Helical polymers for dissymmetric circularly polarized light imaging.

Control of the spin angular momentum (SAM) carried in a photon provides a technologically attractive element for next-generation quantum networks and spintronics1-5. However, the weak optical activity and inhomogeneity of thin films from chiral molecular crystals result in high noise and uncertainty in SAM detection. Brittleness of thin molecular crystals represents a further problem for device integration and practical realization of chiroptical quantum devices6-10. Despite considerable successes with highly dissymmetric optical materials based on chiral nanostructures11-13, the problem of integration of nanochiral materials with optical device platforms remains acute14-16. Here we report a simple yet powerful method to fabricate chiroptical flexible layers via supramolecular helical ordering of conjugated polymer chains. Their multiscale chirality and optical activity can be varied across the broad spectral range by chiral templating with volatile enantiomers. After template removal, chromophores remain stacked in one-dimensional helical nanofibrils producing a homogeneous chiroptical layer with drastically enhanced polarization-dependent absorbance, leading to well-resolved detection and visualization of SAM. This study provides a direct path to scalable realization of on-chip detection of the spin degree of freedom of photons necessary for encoded quantum information processing and high-resolution polarization imaging.

Organic Transistor-Based Chemical Sensors for Wearable Bioelectronics.

Bioelectronics for healthcare that monitor the health information on users in real time have stepped into the limelight as crucial electronic devices for the future due to the increased demand for "point-of-care" testing, which is defined as medical diagnostic testing at the time and place of patient care. In contrast to traditional diagnostic testing, which is generally conducted at medical institutions with diagnostic instruments and requires a long time for specimen analysis, point-of-care testing can be accomplished personally at the bedside, and health information on users can be monitored in real time. Advances in materials science and device technology have enabled next-generation electronics, including flexible, stretchable, and biocompatible electronic devices, bringing the commercialization of personalized healthcare devices increasingly within reach, e.g., wearable bioelectronics attached to the body that monitor the health information on users in real time. Additionally, the monitoring of harmful factors in the environment surrounding the user, such as air pollutants, chemicals, and ultraviolet light, is also important for health maintenance because such factors can have short- and long-term detrimental effects on the human body. The precise detection of chemical species from both the human body and the surrounding environment is crucial for personal health care because of the abundant information that such factors can provide when determining a person's health condition. In this respect, sensor applications based on an organic-transistor platform have various advantages, including signal amplification, molecular design capability, low cost, and mechanical robustness (e.g., flexibility and stretchability). This Account covers recent progress in organic transistor-based chemical sensors that detect various chemical species in the human body or the surrounding environment, which will be the core elements of wearable electronic devices. There has been considerable effort to develop high-performance chemical sensors based on organic-transistor platforms through material design and device engineering. Various experimental approaches have been adopted to develop chemical sensors with high sensitivity, selectivity, and stability, including the synthesis of new materials, structural engineering, surface functionalization, and device engineering. In this Account, we first provide a brief introduction to the operating principles of transistor-based chemical sensors. Then we summarize the progress in the fabrication of transistor-based chemical sensors that detect chemical species from the human body (e.g., molecules in sweat, saliva, urine, tears, etc.). We then highlight examples of chemical sensors for detecting harmful chemicals in the environment surrounding the user (e.g., nitrogen oxides, sulfur dioxide, volatile organic compounds, liquid-phase organic solvents, and heavy metal ions). Finally, we conclude this Account with a perspective on the wearable bioelectronics, especially focusing on organic electronic materials and devices.

Two-dimensional polyaniline (C3N) from carbonized organic single crystals in solid state.

