DPP and reported a series of furan- solution with a pH of 4.6.
flanked DPP-based polymers with highest hole mobility of Another class of promising semiconductors are derived from
3.56 cm2 V−1 s−1 reported for one of the polymers.[71–77] Most the π-conjugated molecules obtained from nature directly or
of the resulting polymers demonstrated high-performance in via nature-inspired synthetic materials. In 2010, Irimia-Vladu
OFET or solar cell devices, and some of them have even been et al. fabricated thin film transistors using a series of natural
processed from non-chlorinated solvents. These reports clearly or nature-inspired materials that were all biodegradable and
revealed the potential of using furan in the construction of significantly less toxic than alternatives; the materials used
semiconducting materials for green electronics. Bao et al. also included naturally occurring beta-carotene and indigo, indan-
designed a DPP-based polymer (polymer diketopyrrolopyrrole- threne yellow G and indanthrene brilliant orange RF (both
phenylenediamine, PDPP-PD) that introduced the imine group derivatives from natural anthraquinone), and PDI, a cosmetic
to the backbone to increase biodegradability under suitable color material.[32] The transistors fabricated with these biode-
conditions.[9] From the structure, as shown in Figure 2, DPP gradable materials demonstrated excellent mobility (10−4 to
and benzene were connected by an imine bond. This bond was 10−2 cm2 V−1 s−1).[32] The indigo device, fabricated on a shellac
quite stable in a neutral-pH condition; however, it was easily substrate with AlOx activated by the biodegradable tetratetrac-
hydrolyzed with a catalytic amount of acid. This characteristic ontane as the gate, was then transferred. Because of the highly

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planar backbone structure and ability to be oxidized and reduced the degradation and cleaning of waste are achieved in parallel.
reversibly, the device showed ambipolar behavior with a hole This is also the primary reason that anaerobic digestion is more
and electron mobility of 10−2 cm2 V−1 s−1.[31] An important review, commonly used in waste management systems. The generated
written by Irimia-Vladu et al., emphasized the H-bonding methane is also used as a source of local, renewable energy.
effects of these naturally occurring molecules as promising After the first two stages are completed, the third stage,
candidatures for biodegradable materials.[78] As shown in assimilation, begins to occur within microbial cells. Before
Figure 2, melanin, indigo derivative, alizarin, purpurin, PDI, entering the cell, certain products generated during the pre-
and NDI all have extensive C = O groups, which could help vious stage must complete a biotransformation reaction to
form intramolecular and/or intermolecular H-bonding interac- ensure all resulting products are transported into the cell.
tions. Although some of these molecules lacked intramolecular For these molecules, a lack of permeable membrane carriers
conjugation, the H-bonded intermolecularly connected mate- does not allow them to go through the cytomembrane; other
rials rendered high-performance for organic electronic devices. molecules do not require this step because they can be easily
Possibilities for future development were proposed using these transported into the cell by membrane carriers. Once all the
types of biodegradable materials from nature or nature-inspired products enter the cell, catabolic pathways are followed, and the
molecules. In fact, the H-bonding interaction has remained sig- products are ultimately oxidized into adenosine triphosphate
nificant in various devices thus far. For example, Yu et al. have and constitutive elements in the structure of the cell. Subse-
completed substantial work focused on improving the copla- quent to this procedure, biodegradability is completed with the
narity of polymers by introducing analogous non-covalent inter- generation of non-harmful constituents. The newly produced
actions to enhance the mobility performance in OFETs.[79] Bao biomass is ready for the next biocycling process.
et al. developed new polymers by introducing various moieties While it might seem like a clear-cut procedure, the
with H-bonding groups to the backbone; through these inter- biodegradable process is a naturally complicated phenomenon.
molecular H-bonding interactions, the materials have been suc- Biodegradation has proven to be difficult to carry out in a labora-
cessfully used in stretchable electronic devices.[80] These types tory; therefore, a simulated process was conducted. As recently
of materials have indicated great potential as biodegradable demonstrated in an excellent review paper by Bao et al., type I and
semiconductors in the future of green electronics. type II degradations were brought forth, as shown in Figure 3-i.[69]
The reason for these two divisions was that it was unnecessary to
let all the materials break down to their oligomers, monomers,
2.2. Biodegradation Mechanisms in Materials and/or biomass and gases in a lab, especially for fundamental
research. Type I materials were the widely studied candidatures
The biodegradation process entails the breakdown of organic mat- with transient behavior and primarily applied to the biomedical
ters by enzymes found in microbes, such as bacteria and fungi. field (i.e., drug delivery and therapeutics).[41] Type II materials
Regarding the mechanism, biodegradation is generally divided were completely biodegradable, ultimately disappearing without
into three different stages–biodeterioration, biofragmentation, a trace; therefore, these types of materials would be helpful in the
and assimilation.[39] The first stage, biodeterioration, occurs on creation of sustainable electronics. In this review, we will elabo-
the surface of materials when they are abandoned in an outdoor rate on the degradation method of biodegradable materials deter-
environment where various abiotic factors exist (i.e., intense sun- mined using laboratory methods.
light, high pressure, high temperature, and various chemicals). In the lab, the degradation method applied most often is the
All these factors induce changes in the mechanical, physical, and/ dissolution method by choosing suitable solvents such as acidic,
or chemical properties. This stage includes mechanical degrada- alkaline, and (some) enzymatic solutions or even simple disso-
tion under compression, tension or shear forces, light degrada- lution in DI water. The main reactions occurring in a solution
tion (for some photosensitive materials), thermal degradation are hydrolysis and oxidation with various mechanisms under
(for materials with a low melting point or glass-transition tem- different conditions, generating small and harmless fragments.
perature), and chemical degradation, such as oxidation. Although These fragments are then discarded in the environment to
biodeterioration is the first stage, in some cases, it occurs simulta- undergo further enzymatic degradation and microbial oxidation
neously with the second stage, which is called biofragmentation. as occur in natural sources, for example, plant-based cellulose,
In biofragmentation, a lytic process occurs in which the alginate, dextran, animal-derived collagen, silk, and chitosan.
chemical bonds are broken down, thereby producing several The dissolution of metallic thin film electrodes or connects has
fragments such as oligomers or monomers. This step is fur- been discussed in Section 2.1.2. Generally, they can dissolve
ther classified according to whether oxygen is or is not present in DI water (metal oxide or hydroxide), simulated body fluids
during the process, and although the materials are broken (HBSS with pH values of 5–8), and acidic or alkaline solvents.[43]
down into fragments in either process, they are called aerobic In this way, although the dissolution rates vary, the similarity
and anaerobic digestion, respectively. Both processes gen- shown was that they could all be completely dissolved in corre-
erate some common by-products, such as carbon dioxide and sponding solutions, generating soluble ionic products which can
water. The difference between aerobic and anaerobic diges- be easily removed or bio-resorbed in the environment.[43]
tion is that an anaerobic reaction generates methane during For synthetic polymers, which generally contain some hydrolys-
the degradation of organic materials. Furthermore, although able or oxidizable groups, as shown in Figure 3-ii, the degradation
aerobic digestion is typically complete in a shorter timeframe, mechanism was hydrolysis, oxidization, or both in the presence
it always increases the volume and mass of the materials. For this of an acid, base, or some enzymes in solutions. As illustrated
reason, anaerobic digestion does exceptional work in that both in Figure 3-ii(C,D), the representative hydrolysis and enzymatic

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Figure 3. i) Two types of biodegradation proposed by Bao et al.: only matrix is fully broken down for Type I materials, while both matrix and active
materials are fully broken down for Type II materials. ii) A: Moieties susceptible to hydrolysis; B: moieties susceptible to oxidation; C: acid catalyzed
ester hydrolysis; D: polyvinyl alcohol enzymatic cleavage mechanism. Reproduced with permission.[69] Copyright 2018, American Chemical Society.

cleavage processes demonstrated that the degraded products were solar energy into electrical energy based on the photovoltaic effect.
ultimately non-toxic, and some were even recyclable compounds. Currently, various solar cell technologies based on crystalline Si,
There were many similar examples for these kinds of polymers thin film, perovskite, and organic semiconducting materials are
described in a published book and review cited in the refs. [69,81,82]. rapidly developing and attaining high efficiency.[84] Nonetheless,
Regarding the most important components, the semiconducting the research community in this field is still focusing great atten-
or conducting materials, degradation, hydrolysis, and oxidation tion upon enhancing efficiency while focusing less attention and
were still the primary mechanisms because of the existing char- concern upon green solar cells with biodegradable materials, as
acteristic groups. However, as aforementioned, organic conju- well as focusing less attention upon recyclable photovoltaics for
gated materials have been reported less in the literature for green e-waste reduction. Nevertheless, a cradle-to-grave life-cycle assess-
electronics because C-C bonds are difficult to degrade. ment of solar cells reveals that both incineration and disposal in
A DPP-based polymer was reported by Bao et al., and the landfills cause a negative impact on the environment through the
fabricated OFET device was completely degraded in acidic formation of photochemical oxidants, water depletion, and eco-
solution within 30 days.[9] From the proposed mechanism, the toxicity.[85] Comparatively speaking, biodegradable and recyclable
polymer was not completely degraded; rather, it transformed solar cells are as important as high-efficiency solar cells and are
into a colorless product. However, it still contained several highly desirable for sustainable development. As mentioned
conjugated structures and functional groups. The C-C bonds above, solar cells can be divided into several layers that mainly
were not degraded in the least, which has proven to be a chal- include a substrate, charge transporting layer, active layer, and
lenging subject to date. Although there have been a few reports electrode. Each layer can be used or combined with biodegrad-
regarding the enzymatic cleavage of C-C bonds, they have only able materials. In this section, recent reports on new-generation
been applicable to particular groups such as the sulphona- solar cells (mainly organic solar cells [OSCs] and perovskite solar
mides, phosphonates, and ethers; therefore, a deeper under- cells [PSCs]) consisting of one or more biodegradable layers are
standing about this particular mechanism is essential.[83] reviewed. It is worth mentioning here that recycling Si crystalline
solar cell or thin film solar cell can recover 90% of the cover glass
for use in new products, as well as 95% of the semiconductor
2.3. Recent Development in Electronic Devices materials for use in new solar modules.
with Biodegradable Materials Solar cells can be fabricated from biodegradable transparent
substrates rather than traditional glass or a polyethylene tereph-
2.3.1. Solar Cells thalate substrate. One example is cellulose, which can be used
as a transparent, flexible substrate in OSCs owing to its high
Solar energy is one type of renewable energy where full utilization optical haze that can scatter the transmitted light and enhance
is expected. Traditionally, a solar cell is the device used to convert solar cell performance.[86] Cellulose is a low-cost biodegradable

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Figure 4. i) Organic solar cell (OSC) structure with cellulose-based paper as substrate and corresponding performance. Reproduced with permis-
sion.[87] Copyright 2018, American Chemical Society. ii) Schematic illustration of ethyl cellulose (EC) passivation on perovskite defects and solar cell
performance. Reproduced with permission.[89] Copyright 2019, American Chemical Society. iii) OSC structure with chitosan derivatives as cathode
interlayer materials and corresponding performance. Reproduced with permission.[90] Copyright 2017, Elsevier.

material, and it is non-toxic and possesses biocompatibility C71-butyric acid methyl ester), as shown in Figure 4-i. A power
properties. Notably, cellulose materials are readily degraded by conversion efficiency (PCE) of 4.98% was achieved for the fab-
bacteria in soil. Zhang et al. added tunicate cellulose nanocrys- ricated flexible inverted device.[87] In another work, Cao et al.
tals (TCNCs) to O-(2,3-dihydroxypropyl) cellulose (DHPC) to combined cellulose with AgNW to fabricate a transparent con-
synthesize a cellulose-based flexible paper substrate with a ductive film used as the substrate in PSCs. In addition, HNO3
high transparency. Significantly, owing to the strong interfacial was applied post-treatment to enhance the bonding strength
interaction between the TCNC and DHPC, the obtained sub- between the cellulose and AgNW. Accordingly, the obtained thin
strate showed increases in the storage modulus and decom- film was observed as 80% transparent with a sheet resistance
position temperature, which were related to mechanically and of 29 Ω sq−1, and the PCE of the PSCs was 4.49% with an open
thermally stable properties, respectively. Furthermore, a thin circuit voltage (Voc) of 1.02 V, a short-circuit current density (Jsc)
layer of ITO was deposited onto the cellulose-based paper and of 9.58 mA cm−2, and a fill factor (FF) of 45.8%.[88]
a solar cell was fabricated with a structure of paper/ITO/ZnO/ Chitosan was used as a biodegradable substrate in another
PTB7-PC71BM/MoO3/Ag (PTB7:poly[[4,8-bis[(2-ethylhexyl)oxy] report. Xiao et al. deposited AgNW onto an antioxidant acid-
benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl) modified chitosan polymer and developed transparent bottom
carbonyl] thieno[3,4-b]thiophenediyl]]; PC71BM:[6,6]-phenyl electrodes for the PSCs. The modified polymer could protect

