Biocompatible and totally disintegrable

semiconducting polymer for ultrathin and

ultralightweight transient electronics
Ting Leia, Ming Guanb, Jia Liua, Hung-Cheng Lina, Raphael Pfattnera, Leo Shawa, Allister F. McGuirec,
Tsung-Ching Huangd, Leilai Shaoe, Kwang-Ting Chenge, Jeffrey B.-H. Toka, and Zhenan Baoa,1
a
Department of Chemical Engineering, Stanford University, Stanford, CA 94305; bDepartment of Materials Science and Engineering, Stanford University,
Stanford, CA 94305; cDepartment of Chemistry, Stanford University, Stanford, CA 94305; dHewlett Packard Labs, Palo Alto, CA 94304; and eDepartment of
Electrical and Computer Engineering, University of California, Santa Barbara, CA 93106

Edited by John A. Rogers, University of Illinois, Urbana, IL, and approved April 4, 2017 (received for review January 26, 2017)

Increasing performance demands and shorter use lifetimes of abundant carbon-based components. Organic electronics can be
consumer electronics have resulted in the rapid growth of electronic synthesized and processed with low-temperature and, more impor-
waste. Currently, consumer electronics are typically made with tantly, have the potential to be environmentally benign candidates
nondecomposable, nonbiocompatible, and sometimes even toxic for electronic applications (4). Organic semiconductors have been
materials, leading to serious ecological challenges worldwide. Here, widely used in chemical and biological sensors (6), health monitors
we report an example of totally disintegrable and biocompatible (7), stretchable devices (8), and electronic skin (9). To date, most
semiconducting polymers for thin-film transistors. The polymer con- studies on organic semiconductors have focused on material syn-
sists of reversible imine bonds and building blocks that can be easily thesis and device fabrication with little emphasis on their environmental
decomposed under mild acidic conditions. In addition, an ultrathin impact and biocompatibility (10, 11). Although some biodegrad-
(800-nm) biodegradable cellulose substrate with high chemical and able small molecules, e.g., β-carotene and indigo derivatives, have
thermal stability is developed. Coupled with iron electrodes, we been investigated (12, 13), these small-molecule semiconductors
have successfully fabricated fully disintegrable and biocompatible have either low carrier mobilities (<0.1 cm2/Vs) or require high-
polymer transistors. Furthermore, disintegrable and biocompatible vacuum deposition processes.
pseudo-complementary metal–oxide–semiconductor (CMOS) flexi- Conjugated polymers can be mechanically flexible, stretchable,
ble circuits are demonstrated. These flexible circuits are ultrathin and solution-processable at low temperatures, making them
(<1 μm) and ultralightweight (∼2 g/m2) with low operating voltage amenable to the low-cost production of flexible and stretchable
(4 V), yielding potential applications of these disintegrable semicon-
electronics using roll-to-roll manufacture (14). The recent devel-
ducting polymers in low-cost, biocompatible, and ultralightweight
opment of donor−acceptor (D−A) polymers has greatly improved
transient electronics.
the device performance, with field-effect transistor (FET) mobil-
ities surpassing that of amorphous silicon (0.1−1 cm2/Vs) and with
|
organic electronics flexible electronics | conjugated polymers | thin-film solar cell efficiencies beyond 10% (15, 16). Conjugated polymers
|
transistors biodegradable materials
have emerged as one of the most promising candidates for flexible
TFTs. Compared with nonconjugated decomposable polymers,
C urrent consumer electronic devices are usually made with
nondecomposable and often toxic inorganic semiconduc-
tors that typically require high-vacuum and high-temperature
molecular design choices for conjugated decomposable polymers
are highly limited because there are only a few decomposable
manufacturing processes. With rapid technological advancement and
Significance
short turnovers for electronic devices, the colossal demand for
electronics has led to a huge amount of waste and rapid consump-
tion of scarce elements like gallium and indium. For example, in- Organic electronics, particularly polymers, can be synthesized
dium gallium zinc oxide (IGZO) has been widely used in many thin- and processed with low temperatures and, more importantly,
film transistor (TFT) applications, such as active-matrix organic have the potential to be environmentally benign candidates