The formation of 2D polyaniline (PANI) has attracted considerable interest due to its expected electronic and optoelectronic properties. Although PANI was discovered over 150 y ago, obtaining an atomically well-defined 2D PANI framework has been a longstanding challenge. Here, we describe the synthesis of 2D PANI via the direct pyrolysis of hexaaminobenzene trihydrochloride single crystals in solid state. The 2D PANI consists of three phenyl rings sharing six nitrogen atoms, and its structural unit has the empirical formula of C3N. The topological and electronic structures of the 2D PANI were revealed by scanning tunneling microscopy and scanning tunneling spectroscopy combined with a first-principle density functional theory calculation. The electronic properties of pristine 2D PANI films (undoped) showed ambipolar behaviors with a Dirac point of -37 V and an average conductivity of 0.72 S/cm. After doping with hydrochloric acid, the conductivity jumped to 1.41 × 10(3) S/cm, which is the highest value for doped PANI reported to date. Although the structure of 2D PANI is analogous to graphene, it contains uniformly distributed nitrogen atoms for multifunctionality; hence, we anticipate that 2D PANI has strong potential, from wet chemistry to device applications, beyond linear PANI and other 2D materials.

A Flexible High-Performance Photoimaging Device Based on Bioinspired Hierarchical Multiple-Patterned Plasmonic Nanostructures.

In insect eyes, ommatidia with hierarchical structured cornea play a critical role in amplifying and transferring visual signals to the brain through optic nerves, enabling the perception of various visual signals. Here, inspired by the structure and functions of insect ommatidia, a flexible photoimaging device is reported that can simultaneously detect and record incoming photonic signals by vertically stacking an organic photodiode and resistive memory device. A single-layered, hierarchical multiple-patterned back reflector that can exhibit various plasmonic effects is incorporated into the organic photodiode. The multiple-patterned flexible organic photodiodes exhibit greatly enhanced photoresponsivity due to the increased light absorption in comparison with the flat systems. Moreover, the flexible photoimaging device shows a well-resolved spatiotemporal mapping of optical signals with excellent operational and mechanical stabilities at low driving voltages below half of the flat systems. Theoretical calculation and scanning near-field optical microscopy analyses clearly reveal that multiple-patterned electrodes have much stronger surface plasmon coupling than flat and single-patterned systems. The developed methodology provides a versatile and effective route for realizing high-performance optoelectronic and photonic systems.

Structural Investigation of Chemiresistive Sensing Mechanism in Redox-Active Porous Coordination Network.

By changing the rate of evaporation, two kinds of crystalline films composed of redox-active porous coordination networks (1 and 2) were selectively prepared on a gold-patterned substrate using a DMF solution of 2,5,8-tri(4-pyridyl)1,3-diazaphenalene and Cd(NO3)2. We found the highly sensitive humidity sensing ability of film 1. Single crystal structures and infrared spectroscopic analyses before and after hydration of a single crystal of 1 revealed the sensing mechanism: exchange of nitrate ions with water on Cd atoms occurred in hydrated conditions to generate a conductive cationic network.

Water Processable Polythiophene Nanowires by Photo-Cross-Linking and Click-Functionalization.

Replacing or minimizing the use of halogenated organic solvents in the processing and manufacturing of conjugated polymer-based organic electronics has emerged as an important issue due to concerns regarding toxicity, environmental impact, and high cost. To date, however, the processing of well-ordered conjugated polymer nanostructures has been difficult to achieve using environmentally benign solvents. In this work, we report the development of water and alcohol processable nanowires (NWs) with well-defined crystalline nanostructure based on the solution assembly of azide functionalized poly(3-hexylthiophene) (P3HT-azide) and subsequent photo-cross-linking and functionalization of these NWs. The solution-assembled P3HT-azide NWs were successfully cross-linked by exposure to UV light, yielding good thermal and chemical stability. Residual azide units on the photo-cross-linked NWs were then functionalized with alkyne terminated polyethylene glycol (PEG-alkyne) using copper catalyzed azide-alkyne cycloaddition chemistry. PEG functionalization of the cross-linked P3HT-azide NWs allowed for stable dispersion in alcohols and water, while maintaining well-ordered NW structures with electronic properties suitable for the fabrication of organic field effect transistors (OFETs).

High-Performance Flexible Organic Nano-Floating Gate Memory Devices Functionalized with Cobalt Ferrite Nanoparticles.