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the AgNW from the degradation of perovskite precursor function of 3.7 eV, conductivity of 22.6 × 106 S m−1, is biode-
without blocking the charge carrier drift. The sheet resistance gradable, and can be dissolved in water.[95] Nevertheless, Mg is
of the composite was 17.1 Ω sq−1, and this initial sheet resist- rarely used in solar cells, probably owing to its easy oxidation
ance was maintained even after 40 days, thereby indicating and reaction in air. Considering the trade-off between biodeg-
good stability of the chitosan-based electrode. Furthermore, the radability and chemical stability, such transient metals can be
AgNW/chitosan composite was used as a bottom electrode to used for specific devices with special designed lifetime, such
fabricate PSCs with the structure of AgNW/chitosan-based elec- as transient electronic devices. Carbon-based materials may
trode/PEDOT:PSS/CH3NH3PbI3/PCBM/Bphen/Al. The PCE be alternatives for noble metals, owing to their low-cost, high-
was 7.9% with a Voc of 1.04 V, Jsc of 21.0 mA cm−2, and FF of stability, and hydrophobic and biodegradable natures. Carbon
36.1%.[91] The performance of the biodegradable substrate- electrode materials have been applied to PSCs, and the PCE
based solar cells was not comparable to that of the conventional approached 15.7%.[96] The screen-printing, doctor-blading,
PSCs, but these works have been innovative and indicated great rolling-transfer, and hot-pressing deposition methods are
potential in the fabrication of biodegradable solar cells. used for carbon electrodes.[97] Significantly, carbon materials
Transparency and haze are vital factors for light management can replace the hole-transport layer (HTL), allowing for the
in cellulose- or chitosan-based flexible substrates. To absorb large-scale fabrication of PSCs without a hole-transport layer.
sunlight more efficiently, substrates with high broadband trans- Despite this development, there is still no report regarding an
mittance and haze are required. Hu et al. developed a “top- assessment for the biodegradability of active (light-absorbing)
down” approach to fabricate an anisotropic flexible paper that materials or the modification of materials to facilitate biodeg-
exhibits both high transparency and haze from pre-­delignified radation. These areas will need to be developed in the future to
wood materials through shear pressing. Significantly, a 14% make a truly biodegradable solar cell.
enhancement in the PCE and an 18% improvement in the
Jsc can be observed after the anisotropic transparent paper is
coated onto a GaAs solar cell, demonstrating efficient light 2.3.2. OFETs
management by the anisotropic paper.[92] The substrate in this
work may be a good option for the fabrication of high-perfor- OFETs are the key components of many organic electronic
mance biodegradable OSCs and/or PSCs. devices.[98–100] OFETs fabricated with biodegradable materials
In addition to utilizing biodegradable cellulose and chitosan show promise in the effort to solve the waste issue of field-effect
materials as substrates, they could also be used to passivate transistors (FETs). An OFET is usually made up of a substrate,
the defects of the PSCs, which act as a charge recombination gate electrode, semiconductor, dielectric, and source/drain elec-
center and suppress the charge-transfer, or interfacial layer, trodes. In fact, each layer can be deposited with suitable biode-
in OSCs. Bao et al. introduced the low-cost and biodegradable gradable materials to make biodegradable OFETs.
ethyl cellulose (EC) into perovskite precursor with different A traditional FET is fabricated on a hard substrate. Although
concentrations. The H-bonding formed between the EC and such a device possesses high charge carrier mobility, there
perovskite effectively passivated the charge defect traps, thereby remains a problem associated with its biodegradability. There-
increasing the PCE from 17.11% to 19.41% (Figure 4-ii).[89] fore, selecting a proper biodegradable substrate is the first step
Wang et al. deposited chitosan derivatives on ITO to act as in fabricating biodegradable OFETs. One safe biodegradable
cathode interlayer materials to fabricate OSCs in which PTB7- material for substrates is poly(lactic-co-glycolic acid) (PLGA). It
Th:PC71BM (PTB7-Th:poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl) is composed of two monomers, lactic acid, and hydroxyacetic
benzo[1,2-b;4,5-b′]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)- acid, which are randomly polymerized. Approved by the Food
3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)]) was and Drug Administration (FDA) of the United States, it is
selected as the active layer material. The work function of the widely used in pharmaceutical, medical, and industrial fields
ITO was successfully decreased from 4.6 to 4.3 eV owing to the because of its biocompatibility, biodegradability, non-toxicity,
formation of an ordered layer-by-layer structure and interfacial and feasibility as capsules and membranes. Gradually, it is
and molecular dipoles, which facilitated the charge-transfer. making its way into the field of green electronics. Bao et al.
The solar cell efficiency approached 10.18% with a chitosan first reported a thin film p-channel 5,50-bis-(7-dodecyl-9H-­
derivatives interlayer, as shown in Figure 4-iii.[90] Chitosan was fluoren-2-yl)-2,20-bithiophene transistor fabricated on a PLGA
also used as an interfacial layer to modify a ZnO electron trans- substrate, as shown in Figure 5-i, with a PVA gate dielectric,
port layer (ETL) for an OSC with PTB7-Th:PC71BM as a bulk- high hole mobility of 0.253 cm2 V−1 S−1, and an on/off ratio
heterojunction (BHJ) active layer, demonstrating an efficiency as high as 9.4 × 103.[101] The similar OFET device fabricated
of 7.54%.[93] with the same semiconductor but Si substrate achieved a hole
Based on the above discussion, biodegradable materials are mobility of 0.39 cm2 V−1 s−1.[102] In addition, PLGA has also
mostly used as substrates, additives, or interlayers in solar cells. been utilized in organic electrochemical transistors as a bio-
However, the back electrodes in solar cells still consist of tra- degradable substrate,[103] water-gated OFET,[104] and transient
ditional metals such as Au, Ag, Cu, Al, or their corresponding hydration sensor.[105]
alloys. These metal electrodes are corrosion-resistant with high As in solar cells, cellulose has been used as a substrate in
conductivity but are typically costly and rare.[94] Mg, Mo, man- OFETs. As a water-insoluble macromolecular polysaccharide,
ganese (Mn), Fe, W, and Zn are environmentally friendly and cellulose has been utilized as a biodegradable material in green
are metabolized under appropriate physiological conditions, as electronics.[109] Cellulose-based substrates have the advantages
mentioned in Section 2.1.2. Among these, Mg exhibits a work of good mechanical flexibility and chemical dissolvability.

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Figure 5. Schematic diagrams of biodegradable organic field-effect transistors (OFETs): i) poly(lactic-co-glycolic acid) (PLGA) Reproduced with per-
mission.[101] Copyright 2010, Wiley-VCH, and ii) cellulose nanofibrillated fiber (CNF) substrate. Reproduced with permission.[106] Copyright 2018, Wiley-
VCH. iii) Bending test of starch paper substrate by adding 0.5 wt% polyvinyl alcohol (PVA) and 5 wt% of crosslinker (left), and biodegradability test by
immersing starch paper in fishbowl water for 24 days (right). Reproduced with permission.[107] Copyright 2018, Wiley-VCH. iv) Schematic diagrams of
OFETs based on biodegradable polypropylene carbonate (PPC) as substrate (left) and dielectric layer (right). Reproduced with permission.[108] Copyright
2018, Nature Publishing Group.

Furthermore, they have been obtained easily and at low-cost. drawbacks mentioned above and could be a potential mate-
Recently, Bao et al. have reported an ultrathin, ultralightweight rial for the next generation of OFETs. Lee et al. demonstrated
cellulose substrate for transient electronics.[110] Not only was OFETs based on a starch paper substrate using different
this substrate proven to be transparent, flexible, and biodegrad- organic semiconductors with the gate dielectric parylene-C, and
able, but it was also more tolerant to high temperature, water, these OFETs performed well.[107] Additionally, it was found that
and organic solvents than many other biodegradable substrates. the mechanical property of this substrate could be improved by
A fully disintegrable and biocompatible polymer transistor adding 0.5 wt% of PVA and 5 wt% of a crosslinker that could
with a low-operating voltage was successfully fabricated on an bind to the PVA, as shown in Figure 5-iii. More importantly, the
ultrathin cellulose (800-nm-thick) biodegradable substrate. In starch paper was fully biodegraded after immersion in fishbowl
addition, by applying Fe electrode, the OFET device exhibited a water for 24 days, suggesting an alternative to the convention-
comparable hole mobility with that of a device fabricated with ally non-biodegradable plastic substrates.
Au electrode (0.12 cm2 V−1 s−1 for Fe vs 0.34 cm2 V−1 s−1 for Au). Another noteworthy environmentally friendly material
Another interesting application for a cellulose substrate was is polypropylene carbonate (PPC). PPC is a biodegradable ali-
reported by Ju et al.[106] Using pentacene as an active organic phatic polyester product of the copolymerization of CO2 and
semiconducting layer and MoO3-buffered indium zinc oxide propylene oxide under catalysis with a Zn complex. Thus, the
(IZO) electrodes on a biodegradable nanofibrillated fiber sub- synthesis of this material not only decreases the greenhouse
strate, the transistor exhibited good performance, as shown gas, CO2, but it also makes a valuable product. Recently, Chu
in Figure 5-ii. With a transmittance greater than 70% and a et al. reported the potential of PPC for use in OFETs as the
preeminent saturation mobility of 1.40 cm2 V−1 S−1, the device substrate and dielectric layer, as shown in Figure 5-iv.[108] The
exhibited good mechanical flexibility after the bending cycle. pentacene organic transistor employing PPC dielectric demon-
Paper, consisting of cellulose, has also been used as a sub- strated a mobility of 0.14 cm2 V−1 S−1, an on/off ratio of 105, and
strate for OFETs. Gao et al. reported a flexible poly(3-hexylth- an operating voltage of 60 V. When the PPC was used as the
iophene) (P3HT) organic transistor with a chitosan smoothing substrate, the device performance of pentacene-based OFET
layer, Au source/drain electrodes, and a reusable ion gel die- was enhanced to 0.27 cm2 V−1 s−1. This result indicated the great
lectric layer fabricated on a paper substrate.[111] Besides good potential application of biodegradable PPC as both substrate
mechanical flexibility and a low-operating voltage (approxi- and dielectric materials. The PPC sheet also exhibited 92%
mately 2 V), the device exhibited an on/off ratio of 104 and a transparency and good mechanical flexibility, thereby demon-
high mobility of 0.97 cm2 V−1 S−1. This hole mobility value is strating its potential in OFET-based electronic displays.
even comparable with that of devices based on P3HT fabri- Regarding gate dielectrics, the demand for high-k-value mate-
cated on flat substrates (1.1 ± 0.9 cm2 V−1 s−1).[112] However, the rials with biocompatible and non-toxic properties has increased
roughness and non-transparency of the commercial paper were for use in green OFETs. Concerning these conditions, natural
drawbacks that would limit its large-scale application in OFETs. materials existing in plants, insects, and animals could pro-
Although transparent paper has been reported, it required an vide clues. Many new gate dielectric materials have been intro-
extra planarization procedure. Starch paper has overcome the duced, and their OFET devices exhibited good performances.

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Natural silk has attracted research interest owing to its excellent gate dielectric and demonstrated an improvement in device per-
properties of non-toxicity, mechanical flexibility, solution-process- formance compared with that of the single chitosan dielectric
ability, and biodegradability. Several works on OFETs that used layer.[122] After mixing the Y2O3 nanoparticle with the chitosan,
different semiconductors demonstrated the outstanding dielec- the leakage current decreased and the on/off ratio increased
tric property of natural silk.[113–117] One significant work reported by 100 times. The P3HT OFET was of bottom-gate top-­contact
a high-performing pentacene OFET fabricated on a PEN sub- structure and used Au/Cr electrodes that exhibited a low-
strate with silk gate dielectrics.[117] A mobility of 23.2 cm2 V−1 s−1 operating voltage, an on/off ratio of approximately 105, and a
was obtained under a low-operating voltage of −3 V, effectively mobility of 8.53 × 10−2 cm2 V−1 s−1. Liu et al. applied gelatine to
outclassing inorganic dielectric SiO2 a hundred times over. Its the gate dielectric of the pentacene OFET, and it exhibited good
excellent charge transport characteristic was attributed to the charge transport characteristics in ambient air.[123] The mobility
improved crystallization of pentacene by silk fibroin (SF) and low was 16 cm2 V−1 s−1 with a voltage of 5 V in the saturation regime.
interface scattering between the SF and pentacene. This high mobility could be attributed to the negatively charged
Keratin protein, a type of structural protein found in animal ions produced by the interaction between water and the polar
hairs and feathers, has proven itself as a feasible material in hydroxyl in the ammonic acids of the gelatine.
green OFETs because of its degradation characteristic with the Furthermore, synthesized biodegradable materials, such as
existence of peptide bonds. Chicken feathers, which contain 90% poly-methacrylate tannic acid (PMTA), PVA, poly(methyl meth-
keratin protein, have been considered useless and treated as gar- acrylate) (PMMA), and poly(4-vinylphenol) (PVP), have been
bage in the food industry. Recently, Ko et al. demonstrated a valu- used as gate dielectrics.[125–127] Kim et al. reported a pentacene
able use for chicken feathers as the gate dielectric layer in biode- OFET with PMTA as the gate dielectric and Au as the source/
gradable OFETs.[118] The chicken feathers were first dissolved in a drain electrodes.[125] The PMTA dielectric exhibited a good elec-
urea and cysteine solution under an alkaline condition and then trical breakdown strength of 5.4 MV cm−1. The OFET exhib-
distilled and centrifuged; a pure keratin solution was acquired ited a mobility of 0.229 cm2 V−1 s−1 at a gate voltage of −20 V.
for device fabrication. The metal/insulator/metal capacitor Owing to the stable structure of PMTA, the device was hyster-
devices with keratin thin film exhibited a low leakage current esis free. An OFET fabricated on a PVA substrate with a PMTA
density of 1.2 × 10−7 A cm−2. Based on the P3HT active layer gate dielectric could fully dissolve in a PBS solution (pH = 7.4)
with a keratin dielectric layer (500-nm-thick), the OFET device at 35 °C after 8 days, which indicated excellent degradability.
exhibited a high on/off ratio of 1.19 × 105, saturation mobility of Iyer et al. demonstrated a high-performance OFET using a con-
2.323 × 10−3 cm2 V−1 s−1, and low threshold voltage of −1 V, as jugated molecule, octadecyl-amine substituted 1,4,5,8-NDI as
shown in Figure 6-i. Although the performance is not high, this the semiconductor, and PVA as the dielectric.[126] Huang et al.
value is much higher than that of device fabricated with SiO2 reported stable OFETs with net-structured cross-linked PVP
gate dielectric (1.08 × 10−7 cm2 V−1 s−1) under completely same inserted between two ultrathin PMMA layers as polymeric die-
fabrication procedures and characterization conditions. Remark- lectrics. The dielectric with a core-shell-like structure exhibited
ably, keratin protein was fed to fish, thereby introducing a new better electrical insulation, which allowed for a 4 V-driven flex-
degradation method. Human hair could also be an ideal source ible OFET with a high mobility of 0.72 cm2 V−1 s−1 and excellent
of keratin protein. Leong et al. reported a p-channel poly[4-(4,4- bias-stress stability in air.[127]
dihexadecyl-4H-cyclopenta[1,2-b:5,4-b]dithiophen-2-yl)-alt[1,2,5] A semiconducting active layer has been highly desired for
thiadiazolo[3,4-c]-pyridine] (PCDTPT) thin film transistor with use in biocompatible and biodegradable materials with high
a human hair keratin dielectric layer with a low-operating mobility for the fabrication of green OFETs. A PDI OFET
voltage.[119] The keratin dielectric layer had a capacitance as high with a glucose gate dielectric exhibited the highest mobility of
as 1.27 µF cm−2. The transistor exhibited good performance with 0.01–0.02 cm2 V−1 s−1.[32] A natural indigo-based OFET was fab-
a mobility value of 0.35 cm2 V−1 s−1 (Figure 6-ii). Although the ricated using natural shellac resin substrates, and its balanced
performance is slightly lower than that of device fabricated with electron and hole mobility were 1 × 10−2 cm2 V−1 s−1, demon-
SiO2 dielectric layer (0.94 cm2 V−1 s−1), the keratin exhibited a strating potential for the fabrication of green electronics with
good degradability in ammonium hydroxide solution. biodegradable and non-toxic semiconductors.[128] Similar with
Other naturally biodegradable materials, including cellulose, solar cells, few reports used biodegradable materials as active
chitosan, chicken albumen, and gelatine, were discussed in layer in OFETs. Natural active materials are with good bio-
reports and used as gate dielectrics.[120–124] Stadlober et al. intro- degradability but poor performance, meanwhile, synthesized
duced an ultrathin hybrid high-k dielectric layer into a pentacene active materials perform reversely. Alternatively, molecular
OFET.[120] The cellulose dielectric layer was obtained by spin- design through combing the advantages of natural and synthe-
coating desilylation of trimethyl-silyl cellulose and regenerated sized active materials can be the promising strategy to enlarge
by exposing it to hydrochloric acid vapors. The device demon- the selectable biodegradable active materials for OFETs. The
strated low leakage currents and a mobility of 0.1 cm2 V−1 s−1. reported performance of OFETs with biodegradable materials is
Huang et al. used ultrasmooth wood-derived cellulose nanopa- summarized in Table 1.
pers (WCNs) as the gate dielectric in organic synaptic transis-
tors.[121] The WCNs showed an excellent ionic conductivity of
7.3 × 10−4 S m−1 and a lateral capacitance of 18.65 nF cm−2 at 2.3.3. LEDs
30 Hz. Significantly, the organic synaptic transistor successfully
mimicked synaptic behaviors at a low-operating voltage of 1.5 V. Optoelectronic devices have played a crucial role in
Ko et al. investigated a blend of Y2O3 nanoparticle/chitosan as a illumination, mobile devices, and smart homes. The use of