CHEMISTRY
light emitting diode backplanes, radio frequency identification tags, for electronic applications. However, there has been no report
electronic paper, and sensor devices (1). The growing trend for de- of totally decomposable polymer semiconductors. Their avail-
vices comprising the so-called “Internet of Things” (IoT) will involve ability will enable low-cost and fully disintegrable transient
an even larger number of electronics, likely straining our existing electronics. We have developed an innovative concept based
natural resource supplies and imposing an even greater influence on on imine chemistry that allows totally disintegrable and bio-
our precious and fragile environment. To address these issues, compatible semiconducting polymers. Using an ultrathin bio-
transient electronics, or “green” electronics, have emerged as a new degradable substrate, we successfully fabricated polymer
class of technologies whose key feature is that they physically “dis- transistors and logic circuits that show high performance and
appear” after being used and/or disposed (2–5). Aside from the are ultralightweight, but they can be fully disintegrable. Our
work significantly advances organic materials to enable envi-
environmental benefits, transient electronics also open up a new
ronmentally friendly and biointegrated electronic applications.
application space, such as (i) implantable medical devices that are
resorbable by the human body, thus bypassing the need for surgery
Author contributions: T.L. and Z.B. designed research; T.L., M.G., J.L., H.-C.L., R.P., L. Shaw,
to extract them and (ii) secure electronics that can totally disinte- A.F.M., T.-C.H., L. Shao, and K.-T.C. performed research; T.L. contributed new reagents/
grate in a controlled fashion, thus rendering them untraceable. In analytic tools; T.L., L. Shaw, and Z.B. analyzed data; and T.L., J.B.-H.T., and Z.B. wrote
pursuit of these goals, silicon-based transient electronics have re- the paper.
cently been reported (2, 3), and are able to degrade under mild base. The authors declare no conflict of interest.
However, devices based on inorganic materials such as silicon are This article is a PNAS Direct Submission.
mechanically brittle and require high-vacuum, high-temperature, and 1
To whom correspondence should be sent. Email: [email protected].
generally high-cost manufacturing processes. Compared with their This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.
inorganic counterparts, organic semiconductors are made of 1073/pnas.1701478114/-/DCSupplemental.

www.pnas.org/cgi/doi/10.1073/pnas.1701478114 PNAS | May 16, 2017 | vol. 114 | no. 20 | 5107–5112

