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Molecular Electronics: From Nanostructure Assembly to Device

Integration
Meng Yuan,¶ Yuchen Qiu,¶ Hanfei Gao, Jiangang Feng,* Lei Jiang, and Yuchen Wu*
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ABSTRACT: Integrated electronics and optoelectronics based on organic semiconductors have attracted considerable interest in
displays, photovoltaics, and biosensing owing to their designable electronic properties, solution processability, and flexibility.
Miniaturization and integration of devices are growing trends in molecular electronics and optoelectronics for practical applications,
which requires large-scale and versatile assembly strategies for patterning organic micro/nano-structures with simultaneously long-
range order, pure orientation, and high resolution. Although various integration methods have been developed in past decades,
molecular electronics still needs a versatile platform to avoid defects and disorders due to weak intermolecular interactions in organic
materials. In this perspective, a roadmap of organic integration technologies in recent three decades is provided to review the history
of molecular electronics. First, we highlight the importance of long-range-ordered molecular packing for achieving exotic electronic
and photophysical properties. Second, we classify the strategies for large-scale integration of molecular electronics through the
control of nucleation and crystallographic orientation, and evaluate them based on factors of resolution, crystallinity, orientation,
scalability, and versatility. Third, we discuss the multifunctional devices and integrated circuits based on organic field-effect
transistors (OFETs) and photodetectors. Finally, we explore future research directions and outlines the need for further
development of molecular electronics, including assembly of doped organic semiconductors and heterostructures, biological
interfaces in molecular electronics and integrated organic logics based on complementary FETs.

1. INTRODUCTION methods that are compatible with organic materials.40,41 The

Integrated and miniaturized electronical devices based on bottom-up integration approach not only enables the assembly
molecular have attracted considerable interest, which requires of organic molecules into designed patterns on flexible
molecular assembly with large-scale, long-range order, pure- substrates but also mitigates the introduction of defects and
orientation, and high resolution. This perspective focuses on disorder in organic solids, thereby enhancing the electrical
the structure−assembly property−function relationship in the performance. Over the past three decades, organic semi-
molecular electronics field, the strategies for integration and conductors have been assembled into integrated devices
miniaturization of molecular assembly, and the integrated through four primary methodologies: evaporation,42,43 micro-
multifunctional devices. π-Conjugated organic molecules and droplet patterning,44−46 mold imprinting,47,48 and photo-
polymers are promising carbon-based semiconductors for lithography49,50 (see the roadmap in Figure 1). Despite these
emerging electronic, optoelectronic, and photonic applica- advances, organic integrated electronics is still in its infancy
tions.1−13 Compared to inorganic materials, organic semi- due to the lack of a versatile platform capable of enabling
conductors offer several intriguing properties, such as design- precise patterning, long-range homogeneity, and highly
able electronic and optical functionality by exploiting the ordered molecular packing simultaneously. Unlike inorganic
chemical diversity of molecules,14−16 feasible solution process- materials, which are bonded by strong covalent and ionic
ability,17 and compatibility with biological systems.18−22 interactions, intermolecular interactions in organic materials,
Driven by these unique advantages, molecular electronics such as van der Waals forces, hydrogen bonding, and π−π
and optoelectronics have been widely implemented in stacking, are relatively weak, leading to the formation of
displays,23,24 photovoltaics,25−29 and biosensing.30−32 How- polymorphs even under similar thermodynamic environ-
ever, further miniaturization and integration of devices require ments.51−53 Nanofabrication processing with multiple inter-
faces and rapid deposition speeds kinetically traps the system
scalable patterning of organic micro/nanostructures with
far from thermodynamic equilibrium, leading to disordered
simultaneously high packing order, resolution, homogeneity,
and tunability.33−35 The fundamental challenge is that most
organic semiconductors are incompatible with CMOS nano- Received: December 12, 2023
fabrication technology due to their relatively poor stability Revised: February 28, 2024
under ultraviolet radiation, solvent environments, and high Accepted: February 29, 2024
temperature.36
Beyond top-down CMOS technology for inorganic materi-
als,37−39 we also witnessed the rise of bottom-up integration

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Figure 1. Roadmap of organic integration technology. We emphasize several science events to highlight the breakthrough of patterning
technologies. Images are reproduced with permission from references; “Soft lithography”, Reproduced or adapted with permission from ref 64.
Copyright 1996 American Chemical Society. “Nanoimprint lithography” from ref 48. Reprinted with permission from 1996 AAAS. “Dip-pen
nanolithography” from ref 44. Reprinted with permission from 1999 AAAS. “Cold-welding” from ref 47. Reprinted with permission from 2000
AAAS. “Laser-induced thermal imaging”, Reproduced or adapted with permission from ref 65. Copyright 2003 John Wiley and Sons. “Surface
treatment assisted PVT”, Reproduced or adapted with permission from ref 42. Copyright 2006 Springer Nature. “Inkjet printing”, Reproduced or
adapted with permission from ref 45. Copyright 2011 Springer Nature. “Solution-shearing method”, Reproduced or adapted with permission from
ref 57. Copyright 2011 Springer Nature. “Liquid bridge for structure alignment”, Reproduced or adapted with permission from ref 72. Copyright
2011 John Wiley and Sons. “Wettability-guided solution-shearing process”, Reproduced or adapted with permission from ref 73. Copyright 2013
John Wiley and Sons. “Capillary-condensation patterning”, Reprinted or adapted with permission under a Creative Commons Attribution 4.0
International License from ref 43. Copyright 2015 Springer Nature. “Capillary-bridge lithography”, Reproduced or adapted with permission from
ref 74. Copyright 2016 John Wiley and Sons. “Monolithic optical microlithography”, from ref 49. Reprinted with permission from 2021 AAAS.

molecular packing in polycrystalline and amorphous states.54 importance of long-range-ordered molecular packing for
However, weak intermolecular interactions make the physical achieving exotic electronic and photophysical properties, as
properties and device performances of organic semiconductors well as high device performance. We then delve into the
extremely susceptible to the fabrication methods.55−57 The methodologies that have been developed for realizing long-
defects and disorders in materials can cause the localization of
electrons, and the trapping and nonradiative recombination of range-ordered molecular assembly and precise, high-resolution
photogenerated carriers, giving rise to low carrier mobility, low patterning by controlling the microfluid dynamics in solution
quantum efficiency, and short carrier diffusion length in processes. In particular, we highlight the unique advantages of
electronic and optoelectronic devices.58−63 Therefore, high- confined capillary bridges at superwetting interfaces in steering
performance integrated electronic devices based on organic nucleation sites and growth orientation of organic crystals,
materials require high-resolution patterning and long-range- resulting in scalable production of single-crystalline organic
ordered molecular assembly. nanostructures and oriented polymers for high-performance
In this perspective article, we examine the current status and
future prospects of integration technology for assembling integrated electronic devices such as high-mobility field-effect
organic molecules into designed patterns for integrated device transistors (FETs), integrated logic circuits, sensors, and
applications. We begin by exploring the relationship between ultrasensitive photodetectors. We also outlook the potential
molecular assembly and electronic properties, emphasizing the directions in this molecular electronics field.