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Figure 6. i) A: Device structure with keratin protein as dielectric layer. B,C: Transfer and output characteristics of keratin dielectric-based organic thin-
film transistor (OTFT). Reproduced with permission.[118] Copyright 2017, Elsevier. ii) A: Schematics of keratin from human hair and various chemical
bonds in keratin. B: Bottom-gate top-contact p-channel poly[4-(4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b]dithiophen-2-yl)-alt[1,2,5]thiadiazolo[3,4-c]-
pyridine] (PCDTPT)/keratin TFT and molecular structure of PCDTPT. C,D: Output and transfer characteristics of PCDTPT/keratin TFT. E,F: Output and
transfer characteristics of reference PCDTPT TFT on SiO2 dielectric layer. Reproduced with permission.[119] Copyright 2017, American Chemical Society.

biodegradable materials in light-emitting devices, such as allowing for the replacement of expensive and unsustainable
LEDs and light-emitting electrochemical cells (LECs), could components without any obvious loss in performance. This
enable the fabrication of renewable and eco-friendly displays section introduces the most used and widely studied biodegrad-
for healthcare electronic devices, as well as other sustainable able materials in LEDs, focusing on their performance, applica-
applications. Several kinds of biodegradable materials such as tion, and feasibility with different types of devices.
naturally occurring materials of living organisms (e.g., eumela- Inorganic LEDs: Inorganic LEDs (ILEDs) are semiconductor-
nins,[131] DNA,[132–134] mucin,[135] serum albumin,[136] and fluo- based light sources made of a compound that combines
rescent proteins[137]) and synthetic or hybrid-natured materials elements such as indium (In), arsenic, gallium, phosphorous,
(e.g., silk,[138,139] cellulose,[140–146] carbon-based materials,[147–151] and nitrogen. When a forward bias is applied to ILEDs, the
and biodegradable polymers[151–154]) have been reported for use injected holes and electrons are combined with the electrons
in individual components of light-emitting devices. Recent pro- in the n-region and holes in the p-region (near the p-n junc-
gress in this field has mainly focused on how to apply biode- tion) to generate fluorescence (i.e., spontaneous emission). The
gradable materials to light-emitting devices properly, thereby energy states of electrons and holes in different semiconductor

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Table 1. Summary of the performance of reported OFETs with biodegradable materials.

Biodegradable materials Functional layer Device structure μ (cm2 V−1 s−1) Ion/Ioff Ref.
PLGA Substrate BGTC 0.253 9.4 × 10 3 [101]
tascPLA Substrate BGTC 0.58 – [129]
Cellulose Substrate BGTC 0.12 >104 [9]
5
CNF Substrate BGTC 1.40 10 [106]
Cellulose paper Substrate BGTC 0.97 104 [111]
Starch paper Substrate BGTC 0.37 4.9 × 105 [107]
PPC Substrate BGTC 0.27 104 [108]
−2
Shellac resin Substrate BGTC 1 × 10 – [128]
Shellac resin Substrate BGTC 0.4 105 [130]
3
Silk fibroin Gate dielectric BGTC 10 10 [113]
Silk fibroin Gate dielectric BGTC 0.39 9.3 × 102 [114]
Silk fibroin Gate dielectric BGTC 0.01 104 [115]
Silk fibroin Gate dielectric BGTC 23.2 3 × 104 [117]
Chicken feather keratin Gate dielectric BGTC 2.323 × 10−3 1.19 × 105 [118]
Human hair keratin Gate dielectric BGTC 0.35 1.1 × 104 [119]
Cellulose Gate dielectric BGTC 0.1 – [120]
WCNs Gate dielectric LCFET 1.25 – [121]
Y2O3 nanoparticle/chitosan Gate dielectric BGTC 8.53 × 10−2 105 [122]
Gelatine Gate dielectric BGTC 16 – [123]
Chicken albumen Gate dielectric BGTC 0.13 104 [124]
PMTA Gate dielectric BGTC 0.229 – [125]
PVA Gate dielectric BGTC 1.0 102 [126]
PVP Gate dielectric BGTC 0.72 2.3 × 10 4 [127]
PDI Semiconductor BGTC 0.01 105 [32]
β-carotene Semiconductor BGTC 4 × 10−4 – [32]
Vat Yellow 1 Semiconductor BGTC 0.012–0.015 – [32]
Vat Orange 3 Semiconductor BGTC 1.75 × 10−3 – [32]
Indigo Semiconductor BGTC 0.01 – [128]

PLGA, poly(lactic-co-glycolic acid); tascPLA, three-arm stereocomplex polylactide; CNF, cellulose nanofibrillated fiber; PPC, polypropylene carbonate; WCNs, wood-derived
cellulose nanopapers; PMTA, poly-methacrylate tannic acid; PVA, polyvinyl alcohol; PVP, poly(4-vinylphenol); PDI, perylene diimide; BGTC, bottom-gate top-contact; LCFET,
laterally coupled field-effect transistor; µ, hole/electron mobilities; Ion/Ioff, on/off current ratios.

materials are different, which causes different energy released The color down-converting material plays a decisive role in
by the recombination. The more energy that is released, the white LEDs because it determines the color temperature, color
shorter the wavelength of light that is emitted.[155] quality, and brightness of the device. In choosing a biodegrad-
In the past 10 years, white ILEDs (WILEDs) have sig- able material for use in a color down-converter, it must not only
nificantly developed and obtained a place in the lighting meet the requirements for luminescence and optical features,
market. They have been widely used for illumination, front but it must also be compatible with the packaging system. Fluo-
automotive lights, signaling, backlighting of liquid crystal dis- rescent proteins (FPs), which were already successfully utilized
plays, etc.[156] There are five components integrated in com- in bio-lasers as color converters,[157] were first reported as the
mercial WILEDs: electronic driver, heat dissipating system, color down-converters in white hybrid LEDs by Costa et al. in
emitting chip, packaging system, and components for light 2015, as shown in Figure 7-i.[137] This new matrix, which com-
extraction and color conversion. Because the electronic driver, bines a branched polymer (trimethylolpropane ethoxylate) and
heating dissipating system, and emitting chip of commercial a linear polymer (polyethylene oxide), was developed to remedy
WILEDs are fabricated with well-established methods, recent the low mechanical stability of the origin hydrogel under the
research on biodegradable materials applied to WILEDs and conditions of moisture and high temperature. An elastomeric
white hybrid LEDs mainly focuses on the substitution of these compound was created from stabilized FPs without cross-
components for light extraction, color conversion, and typical linking reactions, and it exhibited a good performance of
packaging systems. approximately 90% transmittance over the whole visible range

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Figure 7. i) A: Architecture of bio-hybrid inorganic/organic light-emitting diodes (LEDs) with cascade coating based on red, green, and blue fluo-
rescent proteins (FPs). B: Chemical structures of chromophores. C: Photograph of protein-based gels and rubber-like materials upon excitation at
310 nm. Reproduced with permission.[137] Copyright 2015, Wiley-VCH. ii) A: Processing steps of DNA–cetyltrimethylammonium (DNA-CTMA)–curcumin
aqueous solution. B: Comparison of luminous efficiency between DNA-curcumin-based LED and normal UV-LED. Reproduced with permission.[160]
Copyright 2016, Nature Publishing Group.

and withstood temperatures as high as 100 °C. Further progress was made by scientists. OLEDs have a high luminous effi-
in this field was made by Nizamoglu et al., who reported a cre- ciency, simple structure, and low manufacturing cost. With an
ative method to achieve a combination of FPs and blue LED improved transport layer and continuous optimization of this
chips (450 nm) without a polymer matrix.[158] The fabrication structure, the technology should readily advance in the applica-
of these devices was carried out by drying the aqueous solution tion to display devices. Generally, OLEDs have exhibited a sand-
(40 °C for 25 min) with a mixture of enhanced-green FPs and wich-like structure, including a substrate, anode, hole injection
monomeric Cherry protein in a glass reservoir; the devices were layer, HTL, emitting layer, ETL, electron injection layer, and
finally placed on blue LEDs as the color down-converter. Later, metal cathode. The balance of the hole and electron injection
Kumar et al. reported a bovine serum albumin (BSA)-based bio- layers has proven crucial for efficient OLEDs, owing to the
phosphor,[159] which was obtained by mixing natural BSA and structure and mechanism of hole-electron recombination. To
water-soluble carbodiimide 1-ethyl-3-(3-dimethylaminopropyl) date, several individual components of OLEDs that were made
carbodiimide. The cross-linked BSA, with two or three fluores- with biodegradable materials have been reported, and they will
cent dyes, was coated on UV-LEDs as the color down-converter, be introduced in subsequent sections.
and the encapsulation was cascade-like. The hydrogel rendered Cellulose, with its excellent thermal stability, recyclability,
an average thickness of 0.5 mm and CIE color coordinates of sustainability, and flexibility, has become an attractive mate-
(0.36, 0.37). rial for the substrates and/or encapsulations of OLEDs.[142]
In 2016, Reddy et al. reported a crystalline DNA-based com- To meet the requirements of device fabrication, it has been
plex used as the color down-converting material for LEDs.[160] found that cellulose-based substrates must exhibit a low rough-
The DNA double helix structure was first modified with cur- ness and low coefficient of thermal expansion (CTE) to avoid
cumin chromophore and then transformed into its crystalline unreliability and damage to the active materials during the
form. The LEDs fabricated with thick crystalline DNA complex fabrication process under high temperatures. Bacterial-derived
on a UV-LED chip exhibited green emission and a maximum cellulose (BC) containing nanofibers with a low CTE and high
luminous efficiency of 1.6 lm W−1 with a stability of a few hours tensile strength was first reported and applied as a substrate for
when driven at the current of 10 mA (Figure 7-ii). Because of OLEDs by Yano et al.[161] The substrate was prepared with bac-
the novelty and low-cost of the curcumin in this method, the terial Acetobacter xylinum FF-88 and impregnated acrylic resin,
DNA-based color down-converting material could be appealing which exhibited a light transmittance loss of less than 8% com-
and cost-effective in the fabrication of devices. pared with that of acrylic resin, and even the nanofiber content
Organic LEDs: In the past 20 years, with the development of was as high as 70%. Later, they produced acrylic resin with 5%
high-purity organic conductive polymers, much research on BC that exhibited suitable flexibility and mechanical properties.
organic/polymer LEDs was conducted and significant progress Compared with that of the individual resin, the transmission of

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Figure 8. i) Photographs of organic light-emitting diodes (OLEDs) on cellulose nanocrystal (CNC) substrate mounted on glass (left) and illumi-
nated OLED on CNC substrate (right). Reproduced with permission.[143] Copyright 2014, American Institute of Physics. ii) Digital images of working
flexible OLEDs on bacterial-derived cellulose/castor oil polyurethane (BC/PU) composite. Reproduced with permission.[163] Copyright 2015, Royal
Society of Chemistry. iii) Molecular structure of riboflavin-tetra butyrate (RFLT); current density and voltage characteristics; EQE of the RFLT–poly(9-
vinylcarbazole) bilayer photodiode. Reproduced with permission.[166] Copyright 2017, American Chemical Society. iv) Energy levels of DNA-based OLED;
luminance and current density characteristics. Reproduced with permission.[167] Copyright 2014, Nature Publishing Group.

the composite showed a loss of only 8.7% with good bending 2 weeks longer than that of the corresponding standard devices,
properties.[162] However, as a derivative of petroleum, the afore- thereby demonstrating the potential of cellulose acetate as the
mentioned resin was not perfectly biodegradable. In 2014, Kip- encapsulation material of OLEDs.
pelen et al. developed OLEDs with a cellulose nanocrystals The key parameters in a satisfactory transparent electrode
(CNC)-based substrate (Figure 8-i).[143] Two years later, Pinto for OLEDs are good conductivity, transmittance, and feasibility
et al. reported a thin film that combined BC with castor oil pol- in flexible devices. SF was first reported as the material for an
yurethane (PU) and exhibited a high transmittance of 80% and electrode implemented with a composite based on an AgNW
good stability (Figure 8-ii).[163] Recently, Mashkour et al. reported mesh by Sun et al. in 2015.[168] To smooth the film surface and
multi-walled CNTs (MWCNTs)-coated cellulose as electrically improve adhesion, an AgNW mesh was embedded into an SF
conductive cellulose nanopapers (EC-CNPaps).[164] The effects matrix by first drop-casting AgNW solution onto a polished Si
of various drying and stabilization methods on the properties wafer, followed by dropping SF solution onto the AgNW mesh.
of EC-CNPaps were compared for further application. Cellulose The film had a transmittance of 80% in the visible range with
could also be used for the encapsulation material of OLEDs. a sheet resistance of 12 Ω sq−1, while the OLEDs exhibited a
Because moisture and oxygen are the major barriers for encap- good efficiency of 19 cd A−1 at a current density of 40 mA m−2.
sulated OLEDs, Nguyen et al. used cellulose acetate as the Two years later, the same group reported excellent OLEDs
encapsulation material, owing to its transparency, low-cost, and with a smooth substrate created by combining SF with a
hydrophobicity.[165] A comparison between the stability of both photopolymer.[169] They deposited a photopolymer, NOA63 (Nor-
encapsulated and standard OLEDs indicated that the OLEDs land Products, Inc., New Jersey, USA), to form the film (with
encapsulated with cellulose acetate exhibited a stability that was root mean square roughness of 0.682 nm) on a silk substrate