molecular building blocks available. To our knowledge, there have (7, 18, 19), we report here a type of biodegradable ultrathin
not yet been any reports of totally decomposable conjugated poly- (800 nm) substrate based on cellulose for ultra-lightweight (2 g/m2)
mers or polymer-based electronics. electronics (Fig. 1B). Our substrate is highly compatible with
To realize “green” electronics with zero footprint, an ideal electronics fabrication processes due to its stability in a variety of
approach is using semiconducting polymers that can be synthe- commonly-used organic and aqueous solutions, along with its high
sized from natural resources and decomposed back to the envi- temperature stability (glass transition temperature (Tg) >180 °C).
ronment (Fig. 1A). In this work, we demonstrate several key Using these materials, we proceeded to fabricate ultrathin flexible
steps of the “ideal cycle” in Fig. 1A by using imine bonds as the pseudo-complementary metal–oxide–semiconductor (CMOS) cir-
reversible conjugated linker to illustrate an example of a totally- cuits with high gain and rail-to-rail output voltage swings at a low
disintegrable conjugated polymer and its application in organic operation voltage of 4 V. With iron electrodes, fully disintegrable
electronics. Ultrathin electronics provide ultra-lightweight, ex- transient devices are demonstrated, in which we observed these
treme flexibility, and better conformability, which are important devices’ complete disintegration after 30 d upon exposure to mildly
acidic conditions.
for imperceptible electronics (7), conformal biological sensors
(17), and stretchable devices (18). While ultrathin and light- Decomposable Polymer Design and Characterization
weight organic flexible devices on plastic substrates, e.g., poly- Dyes synthesized from natural resources, such as isoindigo or dike-
ethylene terephthalate (PET), have been previously developed topyrrolopyrrole (DPP), are incorporated into conjugated polymers
as they are important molecular building blocks to impart high charge
carrier mobilities (15, 16). DPP is selected because it can be easily
functionalized chemically, and, more importantly, we observed that
the DPP monomer can be degraded further (see below). The imine
bond (–C=N–) is a stable conjugated linker under neutral-pH con-
ditions (20), but it can be readily hydrolyzed with a catalytic amount
of acid (21). Although imine bonds have been used as building blocks
for conjugated polymers and covalent organic frameworks (22, 23),
they have not been explored in the design of decomposable conju-
gated polymers and totally disintegrable electronics. Fig. 1C shows
the synthetic procedure for the decomposable polymer PDPP-PD.
DPP can be synthesized in two steps: (i) react succinic ester and 2-
thiophenecarbonitrile in tert-amyl alcohol; (ii) attach branched alkyl
chains to increase the solubility. The branched alkyl chain was syn-
thesized from octyldodecanol. Among these chemicals, succinic ester
and tert-amyl alcohol can be obtained from natural resources, and
octyldodecanol is a nontoxic ingredient widely used in a variety of
beauty products. Two aldehyde groups were introduced to the DPP
monomer, giving DPP-CHO in 77% yield. PDPP-PD was synthe-
sized through a condensation reaction between DPP-CHO and
p-phenylenediamine under catalysis with p-toluenesulfonic acid
(PTSA). We initially prepared the polymer in the absence of any
drying agent, and the polymer obtained exhibited a low weight-
averaged molecular weight (Mw) of 19.1 kDa. After adding CaCl2
as a drying agent, we are able to obtain a higher Mr of 39.6 kDa.
Removal of reaction-generated water obviously increased the
polymer’s molecular weight. Notably, imine polymerization does
not require any noble metal catalysts or toxic phosphorous ligands
that are typically used for traditional conjugated polymer synthesis.
In this way, the synthesis of imine polymers is more economical
and environmentally friendly. The decomposable polymer is stable
under ambient conditions and was observed to have a decompo-
sition temperature above 400 °C (SI Appendix, Fig. S1). The
highest occupied molecular orbital (HOMO) and lowest unoccu-
pied molecular orbital (LUMO) of the polymer measured by cyclic
voltammetry are –5.11 and –3.54 eV, respectively. These values
agreed well with our predictions as calculated by density functional
theory (SI Appendix, Fig. S2).
Fig. 2A shows the absorption spectrum and color changes of
PDPP-PD after adding 1% (vol/vol) acetic acid in water. The main
absorption peak (680 nm) decreased significantly after 3 h and
completely disappeared after 10 d. Moreover, the solution color
was observed to change from blue to purple during this duration.
After a 10-d decomposition test, the absorption spectrum and
solution color were both similar to that of the pure monomer
Fig. 1. Schematics of polymer-based transient “green” electronics. (A) Polymer
DPP-CHO. After a 40-d test, the purple color was observed to
synthesis, fabrication, and decomposition cycle for transient polymer electronics.
Solid lines indicate the processes demonstrated in this paper. Dashed lines are
disappear completely to become a clear solution, indicating the
the envisioned processes that might be realized in the future. (B) Flexible device polymer was totally disintegrated under acidic conditions. The
using disintegrable polymers as the active material or substrate. Inset shows the polymer decomposition can occur in good solvents (e.g., chloro-
fabrication of the cellulose substrate using a reversible functionalization chem- form), in poor solvents (e.g., THF; SI Appendix, Fig. S3), and in
istry. (C) Synthesis of the disintegrable PDPP-PD using imine chemistry. the thin film. The “good” solvents have a stronger ability to solvate

5108 | www.pnas.org/cgi/doi/10.1073/pnas.1701478114 Lei et al.