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Figure 2. Emergent properties in ordered assemblies of organic molecules. (a−c) Molecular single crystals. (a) Bandlike transport in molecular
crystals. Top: molecular structures of TIPS-pentacene and rubrene. Bottom: temperature-dependent mobility of TIPS-pentacene crystals under
different VD. Reproduced or adapted with permission from ref 90. Copyright 2010 Springer Nature. (b) Long-range exciton diffusion in rubrene
crystals. Top: intensity distribution of the excitation light and PL at rubrene surface. Bottom: excitation light. Inset is the photograph of a rubrene
crystal. Reprinted with permission from ref 91. Copyright 2011 by the American Physical Society. (c) Molecular crystals with high mobility and

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Figure 2. continued

efficient electroluminescence. Top: molecular structure of DPA (left), and photograph of OLEDs based on DPA (right). Bottom: transfer curves of
DPA crystals, yielding mobility of 30 cm2 V−1 s−1. Reproduced or adapted with permission from ref 92. Copyright 2015 Springer Nature. (d−f) 2D
crystalline molecular layers. (d) Single-crystalline molecular 2D layers for high mobility and high-frequency circuit operation. Molecular structure of
C10-DNBDT-NW (top), transfer property (middle), and frequency-dependent normalized Vout of a rectifier (bottom). Inset shows the circuit
diagram of the rectifier. From ref 98. ©The Authors, some rights reserved; exclusive licensee AAAS. Distributed under a CC BY-NC 4.0 license
http://creativecommons.org/licenses/by-nc/4.0/. Reprinted with permission from AAAS. (e) 2D hole gas demonstrated by sheet resistance Rsheet
and Hall carrier density nHall as a function of temperature. Reproduced or adapted with permission from ref 99. Copyright 2021 Springer Nature.
(f) Temperature-dependent momentum and spin relaxation times of single-crystalline molecular layers. Reproduced or adapted with permission
from ref 100. Copyright 2017 Springer Nature. (g−i) Assembled polymer aggregates. (g) Schematic illustration of conjugated polymer nanofibers
with separated donor and acceptor domains for long-range exciton transport. From ref 125. Reprinted with permission from 2018 AAAS. (h)
Double-fibril network morphology constructed by ternary mixture of donors and aceptors for efficient exciton dissociation and a carrier diffusion
length exceeding 100 nm. Schematic of charge transfer (left) and photoinduced force microscopy (right) of fibril network structures. Reproduced
or adapted with permission from ref 128. Copyright 2022 Springer Nature. (i) Self-assembled nanocomposite of organic semiconductor and ionic
liquid for mixed electronic and ionic transport. Reproduced or adapted with permission from ref 130. Copyright 2023 Springer Nature.

2. A BRIEF HISTORY OF INTEGRATED TECHNOLOGY fabrication of organic thin films with single-crystal-like
FOR MOLECULAR ELECTRONICS diffraction57 and they further upgraded this method by
introducing a micropillar patterned blade for regulating the
Chemical diversity of organic molecules boosts the creation of
microfluid in 2013, yielding organic crystalline thin films with
semiconductors with intriguing electronic transport, photo-
aligned crystallographic orientation.80 By patterning the
carrier generation and bright luminescence, which is crucial for
substrate with wettability contrast, this solution-shearing
high-performance devices, such as FETs, light-emitting diodes
method can be utilized for orientating organic crystals, while
(LEDs) and biomedical sensors. The development of
still preserving the grain boundaries.73
integrated electronic devices based on organic semiconductors
In 2011, Jiang and his colleagues presented a versatile
relies on the availability of integration techniques, as illustrated
method for aligning polymer nanowires by taking advantage of
in the roadmap of integration techniques (Figure 1). High-
liquid bridges pinned at superhydrophobic interfaces.72 While
resolution patterning of organic materials was achieved in the
this method works well for polymers, small molecules, and
1990s and early 2000s, with a smallest feature size down to 100
nanoparticles, achieving long-range order and single crystal-
nm, using soft lithography,64 nanoimprinting,48 dip-pen
linity has proven difficult.81 In 2015, Wu and colleagues
lithography,44 cold welding,47 and laser-induced thermal
discovered that organic-molecule vapors undergo capillary
imaging.65 However, these patterned organic structures lacked
condensation along the edges of micropillars, resulting in
long-range order, limiting the potential for high-performance
deterministic patterning of organic single-crystalline micro-
devices. Organic single crystals with eliminated grain boundary wires.43 Through rational design and control of surface
and suppressed defects were introduced in the early 2000s to wettability, Wu et al. further realized confined capillary liquids
fabricate high-mobility FETs.66−68 These single-crystal FETs capable of guiding the nucleation site and growth orientation
exhibited a hole mobility of over 20 cm2 V−1 s−1 after of organic crystalline microstructures during the solution
improving crystal transfer and gate dielectrics.69−71 However, process.74 This confined capillary bridge represents a versatile
scalable integration of FET device arrays was not possible until toolkit for simultaneously controlling the geometry, size, and
the advent of patterned single-crystalline organic micro- crystallographic orientation of single-crystalline micro/nano-
structures, which were realized by Bao and her colleagues in structures. Recently, photolithography has been introduced as
2006.42 Based on these single-crystal arrays deposited by a a technique for patterning semiconducting polymers to
vapor transport method, FET arrays exhibited a high mobility construct elastic integrated circuits.49 A comparison of
of 2.4 cm2 V−1 s−1. different techniques with regard to year, resolution, crystal-
Despite high crystallinity of evaporated single crystals, linity, and orientation is presented in Table S1 of the
solution methods are still highly demanded for single-crystal Supporting Information.
patterning because of its low processing temperature and cost
effectiveness. The development of solution-patterning techni-
ques was underpinned by the development of high-mobility 3. STRUCTURE-PROPERTY RELATIONSHIPS IN
soluble organic semiconductors. The soluble polymers, ORGANIC SEMICONDUCTORS
represented by poly(3-hexylthiophene) (P3HT), were first In the pursuit of high-performance devices, understanding the
introduced to construct FETs,75,76 albeit with mobility much assembly structure−property−performance relationship in
lower than 1 cm2 V−1 s−1. Then, this mobility values were organic semiconductors is crucial. Unlike their inorganic
further improved to above 1 cm2 V−1 s−1 with the invent of a counterparts, which are characterized by rigid crystal lattices
series of highly soluble molecules, such as [1]Benzothieno[3,2- and strong covalent and ionic bonds, organic semiconductors
b]benzothiophene derivatives (Cn-BTBT),77,78 and thieno[3,2- are bonded by inherently weaker intermolecular interactions.