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by spin-coating, which increased the overall smoothness and isothiocyanate as the charge injection and transport layers in
retained the flexibility and transparency of the substrate. The OLEDs.[180] The device with a cytochrome c layer yielded an
OLEDs had a remarkable efficiency of 37.7 cd A−1 and an Lmax of Lmax of 100 cd m−2, which was nearly the same as other pro-
45 545 cd m−2, and these numbers were similar to those of the tein-based OLEDs, as well as an efficiency of 0.02 cd A−1, which
glass-based devices. was 40 times higher than that of the device without cytochrome
In 2017, an ITO-free OLED with eumelanin pigment incor- c. The first report on DNA-based OLEDs was published by
porated into commercial PEDOT:PSS was reported by Pezzella Kobayashi et al. in 2001.[181] Later, they applied salmon DNA, a
et al.[170] Focused on overcoming the drawbacks of PEDOT:PSS, by-product from the salmon industry that can easily be trans-
including instability in water, low adhesion to organic sub- formed into DNA-cetyltrimethylammonium (DNA-CTMA), as
strates, and low conductivity compared with those of ITO, an electron transporter in OLEDs.[182] With good solubility in
they obtained eumelanin-PEDOT:PSS by adding PEDOT:PSS common organic solvents that enabled solution-processability,
to water with a small amount of dimethyl sulfoxide (DMSO) DNA-CTMA was widely studied for its use in functional layers
into isopropyl-dissolved alcohol eumelanin. The film was then throughout the next decade.[183–185] In 2011, Nguyen et al. fab-
fabricated by filtering and spin-coating the blend onto glass, ricated a poly[2-methoxy-5(2′-ethyl-hexyloxy)-1,4-phenylene
followed by heating to remove the water. The thin film exhib- vinylene (MEH-PPV, electroluminescent layer)-based device
ited a high optical transparency greater than 80% in visible with pure DNA as the interlayer and achieved a luminance of
light and a conductivity of 370 S cm−1. 5700 cd m−2 and a current efficacy of 0.80 cd A−1, which were
Carbon-based materials, such as CNTs and graphene, with significantly higher than that of the device without a DNA
their low-cost and good transparency are typically combined layer.[186] In 2014, Gomez et al. applied the adenine (A) and
with conductive materials to prepare flexible electrodes. Previ- thymine (T) nucleobases of DNA into OLEDs.[167] Because of
ously reported carbon-based electrodes include laminated elec- their powder forms and low molecular weights, A and T have
trodes, such as AgNW/graphene,[171] Al/MWCNTs/Al,[172] and helped simplify treatment processes and allowed for the prepa-
graphene/Ag thin film,[173] as well as hybrid compound elec- ration of thin films via molecular beam deposition under high
trodes, such as PEDOT:PSS/single-walled CNTs (SWCNTs)[174] vacuum. The device with T as the electron blocking/hole-trans-
and AgNW/SWCNTs.[175] As electrodes, the compound film port material exhibited an efficiency of 76 cd A−1 and an Lmax of
exhibits superior optoelectronic characteristics. With the devel- 132 000 cd m−2 (Figure 8-iv). One year later, this group evaluated
opment of materials and fabrication techniques, the roughness the performance of OLEDs with layers of various components of
and conductivity of carbon-based flexible electrodes can be DNA, specifically the nucleobases of A, T, cytosine (C), guanine
improved for better performance in the future. (G), and uracil (U).[187] They found that the two pyrimidines, T
Cytochrome c, a common protein with low molecular weight and U, were the most thermally unstable, and the relative dielec-
and an electron carrier in living systems, was first reported as tric constants ranged from 4.0 (G) to 1.6 (U) measured at 1 MHz
an emitter for OLEDs in 2005.[176] However, these devices were with a trend of G < A < C < T < U. A-based OLEDs exhibited the
not stable and exhibited a low external quantum efficiency best performance with a current efficiency of 52 cd A−1 and an
(EQE) of only 6–8 × 10−8% at 13 V. Later, the same researchers EQE of 14.3%. Table 2 summarizes the representative results of
enlarged the protein scope, including myoglobin, hemin, and the OLEDs containing biodegradable materials.
vitamin B12.[177] The electroluminescence spectra and EQE of LECs: LECs are structured so that in between two electrodes,
myoglobin- and vitamin B12-based devices were similar to the an emitter is combined with an ionic species to form an in situ
devices based on cytochrome c. Hemin-based devices exhibited p-i-n junction. This principle simplifies the fabrication conditions
a broad spectra with defined peaks at 550, 580, and 800 nm compared with those of OLEDs, enabling fabrication through
under applied voltages of less than 4.5 V. In addition to these roll-to-roll printing. Similar to OLEDs, LECs are also considered
natural emitters, there have been some OLEDs based on bio- promising and cost-effective white light-emitting sources.
degradable derivatives and hybrid emitters. Similar to previous Recently, biodegradable LECs have attracted significant atten-
research conducted with hybrid LEDs, Richter et al. utilized the tion. In some instances, biodegradable ionic polyelectrolytes
bovine submaxillary mucin (BSM) protein as both the binder were used in LECs. Hernandez-Sosa et al. used biodegrad-
and stabilizer for hydrophobic nanomaterials in devices.[178,179] able PCL as the ion-solvating polymer in solution-processed
The BSM prevented the aggregation of hydrophobic lumi- LECs.[154] The active layer, consisting of a blend of super yellow
nescent polymers, which was a critical issue in multi-layer (SY):PCL:tetrabutyl ammonium tetrafluoroborate (TBABF4),
LEDs.[178] By including BSM, the electroluminescence of devices was spin-coated from anisole solution onto substrates. They
changed from merely yellowish-green (BSM-free) to the whole found that PCL not only exhibited good miscibility with the
visible range. Recently, Hernandez-Sosa et al. reported the emitter, but it also exhibited outstanding ion-solvating capa-
use of riboflavin-tetra butyrate (RFLT), a derivative of vitamin bility. The devices they prepared demonstrated lifetimes of 30 h,
B2, and biodegradability was retained with an improved solu- operating at a current density greater than 150 cd m−2. Later this
bility and less aggregation, and orange-emitting OLEDs were group applied PLGA as the ionic species in the active layer of
obtained.[166] These devices exhibited a high turn-on voltage of LECs.[152] PLGA has an electrochemical window stability ranging
11 V, Lmax of 10 cd m−2, and current efficiency of 0.02 cd A−1, as from -2.6–2 V, which was constant with the variation in the
shown in Figure 8-iii. molecular ratio of lactic and glycolic monomers. The solution
Cytochrome c and DNA can also function as an injection layer used for spin-coating to form the active layer was prepared by
in OLEDs. Mizutani et al. used a micro-contact printing tech- first dissolving PLGA, SY, and TBABF4 in anisole separately, fol-
nique to implement BSA, cytochrome c, and BSA-fluorescein lowed by mixing the desired ratio. By applying different batches

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Table 2. Selected representative results of organic light-emitting diodes (OLEDs) containing biodegradable materials.

Biodegradable materials Functional layer Device structures Turn-on Lmax [cd m−2] (V) Efficiency [cd A−1] Ref.
voltage [V] (luminance)
BC nanofibers Substrate BC/SiO2/ITO/Alq3 6 1200 — [142]
Nanofibrillated cellulose Substrate Cellulose/CNT/MoO3/PEDOT:PSS/green polyfluorene/ 5 — — [145]
Ca/Al
CNC Substrate CNC on glass/MoO3/Au/α-NPD/LiF/Al 3.5 74 600 53.7(100) [143]
Chitin nanofibrils Substrate ChNF/ZnS:Ag:MoO3/NPB/Alq3/Liq:Al 2.5 3890 5 [18]
(ChNF)
AgNW/SF Substrate AgNW/SF/MoO3/TAPC/CBP:Ir(ppy)3(10 wt%)/TPBi/ — 19 000 — [168]
Liq:Al
Eumelanin-PEDOT:PSS Electrode Eu-PH/α-NPD/Alq3/Ca/Al 6 300(12) 1.8 [170]
(Eu-PH)
Cytochrome c Emitting layer ITO/cytochrome c/Al 7 — — [188]
RFLT Emitting layer ITO/PEDOT:PSS/PVK/RFLT/Al 11 10 0.02(10) [166]
Vitamin B12 Emitting layer ITO/Vitamin B12/Al — — — [177]
BSM Emitting layer ITO/BSM-RGB with MWNT/Al–Au — — — [179]
BSA Submonolayer ITO/PEDOT:PSS/BSA/NPB/Alq3/Mg/Al 3.5 20(5) 0.02 [180]
Cytochrome c Submonolayer ITO/PEDOT:PSS/cytochrome C/NPB/Alq3/Mg/Al 3 20(5) 1 [180]
DNA-CTMA Hole-transporting/ ITO/PEDOT-DNA-CTMA (20 nm)/PFO:MEH-PPV/ 6.2 4900 6.3 [185]
electron-blocking layer Cs2CO3/Al
DNA Hole-blocking layer ITO/PEDOT:PSS/MEH-PPV/DNA-CTMA/Al 2.3 5700 0.8 [186]
A Hole-transporting/ ITO/PEDOT:PSS/A/CBP:Ir(ppy)3/BCP: Alq3/LiF/Al 5 82 289 51.8 [187]
electron-blocking layer
G Hole-transporting/ ITO/PEDOT:PSS/G/CBP:Ir(ppy)3/BCP: Alq3/LiF/Al 4.75 17 191 44.3 [187]
electron-blocking layer

BC, bacterial-derived cellulose; Alq3, tris(8-hydroxyquinolinato)aluminium; CNC, cellulose nanocrystal; α-NPD, N,N′-di(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-
diamine; NPB, N,N’-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine; SF, silk fibroin; TAPC, 1,1-bis-(4-bis(4-tolyl)-aminophenyl)cyclohexene; RFLT, riboflavin-tetra
butyrate; bovine submaxillary mucin; BSA, bovine serum albumin; CTMA, cetyltrimethylammonium; MEH-PPV, poly[2-methoxy-5(2′-ethyl-hexyloxy)-1,4-phenylene vinylene;
TPBi, 2,2′,2″-(1,3,5-benzenetriyl)tris-[1-phenyl-1H-benzimidazole]; CBP, 4,4′-bis(N-carbazolyl)-2,2′-biphenyl; Ir(ppy)3, tris[2-phenylpyridinato-C2,N]iridium(III); PFO, poly(9,9-
dioctylfluorene-2,7-diyl); BCP, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; A, adenine; G, guanine.

of PLGA synthesized with lactic:glycolic monomer ratios of implantable devices) that would greatly benefit from the use
85:15, 75:25, and 65:35, the device performance indicated that of biodegradable materials.[189–193] A power source is one of the
the addition of PLGA could reduce the turn-on voltage from most important components in regard to biodegradable elec-
7 V (obtained by the device without PLGA) to 4.7, 4.3, and 4.1 V, tronic devices; however, a fully biodegradable power source
respectively. The devices with a turn-on voltage of 4.1 V were has proven to be a major challenge in the application of such
best-performing with an Lmax of 3800 cd m−2. Recently, this devices (e.g., self-powered diagnostic and therapeutic implants).
group applied a nonhalogenated biodegradable solid polymer Yin et al. reported a high-performance, biodegradable battery as
electrolyte based on poly(ε-caprolactone-co-trimethylene an in vivo on-board power supply. In their work, they used a dis-
carbonate) (PCL-co-TMC) and tetrabutylammonium bis-oxalato solvable Mg anode, which possessed a high theoretical energy
borate (TBABOB) to LECs, and the solution-processable devices density and excellent biocompatibility. Meanwhile, MoO3
exhibited a current efficiency of 2 cd A−1 and a luminance (1 g L−1 in aqueous solution) served as the cathode material, and
greater than 12 000 cd m−2.[146] Additionally, they used an inkjet alginate hydrogel functioned as the electrolyte. Significantly,
printing technique to fabricate LECs on flexible and biodegrad- after coating with polyanhydride/PLGA, the biodegradable bat-
able cellulose-based substrates. The devices showed compatible teries demonstrated a lifetime of 12 days. Moreover, a single
lifetimes with transient applications. These cases demonstrated Mg-MoO3 cell was able to provide sufficient power for an LED,
that the design of new components in LECs using biodegrad- a calculator, and a signal detector, demonstrating its feasibility
able materials could be an effective strategy in enhancing the in ultralow-power implantable devices, while simultaneously
performance of devices, as shown in Figure 9. maintaining strong functions. Furthermore, in vivo experi-
ments demonstrated that the battery could fully degrade after
4 weeks of implantation using the Sprague-Dawley rat model,
2.4. Other Electronic Devices as shown in Figure 10-i.[194] Moreover, a fully biodegradable/
bioresorbable capacitor was also proposed for energy storage
In addition to solar cells, OFETs, and LEDs, there are other unit in an implantable device.[195] The capacitor includes PLA
devices (e.g., batteries, sensors, drug delivery devices, and supporting substrate, PLA nanopillar arrays, self-assembled

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Figure 9. A) Architecture of fully-printed device. B) Photograph of fully-printed device under operation with active layer of 1:0.1:0.075 (SY: PCL-co-TMC
(80:20): TBABOB) (SY: super yellow; PCL-co-TMC: poly(ε-caprolactone-co-trimethylene carbonate); TBABOB: tetrabutylammonium bis-oxalato borate).
C) Photograph of complete device in top view. D,E) Device performance. Reproduced with permission.[146] Copyright 2018, Wiley-VCH.