 and dielectric layers. Because organic solvents are used during the
spin-coating of the polymer films and a water-aided peel-off pro-
cess is used during fabrication (26), good chemical and water
stability are also needed. Other reported biodegradable substrates,
such as silk (3) or poly(lactide-coglycolide) (PLGA) (5, 27), are
either not resistant to water or organic solvent, or are not heat
tolerant. We realized that regenerated cellulose films (RCFs)
are a good candidate because of their high thermal stability
[decomposition temperature (Td) > 210 °C, Tg > 180 °C], high
transparency, good flexibility, and biodegradability (28, 29).
Moreover, cellulose films have been previously used as bio-
degradable substrates in electronics (28–30). However, these
cellulose films are typically made with thicknesses well over
10 μm and thus cannot be used to fabricate ultrathin electronics
with substrate thicknesses below 1–2 μm (7, 18, 19). To the best
of our knowledge, there have been no reports on ultrathin
(1–2 μm) biodegradable substrates for electronics. Thus, to
realize them, we subsequently developed a method described
Fig. 2. Degradability and biocompatibility of PDPP-PD. (A) Absorption spec- herein to obtain ultrathin (800 nm) cellulose films (Fig. 1B and
trum changes in PDPP-PD’s decomposition process. (Inset) Photos of polymer SI Appendix, Fig. S8). First, microcrystalline cellulose powders
solution color changes after decomposition for 10 d and for 40 d. (B) Absorption were dissolved in LiCl/N,N-dimethylacetamide (DMAc) and
spectrum changes for a polymer film before and after decomposition in a
reacted with hexamethyldisilazane (HMDS) (31, 32), providing
pH 4.6 buffer solution. (Inset) Photos of the film before and after decomposition.
(C) Fluorescent images of live HL-1 cardiomyocytes stained with calcein-AM (green)
trimethylsilyl-functionalized cellulose (TMSC) (Fig. 1B). To fabri-
and EthD-1 (red). (Scale bar: 100 μm.) (D) Viability of HL-1 cardiomyocytes on 2, 4, cate films or devices, TMSC in chlorobenzene (CB) (70 mg/mL) was
and 6 d of in vitro culture (n > 1,000 cells for each data bar). spin-coated on a thin dextran sacrificial layer. The TMSC film was
measured to be 1.2 μm. After hydrolyzing the film in 95% acetic
acid vapor for 2 h, the trimethylsilyl groups were removed, giving
the polymer and facilitate the separation into individual chains. a 400-nm-thick cellulose film. The film thickness significantly
On the contrary, for the “poor” solvent, the polymer tends to
aggregate in solution. As shown in Fig. 2B, after soaking the spin-
coated polymer film (40 nm) in a pH 4.6 aqueous buffer solution,
the polymer thin-film absorption decreased steadily over time,
indicating its degradation. These results suggest that the polymer
can be decomposed not only in solution (either as free polymer or
as aggregates) but also in solid state. In contrast, the polymer is
stable under neutral and basic conditions, as we did not observe
noticeable decomposition of the polymer in solution (SI Appendix,
Fig. S4). Based on the absorption spectra and in situ NMR studies
(SI Appendix, Figs. S5 and S6), we propose that the polymer de-
composition proceeds in two steps (SI Appendix, Fig. S7): (i) the
imine bonds are hydrolyzed under acid catalysis and (ii) water
further decomposes the DPP monomers through the hydrolysis
of the lactam rings. In the first step, we observed clear NMR
signatures of the DPP-CHO and phenylenediamine monomers,
consistent with polymer decomposition. In the second step, the
lactam ring hydrolyzation is supported by the absorption spectrum,
where the purple-colored DPP-CHO became colorless after

CHEMISTRY
decomposition.
Biocompatibility is a highly desirable requirement for implant-
able medical devices or sensory devices that directly interface with
living tissue (4). Semiconducting polymers with good biocompat-
ibility enable the development of organic FET devices for bio-
sensors and prosthetic skins (24). To prove the biocompatibility of
PDPP-PD, we performed in vitro cell culture experiments using
our polymer coated on a glass slide as the substrate (Fig. 2 C and
D). HL-1 cardiomyocytes were used for biocompatibility test, be-
cause HL-1 cell is a standard cell line for electrophysiological
testing. We can potentially use the fabricated electronics to detect
the electrophysiological signals (25). Our cell viability measurements
showed that the PDPP-PD has negligible effect on the viability of
HL-1 cardiomyocytes from 2 to 6 d at pH 7.4. Fig. 3. Characterization of the ultrathin cellulose film and PDPP-PD polymer
transistor. (A) Optical transmittance of an 800-nm-thick cellulose film. (Inset)
Ultrathin Cellulose Substrate for TFTs Photo of a cellulose film floating on water. (B) Film thickness changes of a cellulose
film soaked in a 1 mg/mL cellulase buffer solution (cellulase from Trichoderma
To realize ultrathin transient electronics, substrates that are tough, viride; pH 4.6). The film shows a linear decomposition speed of 3.7 nm/h. (C) AFM
compatible with mild processing conditions, and biodegradable are height image of a cellulose film. (D) 2D-GIXD image of the polymer film (color
needed. In addition, the substrate should have high temperature scale is linear). (E) Transfer and output characteristics of PDPP-PD fabricated on a
stability to allow for the thermal annealing of the semiconducting 800-nm cellulose substrate (50-nm Al2O3, VDS = –10 V).