b]thiophene-thiophene copolymer (PBTTT).79 This material This presents a significant challenge in achieving long-range
innovation enables an inkjet printing method for the patterning order and uniformity. On one hand, static disorder occurs at
of organic single-crystal arrays,45 allowing FETs with an multiple scales, from local molecular packing defects to
average mobility of 16.4 cm2 V−1 s−1. Beyond single broader issues such as interfaces, textures, phase segregation,
crystallinity, pure crystallographic orientation is another and crystallographic misalignment. For a concise overview, we
attribute for efficient charge transport. In 2011, Bao and her refer to ref 82, which provides detailed insights into the
colleagues developed a solution-shearing method for the structure and characterization of static disorder in organic
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semiconductors. This disorder can lead to traps or scattering enables the operation of high-speed transistors with
centers that reduce carrier mobility, photocarrier lifetime, and frequencies exceeding 20 MHz (Figure 2d). Second, the
the quantum efficiency of radiative recombination, which are ultrathin carrier transport channels and minimized static
directly linked to photocurrent and voltage losses in organic disorder in 2D single-crystalline molecular layers facilitate the
solar cells,83,84 elevated noise levels in photodetectors,85,86 and exploration of metal−insulator transitions and the creation of a
inefficient carrier transport in OFETs.87 On the other hand, 2D hole gas at the interface between a 2D organic
dynamic disorder, stemming from electron−phonon inter- semiconductor and an electric double layer using ionic
actions in organic molecules, often results in carrier local- liquids.99 These advancements lead to an extraordinarily high
ization. For an in-depth understanding of this phenomenon, we hole-gas density of 1014 cm−2 and a low sheet resistance of 6
direct readers to ref 59, which comprehensively reviews the kΩ (Figure 2e). Third, the inherent weak spin−orbit coupling
influence of dynamic molecular vibrations on carrier transport. and extended spin relaxation time in organic semiconductors
In this perspective, we will focus on the methods to suppress have paved the way for innovations in spintronics.101 This
static and dynamic disorders through rational control of unique combination of coherent bandlike carrier transport and
molecular packing in the self-assembly processes. It is an ultralong spin lifetime in 2D crystalline molecular layers has
important to note the crucial role that molecular structure enabled the demonstration of micrometer-scale spin diffusion
design plays in attaining high performance in organic (Figure 2f).100
semiconductors. However, an in-depth discussion of this Given the remarkable successes of small-molecule crystals in
topic falls beyond the scope of this perspective. For electrical transport, photocarrier diffusion, light emission, and
comprehensive insights into design strategies specific to spin diffusion, we now turn our attention to the structure−
organic semiconductors, we refer interested readers to property relationships and the interplay between electrical
references to refs 15, 16. properties and assembly methods. First, a fundamental
We begin our discussion with small-molecule semiconduc- observation is that single crystals demonstrate anisotropic
tors. In small molecules, the most straightforward way to charge transport. This is predominantly influenced by
minimize static disorder and defects is through the fabrication molecular packing, which dictates one or more optimal
of single-crystal structures. For example, rubrene bulk crystals intermolecular charge transfer directions.59,101 This under-
demonstrate exceptional carrier mobility, exceeding 10 cm2V−1 scores the criticality of aligning these optimal charge transfer
s−1, and exhibit bandlike transport behavior, as evidenced by directions with conduction channels in devices during material
the negative temperature dependence of mobility (Figure assembly. Commonly, an edge-on assembly of organic
2a).88,89 This bandlike transport is similarly observed in molecules promotes in-plane carrier transport along π−π
solution-processed 6,13-bis(triisopropylsilylethynyl) pentacene stacking directions, thereby facilitating high-mobility FETs.102
(TIPS-pentacene) crystalline thin films.90 Due to reduced Conversely, face-on assembly is more conducive to enhancing
static disorder, these molecular crystals combine long carrier performance in devices reliant on vertical carrier transport,
lifetimes with highly mobile excitons, leading to an ultralong such as solar cells and LEDs.103 To maintain organic crystals in
exciton diffusion length. In rubrene crystals, a diffusion length a pure orientation, several methodologies have been explored.
of approximately 4 μm has been directly observed using Techniques like epitaxy,104,105 solution shearing,57,80,106 and
spatially resolved photoluminescence (PL) measurements capillary-bridge lithography107 leverage interfacial interactions
(Figure 2b).91 This combination of high mobility and high and directional microfluidics to align molecules effectively.
emission quantum efficiency is critical for the performance of Notably, these oriented crystals outperform randomly oriented
electroluminescence (EL) devices. It can be achieved by films, exhibiting significantly higher carrier mobilities.57,63,80,108
rational molecular design and the construction of high-quality Second, although single crystals generally exhibit a
single-crystalline structures. For instance, single-crystalline 2,6- significantly lower density of disorder within their interior,
diphenylanthracene (DPA) exhibits a strong luminescent surface defects and disorder remain inevitable. This neces-
anthracene core, achieving an absolute PL quantum efficiency sitates surface doping or trap passivation to achieve improved
of 41.2%, and its ordered molecular packing enables a high device performances. For example, Lee et al. employed
hole mobility of 34 cm2 V−1 s−1 (Figure 2c).92 Furthermore, perfluoropolyether to accumulate mobile holes on the surface
the introduction of various dopants, including tetracene and of a rubrene single crystal, leading to the healing of traps and
pentacene, into these single-crystalline DPA structures allows the emergence of ultralow-noise, trap-free, and anisotropic
for the realization of color-tunable EL.93 transport, as observed in Hall-effect measurements.109 Another
In the realm of organic integrated devices, ultrathin 2D case is N,N′-bis(heptafluorobutyl)-2,6-dichloro-1,4,5,8-naph-
molecular crystals present a viable solution compared to bulk thalene tetracarboxylic diimide (Cl2-NDI), a prototypical n-
molecular crystals, which pose challenges for on-chip type semiconductor.102 Despite its high electron mobilities of
integration. These 2D crystals, with a thickness of less than up to 8.6 cm2 V−1 s−1, step edges on crystal surfaces act as
10 nm, can be produced through epitaxial growth in a physical electron traps.110 To overcome this, N-silane has been used to
vapor transport process94,95 or meniscus-guided coating in a bond with step edges on the Cl2-NDI surface, facilitating site-
solution process, enabling practical on-chip integration. Takeya specific doping. This approach has resulted in a 10-fold
and colleagues have advanced the field of electronic physics increase in mobility and a transition from thermally activated
and device implementation using 2D molecular crystals.96,97 to bandlike transport.111 Despite these advancements, the
Their first major contribution involves using a benchmark understanding of surface passivation and doping in organic
molecule, 3,11-dioctyldinaphtho[2,3-d:2′,3′-d′]benzo[1,2- crystals remains limited. The primary challenge lies in the
b:4,5-b′]dithiophene (C8-DNBDT-NW), to facilitate wafer- poorly understood surface states and trapping mechanisms for
scale fabrication of bimolecular layers. These layers exhibited most organic crystals. Addressing this issue requires the use of
an intrinsic carrier mobility surpassing 10 cm2 V−1 s−1.98 This advanced surface-sensitive characterization technologies. Tech-
breakthrough in conductivity and reduced contact resistance niques such as scanning Kelvin probe microscopy and scanning
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Figure 3. Comparison of large-scaled integration techniques. (a, b) Schematic illustrations and radar plots of integration strategies with nucleation-
site control, including dip-pen lithography and inkjet printing. (c, d) Schematic illustrations and radar plots of integration strategies with
crystallographic-orientation control, including meniscus-guided coating and dip coating. (e, f) Schematic illustrations and radar plots of integration
strategies with the regulation of nucleation and orientation, including capillary-condensation patterning and capillary-bridge lithography. Versatility
of the technique represents the universal processing ability for different materials.