zinc oxide nanoporous layer, PVA/PBS hydrogel, and Fe film construct wireless sensor.[197] After being implanted into a rat
(Figure 10-ii(A)). Long-term normal work time was reached up model, the device showed good sensitivity for blood flow. The
to 30 days in PBS and 50 days in Sprague-Dawley rat. Signifi- sensor was partially degraded after 12 weeks with only PHB/
cantly, the capacitor can be fully degraded after immersing into PHV remaining. In addition to blood flow monitors, var-
PBS for 4 months in the in vitro experiment, and 5 months in ious types of diagnostic and therapeutic implantable devices
the in vivo experiment (Figure 10-ii(B,C)). Further, for the longer can also be used for clinical medicine, which highly demand
life-time implants (such as powering pacemakers), biodegrad- biodegradability and bioresorbability as well to avoid the unnec-
able self-powered monocrystalline silicon photovoltaics meet essariness of additional secondary surgery.[198] For instance,
the requirement and can be the choice, through implanting biodegradable/bioresorbable temperature sensors,[199] pH sen-
the device under 4 mm of porcine skin and fat to utilize near- sors,[200] and electrophysiological sensors[190] can be used for
infrared illumination.[196] Therefore, the reported biodegradable real-time monitoring of tissues or organs after primary surgery.
power source devices, which possess excellent power output Moreover, biodegradable/bioresorbable actuators can be used
performance with different normal work time and fully degra- for surgical site therapy and accurate drug delivery based on the
dable time, offer a choice for the design of implantable devices feedback signal from biodegradable/bioresorbable sensors.[201]
with specific life-time. Typically, a wirelessly controlled therapeutic actuator was devel-
Blood flow monitors are crucial in clinical medicine and oped with biodegradable structure of silk substrate/Mg serpentine
need biodegradable, implantable, and wireless sensors for accu- resistor and power-receiving coil/silk overcoat. Such actuator
rate detection. Recently, Bao et al. designed an arterial-pulse can serve as thermal heater to combat infection in the surgical
sensor for vessel anastomoses monitoring to avoid surgery site, as well as drug delivery system with controllable drug
for extraction of the implant. Of great importance, the sensor release kinetics (Figure 11). Commonly, Mg is an important
was wireless and used a well-established radio-frequency cou- component as electrode or functional part in a transient device,
pling method. Additionally, it was made entirely of biodegrad- which shows great potential to construct fully biodegradable
able materials that could be resorbed after several months, device by combining with natural biodegradable substrate.
thus eliminating the need for device removal. In this work, the Significantly, integration of biodegradable/bioresorbable sen-
device was fabricated by laminating the Mg electrical intercon- sors and actuators with circuit to construct fully biodegradable
nect with the PGS dielectric layer for the pressure sensitive implants will be meaningful for future clinical medicine.
regions. The poly(octamethylene maleate (anhydride) citrate), The above biodegradable electronics are mainly implant-
polyhydroxybutyrate/polyhydroxyvalerate (PHB/PHV) pack- able devices for clinical medicine. Actually, there are many
aging layers, and PLA spacer were used for the bilayer coils, types of biodegradable electronic devices beyond implantable
which were then combined with a LCR resonator circuit to devices. Hu et al. demonstrated a novel all-wood-structured

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Figure 10. i) A: Schematic illustration of battery structure. B–D: Light-emitting diode, calculator, and electrocardiogram powered by battery. E: In
vivo degradation evaluation of battery in subcutaneous area of Sprague-Dawley rats upon implantation and after 2 and 4 weeks. Reproduced with
permission.[194] Copyright 2018, Wiley-VCH. ii) A: Structure schematic of biodegradable capacitor. B,C: Full degradation in PBS with in vitro experiment
and in Sprague-Dawley rat with in vivo experiment. Reproduced with permission.[195] Copyright 2019, Wiley-VCH.

biodegradable supercapacitor, including activated wood carbon capacity origami cathode with high mass loading, and a bilayer
anode, thin wood membrane separator, and MnO2/wood carbon battery packaging (Figure 12-iv).[205] Significantly, all compo-
cathode (Figure 12-i).[202] Owing to the porous and biodegrad- nents can be dissolved into alkali solution. Therefore, based
able nature of carbonized wood, the proposed supercapacitor on the above-listed electronic devices, integrating synthesized
exhibited a high areal capacitance and a high energy/power den- biodegradable active material/electrode with natural biodegrad-
sity, and can be biodegraded in the nature. Biodegradable strain able substrate is a popular and useful method to construct fully
gauges were constructed by evaporation-condensation-mediated biodegradable electronic devices with high performance.
laser printing and sintering of biodegradable Zn nanoparticles
onto sodium carboxymethylcellulose bioresorbable substrate
(Figure 12-ii), showing high sensitivity subjected to stretch or 3. Green Processing for Green Electronics
deflection.[203] Zhou et al. demonstrated a biodegradable and
recyclable antenna.[204] Transient circuits were first constructed Device fabrication by means of green processing is as impor-
by combining room-temperature liquid metals (RTLM) as the tant as the use of biodegradable materials in green electronics,
electronic circuit and water-soluble PVA as the packaging mate- and it includes the use of non-toxic solvents, eco-friendly func-
rial. Subsequently, the surface patterning and packaging of tional layers, and large-scale, low-cost fabrication methods.
RTLM can be applied as a transient antenna for a passive near- Essentially, green processing can effectively suppress the emis-
feld communication (NFC) tag, showing good communica- sion of toxic substances into the environment during device
tion between NFC tag and cell phone (Figure 12-iii). Moreover, fabrication. Simultaneously, high-performance devices created
Hu et al. reported biodegradable transient lithium-ion battery, through green processing are also needed, especially when
including a trilayer anode with integrated structure, a high- compared with conventional methods. Therefore, balancing

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and perovskite layer, which are extremely harmful to both the

environment and human health, even though they are benefi-
cial in producing high-quality film. Moreover, environmentally
friendly Pb-free perovskite is highly desired, owing to the tox-
icity that currently exists in conventional perovskite with lead
ions. In fact, tin (Sn), Ge, bismuth (Bi), and stibium (Sb) ions
are considered as alternative ions for the fabrication of envi-
ronmentally friendly PSCs.[208–211] Furthermore, scalable fabri-
cation techniques with less raw material waste are also being
sought for the commercialization of PSCs. Therefore, we will
summarize the progress of recent research based on the green
processing concept for PSCs.
Green Solvents for PSCs: Significantly, the solvent is an impor-
tant factor in creating high-quality film for the ETL, HTL, and
perovskite layer. Commonly, the solvents used throughout
the entire fabrication process of PSCs include toxic N,N-­
dimethylformamide (DMF),[212] DMSO,[213] dimethylacetamide,[214]
and N-methyl-2-pyrrolidone (NMP)[215] in the precursor solution,
while chlorobenzene (CB),[216,217,218] toluene (TLN),[219] and diethy-
lether[220] are used as the antisolvents during spin-coating or as
solvents to dissolve the electron/hole-transport materials.
Recently, non-hazardous and low-toxicity solvent systems
were used as alternatives to conventional toxic solvents in a
perovskite precursor solution, and smooth pinhole-free perov-
skite films were obtained. Inspired by the “healing” process
with methylamine (MA) gas in a post-fabrication strategy,[221]
Snaith et al. bubbled MA gas into its low boiling point with
Figure 11. Schematic structure of the wirelessly controlled therapeutic highly polar and aprotic acetonitrile (ACN) to form an indus-
actuator with thermal heating and drug delivery functions. Reproduced trially scaled ACN/MA green solvent system, which could
with permission.[201] Copyright 2014, National Academy of Sciences. enhance the dissolution of CH3NH3PbI3 precursor salts.[222]
The proposed method was significantly beneficial in forming
green processing with device performance is the key for suc- ultrasmooth pinhole-free perovskite film on substrate areas as
cessful green fabrication. The following sections will provide an large as 125 cm2, which was comparable to the film prepared
overview regarding the green processing applied during device by the DMF solvent method, owing to the rapid crystallization
fabrication and illuminate the feasibility of green processing for of the perovskite at room temperature in an ACN/MA solvent
high-performance electronics such as solar cells, OFETs, LEDs, system. The morphology of the crystalline film and mirror-like
and other devices. 125 cm2 perovskite on substrate processed from the ACN/MA
solvent system are shown in Figure 13-i. The obtained high-
quality perovskite films allowed for a device efficiency of 19%
3.1. Green Processing of Solar Cells for 0.09 cm2 and greater than 15% for 0.7 cm2. A non-hazardous
solvent system is also necessary for the solution-processing of
High-performance photovoltaics are being pursued by photo- PSCs, which is important in terms of occupational safety in
voltaic researchers. Notably, emerging photovoltaics, especially industrial manufacturing. Tait et al. used the Hansen solubility
solution-processed PSCs and OPVs,[67,206,207] are expected to be parameters (HSP) as guidelines and determined a solvent mix-
commercialized and may account for a great percentage of the ture miscible with perovskite precursors (CH3NH3I, PbAc2, and
international photovoltaics market. However, green processing PbCl2).[223] A non-hazardous solvent system, γ-butyrolactone/
is highly desired in device fabrication, owing to the intrinsic ethanol/acetic acid (60/20/20 vol%), was chosen to fabricate a
toxicity of the components and solvents used in photovoltaics. pinhole-free perovskite film. The best performance obtained
Based on the green concept, this section reviews recent reports was 14.5% for 0.13 cm2, which was equivalent to the reference
regarding green processing in the fabrication of PSCs and OPVs. DMF-based PSCs. Moreover, the non-hazardous solvent system
was used as perovskite ink to implement blade-coating, and the
blade-coated 4 cm2 solar modules showed an efficiency of 11.9%
3.1.1. Green Processing of PSCs with impressive pinhole-free perovskite film. Water was consid-
ered the ideal green solvent; however, its solubility was limited
Solution processing with one-step spin-coating is one of the by lead halide and organic methylammonium iodide (MAI) or
most effective methods for the fabrication of high-quality perov- formamidinium iodide (FAI). Triggered by the environmentally
skite film on a laboratory scale. Unfortunately, these highly effi- friendly concept, Song et al. introduced aqueous Pb(NO3)2 into
cient PSCs are fabricated through the utilization of high boiling a two-step spin-coating process to fabricate a perovskite active
point and polar or halogenated toxic solvents for the ETL, HTL, layer.[224] The aqueous Pb(NO3)2 and MAI in isopropanol were

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Figure 12. i) Schematic illustration of the construction of all-wood-structured supercapacitor. Reproduced with permission.[202] Copyright 2017, Royal
Society of Chemistry. ii) Schematics of biodegradable strain gauges constructed by laser printing process and dissolving test in distilled water. Repro-
duced with permission.[203] Copyright 2017, Wiley-VCH. iii) Liquid metal transient circuit fabrication process and biodegradable antenna. Reproduced
with permission.[204] Copyright 2019, Wiley-VCH. iv) Schematic of transient Li-ion battery demonstration and degradation test in 1.5 m KOH aqueous
solution. Reproduced with permission.[205] Copyright 2016, Wiley-VCH.

successively spin-coated on mesoporous TiO2 film. A rela- tate crystallization and achieve high-performance PSCs. How-
tively high coverage of perovskite was observed, and the best ever, the widely used antisolvents have high toxicity and fur-
PSC performance was 13.7%. Although the efficiency of this ther hinder large-scale manufacturing. Recently, anisole (with
approach was lower than conventional processing with a toxic its relative non-toxicity, high boiling point, and frequent use
solvent, the water system indicated great potential to replace in cosmetics and food)[227] was proposed as an environmen-
toxic solvents and speed up industrial-scale commercialization. tally friendly antisolvent that could be induced to obtain high-
Owing to the limited solubility of perovskite precursors in polar quality perovskite film. The best efficiency attained with the
solvent (except DMSO and DMF) and polar nature of green anisole antisolvent step approached 20%, which was on par
solvents, the selectable green solvents for perovskite precursor with the toxic CB and TLN antisolvent process, and it indicated
dissolution are limited. Furthermore, it is still difficult to bal- great potential as a green solvent for the fabrication of PSCs.
ance the solubility and film quality with singular green solvent. Zhang et al. fabricated planar PSCs by using anisole as a green
Mixture green solvents (non-halogenated and non-aromatic antisolvent and obtained smooth surfaces, large grains, and a
solvents, esters, alcohols, and water) with HSP as guidelines low defect density, resulting in a superior efficiency of 19.42%,
show great potential to dissolve perovskite precursors and form which was comparable to the toxic CB antisolvent process.[228]
perovskite film with high quality, which can be the guidance for To further investigate the influence of anisole antisolvent on
green solvent selection. the process window, Jung et al. prepared perovskite thin film
Besides the precursor solution, an antisolvent step has been using one-step spin-coating with anisole, CB, TLN, and other
commonly utilized in one-step spin-coating fabrication to facili- antisolvents.[229] The comparison was made under different

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Figure 13. i) A,B: Morphology and mirror-like perovskite film prepared from acetonitrile/ methylamine (ACN/MA) green solvent system. C: Current–
voltage (J–V) curves from obtained perovskite solar cell (PSC) with active area of 0.09 cm2. Reproduced with permission.[222] Copyright 2017, Royal
Society of Chemistry. ii) A,B: Scanning electron microscope (SEM) images of perovskite using anisole as antisolvent both inside and outside glovebox.
C: J–V curve of PSC with anisole as antisolvent. D: J–V curve of PSC with anisole as antisolvent and solvent for hole-transporting materials. Reproduced
with permission.[225] Copyright 2018, Wiley-VCH. iii) Schematic illustration of fabrication procedure of all-vacuum-deposition method. Reproduced with
permission.[226] Copyright 2019, Wiley-VCH.

process conditions such as the DMF/DMSO ratio, antisolvent systematic health risks. They also fabricated the device with
dripping times, and antisolvent dripping volumes. Significantly, anisole as both the antisolvent and solvent for hole-transporting
the anisole antisolvent method exhibited an ultrawide process materials (HTM), and the unprecedented efficiency was close
window for perovskite thin film fabrication. The best efficien- to 20.5% (Figure 13-ii). This was the best recorded efficiency
cies were 19.76% and 17.39% for devices with a small (0.14 cm2) using anisole for wholly green non-halogenated solvent pro-
and large (1.08 cm2) active area, respectively. Accordingly, the cessing, and it demonstrated the excellent potential of anisole
superiority of anisole is due to its unique physicochemical prop- in the green processing fabrication of PSCs. Furthermore,
erties (e.g., high boiling point and viscosity) and H-bonding this green anisole antisolvent processing technique was also
with DMF/DMSO to form excessive nucleation. This green anti- used for flexible PSCs and attained an efficiency over 17% with
solvent with an ultrawide process window opened a pathway for excellent stability under different bending radii. Based on the
the industrialization of environmentally friendly PSCs, as well above discussion, anisole-based antisolvent processing seems
as releasing experimenters from the skillful handling of spin an alternative green processing. However, anisole is still clas-
coating tricks. Furthermore, Saliba et al. applied the greener sified as aromatic-contained solvents though with low/non-
and nonhalogenated anisole as antisolvent to fabricate devices toxicity. Actually, antisolvent-free processing is expected in the
both inside and outside a glovebox and demonstrated efficien- future industrial manufacture, which needs to deeply study
cies of 19.9% and 15.5%, respectively.[225] Specifically, the green the crystallization kinetics of pervoskite in green solvents to
processing fabrication that occurred outside the glovebox was realize high quality film without antisolvent step. Additionally,
meaningful in terms of large-scale industrialization, as it could ethyl acetate, o-xylene (o-XY), and 1,2,4-trimethylbenzene (TMB)
definitely simplify the fabrication of devices while reducing were recently reported as low-toxic non-halogenated antisolvents