Lei et al. PNAS | May 16, 2017 | vol. 114 | no. 20 | 5109
decreased to one-third of the original film thickness, largely due to 0.04 cm2/V·s (SI Appendix, Figs. S9 and S10), nearly one order of
the removal of the bulky trimethylsilyl groups. The hydrolyzed magnitude higher than the former. Unlike many high-mobility
cellulose film is insoluble in most organic solvents, for example, conjugated polymers that show kinked transfer characteristics (33),
toluene, THF, chloroform, CB, and water. Thus, we can sequen- PDPP-PD exhibited nearly ideal transfer characteristics. The device
tially repeat the above steps to obtain an 800-nm-thick film, which performance on the 800-nm cellulose film with atomic layer de-
is robust enough for further device fabrication and peel-off. By position (ALD) deposited Al2O3 as the dielectric layer is shown in
soaking the device in water, the dextran layer is dissolved, starting Fig. 3E. The device possessed hole mobilities of 0.21 ± 0.03 cm2/V·s
from the edges of the device to the center. This process ultimately with good on/off ratios (SI Appendix, Fig. S11). Because of the
releases the ultrathin substrate and leaves it floating on water low-lying HOMO level of PDPP-PD, the device is water- and air-
surface (Fig. 3A, Inset). stable even without any encapsulation. To analyze the polymer
For optoelectronic applications, high optical transparency is film microstructure, grazing-incidence X-ray diffraction (GIXD)
desirable. The optical properties of the cellulose film were was performed (Fig. 3D and SI Appendix, Fig. S12). Distinct out-
characterized with UV-vis spectroscopy. The 800-nm-thick film of-plane peaks from the (h00) reflections can be seen up to third
exhibited a high transmittance of 99.7% at 550 nm (Fig. 3A) order with a weak fourth-order peak convolved with a halo of
and >98% from 400 to 1,800 nm. The surface rms roughness diffuse alkyl scattering and π-stacking diffraction. The crystalline
characterized by atomic force microscopy (AFM) is 3.9 nm (Fig. lamella have a Q(100) value of 0.36 Å−1, which is equivalent to
3C), smaller than other RCFs (6–7 nm) and commercial PET a d-spacing of 17.5 Å. The (010) peak occurs at 1.51 Å−1, which
films (7.0 nm) (30). Low surface roughness allows for electronics corresponds to a π-stacking distance of 4.16 Å, a distance slightly
to be fabricated directly on the film and also provides higher larger than typical for most semiconducting polymers (∼3.6–3.9 Å)
device yields and performance. The cellulose film is stable in (15), possibly due to a less-planar polymer backbone (SI Appendix,
organic solvents and neutral aqueous media, but can be easily Fig. S13). Both edge-on and face-on packing are found in the thin
disintegrated by cellulase in mild acid conditions. The degrad- film, which has previously been shown to be beneficial for charge
ability of the cellulose film was monitored by soaking the cellu- transport (34).
lose film in a 1 mg/mL cellulase (from Trichoderma viride) buffer
solution (pH 4.6) (Fig. 3B). The film degraded at a constant rate Solution-Processed Disintegrable Pseudo-CMOS Circuits
about 3.7 nm/h. Under these conditions, an 800-nm-thick cellu- To demonstrate the potential of our decomposable polymer
lose film completely disintegrated after 10 d. semiconductor and substrate, we proceed to fabricate pseudo-
The electrical performance of PDPP-PD was first evaluated by CMOS logic circuits (Figs. 1B and 4A). Such circuits use only one
spin-coating 5 mg/mL polymer solutions on octadecyltrimethoxysilane type of semiconductor but have performance comparable to
(OTS)-treated SiO2 (300 nm)/n++-Si substrates. The bottom-gate/ complementary-type logic circuits, which significantly reduces
top-contact device configuration was used with gold for the source- the fabrication complexity (35). Based on this design, high-
drain electrodes. For low–molecular-weight PDPP-PD (Mr = performance organic small-molecule and metal oxide flexible
19.1 kDa), the polymer exhibited low hole mobilities of 0.042 ± circuits have been demonstrated (36, 37). The good chemical and
0.006 cm2/V·s. In contrast, higher molecular-weight PDPP-PD thermal stability of the cellulose substrate allow for direct device
(Mr = 39.6 kDa) demonstrated hole mobilities of 0.34 ± fabrication on top. Gold was used as the gate, source, drain, and