tunneling microscopy are essential for revealing surface characterized by their complex chain conformation and
potential and structure,101 while angle-resolved photoemission packing, are more prone to static disorder. Within a polymer
spectroscopy is pivotal for uncovering electronic structures in chain, energy migration at room temperature is typically
both the bulk and on the surface.112 Subsequent correlation of coherent.116 However, the interchain energy or charge transfer
these surface material and electronic structures with electrical becomes a critical step in the transport properties of polymer
transport, as revealed by temperature-dependent Hall-effect aggregates. Salleo and colleagues were pioneers in elucidating
measurements, is important. Finally, the rational design or the structure−property relationship in conjugated polymers.
selection of electron donors/acceptors for passivating or They discovered that an interconnected network of ordered
doping specific trapping sites is a crucial step forward in this domains within the polymers is key to facilitating long-range
field. carrier transport.117 Furthermore, in blends of polymer and
Third, once static disorder is suppressed both on the surface insulator materials, charge transport can also be achieved
and in the bulk, and an optimal orientation is selected, the through effective electronic tunneling between isolated
inherent dynamic disorder arising from molecular vibrations conductive domains.118 These findings are not only con-
becomes the determining factor for the upper limit of electrical structive in understanding efficient charge transport in
transport in organic crystals. Essentially, dynamic disorder is disordered conjugated polymers but also underscore the
linked to the rigidity of molecular crystals and can be significance of highly ordered packing of polymer chains for
intrinsically improved through the rational design of molecular optimizing electrical transport. Organometallic materials small-
structures.15,113,114 It is feasible to utilize extrinsic strain to molecule metal complexes, polymer metal complexes, and
further reduce dynamic disorder.115 From a molecular self- clusters composed of designable inorganic nodes and organic
assembly standpoint, this lattice strain can be introduced ligands show great flexibility in the material construction and
during the self-assembly of organic molecules.57 property regulation.119,120 Compared to their pure-organic
Contrasting with small-molecule crystals, where static counterparts, these materials exhibit unique advantage of
disorder can be substantially suppressed, conjugated polymers, combining tunable excited-state characteristics, good proton
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conductivity and catalytic activity, as well as high stability, thus and biomacromolecules with ultrahigh resolution of sub-10
leading to a wide range of applications in electronic/ nm. The physical transport process in the dip-pen lithography,
optoelectronic devices.121−124 including dissolution, diffusion and assembly, are affected by
To achieve ordered chain packing, organic semiconducting ink composition, liquid viscosity, interfacial energy, and
nanofibers composed of a crystalline poly(di-n-hexylfluorene) environmental parameters, which restrict its versatility for
core surrounded by solvated coronas have been successfully processing different materials, the crystallinity and orientation
fabricated (Figure 2g).125 These high-quality nanofibers create of patterns, and processing area and throughput. For large-area
a uniform exciton energetic landscape, facilitating efficient fabrication with high throughput, two-dimensional soft
exciton diffusion from the crystalline core to the lower-energy elastomeric polydimethylsiloxane (PDMS) arrays with about
coronas in the end blocks. This process results in an impressive 11 million pyramid-shaped pens are employed as the polymer
diffusion length of over 200 nm and a diffusion coefficient of pen array to generate gold dot arrays with programmable
0.5 cm2 s−1. However, despite their capability for ultralong patterns and an expansive area of more than 1 cm2.46 The
carrier diffusion, the large-scale fabrication of these materials applied pressure and contact time can be varied to
remains challenging, limiting their broader application in continuously tune the size of patterned dots from 90 nm to
optoelectronic devices such as solar cells, LEDs, and over 10 μm.143 Supplementing this strategy, various tip
photodetectors. Controlled microfluidics and mass transport structures144−146 and external energy sources, such as
techniques, like solution shearing63,126 and capillary-bridge electrical,147 thermal,148 mechanical,149 or optical,150 have
lithography,127 represent promising approaches for the scale- been introduced to expand its versatility. Owing to these
up fabrication of these nanofibers. These methods have been features, dip-pen lithography is widely used in applications of
developed to fabricate polymer structures with multiscale optics,151 biology,152 and catalysis,153 instead of electronics and
ordering and long-range homogeneity. optoelectronics.
Alternatively, phase separation has been employed to create Inkjet printing (Figure 3b) is a noncontact patterning
polymer blends of donors and acceptors that form technique for not only solution-processable but also suspen-
bicontinuous networks, facilitating efficient exciton generation, sible materials, including organic semiconductors, metal halide
dissociation, and long-range free-carrier transport, thus leading perovskites, quantum dots, and metal−organic frameworks
to efficient solar cells.128,129 For example, rational design of (MOFs).154−156 The two steps of this method, spraying
ternary blends of donor−acceptor polymers has yielded microdroplets and assembling in microdroplets, cause the low
bicontinuous double-fibril networks, which demonstrate an resolution and massive defects of generated structures. The
exciton diffusion length of 40 nm and a free carrier diffusion resolution depends on the size of microdroplets further
length of over 100 nm, resulting in high-performance organic decided by the caliber of nozzle, yet which is limited by
solar cells with a certified power conversion efficiency of 19.2% clogging and in contradiction with suitable viscosity and
(Figure 2h).128 In addition to their exceptional electronic surface tension ranges of inks. To overcome this limitation,
transport properties, organic semiconductors have demon- strategies have been developed to reduce the size of
strated the ability to achieve multifunctionality by integrating microdroplets for the fabrication of microstructure arrays
electronic and ionic conduction through ordered self-assembly with a width of about 1 μm, such as electrohydrodynamic
with ionic liquids (Figure 2i).130 The construction of self- ejection157 and piezoelectric actuation.158 The out-of-equili-
assembled lamellae composed of semiconducting polymer brium evaporation systems have posed a challenge to the
sheets and ionic liquid layers has enabled the realization of a attainment of high crystallinity, predominantly due to the
monolithic nanocomposite with both liquid-like ionic transport microfluidic dynamics and disordered mass transport caused
and efficient electron conduction. Therefore, long-range- by the coffee-ring effect. Advances in Marangoni flows,
ordered self-assembly of organic semiconductors is a promising modulation of substrate surface energy, and the employment
avenue for discovering emergent properties and creating high- of templates offer an opportunity to suppress the coffee-ring
performance devices. effect toward achieving a more uniform morphology.