Nano-floating gate memory (NFGM) devices are transistor-type memory devices that use nanostructured materials as charge trap sites. They have recently attracted a great deal of attention due to their excellent performance, capability for multilevel programming, and suitability as platforms for integrated circuits. Herein, novel NFGM devices have been fabricated using semiconducting cobalt ferrite (CoFe2O4) nanoparticles (NPs) as charge trap sites and pentacene as a p-type semiconductor. Monodisperse CoFe2O4 NPs with different diameters have been synthesized by thermal decomposition and embedded in NFGM devices. The particle size effects on the memory performance have been investigated in terms of energy levels and particle-particle interactions. CoFe2O4 NP-based memory devices exhibit a large memory window (≈73.84 V), a high read current on/off ratio (read I(on)/I(off)) of ≈2.98 × 10(3), and excellent data retention. Fast switching behaviors are observed due to the exceptional charge trapping/release capability of CoFe2O4 NPs surrounded by the oleate layer, which acts as an alternative tunneling dielectric layer and simplifies the device fabrication process. Furthermore, the NFGM devices show excellent thermal stability, and flexible memory devices fabricated on plastic substrates exhibit remarkable mechanical and electrical stability. This study demonstrates a viable means of fabricating highly flexible, high-performance organic memory devices.

Use of heteroaromatic spacers in isoindigo-benzothiadiazole polymers for ambipolar charge transport.

Inspired by the outstanding charge-transport characteristics of poly(isoindigo-alt-benzothiadiazole) (PIIG-BT) in our previous study, herein we present two new polymers (PIIG-DTBT and PIIG-DSeBT) involving IIG and BT blocks constructed using five-membered heteroaromatic spacers such as thiophene (T) and selenophene (Se) and investigate the effects of the spacer groups on the optical, electrochemical, and charge-transport properties. As a consequence of the red-shifts induced by the more extended conjugation and enhanced intramolecular charge transfer (ICT), both PIIG-DTBT and PIIG-DSeBT show smaller bandgaps compared to PIIG-BT. Interestingly, the LUMO energy levels (-3.57 eV) for the two polymers are the same, but the HOMO levels (-5.39 and -5.26 eV for PIIG-DTBT and PIIG-DSeBT, respectively) clearly vary as a function of the structural modification of the spacers. In addition to the changes in their optical properties and energy levels induced by the incorporation of the spacers, ambipolar charge transport behaviors with hole and electron mobilities of up to 7.8 × 10(-2) and 3.4 × 10(-2) cm(2) V(-1) s(-1), respectively, are observed for PIIG-DTBT films with highly ordered lamellar packing. This represents the second example of IIG-based polymers exhibiting ambipolar charge transport in OFETs reported to date.

Siloxane-based hybrid semiconducting polymers prepared by fluoride-mediated suzuki polymerization.

Siloxane-containing materials are a large and important class of organic-inorganic hybrids. In this report, a practical variation of the Suzuki polymerization to generate semiconducting polymeric hybrids based on siloxane units, which proceeds under essentially nonbasic conditions, is presented. This method generates solution-processable poly(diketopyrrolopyrrole-alt-benzothiadiazole) (PDPPBT-Si) consisting of the hybrid siloxane substituents, which could not be made using conventional methods. PDPPBT-Si exhibits excellent ambipolar transistor performance with well-balanced hole and electron FET mobilities. The siloxane-containing DPP-thiophene polymer classes (PDPP3T-Si and PDPP4T-Si), synthesized by this method, exhibit high hole mobility of up to 1.29 cm(2) V(-1) s(-1) . This synthetic approach should provide access to a variety of novel siloxane-containing conjugated semiconductor classes by using a variety of aryldihalides and aryldiboronic acids/esters.

Graphene-ruthenium complex hybrid photodetectors with ultrahigh photoresponsivity.