Fig. 4. Disintegrable pseudo-CMOS circuits based on PDPP-PD. (A) Device structures of the pseudo-CMOS circuits. (B) After dissolving the dextran layer, the
device floated on water. (Scale bar: 5 mm.) (C) Device was picked up by a human hair. (Scale bar: 5 mm.) (D) Device was transferred onto the rough surface of
an avocado. (Scale bar: 10 mm.) (E) Device transferred onto a PDMS substrate for electrical measurement. (Scale bar: 5 mm.) (F) Device was transferred onto a
human brain model. (Scale bar: 5 mm.) (G–L) Optical microscopic images, circuit diagrams, and input–output characteristics for different logic gates. (Scale bar:
500 μm.) G and J, Inverter. H and K, NOR gate. I and L, NAND gate. VDD = +4 V, VSS = –4 V.

5110 | www.pnas.org/cgi/doi/10.1073/pnas.1701478114 Lei et al.

interconnects, and 25-nm ALD Al2O3 was used as the dielectric rapidly under this condition, typically within 1 h (SI Appendix, Fig.
layer. The ALD-deposited Al2O 3 can be decomposed in the S20). Other materials, including the conjugated polymers, cellulose
pH 4.6 buffer solution with a rate of 1.5 nm/d (SI Appendix, Fig. substrate, and alumina, are all observed to be completely degraded
S14). After self-assembled monolayer (SAM) modification, PDPP- within 30 d. For practical applications, the degradation speed of the
PD can be directly spin-coated and patterned on the substrate device can be potentially controlled using appropriate decomposable
using a fluoropolymer-protected oxygen plasma etching technique encapsulation materials (SI Appendix, Fig. S21).
(Materials and Methods). Gold electrodes were deposited to form For reference, compared with the pH 4.6 buffer solution used
a top-contact configuration to complete the device. All of the for the complete dissolution of the devices, common fermented
fabrication processes, including spin-coating, photolithography, vinegar contains 5–20% acetic acid and has a pH of 2–3, and the
evaporation, and etching, were handled on rigid substrates. These pH of gastric acid in the human stomach is about 1.5–3.5. Thus,
processes are scalable to large device sizes. The device was then pH 4.6 or lower is a condition that exists in many biological pro-
immersed in water to dissolve the dextran layer and release the cesses. After disposing these electronics, they are likely to de-
ultrathin device (Fig. 4B). Fig. 4C shows that the device membrane compose under acidic biological conditions with little influence on
can be picked up by a human hair. Furthermore, the device can be our environment. Our ultrathin device is extremely lightweight at
transferred onto any target substrate. For example, the thin device
only 0.19 mg/cm2 (SI Appendix, Table S1) or 1.9 g/m2, which
conforms well on a rough surface (Fig. 4D). For bio-integrated
makes it among the lightest electronic devices reported to date (7,
electronics, highly conformal coverage decreases the spacing be-
tween sensor devices and tissues with wrinkled surfaces, for ex- 18, 19, 26). For comparison, our device is about 40 times lighter
ample, the gyri and sulci of the brain, and therefore provides better than a sheet of typical office paper (80 g/m2). The ingredients that
recording of signals (38). Fig. 4F compares our device with a 25-μm might be potential hazards in the decomposed device are alumi-
polyimide (PI) substrate on a human brain model. PI films, 25 μm num (5.9 μg/cm2) and p-phenylenediamine (PPD) (0.48 μg/cm2)
or thicker, are often used as the substrate for flexible electronics (SI Appendix, Table S1). Based on published toxicity data, the
(39, 40). Our device showed much better conformal coverage, aluminum content in our 1-cm2 device is no greater than that in
suggesting its potential applications in biointegrated electronics. 100 mL of regular drinking water, and PPD is permitted by the US
The ultrathin transistor-covered sheet was transferred onto a poly- Food and Drug Administration for use as a hair dye. The 50%