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and/or solvents that could dissolve the ETL/HTL.[230,231] There- (FASnI3), and cesium tin iodide (CsSnI3) with direct bandgaps
fore, realizing fully green solvents in the fabrication of PSCs is of 1.20, 1.41, and 1.30 eV, respectively.[240] These bandgaps are
possible through HSP and crystallization kinetics as guidelines. narrower than those of the Pb-based perovskites, endowing
In practice, vapor deposition is an effective method to avoid them with an extended absorption spectra to 1000 nm.[241] How-
the use of toxic solvents, although it incurs high production ever, Sn2+ is easily oxidized to Sn4+, which generally induces
costs. Most recently, Fan et al. developed the all-vacuum-deposi- a low Voc because of its role as a p-type dopant.[240] To resolve
tion process to fabricate planar PSCs, including the sputtering this issue, several methods have been proposed to alleviate
of SnO2 ETL at room temperature, vapor deposition of lead and suppress oxidation. Song et al. applied a two-step cation-
halides and organic iodides, and thermal evaporation of CuPc, exchange approach to deposit the MASnI3 layer with the sup-
HTL, and Au electrodes, as illustrated in Figure 13-iii.[226] The pression of Sn2+ oxidation. In this work, a hydrazinium tin
whole fabrication procedure, which totally avoided the use of iodide (N2H5SnI3, HASnI3) layer was first deposited onto
solvents, improved the perovskite film quality. Consequently, a mesoporous substrate. Then, the HASnI3 film was trans-
the top-performing device, based on MA0.56FA0.44PbI2.67Br0.33, formed in situ into MASnI3 in a methylamine atmosphere.
delivered a PCE of 15.14% with a Voc of 1.02 V, Jsc of The obtained efficiency approached 7.13% with good reproduc-
19.16 mA cm−2, and an FF of 77.3%. Xie et al. also applied a fully ibility, as shown in Figure 14-i.[242] Fan et al. achieved a record
green vapor deposition to fabricate stable and scalable 3D–2D stability of FASnI3 with only 20% degradation in the PCE for
planar PSCs. Owing to the stabilized effect of 2D perovskite, the encapsulated device exposed to air for more than 500 h. The
the obtained efficiency was 16.5%. Significantly, the unencap- introduced hydroxybenzene sulfonic acid and/or its salt played
sulated devices retained 81% and 74% of the initial efficiency a significant role in effectively passivating the grain surface and
after 30 days under 55% humidity and heating at 80 °C, thereby suppressing the oxidation of Sn2+ (Figure 14-ii).[243] Moreover,
demonstrating the great commercial potential of fully green Islam et al. applied 5-ammonium valeric acid iodide (5-AVAI)
vapor deposition in the fabrication of PSCs.[232] To avoid the as an additive to the perovskite that could form H-bonds with I−
large energy consumption of vacuum-deposition, a solvent- present in the SnI64− octahedron to promote the crystal growth
and vacuum-free route was proposed by Han et al.[233] In their of the perovskite, thereby resulting in a pinhole-free, homo-
innovative method, CH3NH3I or PbI2 powder was blown with geneous, and stable FASnI3 solar cell with an efficiency of 7%
dried CH3NH2 gas to form CH3NH2I·3CH3NH2 (liquid) and (Figure 14-iii).[244] Despite low toxicity of Sn-based perovskites,
PbI2·CH3NH2 (paste). Then, the liquid CH3NH2I·3CH3NH2 the poor stability due to the easy oxidation of Sn2+ and the
and paste PbI2·CH3NH2 were blended stoichiometrically, severe recombination make them difficult to replace Pb-based
aiming for the rapid conversion of amine complex precursors perovskites. Accordingly, additives included in the perovskite
to perovskite films, followed by a pressure application step. precursor appeared to be an effective way to suppress the oxida-
The solvent- and vacuum-free route reached a certified PCE of tion of Sn2+ to Sn4+ and achieve enhanced PSC performance.
12.1% in 36 cm2 PSC modules. Importantly, this method offers Ge was proven to be another alternative for Pb-free perov-
a chance for the fully green processing of non-toxic solvent or skite through a theoretical and experimental investigation.[209]
solvent-free, heavy metal-free, and low energy consumption in However, Ge-based PSCs exhibited poor device performance
future PSC industry. when compared to that of Sn- and Pb-based PSCs, most likely
Lead-Free PSCs: At present, the highest efficiencies of PSCs because of its high oxidization tendency and poor film mor-
are all from Pb-based hybrid perovskite,[234] owing to the sig- phology.[245] Adjusting the B-site to form mixed Sn-Ge perov-
nificant role of the Pb2+ ion with a lone pair of electrons (6s2) skite could be a promising approach to enhance PSC perfor-
in the determination of the perovskite electronic structure.[234] mance. FA0.75MA0.25Sn0.95Ge0.05I3 with an ideal bandgap of
However, the intrinsic toxicity of the lead ion in perovskite 1.4–1.5 eV was obtained, and the efficiency increased to 4.48%
causes concerns regarding its environmental friendliness, when measured in air without encapsulation. Interestingly,
which may hinder the speed of its commercialization. Although after 72 h in a dark atmosphere containing nitrogen, the same
there is less than 1 g m−2 of metal in a solar panel, perovskite device displayed an increased efficiency to 6.90%, owing to the
tends to be dissolved or degraded into harmful compounds increments in Jsc and FF.[246] CsSn0.5Ge0.5I3 perovskite realized
with heavy metal under appropriate external conditions, which native-oxide passivation, which allowed the resultant device
may leach into the surrounding environment and be ingested to exhibit a quite stable performance and a drop of less than
by a human body through gastrointestinal, respiratory, and/or 10% in the PCE upon continuous work for 500 h in a glovebox
dermal uptake.[236] Therefore, it is desirable to uncover alterna- under 1-sun illumination.[247]
tives to fabricate Pb-free PSCs. As mentioned above, a variety of Bi- and Sb-based perovskites are stable in air, and photoac-
potential materials can be used for low-toxic Pb-free perovskite. tive structures with a chemical formula of A3M2I9 (A: MA, Cs;
Among them, Sn is being widely explored as a substitute for M: Bi, Sb) are perovskite-like with either a 0D or 2D struc-
Pb, and in recent reports, it is holding a record efficiency of ture.[211] However, the highest efficiencies of Bi- and Sb-based
9.6% among all Pb-free PSCs.[208] Other perovskites, such as PSCs are 3.17% and 2.77%, respectively, which are much lower
those based on Bi and Sb, are stable in air but exhibit poor solar than those of Sn- and Pb-based PSCs.[248,249] The low efficiency
cell performance.[237,238] is ascribed to the poor surface coverage of perovskite film and
Sn is in the same periodic group as Pb and exhibits proper- high exciton binding energies, resulting in low short-circuit
ties similar to Pb, thereby attracting great interest as a potential current densities and efficiencies.[245] Therefore, high-quality
alternative.[239] Common Sn-based perovskites are methyl- Bi- and Sb-based perovskite films are desirable to improve Pb-
ammonium tin iodide (MASnI3), formamidinium tin iodide free PSC performance. Table 3 summarizes the performances

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Figure 14. i) A: Device architecture of mesoporous perovskite solar cell (PSC) with two-step MASnI3 deposition. B: Current–voltage (J–V) curves of
devices based on one-step or two-step MASnI3 layer. Reproduced with permission.[242] Copyright 2019, Wiley-VCH. ii) A: STEM-HAADF image and
STEM-EELS maps of FASnI3 grain boundary with 10% potassium salt of hydroquinone sulfonic acid (KHQSA) modification. B: Sn4+ content determina-
tion in pristine- and KHQSA-bulk film after exposed to air (relative humidity ≈20%) for 10 h or stored in glovebox. Reproduced with permission.[243]
Copyright 2019, Wiley-VCH. iii) A: Scanning electron microscope (SEM) images of pristine and 5-ammonium valeric acid iodide (5-AVAI) added FASnI3
films. B: J–V curves of pristine and 5-AVAI added FASnI3 devices with area of 0.25 cm2. Reproduced with permission.[244] Copyright 2018, American
Chemical Society.

of recently reported Pb-free PSCs. Clearly, the relatively low process to recycle the substrates of mesoporous PSCs. The
performances do not meet the requirements necessary for com- photovoltaic parameters (Voc, Jsc, FF, and PCE) of devices fabri-
mercialization, owning to the non-cubic crystal structure of cated on recycled substrates were similar compared with those
Bi- and Sb-based perovskite with large bandgap. Most probably, of the original values, as shown in 15-ii.[271] Moreover, Kim
Sn-based perovskite is a promising green material for green et al. applied a selective mechanism to treat with halide perov-
processing of solar cells, once solving the problem of Sn2+ skites and recovered a mesoporous-TiO2-coated FTO substrate
oxidation and enhancing their efficiency and stability greatly. (Figure 15-iii).[272] The device performance remained the same
Nevertheless, great efforts are still necessary to improve the as the initial value of 15% even after recycling had occurred ten
efficiency and stability of Pb-free PSCs. times. The recycling of PSCs could reduce energy consumption
Recycling of PSCs: Upon closer examination of the device and fabrication costs.
architecture of PSCs, the metal electrode, transparent con-
ductive oxide, and Pb-based perovskite are what impact the
environment the most. Encapsulation is an effective way to 3.1.2. Green Processing of Organic Photovoltaics
prevent the leakage of Pb during the working lifetime of a
device. However, international e-waste disposal regulations sug- Over the past decades, great efforts were made in the research
gest collecting obsolete devices and discarding them immedi- of OPVs that led to an increased PCE of more than 16%, which
ately.[268] Moreover, the manufacturing of FTO with compact meets the threshold value required for industrialization and
and mesoporous TiO2 consumes most of the primary energy commercialization.[273–277] Historically, OPVs were typically fab-
of embedded materials and contributes to most of the carbon ricated via a simple solution printing technique in a laboratory,
footprint.[269] Thus, to fully realize the recovery and/or recycling and halogenated and/or aromatic solvents were chosen as the
of valued components is significantly meaningful in terms of processing solvents to meet the requirements of phase separa-
the green processing of PSCs. tion. Highly π-conjugated structures within the light-harvesting
Docampo et al. applied a solution process to dissolve most materials can be dissolved according to the “like-dissolves-like”
of the layers in a PSC device to recycle the PbI2 and glass/ rule. Good dissolution indicates that the light-harvesting mate-
FTO.[270] For example, the HTM can dissolve in CB; the perov- rials have good film-forming potential and favorable morphology,
skite can be transformed into MAI and PbI2, and the MAI can which makes a significant difference in exciton diffusion, charge
be extracted in water. PbI2 and TiO2 can be removed by DMF, generation, and transport.[278–281] However, these highly toxic
and the PbI2 can be further recovered for recycling, as shown halogenated and aromatic solvents are harmful to the health
in Figure 15-i. The recycled PbI2 and glass/FTO can then be of humans and the environment, which goes against sustain-
used for the fabrication of recycled devices. The efficiency was able development and indicates they are not suitable for the
approximately 15% for devices fabricated with three-time recy- mass production and commercialization of OPV technology.[282]
cling, maintaining the 14.6% efficiency of the fresh devices and Therefore, it is urgent that environment-friendly alternatives are
sufficiently demonstrating the effectiveness of recycling in this found to remove toxic solvents from the OPVs, which achieve
procedure. At the same time, Hagfeldt et al. developed a similar efficiencies similar to their halogenated counterparts. In this

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Table 3. Summary of recently reported performances of lead-free perovskite solar cells (PSCs).

Device structures Jsc [mA cm−2] Voc [V] FF [%] PCE [%] Ref.
ITO/PEDOT:PSS/GA0.2FA0.78SnI3-1% EDAI2/C60/BCP/Ag 21.2 0.619 0.729 9.6 [208]
ITO/PEDOT:PSS/FASnI3/PCBM/BCP/Ag 18.89 0.59 0.62 7.0 [244]
ITO/PEDOT:PSS/FA0.75MA0.25SnI3/C60/BCP/Al 24.3 0.55 67.3 9.06 [250]
FTO/c-TiO2/mp-TiO2/MASnI3/PTAA/Au 22.91 0.486 64 7.13 [242]
ITO/NiOx/FASnI3/PCBM/Ag 17.64 0.552 69.4 6.76 [243]
ITO/PEDOT:PSS/CsxFA1−xSnI3/C60/BCP/Ag 20.70 0.44 66.8 6.08 [251]
ITO/PEDOT:PSS/FA0.75MA0.25SnI3/C60/BCP/Ag 19.4 0.55 0.67 7.2 [252]
ITO/PEDOT:PSS/FA0.75MA0.25SnI3 + 10% SnF2/C60/BCP/Ag 21.2 0.61 62.7 8.12 [253]
ITO/PEDOT/FASnI3 + 10% SnF2 + TMA/C60: 1 wt% TBAI/Ag 22.45 0.47 67.8 7.09 [254]
ITO/c-TiO2/CsSnI3 (quantum rods)/Spiro-OMeTAD/Au 23.2 0.86 65 12.96 [255]
ITO/c-TiO2/CsSnBr3 (quantum rods)/Spiro-OMeTAD/Au 21.23 0.85 58 10.46 [255]
ITO/c-TiO2/CsSnCl3 (quantum rods)/Spiro-OMeTAD/Au 19.82 0.87 56 9.66 [255]
FTO/c-TiO2/mp-TiO2/[en]FASnI3 + 15% SnF2/TPE/Au 22.54 0.46 69.74 7.23 [256]
ITO/LiF/ PEDOT:PSS/(PEA, FA) SnI3/C60/BCP/Ag 20.07 0.47 74 6.98 [257]
FTO/c-TiO2/[en]FASnI3 + 15% SnF2/PTAA/Au 22.54 0.48 65.96 7.14 [258]
FTO/PCBM/CsSn0.5Ge0.5I3/native oxide/Spiro-OMeTAD/Au 18.61 0.63 60.6 7.11 [247]
FTO/c-TiO2/MAGeI3/Spiro-OMeTAD/Au 4.0 0.15 30 0.20 [209]
FTO/c-TiO2/CsGeI3/Spiro-OMeTAD/Au 5.7 0.074 27 0.11 [209]
FTO/c-TiO2/mp-TiO2/MA3Bi2I9/Spiro-OMeTAD/Au 1.10 0.653 49.6 0.356 [259]
FTO/c-TiO2/mp-TiO2/MA3Bi2I9/Spiro-OMeTAD/Au 2.95 0.81 69 1.64 [237]
FTO/c-TiO2/mp-TiO2/MA3Bi2I9/P3HT/Au 4.02 1.01 78 3.17 [248]
FTO/c-TiO2/CsBi3I10/carbon 4.75 0.46 69.18 1.51 [260]
FTO/c-TiO2/MABi3I10/carbon 3.40 0.47 41.44 0.67 [260]
FTO/c-TiO2/FABi3I10/carbon 3.88 0.45 49.73 0.87 [260]
FTO/c-TiO2/mp-TiO2/PHABiI4/P3HT/Au 6.03 0.58 22 0.78 [261]
FTO/c-TiO2/[AT][BiI4]/ZrO2/carbon 3.29 0.37 39 0.47 [262]
FTO/c-TiO2/mp-TiO2/AgBi2I7/P3HT/Au 3.30 0.56 67.41 1.22 [263]
FTO/c-TiO2/CsAgBiBr6/MoO3/Ag 3.82 1.01 65 2.51 [264]
ITO/PEDOT:PSS/perylene/HI-CB-MA3Sb2I9/PC70BM/C60/BCP/Al 5.98 0.69 59.62 2.46 [249]
FTO/c-TiO2/FA3Sb2I9/Spiro-OMeTAD/Au 1.84 0.66 63 0.76 [238]
FTO/c-TiO2/mp-TiO2/MA3Sb2ClxI9–x/Spiro-OMeTAD/Au 5.04 0.69 63 2.19 [265]
FTO/c-TiO2/Cs3Sb2I9/Au 3.55 0.61 55.85 1.21 [266]
ITO/c-TiO2/(N-EtPy)[SbBr6]/P3HT/Au 5.1 1.28 58 3.8 [267]