The maximum responsivity of a pure monolayer graphene-based photodetector is currently less than 10 mA W(-1) because of small optical absorption and short recombination lifetime. Here, a graphene hybrid photodetector functionalized with a photoactive ruthenium complex that shows an ultrahigh responsivity of ≈1 × 10(5) A W(-1) and a photoconductive gain of ≈3 × 10(6) under incident optical intensity of the order of sub-milliwatts is reported. This responsivity is two orders of magnitude higher than the precedent best performance of graphene-based photodetectors under a similar incident light intensity. Upon functionalization with a 4-nm-thick ruthenium complex, monolayer graphene-based photodetectors exhibit pronounced n-type doping effect due to electron transfer via the metal-ligand charge transfer (MLCT) from the ruthenium complex to graphene. The ultrahigh responsivity is attributed to the long lifetime and high mobility of the photoexcited charge carriers. This approach is highly promising for improving the responsivity of graphene-based photodetectors.

Fabrication of one-dimensional organic nanomaterials and their optoelectronic applications.

This paper reviews the recent research and development of one-dimensional (1D) organic nanomaterials synthesized from organic semiconductors or conducting polymers and their applications to optoelectronics. We introduce synthetic methodologies for the fabrication of 1D single-crystalline organic nanomaterials and 1D multi-component organic nanostructures, and discuss their optical and electrical properties. In addition, their versatile applications in optoelectronics are highlighted. The fabrication of highly crystalline organic nanomaterials combined with their integration into nanoelectronic devices is recognized as one of the most promising strategies to enhance charge transport properties and achieve device miniaturization. In the last part of this review, we discuss the challenges and the perspectives of organic nanomaterials for applications in the next generation soft electronics, in terms of fabrication, processing, device integration, and investigation on the fundamental mechanisms governing the charge transport behaviors of these advanced materials.

Direct solvothermal synthesis of B/N-doped graphene.

Heteroatom-doping into graphitic networks has been utilized for opening the band gap of graphene. However, boron-doping into the graphitic framework is extremely limited, whereas nitrogen-doping is relatively feasible. Herein, boron/nitrogen co-doped graphene (BCN-graphene) is directly synthesized from the reaction of CCl4 , BBr3 , and N2 in the presence of potassium. The resultant BCN-graphene has boron and nitrogen contents of 2.38 and 2.66 atom %, respectively, and displays good dispersion stability in N-methyl-2-pyrrolidone, allowing for solution casting fabrication of a field-effect transistor. The device displays an on/off ratio of 10.7 with an optical band gap of 3.3 eV. Considering the scalability of the production method and the benefits of solution processability, BCN-graphene has high potential for many practical applications.

Axially Chiral Organic Semiconductors for Visible-Blind UV-Selective Circularly Polarized Light Detection.

Technologies that detect circularly polarized light (CPL), particularly in the UV region, have significant potential for various applications, including bioimaging and optical communication. However, a major challenge in directly sensing CPL arises from the conflicting requirements of planar structures for efficient charge transport and distorted structures for effective interaction with CPL. Here, a novel design of an axially chiral n-type organic semiconductor is presented to surmount the challenge, in which a binaphthyl group results in a high dissymmetry factor at the molecular level, while maintaining excellent electron-transporting characteristics through the naphthalene diimide group. Experimental and computational methods reveal different stacking behaviors in homochiral and heterochiral assemblies, yielding different structures: Nanowires and nanoparticles, respectively. Especially, the homochiral assemblies exhibit effective π-π stacking between naphthalene diimides despite axial chirality. Thus, phototransistors fabricated using enantiomers exhibit a high maximum electron mobility of 0.22 cm2 V-1 s-1 and a detectivity of 3.9 × 1012 Jones, alongside the CPL distinguishing ability with a dissymmetry factor of responsivity of 0.05. Furthermore, the material possesses a wide bandgap, contributing to its excellent visible-blind UV-selective detection. These findings highlight the new strategy for compact CPL detectors, coupled with the demonstration of less-explored n-type and UV region phototransistors.

Impact of Packing Geometry on Excimer Characteristics and Mobility in Perylene Bisimide Polycrystalline Films.