dimethylsiloxane (PDMS) or PI substrate to test their flexibility lethal dose (LD50) of PPD is 80 mg/kg for rats, corresponding to
against bending at different radii of curvature (SI Appendix, Fig. 5.6 g for a 70-kg human. This is over 107 times higher than the
S16). We observed less than a 5% change in the transfer charac- maximum PPD concentration (0.48 μg/cm2) in our device. Toxicity
teristics of the devices before and after bending. As shown in Fig. 4 data for the decomposed product of DPP-CHO are not available;
B and J, the PDPP-PD based pseudo-D inverter showed almost however, DPP derivatives are widely used as pigments in industrial
rail-to-rail output (i.e., output voltages close to the supply volt- coatings, printing inks, and tattoos. Toxicity studies showed that
ages, 4 or 0 V) with a sharp switching at VDD = 1.9 V, very close short-term inhalation of DPP pigments (6 h/d on 5 consecutive
to one-half of VDD (2 V). The flexible inverter showed a large days) at high doses (30 mg/m3) only caused minor effects on an-
noise margin of 1.2 V (60% of the 1/2 VDD; SI Appendix, Fig. imal lungs (SI Appendix, Table S1). No expected ecological or
S17), comparable to the state-of-the-art organic and carbon toxicological threats to either human health or the environment
nanotube-based flexible logic circuits (41, 42). NOR and NAND were observed for DPP dyes used for tattoos. Moreover, com-
gates consisting of six transistors were also fabricated using the pared with these commercial applications, the DPP concentration
pseudo-CMOS design. The input voltages, VA and VB, were set in our device is extremely low (3.92 μg/cm2). Therefore, our devices
to be 4 or 0 V to represent logic “1” and “0,” respectively (Fig. 4
K and L). Both NOR and NAND showed almost rail-to-rail
voltage swings from 0 to 4 V, suggesting the potential of using
these logic gates to construct more complex logic circuits. Al-
though some traditional processes, such as lithography and vapor
deposition, were included in the fabrication of the disintegrable
circuits, we envision that these traditional processes can be
replaced by other low-cost solution processes through further
material optimization and process engineering (43, 44).

CHEMISTRY
Totally Disintegrable Electronics
To date, almost all of the organic disintegrable electronics are fab-
ricated using gold as the electrodes (4, 45). Although gold is a bio-
compatible material and has been widely used in implantable
electronics (12, 38), it is not dissolvable and cannot “physically dis-
integrate” (46). To achieve completely disintegrable “transient”
electronics, we investigated iron as the gate and source-drain elec-
trodes for the polymer (Fig. 5A), because the work function of iron
(4.8 eV) is close to the HOMO level of the polymer (5.11 eV). Fig.
5B shows the transfer characteristics of the iron devices. Compared
with gold electrodes (work function: 5.1 eV), devices with iron
electrodes showed a more negative threshold voltage, largely due to
the mismatch between iron work function and the polymer HOMO
level. However, the iron-based devices still showed reasonable hole
mobilities of 0.12 ± 0.04 cm2/V·s with on/off ratios >104 (SI Ap-
pendix, Fig. S18). We observed that our prepared devices are highly Fig. 5. Totally disintegrable electronics using iron as electrodes. (A) Sche-
stable for several days in DI water (SI Appendix, Fig. S19) but can be matic of the materials and device structure used for totally disintegrable
rapidly degraded in a pH 4.6 buffer solution (containing 1 mg/mL electronics. (B) Transfer characteristic using Fe as the gate and source-drain
cellulase). Fig. 5C displays the degradation process of our flexible electrodes. VDS = –10 V. (C) Photographs of a device at various stages of
devices. Specifically, we observed that the iron electrodes degrade disintegration. (Scale bars: 5 mm.)