part of the review, two basic strategies to fabricate OPVs (sol- green-solvent processable materials, but for polymer donor
vent selection for active layer spin-coating and alternative green materials, mismatched HSP is possible because of the indefi-
techniques) are discussed. Basic considerations and the main nite molecular weight of polymers.[283] Therefore, green solvents
problems associated with each strategy are introduced first. can be selected through empirical or trial-and-error methods
Then, recent developments in the two main strategies for the by comparing their solution parameters with 1,2-dichlorobenzene,
improvement of the PCE of devices will be discussed. chlorobenzene (CB), and so on.
Solvent Selection: Compared with toxic halogenated and First, it is necessary to mention that the green solvents
aromatic solvents, green solvents are advantageous for indus- listed here are liquids of lower toxicity than halogenated sol-
trial production that corresponds with sustainable development vents rather than well-defined solutions without toxicity. Based
measures, as they decompose quickly; because the decompo- on their toxicity levels (from high to low), we can classify the
sition products are also environmentally friendly, the overall processing solvents into four types, namely i) halogenated and
accumulation in the environment is reduced. However, active aromatic, ii) non-halogenated and aromatic, iii) non-halogen-
layer materials exhibit low solubility in green solvents at times, ated and non-aromatic, and iv) ketones, esters, alcohols, and
which can impact the efficiency of devices. HSP analysis can water, as shown in Figure 16. Type (i) solvents are highly toxic
be introduced to screen for appropriate green solvents and and should be avoided in green processing. Therefore, in this

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Figure 15. i) A: Recycling procedure for perovskite solar cells (PSCs). B: Current–voltage (J–V) characteristics of PSCs prepared on recycled fluorine-
doped tin oxide (FTO)/glass substrates. C: Bar diagram of efficiency based on different numbers of rounds of recycling devices. Reproduced with
permission.[270] Copyright 2016, American Chemical Society. ii) A: Recycling process of FTO-coated glass substrates with mesoporous TiO2; B: PSC
performance of 30 samples before and after recycling. Reproduced with permission.[271] Copyright 2016, Royal Society of Chemistry. iii) A: Detailed
process of recycling PSCs via selective dissolution. B: Comparison of J–V curves between new and recycled MAPbI3 and (FAPbI3)0.85(MAPbI3)0.15-based
PSCs. Reproduced with permission.[272] Copyright 2016, Nature Publishing Group.

Figure 16. Four types of common solvents utilized in solution printing technique.

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part of review, we will focus on recent research that discusses solubility of active materials into non-halogenated and non-
advances in the processing of OPVs using the other three types aromatic solvents, achieving high performance of polymer solar
of solvents. cells.[289,290] For side chain modification strategy, polymer donor
Non-Halogenated Aromatics: The most common non- material (PBDB-BzT) was synthesized by modifying flexible
halogenated aromatics used in OPV processing are TMB and alkyls side chain of poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-
o-XY. Kim et al. synthesized a new kind of donor polymer, P1, 2-yl)benzo[1,2-b:4,5-b′]dithiophene)-co-(1,3di(5-thiophene-2-yl)-
and blended it with PC71BM to test in non-halogenated aromatic 5,7-bis(2-ethylhexyl)-benzo[1,2-c:4,5-c′]dithiophene-4,8-dione))]
solvents (please note that the chemical structures of the poly- (PBDB-T), improving the solubility and enhancing aggregation
mers mentioned in this section are shown in Figure 17). After effect in tetrahydrofuran (THF). An impressive PCE of 12.10%
comparing the PCEs of the devices casted from CB (halogen- was achieved with PBDB-BzT:3,9-bis(2-methylene-((3-(1,1-
ated solvent) and o-XY (non-halogenated solvent), they found dicyanomethylene)-6/7-methyl)-indanone))-5,5,11,11-tetrakis(4-
that the green solvent-processed OPVs demonstrated a PCE of hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]
5.01% (Voc = 0.81 V, Jsc = 10.41 mA cm−2, and FF = 58.74%), dithiophene (IT-M) blends under THF solvent.[289] For ternary
which was comparable to that of the device processed with copolymerization strategy, ester group-substituted thiophene
CB (PCE = 5.29%).[284] Moreover, adding diphenyl ether (DPE) (EST) unit into the benzo[1,2-b:4,5-b′]dithiophene (BDT)–
additive improved the solubility, as well as the efficiency, of the benzo[1,2-c:4,5-c′]dithiophene-4,8-dione (BDD) alternating
blended materials. polymer PBDB-TF donor was proposed by copolymeriza-
In fact, at times, it was difficult to remove high-boiling-point tion strategy. Significantly, the proposed copolymer showed
solvent additives and induce anomalous current–voltage (J–V) high solubility in THF/NMP non-halogenated and non-aromatic
curves or low reproducibility. Therefore, a single green sol- solvents. Excitingly, copolymer PBDB-TF:IT-4F blends with
vent was the best choice. Chen et al. designed two copolymer THF/NMP solvents showed 14.2% in 0.0375 cm2 and 13.7%
donors with random backbones, PBDT-2TC and PBDT-S-2TC. in 1.07 cm2.[290] Therefore, in-depth study of the correlation
The random backbone conformation allowed the materials to between molecular structure/functional groups in active mate-
dissolve in TMB. The devices fabricated with PBDT-2TC:ITIC rials and green solvents followed by designing/modifying mole-
or PBDT-S-2TC:ITIC exhibited high PCEs of 9.36% and 9.55%, cular functional groups are effective strategies to improve the
respectively. These performances were comparable to that of the solubility in green solvents and efficiency for green processing.
device obtained from casting with CB.[285] Because of their excel- Ketones, Esters, Alcohols, and Water: Ketones, esters, alco-
lent photoelectric properties, fluorine or sulfur atom-­substituted hols, and water are the least toxic of the four types of solvents
BDT and 2TC were then combined with the same group to syn- reviewed; therefore, they are highly desirable as green solvents
thesize another two new copolymers, PBDT-F-2TC and PBDT- to dissolve donor/acceptor materials. However, the ion group
SF-2TC. For the devices fabricated with PBDT-F-2TC:IT-4F or substituted materials exhibit very low photoelectric responses
PBDT-SF-2TC:IT-4F as the active layer casted from TMB, the because the ionic and related groups can trap or quench the
PCEs obtained were 10.75% and 11.07%, respectively.[286] charges.[291] Therefore, solution deposition with these green
Non-Halogenated and Non-Aromatics: Chen et al. conducted polar solvents is quite challenging. Nevertheless, Kim et al.
HSP analysis on the solutes and solvents and predicted the developed an aqueous processing method for the eco-friendly
optimal ratio for the mixture solvents. Efficiencies of 8.30% fabrication of polymer photovoltaics, which shows great poten-
and 9.39% were obtained for the OPV devices fabricated with tial for application on an industrial scale. The oligoethylene
PTB7 and PTB7-Th, respectively, in which PC71BM was used glycol side chain-based donor/acceptor, polymer PPDT2FBT-A
as the acceptor and 1,4-dioxane (DIOX) and terpinolene (TPO) and fullerene PC61BO12, can be dissolved in a 1:1 (molar ratio)
were used as the non-halogenated and non-aromatic solvents, water-ethanol mixed solvent. The maximum PCE of the fabri-
respectively. Although DIOX, as a single processing solvent, did cated device is 2.05%.[292] In another example, Di-Nicola et al.
not exhibit high efficiency in these two donor-based devices, fabricated devices with the water-soluble donor materials, poly[3-
a binary solvent that utilized both DIOX and TPO was found [(6-sodium sulfonate)hexyl]thiophene] (PT6S) and poly[3-[(6-tri-
to be more effective. The PCEs of the two devices were both methylammoniumbromide)hexyl]thiophene] (PT6N), which can
higher than their counterparts casted from CB.[287] In another both act as a charge collection layer. Processed by H2O/H2SO4
example, chloroform (CF) and carbon disulfide (CS2) were (pH = 1), the device (with a structure of ITO/PT6S/PT6H-PCBM
used as the solvents in the small molecule OSCs. Peng et al. 1:1 w/w/PT6N/Al) yields a higher PCE of 4.78%.[293] However,
designed two innovative small molecules, namely BDTTNTTR the performance of devices processed with such polar and low/
and BDTSTNTTR, by using benzo[1,2-b:4,5-b’] dithiophene non-toxic solvents is still behind the non-halogenated aromatic,
(BDT) as the central core. The PCEs of the devices fabricated and non-halogenated and non-aromatic solvent processing
with the small molecules as donors and PC71BM as the acceptor devices, mainly owing to the limited selectable active materials
processed with CF were 8.06% and 9.71%, respectively, which to dissolve in ketones, esters, alcohols, and water. Molecular
increased to 10.02% and 11.53%, respectively, when the solvent design or modifying is a promising strategy with the purpose to
was changed to CS2.[288] In addition to applying green solvents improve the polarity of high-performance active materials, and
to dissolve small-molecule/polymer active materials, signifi- enhance the solubility in ketones, esters, alcohols, and water.
cantly, molecular design strategies are also the key method for Table 4 summarizes the performances of reported OPVs
simultaneously improving efficiency and green processability. processed with different types of green solvents by solvent
Hou’s group successfully applied alkyl side chain modifica- engineering strategy or material design strategy. Despite some
tion and ternary copolymerization strategies to improve the devices with a low efficiency, several devices yielded a decent

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Figure 17. Chemical structure of light-harvesting materials soluble in i) non-halogenated and aromatic solvents; ii) non-halogenated and non-aromatic

© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2001591 (30 of 40)
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Table 4. Summary of recently reported performances of organic photovoltaics (OPVs) by using green solvents.

Light-harvesting layer Solvent Voc [V] Jsc [mA cm−2] FF [%] PCE [%] Ref.
Non-halogenated aromatic d1:PC71BM o-XY/DPE 0.81 10.41 58.74 5.01 [284]
PV2000:PC71BM o-XY 0.772 20.1 65 10.1 [294]
poly(3HTBT-TPA):PC71BM o-XY 0.86 6.61 42 2.39 [295]
p-DTS(FBTTh2)2: NIDCSN o-XY 1.04 5.41 52 2.92 [296]
DPPEZnP-O:PC61BM o-XY + 1% MN + ANN 0.75 15.73 50 5.75 [297]
PTB7:PC71BM m-XY 0.704 16.56 56.98 7.05 [298]
PBDTTT-CT:PC71BM m-XY + DIO 0.771 14.39 64.45 7.1 [299]
poly(3HTBT-TPA):PC71BM TMB 0.85 6.31 40 2.15 [295]
PBDT-2TC:ITIC TMB 0.903 16.87 61.46 9.36 [285]
PBDT-S-2TC:ITIC TMB 0.919 17.32 60.05 9.55 [285]
PBDT-F-2TC:IT-4F TMB 0.917 18.9 62.51 10.75 [286]
PBDT-SF-2TC:IT-4F TMB 0.936 20.73 57.45 11.07 [286]
N(Ph-2T-DCN-Et)3:PC71BM Benzaldehyde 0.96 8.27 46.75 3.71 [283]
N(Ph-2T-DCN-Et)3:PC71BM Benzaldehyde/ 0.96 8.37 46.68 3.75 [283]
mesitylene
PTB7-Th:PDI2-R TLN 0.96 12.4 47 5.4 [300]
p-DTS(FBTTh2)2:NIDCSN TLN 1.08 6.06 50 3.30 [296]
DPPEZnP-O:PC61BM TLN + 1% MN + ANN 0.77 14.7 48.3 5.46 [297]
P3HT:PC61BM Anisole:THN 0.57 9.09 65 3.37 [301]
PBDTTT-C:PDIate Anisole 0.71 1.91 33.1 0.45 [302]
PBDTTT-C:oo-2PDIate Anisole 0.676 8.76 37.9 2.24 [302]
PTB7:P(NDI2OD-T2) 2-Methyl anisole 0.76 15.40 58.03 6.79 [303]
P3HT:P(NDI2OD-T2) 2-Methyl anisole 0.68 12.9 63.84 5.6 [304]
Non-halogenated and non-aromatic PTB7:PC71BM DIOX/TPO 0.76 15.34 71.19 8.30 [287]
PTB7-Th:PC71BM DIOX/TPO 0.80 17.2 68.26 9.39 [287]
BDTTNTTR:PC71BM CS2 0.89 15.70 71.7 10.02 [288]
BDTSTNTTR:PC71BM CS2 0.93 16.21 76.5 11.53 [288]
p-DTS(FBTTh2)2:NIDCSN THF 1.07 5.23 54 3.02 [296]
BDT3TR-SF:NBDTP-Fout THF 0.798 21.87 64.37 11.2 [305]
HFAQx-T:N2200 THF 0.92 12.47 65 7.45 [306]
HFQx-T:N2200 THF 0.90 11.69 59 6.2 [306]
PBDB-BzT:IT-M THF 0.96 17.97 70 12.10 [289]
PBDB-TF:IT-4F THF/NMP 0.887 21.1 76 14.2 [290]
PBTA-TF:IT-M THF/IPA 0.96 18.37 67 12.0 [307]
PTB7-Th:tPDI-Hex Me-THF 0.94 11.6 43.7 4.8 [308]
PTB-EDOTS:ITIC-Th:J71 Me-THF 0.90 18.02 75.6 12.26 [309]
PTzBI-Si:PBTA-Si:N2200 Me-THF 0.85 14.89 75.65 9.56 [310]
PBTA-PEG-2%:N2200 Me-THF 0.83 16.89 66.13 9.27 [311]
FTAZ (R)-(+)-limonene/ 0.958 18.3 70 12.5 [312]
Me-THF
PBDTTTTEG:PC71BM NMP 0.66 13.53 58.55 5.23 [313]
PBDTTTTEG:PC71BM NEP 0.66 13.74 56.18 5.06 [313]
PTB7:PC71BM TPO 0.77 13.5 61.6 6.42 [314]
Ketones, esters, alcohols, and water PPDT2FBT-A:PC61BO12 Water/ethanol 0.76 5.08 53 2.05 [292]
P3HT:PC61BM SDS-water/chloroform 0.38 7.1 44 1.2 [315]
PCDTBT:PC71BM CS2/acetone 0.91 10.72 68.20 6.62 [316]
PT6H-PC61BM H2O/H2SO4 (pH = 1) 0.65 13.11 56 4.78 [293]