4.2. Control of Crystallographic Orientation. The
4. LARGE-SCALE INTEGRATION OF MOLECULAR manipulation of directional liquid flows via shear forces allows
ELECTRONICS for the control of crystallographic orientation (Figure
After summarizing the history and emergent properties of 3c,d).57,73,80,159 First, the solution-shearing method harnesses
organic molecules in long-range order for electronics, this a blade to produce directional fluids for regulating the mass
section will discuss the strategies and technology for large-scale transport in the crystallization process, yielding crystals with
assembly of molecules. We would like to examine state-of-the- pure crystallographic orientation (Figure 3c). For instance, Bao
art assembly techniques based on factors of resolution, and her colleagues introduced a solution-shearing method for
crystallinity, orientation, scalability, and versatility. These the fabrication of an organic crystalline film with single-crystal-
assembly techniques are categorized into three groups: like diffraction.57 They also correlated the shearing speed and
nucleation control, crystallographic-orientation control, and lattice strain of generated organic films, thus producing the
simultaneous control of nucleation and orientation (Figure 3 shorter p-p stacking distance for delocalized and high-mobility
and Table S2). carrier transport. They further developed solution shearing by
4.1. Control of Nucleation Site. To control the designing a micropillar-patterned printing blade for controlling
nucleation sites, an organic solution was positioned at the the recirculation of organic inks, yielding oriented growth of
assigned locations to provide a well-patterned micro/nanoscale organic crystals with an unprecedented mobility of 11 cm2 V−1
space for the crystallization131 through the dip pen,44,46,132,133 s−1.80 By regulating the fluid during solution-shearing process,
ink jet,45,134−138 and soft template.139−142 alignment and multiscale ordering of conjugated polymers
As a typical microdroplet method, dip-pen lithography were achieved, yielding efficient carrier transport and high
(Figure 3a) can be used to pattern polymers, nanoparticles, stretchability.63 For size control, alternating regions with
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Figure 4. Capillary-bridge lithography method. (a−d) Organic ultrathin nanostructure arrays. Reprinted or adapted with permission under a
Creative Commons Attribution 4.0 International License from ref 107. Copyright 2019 Springer Nature. (a) Schematic illustration of organic arrays
assembly processing under pressure. (b) SEM image and GIWAXS pattern of organic semiconductor arrays. (c) Morphology tailoring of single-
crystalline organic ultrathin nanostructured arrays with tunable shapes of hexagon and six-sided ring. (d) Tunable thickness of nanobelts at different
solution concentrations and pressures and the distribution diagram of mobility corresponding with the height of belts. (e−g) Organic wafer-scale
integration. Reprinted or adapted with permission under a Creative Commons Attribution 4.0 International License from ref 127. Copyright 2021
Springer Nature. (e) Schematic illustrations and the corresponding cross-sectional view schemes of dewetting and assembling processes of
curvilinear polymer microstructures. (f) SEM image and GIWAXS pattern of large-area curvilinear polymer microstructure arrays. (g) Schematic
illustration, optical image and statistical mobilities of fully stretchable OFET arrays. Optical images and output−input characteristic curves of
stretchable NAND gate. Scale bars: (b) 10 μm, (c) 20 μm (left) and 10 μm (right), (f) 100 μm, and (g) 4 mm and 100 μm.

different wettability, formed through the selective modification 4.3. Regulation of Nucleation and Orientation.
of fluorosilane and octadecyltrichlorosilane (OTS) substrates, Simultaneous control over the nucleation and orientation of
split liquid films to fabricate organic microwire arrays with a organic crystals requires regulation of both the location and
width of 0.5 μm.73 Second, because the drying speed can be spreading/dewetting direction of organic vapors or solutions.
quantitatively controlled during the dip coating process by Wu and his colleagues achieved this by utilizing confined
adjusting the substrate lifting rate, the dip coating method is capillary liquids (Figure 3e).160 They utilized capillary
suitable for depositing organic semiconductors with uniaxial condensation, a phase transition from vapor to liquid in a
orientation and controlling their morphologies. For growth narrow gap between two solid surfaces, for patterning organic
direction control, a patterned microchannel dip-coating crystal line structures (Figure 3e). By developing a micropillar
(PMDC) method has been developed, which combines surface template with wettability contrast, Wu et al. achieved the
selective crystallization with dip-coating, leading to precisely condensation of organic vapors and directional growth of
patterned organic semiconductor arrays at designed locations organic single-crystalline microwires along the edge of
in large area. Despite great success in the fabrication of organic micropillars.43 Through the careful design of the geometry of
thin films with high crystallinity and pure crystallographic micropillars, joining of organic crystals has been demonstrated
orientation, grain boundaries are inevitable during solution- for low-loss optical waveguiding. This method has also been
shearing process, which restricts the precision and homoge- extended to fabricate multicomponent organic single-crystal-
neity of organic patterns, as well as long-range homogeneity of line microwires, resulting in white-light emission and active
carrier transport in crystalline organic films. waveguides.160
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Figure 5. Organic field-effect transistors and organic photodetectors. (a−e) Organic field-effect transistors. (a) Device structure of the most
commonly studied FET configurations. (b) Photographs of the red, green, blue, and off state organic permeable base light-emitting transistor pixels.
Reproduced or adapted with permission from ref 24. Copyright 2021 Springer Nature. (c) vOECTs. Reprinted or adapted with permission under a
Creative Commons Attribution 4.0 International License from ref 161. Copyright 2023 Springer Nature. (d) Concepts used for strain sensing.
Reproduced or adapted with permission from ref 18. Copyright 2018 Springer Nature. (e) Demonstration of autarkic magnetic e-skin attached to
human skin. From ref 162. ©The Authors, some rights reserved; exclusive licensee AAAS. Distributed under a CC BY-NC 4.0 license http://
creativecommons.org/licenses/by-nc/4.0/. Reprinted with permission from AAAS. (f−j) Organic photodetector. (f) Schematic working
mechanisms of three typical photodetector structures: photodiode, photoconductor, and phototransistor. (g) Working principle of near-infrared
(NIR) photoplethysmography. Reproduced or adapted with permission from ref 163. Copyright 2019 John Wiley and Sons. (h) Optical
microscopy image of the flexible device. Reprinted or adapted with permission under a Creative Commons Attribution 4.0 International License
from ref 164. Copyright 2022 Springer Nature. (i) Image of using the organic image sensor to sense a pentacle pattern. Reproduced or adapted with
permission from ref 165. Copyright 2019 John Wiley and Sons. (j) Device structure of the organic photodetectors with PBDTT-DPP and PC71BM
as organic active layer. Reproduced or adapted with permission from ref 166. Copyright 2017 John Wiley and Sons.