Lei et al. PNAS | May 16, 2017 | vol. 114 | no. 20 | 5111
are unlikely to present any potential hazards to either environment by thermal evaporation of 2-nm Ti/40-nm Au through a shadow mask. Be-
or human body. fore polymer deposition, the Al2O3 layer was modified with butylphosphonic
In summary, we have demonstrated a fully decomposable and acid as the SAM layer by spin-coating 2 mM butylphosphonic acid in tri-
chloroethylene (TCE) at 3,000 rpm (Laurell, Model WS-650-23B) for 30 s and
biocompatible semiconducting polymer and totally disintegrable
annealing at 100 °C for 10 min. A thin film of the polymer was deposited on
flexible circuits. We showed that, using reversible imine chemistry,
the treated substrate by spin-coating PDPP-PD solution (5 mg/mL in TCE) at
a completely decomposable conjugated polymer with high charge 1,000 rpm (Laurell, Model WS-650-23B) for 60 s, followed by thermal annealing
carrier mobility for various logic circuits is achievable and has at 150 °C under nitrogen.
electrical performance and solution processability comparable to To pattern the polymer semiconducting layer, a fluoropolymer-protected
traditional conjugated polymers. We further report a highly chem- dry etching process was performed as follows. A 400-nm-thick PTFE AF 2400
ically and thermally stable ultrathin cellulose film as an optimized (poly[4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole-cotetrafluoroethylene])
biodegradable substrate for transient and biodegradable electronics. was spin-coated on the PDPP-PD layer. In addition, an 80-nm-thick copper layer
Lastly, we prepare ultralightweight pseudo-CMOS logic circuits and was thermally evaporated through a shadow mask to define the semi-
totally disintegrable polymer transient electronics. Our described conducting layer. Oxygen plasma (150 W for 2 min) was used to etch away the
advances provide unique capabilities and broader applications for PDPP-PD layer where the copper layer was not covered. The copper layer was
environmentally friendly and biointegrated organic electronics. then etched away by copper etchant (sodium persulfate). The PTFE AF 2400 was
removed by soaking in fluorinated solvent (methoxyperfluorobutane) for
Materials and Methods 5 min. After the polymer layer was patterned, 40-nm gold was then deposited
as the source and drain contacts using a shadow mask. To facilitate the dextran
Materials. Detailed synthesis of the decomposable polymer can be found in
dissolution, the chip border was mechanically scratched. After the dextran was
SI Appendix.
fully dissolved, the ultrathin device can be released and floated onto water. The
device can be picked up and transferred to a target substrate (e.g., PDMS or
Fabrication of the Ultrathin Disintegrable Logic Circuits. On the cellulose sub-
polyimide film). All of the devices were tested under ambient conditions.
strate, patterned gate electrodes consisting of 2.5-nm Ti/35-nm Au/2.5-nm Ti
were thermally evaporated onto the cellulose substrate through a shadow
mask. The first Ti layer was used for adhesion and the top Ti layer was used to ACKNOWLEDGMENTS. This work was supported by Air Force Office for
Scientific Research Grant FA9550-15-1-0106. It was partially supported by
provide nucleation sites for a 25-nm layer of Al2O3, which was deposited by
BASF. R.P. acknowledges support from Marie Curie Cofund, Beatriu de Pinós
ALD at 150 °C. The measured specific capacitance for the 25-nm Al2O3 is Fellowship AGAUR 2014 BP-A 00094. L. Shaw gratefully thanks the Kodak
280 nF/cm2, slightly less than theoretical value of 301 nF/cm2 (dielectric con- Graduate Fellowship for their support. Use of the Stanford Synchrotron
stant: 8.5). Vertical interconnect access holes were defined by photolithog- Radiation Lightsource, SLAC National Accelerator Laboratory, was supported
raphy using S1813 as photoresist and etched by an aluminum etchant for by the US Department of Energy, Office of Science, Office of Basic Energy
about 2 min. Interconnects (without source-drain electrodes) were patterned Sciences under Contract DE-AC02-76SF00515.

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5112 | www.pnas.org/cgi/doi/10.1073/pnas.1701478114 Lei et al.