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Figure 18. i) Molecular structural formulae of boron dipyrromethenes and corresponding solar cell performances. Reproduced with permission.[318]
Copyright 2018, Royal Society of Chemistry. ii) Molecular structural formulae of antiBTDC, iBuBTDC, and nBuBTDC and corresponding solar cell per-
formances. Reproduced with permission.[319] Copyright 2018, Wiley-VCH. iii) Ternary organic photovoltaic (OPV) with two donors, DTTz and DTDCTB;
one acceptor, C70; and corresponding solar cell performances. Reproduced with permission.[320] Copyright 2016, American Chemical Society.

efficiency (near to or greater than 10%), indicating good poten- Moreover, Kim et al. fabricated ternary OPV devices by vacuum
tial for their use as green solvents in the processing of OPVs. deposition of two donors and a C70 acceptor (Figure 18-iii). In
Alternative Green Techniques: Vacuum deposition is an alter- the active layer, 2-((2-(5-(4-(diphenylamino)phenyl)thieno[3,2-b]
native green technique that avoids the use of toxic solvents and thiophen-2-yl)thiazol-5-yl)methylene)malononitrile (DTTz) and
offers a unique advantage of accurate thickness controllability 2-((7-(5-(dip-tolylamino)thiophen-2-yl)benzo[c]-[1,2,5]thiadiazol-
in multi-layer device fabrication.[318] Li et al. synthesized boron 4-yl)methylene)malononitrile (DTDCTB) were used for visible
dipyrromethene with mesoperfluorinated alkyl substituents and near-infrared absorption, respectively.[320] The obtained PCE
and used near-infrared-absorbing donors in vacuum-deposition of 8.02% demonstrated the potential of vacuum deposition in
processing. The fabricated solar cells achieved an efficiency ternary OPV device fabrication.
greater than 6.0% with the highest EQE of 70%, as shown in
Figure 18-i.[318] Forrest et al. conducted vacuum deposition to
fabricate OPVs based on donor–acceptor–acceptor type small 3.2. Green Processing of OFETs
molecular semiconductors. By varying the side chains, isobutyl
substituted iBuBTDC was found to pack densely, and the resulting In the fabrication of OFETs, spin-coating is a low-cost, simple,
device achieved the highest PCE of 9.3% (Figure 18-ii).[319] and effective way to form a uniform semiconductor thin film.

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Although halohydrocarbon and arene are commonly used and synthesized intercrossed carbon nanorings (IC-CNRs) as the
considered good solvents for most conjugated organic semi- phosphors; these IC-CNRs were not only low-cost because of
conductors, the harm caused by them to the environment and their simple synthesis, but they were also environmentally
human beings is non-negotiable. Halohydrocarbon and arene friendly.[149] The obtained color coordinates (0.28, 0.27) for the
are both carcinogens, which pose a great threat to health. In device based on IC-CNRs were observed to be comparable
addition, halohydrocarbon is degradation-resistant and will to those of the WILEDs (0.33, 0.33). Recently, yellow carbon
destroy the ozonosphere and cause the greenhouse effect upon quantum dots (Y-CDs) were prepared by Zhong et al., and water
accumulation. Considering these circumstances, safe solvents and o-phenylenediamine were used as the solvent and carbon
including alcohols, esters, and water are favored. However, the source, respectively.[326] A yellowish luminescence with long
solubility of organic semiconductors in these safe solvents is wavelength was easily achieved with the resulting Y-CDs thin
unsatisfactory. Therefore, scientists are trying to introduce an films. Besides carbon-based materials used as color converters
appropriate functional group into semiconductors to obtain in WILEDs, Chao et al. fabricated WILEDs based on a blend
good solubility in green solvents. of Au nanoclusters and blue-emitted organic materials that
One possible method is the introduction of ionic side sub- obtained color coordinates (0.27, 0.33).[327] The Au nanoclusters
stituents to hydrophobic backbones. However, these ionic were modified with trioctylphosphine capping groups that were
groups are only stable in certain pH conditions, which impedes non-toxic and eco-friendly. The recently discovered A2MF6:Mn4+
the aggregation of the polymers.[321] Another drawback of material, which exhibits superior photoluminescent properties,
these ionic groups is that they may mingle to active layers is considered a promising alternative to commercial phosphors.
of the OFETs, which may decrease their stability.[322] There- Wu et al. reported that K2SiF6:Mn4+ (as a red emitter) can be
fore, another approach was adopted that involves attaching synthesized with a green process in which H3PO4/KHF2 liquid
some high polar, neutral side groups to π-conjugated back- is used to replace the hydrogen fluoride (HF) solvent, thereby
bones to increase the water solubility of the polymers.[323] The avoiding toxicity and volatility.[328] Xu et al. recently reported
introduction of hydrophilic 3-(2-(2-(2-methoxyethoxy)ethoxy) the utilization of tetramethyl-substituted aluminium phth-
ethoxy)methyl side chains to polythiophene produces the alocyanine (AlMePc) as the modification layer of ITO electrodes
polymer, P3TEGT, which joins water as the green solvent in in OLEDs. AlMePc allows green solvent processing in alcohol
the fabrication of OFET devices and exhibits a hole mobility and is helpful in promoting balanced charge carrier injection
of 3.5 × 10−5 cm2 V−1 s−1 under ambient conditions.[324] Further and transport, thereby demonstrating higher device perfor-
decrements in the side chain length may improve this mobility. mance and green processing fabrication of OLEDs.[329]
Another group introduced a similar type of side chains to a
non-ionic polymer, poly[(2,5-bis(1,3-bis(2-(2-(2-methoxyethoxy)
ethoxy)ethoxy)propan-2-yloxy)phenylene)-alt-(5,6-difluoro-4,7- 3.3.2. Quantum Dots and Perovskite LEDs
di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2FBT-A),
which exhibits good solubility in ethanol. The fabricated OFET, As for next-generation light-emitting techniques such as
with simple ethanol as the solvent, exhibits a high hole mobility quantum dots LEDs (QLEDs) and perovskite LEDs (PeLEDs),
of 1.0 × 10−2 cm2 V−1 s−1 because of the high edge-on oriented there remain solution processes during fabrication that con-
crystalline nature of PPDT2FBT-A films spin-coated from ethanol tain toxic materials. Ray et al. replaced toxic phosphine with
solutions.[325] However, the mobility of green solvent processed olive oil as the capping agent to synthesize CdSe QDs, and the
OFETs is still lower than that of traditional devices processed material showed a sharp and well-defined emission peak of
from toxic solvents such as CB, TLN, and CF. Additionally, unlike 568 nm at room temperature.[330] Later, Yu et al. fabricated low-
OPVs and PSCs, the development of green processing and semi- toxicity AgIn5S8/ZnS-based QLEDs that exhibited a significantly
conducting materials that are compatible with green solvents are enhanced efficiency after surface treatment with 1,2-ethan-
very limited, and more efforts should be directed to this area to edithiol.[331] Similar to PSCs, the B-site in the ABX3 structure
fulfill the realization of truly green electronic devices. was typically heavy metal Pb2+, and some researchers have
made an effort to replace it with other low-toxicity metals, such
as Sn,[332,333] Sb,[334,335] and Bi.[336–339] Additionally, the antisol-
3.3. Green Processing of LEDs vents used in the synthesis of perovskite thin film or nanocrys-
tals are typically TLN and CB. Because of the toxicity of TLN,
3.3.1. Inorganic LEDs Yang et al. employed tetraethyl orthosilicate as the antisolvent
to achieve all-inorganic perovskite nanocrystals which presented
The toxic solvents and heavy metals used in the preparation tunable large-span emission wavelengths in the range of 626–
of light-emitting devices have resulted in serious harm to both 437 nm.[340] Recently, Yu et al. applied isopropyl alcohol (IPA)
humans and the environment. There have been numerous as the antisolvent to fabricate PeLEDs, which exhibited good
reports exploring potential green solvents and low-toxicity performance; the maximum luminance, current efficiency, and
materials for use in the preparation process of LEDs. Although turn-on voltage were 7 960 cd m−2, 2.2 cd A−1, and 2 V, respec-
WILEDs have offered a promising technique in regard to sus- tively.[341] The results indicated that high efficiency devices could
tainability because of their advantages in working lifetime and be fabricated with a green solvent. In future development, the
electricity consumption, the cost of conventional phosphors as trade-off between green processing and the performance of
color converters has remained high and some rare-earth raw devices needs consideration, and a push for eco-friendly, light-
materials were required. To address this problem, Zeng et al. emitting devices over commercial products is necessary.

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3.4. Green Processing of Other Devices materials or solvents that incur low-costs and are capable of
large-scale implementation are acceptable solutions for the
Other devices (e.g., batteries, sensors, generators, memris- fabrication of green electronic devices. However, biodegrad-
tors, and photodetectors) are also suitable for green processing able materials and green process-based electronics are still in
with low-toxicity materials and low-cost fabrication to achieve their infancy. Moreover, the performance of green electronic
green electronics.[342–345] Aqueous lithium-ion batteries that use devices is not yet up to par with conventional devices, owing
water-based electrolytes are a promising alternative to address to the limitations of the selective biodegradable materials and
the issues of safety and environmental problems caused by undeveloped green processing. The database of biodegrad-
highly toxic and flammable organic electrolytes.[346] Currently, able materials needs to be expanded by further studying the
the highest operating voltage of aqueous lithium-ion batteries physicochemical characteristics of various substances and the
exceeds 4 V by using a graphite-based cathode with bromine and corresponding performances they induce in devices. Indeed,
chlorine that is protected by the water-based electrolytes through synthesized organic materials are promising biodegradable can-
confining reactive electrode materials in the solid salt particles didates for high-performance electronics, but the synthetic pro-
around the electrode.[347] Moreover, water-based concepts can cesses are usually associated with non-green methods involving
be applied to a triboelectric nanogenerator (TENG), which is a toxic solvents. Therefore, the design of green electronics with bio-
promising energy harvesting technology that efficiently converts degradable materials should take the green process into consid-
ambient mechanical energies into electricity. Hao et al. applied eration. Further, recycling different functional layers in devices is
physical-crosslinking PVA hydrogel as a substrate material to also a key solution to reduce e-waste and the cost of devices.
fabricate fully flexible and environmentally friendly TENG. This Efficacy, stability, and environmental friendliness are crucial
hydrogel-TENG is not only low in cost, but it can also utilize the factors in determining the potential of commercialization and
energy harvested from human motions (i.e., bending, twisting, widespread use of green electronics in the future. Based on
and stretching), thereby achieving a self-powered sensor.[348] these concepts, guidelines for the green electronic design are
Nanomaterial green printing, which greatly reduces energy con- as follows:
sumption and environmental pollution from the sources, is a Deeply study and modify existing biodegradable natural/
promising green process to fabricate electronics. However, the synthesized materials to enhance their biodegradation in mild
challenge in this technique is that liquids must work on very conditions, so they can be used as biocompatible and biode-
small scales, which is virtually impossible, owing to the fact gradable substrates.
that the conventional nozzle has a minimum of 10 µm drop- Change the molecular bonds of conductive organic materials
lets. Song et al. developed a novel gas–liquid–solid three-phase through chemical modification, rendering them sensitive to
contact line (TCL) that can be manipulated to assemble and weak acids while retaining their ability of fast charge-transfer,
deposit the nanoparticles covered by the liquid droplet fol- which can be used as active layers with high performance.
lowing the TCL pattern, obtaining a nanoscale conductive curve Develop non-noble metals (e.g., Fe and Mg) with environ-
array.[349,350] In this manner, they introduced Ag nanoparticles mentally friendly and non-toxic properties that are harmless to
on a PDMS substrate. The fabricated flexible sensors have been humans, can be used as electrodes, and are easily degraded in a
applied to human facial skin and can deliver real-time data for mild acid/base or water solution.
multi-analysis of human skin micromotions.[351] Combine the HSP model with drying kinetics to predict the
solubility of solutes in low/non-toxic green solvents.
Modify the chemical structure of existing high-performance
4. Conclusion and Outlook materials through the introduction of polar functional groups,
thereby increasing the solubility in polar green solvents.
E-waste resulting from the rapid development of the electronics Explore and develop non-toxic, solvent-free, annealing-free,
industry is a real and urgent issue that needs to be addressed. and low-cost alternative manufacturing processes to fabricate
Green electronics is an effective way to manage e-waste through green electronics.
the use of biodegradable materials and green fabrication pro- Overall, we need to face up to the environmental issues
cessing. In addition to microminiaturization, integration, caused by the conveniences of modern electronics. The sig-
and multi-functionalization, greenization is one of the most nificant progress achieved in green electronics is very encour-
vital movements concerning the future e-market. Fortunately, aging, especially the development of high-performance green
research communities are aware of the importance of green electronics fabricated with biodegradable materials through
electronics and have taken action to achieve this goal. This green processing. “Treatment after pollution” is inadvisable for
review summarizes the most current biodegradable materials sustainable development. Therefore, more efforts are necessary
and green processes for green electronics, including solar cells, for the integrative exploration combining biodegradable mate-
OFETs, LEDs, and other electronic devices. The reports herein rials and green processing for the fabrication of future green
provided comprehensive knowledge regarding the potential for electronics.
the fabrication of green electronics.
With regard to the biodegradable materials used in green
electronics, both natural and synthesized biodegradable mate- Acknowledgements
rials can be used as substrates, electrodes, and active materials. W.L. and Q.L. contributed equally to this work. A.K.K.K. is grateful to
At present, the most widely studied biodegradable materials are the Guangdong University Key Laboratory for Advanced Quantum Dot
cellulose, chitosan, and SF. For the green process, low-toxicity Displays and Lighting (No. 2017KSYS007); Shenzhen Science, Technology

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