While the capillary-condensation method can be applied to example, control of crystal growth in all three dimensions is
assemble organic small molecules with low sublimation achievable through developing deformable micropillar tem-
temperatures, it is unsuitable for molecules with a large plates. While deterministic x and y patterning of microcrystals
molecular weight, such as polymers. To address this challenge, has been achieved with ridge silicon micropillar templates,
Wu and his colleagues further developed a capillary-bridge control in the z direction, determined by the thickness of the
lithography method (Figure 3f), which can assemble organic capillary bridge, is lacking. This challenge has been effectively
molecules into long-range-ordered single-crystalline patterns in accommodated by a deformable micropillar template. The
a solution process.74 This method harnesses the dewetting capillary bridges confined between this template and a
process of capillary bridges, in which directional microfluids substrate exhibit a tunable thickness when pressure is applied
from liquid bulk to three-phase contact lines enable regulated (Figure 4a).
mass transport, leading to ordered crystallographic orientation. After overviewing self-assembly based on confined capillary
The position and geometry of capillary bridges can be liquids (Figure 3e,f), we showcase large-scale fabrication of
controlled by designing micropillars for deterministic pattern- organic nanostructures with high precision in this platform. In
ing of organic structures. contrast to the previously described methods that rely on
After reviewing self-assembly based on confined capillary microdroplets and shearing fluids (Figure 3a−d), the
liquids (Figure 3e,f), we highlight the large-scale fabrication of techniques employing confined capillary bridges enable the
organic nanostructures with high precision using this platform. incorporation of both geometric and chemical ingredients to
Unlike the methods mentioned above that are based on control crystal growth under confinement. A typical example is
microdroplets and shearing fluids (Figure 3a−d), capillary- the 3D control of crystal growth facilitated by the introduction
bridge platform can integrate both geometric and chemical of deformable micropillar templates.74 While deterministic
factors to control crystal growth under confinement. For patterning in the x and y axes has been accomplished using
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ridge silicon micropillar templates, control in the z-axis, performance.63 Driven by the π−π interaction, polymers and
governed by the thickness of the capillary bridge, previously graphene can be successfully integrated with enhanced
remained elusive. On the basis of a deformable template, Gao crystallinity, leading to an average hole mobility of 8.48 cm2
et al. demonstrated capillary bridges with a controllable V−1 s−1 and enhanced thermal stability.167 Second, in recent
thickness when pressure is applied, yielding organic nano- years, monolithic integration of organic semiconductors and
structures with thicknesses from less than 10 nm to up to 1 μm other functional materials can create multifunctional field-
(Figure 4a, d).107 Meanwhile, patterns in x, y dimensions were effect devices in low cast, lager area, plastic circuits, such as
determined by the micropillar geometry (Figure 4c,d). organic light-emitting transistors (OLETs),168 organic electro-
Notably, even when reduced to a thickness of just a few chemical transistor (OECT),169 and OFETs based circuits.
molecular layers, these nanostructures maintain a high degree OLETs exhibit dual ability in switching as OFETs and light
of crystallinity, thereby enabling efficient carrier transport with emission as organic light-emitting diode (OLED) in a single
high mobilities (Figure 4b,d). device, which are potential to be the smallest integrated
In capillary bridges, the tendency for organic microcrystals optoelectronic, smart display device (Figure 5b).23,24,170−175
to grow sequentially from the edges to the center of a template By bleeding light-emitting semiconductors with photochromic
can introduce size inhomogeneity across large areas. This molecules diarylethenes (DAEs), Samori ̀ et al.176 fabricated an
phenomenon poses a limitation for the fabrication of organic optically switchable OLETs. Irradiation of the organic films at
nanostructures on a large scale, such as at the wafer level. To selected wavelengths enables the efficient and reversible tuning
address this challenge, Qiu et al. employed an approach by of charge transport and electroluminescence (EL) simulta-
rationally designing the micropillar geometry, specifically neously, with a high degree of modulation (on/off ratios up to
creating a curvilinear micropillar.127 This design establishes a 500) in the three primary colors. This approach opens
capillary gradient that facilitates the sequential dewetting of intriguing perspectives for the development of novel optically
organic liquids. Within this template, dewetting initially occurs gated, integrated full-color displays, active optical memories,
at sites with large spacing, thereby concentrating the organic microsized light sensors, light-controlled inverters, and logic
solutions into curvilinear arcs (Figure 4e). These arcs act as circuits. OECT consists of an organic semiconductor layer that
microreservoirs, enabling a uniform spatial distribution of the is in contact with an electrolyte, in which an electrode (the
organic liquids over a 4-in. wafer. Subsequent evaporation and gate) is immersed (Figure 5c).22,161 Fully stretchable electronic
formation of capillary bridges lead to the generation of materials are central to advancing new types of mechanically
curvilinear organic structures with long-range homogeneity agile and skin-integrable optoelectronic device technologies.177
(Figure 4f). This technique has been successfully applied in the Over the past decade, the development of organic semi-
fabrication of conjugated polymer microstructures on an elastic conducting sensor systems (Figure 5d,e), such as those for
substrate, enabling the integration of intrinsically stretchable sensing pressure,19 strain,18,178,179 temperature,180,181 mag-
OFETs (Figure 4g). Remarkably, these OFETs maintain a high netic,162 image,182 and biological potential,183 has attracted
mobility exceeding 1 cm2 V−1 s−1 under cyclic strain. increased research attention owing to prospective utilization in
Moreover, the interconnection of these OFETs facilitates the applications such as electronic skins (e-skins),184 robotics,185
construction of organic logic gates capable of operating under and future bio-integrated consumer electronics.186
100% strain. Therefore, capillary-bridge lithography has 5.2. Photodetectors. Photodetectors, which convert light
emerged as a pivotal technique in the creation of organic signals into electrical signals, can be classified into photodiode,
micro/nanostructures characterized by high precision, control- photoconductor, and phototransistor with different working
lable geometry and size, long-range order, and homogeneity, mechanisms and architectures that can meet different require-
effectively bridging functional organic molecules and high- ments of a variety of applications (Figure 5f).17 With the
performance semiconductor devices. development of emerging integrated technologies, high-
performance photodetectors combine ease of processing,
5. DEVICE APPLICATIONS tailorable optoelectronic properties, facile integration, and
Because of the absence of grain boundaries, the long-range compatibility with flexible substrates, which can realize the
order as well as the minimized traps and defects, the devices miniaturization and integration of devices.
based on organic semiconductor single crystalline micro/nano- A novel ultranarrow-bandgap OPD163 demonstrates ex-
structures are ideal candidates for high-performance integrated cellent near-infrared (NIR) sensing performance, and show-
devices, such as OFETs and organic photodetectors, and cases a remarkable responsivity over 0.5 A W−1 (Figure 5g).