Efficient exciton transport is essential for high-performance optoelectronics. Considerable efforts have been focused on improving the exciton mobility in organic materials. While it is feasible to improve mobility in organic systems by forming well-ordered stacks, the formation of trap states, particularly the lower-lying states referred to as excimers, remains a significant challenge to enhancing mobility. The mobility of excimer excitons intricately depends on the strength of excitonic coupling in terms of Förster-type diffusive exciton transfer processes. Given that the formation and mobility of excimer excitons are highly sensitive to molecular arrangements (packing geometries), conducting comprehensive investigations into the structure-property relationship in organic systems is crucial. In this study, we prepared three types of polycrystalline films of perylene bisimide (PBI) by varying substituents at the imide and bay positions, which allowed us to tailor the properties of excimer excitons and their mobility based on packing geometries and excitonic coupling strengths. By utilizing femtosecond transient absorption spectroscopy, we observed ultrafast excimer formation in the higher coupling regime, while in the lower coupling regime, the transition from Frenkel to excimer excitons occurs with a time constant of 500 fs. Under high pump-fluence, exciton-exciton annihilation processes occur, indicating the diffusion of excimer excitons. Intriguingly, employing a three-dimensional diffusion model, we derived a diffusion constant that is 3000 times greater in the high coupling regime than in the low coupling regime. To investigate the optoelectronic properties in the form of a bulk system, we fabricated n-type organic field effect transistors and obtained 8000 times higher mobility in the high coupling regime. Furthermore, photocurrent measurements enable us to investigate the charge carrier transport by mobile excimer excitons, suggesting a 230-fold improvement in external quantum efficiency with tightly packing PBI molecules compared to the low coupling regime. These findings not only offer valuable insights into optimizing organic materials for optoelectronic devices but also unveil the intriguing potential of exciton migration within excimers.

A pattern recognition artificial olfactory system based on human olfactory receptors and organic synaptic devices.

Neuromorphic sensors, designed to emulate natural sensory systems, hold the promise of revolutionizing data extraction by facilitating rapid and energy-efficient analysis of extensive datasets. However, a challenge lies in accurately distinguishing specific analytes within mixtures of chemically similar compounds using existing neuromorphic chemical sensors. In this study, we present an artificial olfactory system (AOS), developed through the integration of human olfactory receptors (hORs) and artificial synapses. This AOS is engineered by interfacing an hOR-functionalized extended gate with an organic synaptic device. The AOS generates distinct patterns for odorants and mixtures thereof, at the molecular chain length level, attributed to specific hOR-odorant binding affinities. This approach enables precise pattern recognition via training and inference simulations. These findings establish a foundation for the development of high-performance sensor platforms and artificial sensory systems, which are ideal for applications in wearable and implantable devices.

Boosting the ambipolar performance of solution-processable polymer semiconductors via hybrid side-chain engineering.

Ambipolar polymer semiconductors are highly suited for use in flexible, printable, and large-area electronics as they exhibit both n-type (electron-transporting) and p-type (hole-transporting) operations within a single layer. This allows for cost-effective fabrication of complementary circuits with high noise immunity and operational stability. Currently, the performance of ambipolar polymer semiconductors lags behind that of their unipolar counterparts. Here, we report on the side-chain engineering of conjugated, alternating electron donor-acceptor (D-A) polymers using diketopyrrolopyrrole-selenophene copolymers with hybrid siloxane-solubilizing groups (PTDPPSe-Si) to enhance ambipolar performance. The alkyl spacer length of the hybrid side chains was systematically tuned to boost ambipolar performance. The optimized three-dimensional (3-D) charge transport of PTDPPSe-Si with pentyl spacers yielded unprecedentedly high hole and electron mobilities of 8.84 and 4.34 cm(2) V(-1) s(-1), respectively. These results provide guidelines for the molecular design of semiconducting polymers with hybrid side chains.

Nitrogen-doped graphene nanoplatelets from simple solution edge-functionalization for n-type field-effect transistors.

The development of a versatile method for nitrogen-doping of graphitic structure is an important challenge for many applications, such as energy conversions and storages and electronic devices. Here, we report a simple but efficient method for preparing nitrogen-doped graphene nanoplatelets via wet-chemical reactions. The reaction between monoketone (C═O) in graphene oxide (GO) and monoamine-containing compound produces imine (Shiff base) functionalized GO (iGO). The reaction between α-diketone in GO and 1,2-diamine (ortho-diamine)-containing compound gives stable pyrazine ring functionalized GO (pGO). Subsequent heat-treatments of iGO and pGO result in high-quality, nitrogen-doped graphene nanoplatelets to be designated as hiGO and hpGO, respectively. Of particular interest, hpGO was found to display the n-type field-effect transistor behavior with a charge neutral point (Dirac point) located at around -16 V. Furthermore, hpGO showed hole and electron mobilities as high as 11.5 and 12.4 cm(2)V(-1)s(-1), respectively.

Wafer-scale patterning of reduced graphene oxide electrodes by transfer-and-reverse stamping for high performance OFETs.

A wafer-scale patterning method for solution-processed graphene electrodes, named the transfer-and-reverse stamping method, is universally applicable for fabricating source/drain electrodes of n- and p-type organic field-effect transistors with excellent performance. The patterning method begins with transferring a highly uniform reduced graphene oxide thin film, which is pre-prepared on a glass substrate, onto hydrophobic silanized (rigid/flexible) substrates. Patterns of the as-prepared reduced graphene oxide films are then formed by modulating the surface energy of the films and selectively delaminating the films using an oxygen-plasma-treated elastomeric stamp with patterns. Reduced graphene oxide patterns with various sizes and shapes can be readily formed onto an entire wafer. Also, they can serve as the source/drain electrodes for benchmark n- and p-type organic field-effect transistors with enhanced performance, compared to those using conventional metal electrodes. These results demonstrate the general utility of this technique. Furthermore, this simple, inexpensive, and scalable electrode-patterning-technique leads to assembling organic complementary circuits onto a flexible substrate successfully.

Organic Mixed Ionic-Electronic Conductors for Bioelectronic Sensors: Materials and Operation Mechanisms.

The field of organic mixed ionic-electronic conductors (OMIECs) has gained significant attention due to their ability to transport both electrons and ions, making them promising candidates for various applications. Initially focused on inorganic materials, the exploration of mixed conduction has expanded to organic materials, especially polymers, owing to their advantages such as solution processability, flexibility, and property tunability. OMIECs, particularly in the form of polymers, possess both electronic and ionic transport functionalities. This review provides an overview of OMIECs in various aspects covering mechanisms of charge transport including electronic transport, ionic transport, and ionic-electronic coupling, as well as conducting/semiconducting conjugated polymers and their applications in organic bioelectronics, including (multi)sensors, neuromorphic devices, and electrochromic devices. OMIECs show promise in organic bioelectronics due to their compatibility with biological systems and the ability to modulate electronic conduction and ionic transport, resembling the principles of biological systems. Organic electrochemical transistors (OECTs) based on OMIECs offer significant potential for bioelectronic applications, responding to external stimuli through modulation of ionic transport. An in-depth review of recent research achievements in organic bioelectronic applications using OMIECs, categorized based on physical and chemical stimuli as well as neuromorphic devices and circuit applications, is presented.

Hierarchically manufactured chiral plasmonic nanostructures with gigantic chirality for polarized emission and information encryption.

Chiral metamaterials have received significant attention due to their strong chiroptical interactions with electromagnetic waves of incident light. However, the fabrication of large-area, hierarchically manufactured chiral plasmonic structures with high dissymmetry factors (g-factors) over a wide spectral range remains the key barrier to practical applications. Here we report a facile yet efficient method to fabricate hierarchical chiral nanostructures over a large area (>11.7 × 11.7 cm2) and with high g-factors (up to 0.07 in the visible region) by imparting extrinsic chirality to nanostructured polymer substrates through the simple exertion of mechanical force. We also demonstrate the application of our approach in the polarized emission of quantum dots and information encryption, including chiral quick response codes and anti-counterfeiting. This study thus paves the way for the rational design and fabrication of large-area chiral nanostructures and for their application in quantum communications and security-enhanced optical communications.