guiding the future application of molecular electronics and The presented photodetectors can also be integrated in
optoelectronics. photoplethysmography for real-time heart-rate monitoring,
5.1. Transistors. As an essential component of organic suggesting its potential for practical applications. CPL carrying
electronics, OFETs have attracted extensive research interest in photons with spin angular momentum have attracted a wide
recent years, which are needed to create logic circuits, and range of interests for its practical applications in circularly
smart pixels in displays (Figure 5a). First, integration of single- polarized ellipsometry tomography, optical communication of
crystalline (or ordered) molecular crystals and conjugated spin information, quantum-based optical calculation, biology,
polymers with long-range ordered molecular arrangement and and medicine, etc. Chiral organic semiconductors combine
strong intermolecular interactions especially π−π stacking are high optical rotatory power with strong circular dichroism
promising for creating high-performance devices, in terms of (CD), enabling them extremely promising as building blocks
mobility, subthreshold swing, and stability. By combining the for CPL detection (Figure 5h),164 which holds the promise of
solution-shearing method with the nanoconfinement effect, large-scale circularly polarized light integrated photonic
polymer with aligned chain conformation and promoted short- applications. A highly responsive organic image sensor based
range π−π ordering can be achieved for reducing the energetic on monolithic, vertically stacked two-terminal pixels is
barrier of charge carrier transport and improving electrical presented in Figure 5i,165 which is achieved using pixels of a
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Figure 6. Photodetectors of organic−inorganic hybrid perovskites. (a) The structures of the organic−inorganic hybrid perovskites and the
conjugated organic ligands. Reproduced or adapted with permission from ref 193. Copyright 2019 Springer Nature. (b) 2D quantum well structure
illustration. (c,d) Reproduced or adapted with permission from ref 206. Copyright 2018 Springer Nature. (c) Illustration of photodetectors based
on single-crystalline nanowire arrays of organic−inorganic hybrid perovskites. (d) Statistics of detectivities of organic−inorganic hybrid perovskite
nanowires. (e,f) Reproduced from ref 210. Copyright 2021 American Chemical Society. (e) Crystal structures of chiral organic−inorganic hybrid
perovskite nanowires. (f) Wavelength-dependent responsivities of chiral-perovskite nanowire devices under different CPL illuminations. (g) Lateral
heterostructures of layered perovskites. Top, optical images; bottom, photoluminescence images. Reproduced or adapted with permission from ref
213. Copyright 2020 Springer Nature. (h) Optical image of heterostructures of layered perovskites on Si/SiO2 substrates. Reproduced or adapted
with permission from ref 214. Copyright 2020 Springer Nature.

vertically stacked diode-type OPD with photomultiplication. A surfactant monolayers at liquid−air interfaces, preferential
blend of conjugated polymer was used as the organic active nucleation and directional growth of perovskites are
layer to obtain a high photocurrent gain in OPDs, which realized.197,198 By developing an electrostatic−epitaxy method,
exhibited a normalized detectivity (D*) over 1014 Jones at a the nucleation of perovskites occurs at liquid−air interfaces,
low voltage (Figure 5j).166 These pave a new way for followed by the directional growth with the receding of liquid
realization of highly sensitive detectors with fast response front for fabricating crystallographically aligned perovskites.199
toward the single photodetection. The interaction between the interlayer cations improves
From the perspective of molecular electronics, 2D organic− crystallinity and purifies the crystallographic orientation of
inorganic hybrid perovskites provide a platform with a perovskite nanowires, thus enabling efficient exciton diffusion
semiconducting framework composed of inorganic metal- along the perovskite layers and carrier conduction along the
halide octahedra and functional organic cations, thus multi- layer edges.200−205 Ultrasensitive photodetectors can be
functionality can be realized by introducing various functional fabricated based on a low dark current and a considerable
molecules.187−192 By incorporating a series of designed organic photocurrent (Figure 6c,d).206 The intercalated organic
conjugated cations, Dou and co-workers realized 2D perov- cations in organic−inorganic hybrid perovskites introduce
skites with bandgap tunability, as well as different type-I and additional functionalities and exotic lattice symmetry of
type-II energy level alignment (Figure 6a,b).193 Compared to chirality,207,208 carrier delocalization,193 and triplet energy
the abundant grain boundaries and surface defects in transfer.209 The different response to CPL, inherited from the
disordered polycrystalline thin films, single crystal, or single- interlayer chiral cations, allows for ellipticity photodetection,
crystalline domains with long-range crystallographic order are while the nanowires with anisotropic dielectric function
thus highly desirable due to their high phase purity, eliminated facilitate anisotropic photocurrents with the rotation of linear
grain boundaries, and lower trap density ranging from 109 to polarization (Figure 6e,f).210−212 Epitaxial heterostructures
1011 cm−3.40,194 Although the charge carrier mobility of single based on organic−inorganic hybrid perovskites form the
crystals is much higher than thin films, single-crystal devices foundation of molecular electronics and optoelectronics
are limited to fundamental charge-transport research for owing to their high stability and programmable structures,
manualed-fabrication, thus difficult to large-scaled integration including lateral epitaxial multiheterostructures (Figure 6g)213
for technological applications. High-performance optoelec- and arbitrary vertical heterostructures (Figure 6h).214 Such
tronic devices of organic−inorganic perovskites require designed heterostructures exhibit interesting interlayer proper-
stringent control of crystallinity and crystallographic orienta- ties, such as interlayer carrier transfer and reduction of the
tion.195,196 By harnessing capillary bridges and self-assembled photoluminescence line width, could enable the exploration of
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Figure 7. Digital circuits, digital logic gates and integrated applications based on organic materials. (a−c) Circuit diagram and photograph. (a) An
integrated organic complementary inverter. Reproduced or adapted with permission from ref 215. Copyright 2021 Springer Nature. (b) An
enhancement-depletion mode amplifier. Reprinted or adapted with permission under a Creative Commons Attribution 4.0 International License
from ref 218. Copyright 2021 Springer Nature. (c) A five-stage organic complementary ring oscillator. Reproduced or adapted with permission
from ref 219. Copyright 2017 Springer Nature. (d−f) Optical microscopy images and schematic circuit diagrams. Reprinted or adapted with
permission under a Creative Commons Attribution 4.0 International License from ref 220. Copyright 2020 Springer Nature. (d) NOT, (e) NAND,
and (f) NOR logic gates. (g) An artificial afferent nerve made of pressure sensors, an organic ring oscillator, and a synaptic transistor. Reprinted
with permission from ref 221. Copyright 2018 AAAS. (h) The Digital Tactile System (DiTact) is composed of a pressure-sensitive tactile element
and an organic ring oscillator. Reproduced with permission from ref 222. Reprinted with permission from ref 222. Copyright 2015 AAAS.

exciton physics and optoelectronics, and demonstrate a integrated wearable electrocardiogram (ECG) and pulse
materials platform for complex and molecularly thin super- sensors for high-precision health monitoring and real-time
lattices, devices and integrated circuits. cloud-based diagnosis were achieved. High-performance
5.3. Integrated Circuits. Organic integrated circuits organic ring oscillators on polymer substrates with high
(OICs) are undergoing rapid development with the extensive oscillation speeds and low operation voltage were fabricated
research on organic semiconducting materials and the by surface neutralization the polymer substrates with a few-
performance improvement of OFETs. Recently, OICs not layer triptycene film, which significantly improve the
only cover all the major circuits types, their complexity, degree crystallinity of organic semiconducting materials and the
of integration, and performance have also been improved. overall performance of OFETs (Figure 7c).219 Similar to
According to the working principle, digital circuits that process inverters, digital logic gates such as NOTs, NANDs, and NORs
digital signals can be classified into inverter, amplifier, ring perform logical operations as well. Logic gates process two or
oscillator, logic gates, and so on. The basic structure of a more input signals. For example, a complementary NAND gate
complementary inverter or a monotype OFET-based inverter have two inputs and requires four transistors. As shown in
consists of two transistors (n-channel and p-channel OFETs) Figure 7d−f, NOT, NAND, and NOR logic gates were
connected in series (Figure 7a).215 Patterning of p-type and n- successfully fabricated by all-photopatterning polymer
type semiconductors is difficult in fabricating complementary OFETs.220
circuits in solution processing for the following reasons: (1) In biological nervous systems, neurons and synapses process
solvents used in the subsequent operations can dissolve and information on the basis of distributed, parallel, and event-
then destroy the previously formed structures, and (2) various driven computation. Device structures that emulate the
organic materials in solutions exhibit versatile assembly and functionality and signal processing of biological components
fluid behaviors. One way to solve these problems is to fabricate may potentially simplify complex circuits by mimicking
two types of devices in different layers.216 Organic vertical n- multiple synapses with a single device. Kim et al.221
channel permeable single- and dual-base transistors can be constructed an organic artificial afferent nerve in which
used to create integrated complementary inverters, which multiple ring oscillators were used to collect and react to the
exhibit small switching time constants at 10 MHz. Another way voltage changes�acting as the supply voltage of the ring
to address two-component patterning challenge is to choose oscillators�from the pressure sensors and the out-puts were
the semiconductor materials with orthogonal solvent engineer- sent to a synaptic transistor (Figure 7g). The supply voltage
ing.217 Amplifier circuits with ultrahigh voltage gain of 1.1 × and the frequency of the ring oscillator (0 to 100 Hz) have a
104 were realized (Figure 7b).218 Further, battery-powered, one-to-one relationship for calculating the value of pressure (1
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to 80 kPa), which matches biological action potentials. More transistors, memory devices, and multicolor displays. Com-
than detecting pressure, the artificial afferent nerve can also be pared with one-component material devices, heterostructures
connected to an efferent nerve for building a hybrid reflex arc have obvious advantages such as programmable physical
to drive muscles. Bao and co-workers222 presented a power- properties that can be controlled by designing the geometric
efficient skin-inspired mechanoreceptor with a flexible organic structures and tunable optoelectronic device performances that
transistor circuit, which can transduce pressure into digital are induced by adjusting the components of materials. For
frequency signals directly (Figure 7h). Furthermore, the output high-performance optoelectronic devices, the long-range order,
of the sensors was used to stimulate engineered mouse crystallographic orientation and layer-by-layer assembly of
somatosensory neurons of mouse cortex in vitro that achieved heterostructure materials are important for not only the
stimulated pulses in accordance with pressure levels. morphology but also the electronic properties of the devices.
Solution-processed techniques for assembling single-compo-
6. CONCLUSIONS AND PERSPECTIVE nent materials have been extensively investigated, yet the
Throughout this Perspective, we have summarized the recent preparation of high-quality heterostructures still remains
developments of organic electronics related to integrated challenging, such as the undesirable occurrence of phase
techniques of organic semiconductor materials and large-scale separation that leads to poor performance. By regulating the
integrated micro/nano-structures electronic devices. Organic noncovalent interactions, such as hydrogen bond, halogen
electronics has been developing rapidly in recent years, not bond, and π−π interaction, the longitudinally/horizontally
only in terms of innovation in organic materials but also in epitaxial growth of 1D organic heterostructures are realized.226
large-scale integration methods. Increasingly more organic Long-range Coulomb interactions in organic semiconductors
small molecules and polymers, as well as organic−inorganic provide a workaround for enabling continuous tuning the band
hybrid perovskites, are being used in organic electronic devices. gap and band-edge energies in organic blends.227
Recent progress toward the development of integrated 6.3. Interface Engineering of Organic Semiconductor
techniques regulating the crystallization position and crystal- and Biology Interface. A Schottky barrier (e.g., >0.2 eV) at
lization orientation simultaneously based on both lithography the metal−organic semiconductor interface limits charge
and self-assembly clearly shows that long-range ordered and injection and degrades channel transport. The charge injection
integrated organic materials micro/nano-structures can be in single-crystal-based OFETs is generally not efficient, which
fabricated, which will allow further promoting of the electronic is part of the reason for the observed nonlinear transfer curves.
properties of devices. Interfacial engineering to better align the energy level and new
Perspective of future research directions, including funda- methods to process thinner single crystals can potentially
mental researches into assembly doping of organic molecules, improve the nonlinear behavior. With sophisticated device
assembly of organic heterostructures with band structure design and interfacial engineering, OFETs based on organic
engineering, interface engineering of organic semiconductor single crystals have a good chance of leading the high-
and biology interface, and applied researches into electronics frequency study to above 100 MHz. Biology interface tissue is
and multifunction integrated devices, is presented in the next affected by micro- and macromotion of rigid electrodes,
section. through which an immune response and formation of an
6.1. Assembly of Doped Organic Semiconductors. In insulating glia layer is initiated. Successful formation of biology
the previous discussion, we talked about many options on how interfaces between living cells and long-range-ordered semi-
to improve the intrinsic properties (mobility, diffusion length) conductors hinges on the ability of obtaining an extremely
of the material, but in a real device, the type and concentration close and high surface-area contact, which preserves both
of carriers are very important for the construction of the semiconductor performance and cell viability.228
device. Like inorganic materials, organic materials can be 6.4. Integrated Organic Logics Based on Comple-
doped to control carrier concentration. Doping with strong mentary FETs. Integrated organic circuits based on
acceptors (donors) has proven to be a powerful tool for complementary FETs remain promising but challenge. In
enhancing hole (electron) transport and injection into organic molecular electronics, the integration of n-type and p-type
semiconductors, primarily by increasing the mobile charge- organic semiconductors onto the same substrate is indis-
carrier density and helping to alleviate some of the effects of pensable for fabricating complementary logics and circuits.
molecular disorder, such as by filling trap states in the host However, the current mainstream work for integrated organic
organic semiconductors.223−225 However, in most cases, the circuits typically uses polycrystalline thin films and bulk
poor doping efficiency and poor doping stability still limit the crystals, which have limitations in carrier transport and device
further development, and the related dopant diffusion is a integration. Therefore, the development of a large-area
critical issue to control. Subsequent research could focus on integration technique with high-resolution patterning and
delicate studies, such as more precise doping density and high-quality crystallographic growth for multicomponent
distribution control, which is essential to achieve practical organic molecules will be a research priority for integrated
organic devices with doped components. We expect that by organic logic circuits. In addition to following the example of
promoting fundamental understanding and methods of doping, silicon-based electronics, the design of integrated organic
high-performance devices with doped components for future circuits should target the latest applications such as neural
organic electronics will develop rapidly. networks, artificial intelligence, and the Internet of Things. The
6.2. Assembly of Organic Heterostructures with Band advantages of organic logics based on complementary FETs,
Structure Engineering. Organic heterostructures integrated including low cost, scalability, flexibility, and biocompatibility,
from multiple materials with different electronic properties can be fully utilized with high levels of integration and precisely
onto a same substrate are the basis for the high-performance optimized circuit design techniques. Concerning industrial
and multifunctional electronic micro/nanostructure devices, applications, the long-term and dynamic operational stability of
such as ambipolar field-effect transistors, field-effect tunneling integrated organic logics needs to be further improved. We
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believe that in the future, integrated organic logics based on

complementary FETs will exhibit higher performance,
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¶
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